CN105026505B - Adhesive composition and its application in Anti-dew coating composition - Google Patents
Adhesive composition and its application in Anti-dew coating composition Download PDFInfo
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- CN105026505B CN105026505B CN201380074011.8A CN201380074011A CN105026505B CN 105026505 B CN105026505 B CN 105026505B CN 201380074011 A CN201380074011 A CN 201380074011A CN 105026505 B CN105026505 B CN 105026505B
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- 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
- C09J133/00—Adhesives 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; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- 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
- C09D125/00—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 an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/54—Aqueous solutions or dispersions
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention provides a kind of adhesive composition for the coating lower than critical pigment volume concentration.Described adhesive composition includes: a) at least one aqueous emulsion polymers of based on total weight in wet base of described adhesive composition 10 weight in wet base % to 80 weight in wet base %, and b) by the second polymer of the 2 dry weight % of overall dry weight to 10 dry weight % of described adhesive composition, the second polymer includes sodium styrene sulfonate, 2- acrylamide-2-methyl propane sulfonic or combinations thereof；Wherein the molecular weight of the second polymer is 10,000 to 70,000.A kind of water-based paint compositions include the adhesive composition with improved liquid stain fastness.
Description
Technical field
The present invention relates to a kind of coating compositions.Itself more particularly to one kind have improved liquid stain fastness
The water-based paint compositions of (liquid stain repellency).
Background technique
In building coats application, dew forms (also referred to as condense) under conditions of high humidity and high temperature or there are larger
Occur at the interface boundary of temperature and humidity difference.Dew leaves dry trace on wall, and negatively affects its appearance.
Dew, which may also lead to, often grows the microorganism of human health.According to the CN of ancient architecture brave (GU Jian-yong) et al.
102072921A, these problems as caused by condensing are being lower than critical pigment volume concentration (critical pigment volume
Concentration, CPVC) coating in it is more prominent.
Porous pigment has been used in the manufacture of Anti-dew coating.The Japan of stone Tian Yiyi (Ishida Yoshiichi) et al. is specially
Benefit JP 02552859B2 discloses a kind of covering composition, and the powdered calcium silicate crystals of porous, inorganic are incorporated into middle conjunction
At in resin emulsion and reducing moisture condensation.However, porous pigment negatively affects coating performance, for example, scrub resistance, elasticity and
Drying time.
Another common method for reducing moisture condensation is using surfactant.Yi Lusida (Irusta) et al., " application
Polymer science magazine (Journal of Applied Polymer Sciences) " volume 111,2299 (2009) compare two
Kind Anti-dew additive (fatty mono glyceride and N- stearoylketene base diethanol amine fatty-acid monoester) is in low density polyethylene (LDPE)
(LDPE) and the validity in the different components of Ethylene/vinyl acetate (EVA) co-polymer membrane.However, those low molecular weights
Surfactant negatively affects the waterproofness of paint film.
Accordingly, it is desirable to provide a kind of hydrophilic polymer, the polymer is had when being added in matrix polymer
There is the coating (coating) of coating (coating) performance of the moisture condensation resistance of enhancing without damaging other aspects.
Summary of the invention
The present invention provides a kind of adhesive composition for the coating lower than critical pigment volume concentration, it includes: a)
At least one aqueous emulsion polymers of based on total weight in wet base of described adhesive composition 10 weight in wet base % to 80 weight in wet base %；And b) by institute
The second polymer of the 2 dry weight % of overall dry weight to 10 dry weight % of adhesive composition is stated, the second polymer includes benzene second
Alkene sodium sulfonate, 2- acrylamide-2-methyl propane sulfonic or combinations thereof；Wherein the molecular weight of the second polymer is 10,000 to arrive
70,000。
The present invention further provides a kind of coating compositions, and it includes described adhesive compositions.
Specific embodiment
For the purpose of component in the description present composition, the included circle of all phrase instructions comprising round parentheses is included
Substance in number and its there is no any one of or both.For example, phrase " (co) polymer " includes (in alternative
In case) polymer, copolymer and its mixture；Phrase " (methyl) acrylate " means acrylate, methacrylic acid
Ester and its mixture.
As used herein, term " polymer " " should include homopolymer and copolymer.
As used herein, term " acrylic compounds " shall mean that (methyl) acrylic acid, (methyl) alkyl acrylate, (first
Base) acrylamide, (methyl) acrylonitrile and its modified forms, such as (methyl) acrylic acid hydroxy alkyl ester.
As used herein, term " aqueous " shall mean that water or can with the 50wt% based on the weight of mixture or less water
The water of miscible solvent mixing.
As used herein, term " pigment volume concentration (PVC) (PVC) " is percent by volume of the pigment in dried paint.It is critical
Pigment volume concentration (PVC) (CPVC) is interpreted as wherein adhesive and is just enough to provide the complete adsorption layer of adhesive on the surface of the pigment simultaneously
And fill the pigment volume concentration (PVC) in all gaps between particle in sealing system.
CPVC can be measured by soaking non-aqueous pigment with just enough linseed oil with forming the block of bonding.
The method obtains the value of referred to as " oil absorption (oil absorption, OA) ".It indicates oil needed for soaking 100 grams of non-aqueous pigments
Amount.Method for measuring the OA is described in British Standard 3483 (BS3483).CPVC can be calculated by following formula by OA:
CPVC=100%/(1+ (densityPigment/ densityResin))×(OA/100)。
If the pigment or resin must be used mixed using the mixture of the pigment or resin with different densities
The corresponding averag density of object is closed to be calculated.For measuring the CPVC of specific coating composition, it is preferred to use described
Resin used in coating composition or resin compound, rather than method described in BS3483 is carried out with linseed oil.
The invention is particularly applicable to be lower than the coating of critical pigment volume concentration.
Adhesive composition of the invention includes based on total weight in wet base of adhesive composition 10 weight in wet base % to 80 weight in wet base %, excellent
20 weight in wet base % of selection of land is to 60 weight in wet base %, and at least one aqueous emulsion polymers of the more preferably 30 weight in wet base % to 50 weight in wet base %.
Aqueous emulsion polymers are by the unsaturation non-ionic monomer combined polymerization of alkene system.Herein, " non-ionic monomer " means altogether
Polymerized monomer residue is between pH=1-14 without ionic charge.For the alkene system unsaturation non-ionic monomer packet in the present invention
Such as (methyl) acrylate monomer is included, wherein (methyl) acrylate instruction methacrylate or acrylate, including third
E pioic acid methyl ester, ethyl acrylate, butyl acrylate, 2-EHA, decyl acrylate, lauryl acrylate, methyl
Methyl acrylate, butyl methacrylate, isodecyl rouge, lauryl methacrylate, hydroxyethyl methacrylate second rouge,
Methacrylic acid hydroxypropyl rouge；(methyl) acrylonitrile；(methyl) acrylamide；Amino functional and urea/ureido functional monomer；It has
The monomer of acetoacetate functionality；Styrene and substituted styrene；Butadiene；Ethylene, propylene, alpha-olefin (such as 1-
Decene)；Vinyl acetate, vinyl butyrate, tertiary ethylene carbonate (vinyl versatate) and other vinyl acetates；And second
Alkenyl monomer, such as vinyl chloride, vinylidene chloride.
Aqueous emulsion polymers of the invention further include most 10 weight % based on the dry weight of polymer, preferably up to
The alkene system unsaturated monomer for carrying at least one functional group selected from the following of 5 weight %, more preferably up to 2.5 weight %:
Carboxyl, carboxylic acid anhydrides, hydroxyl, amide, sulphonic acid ester, phosphonate ester and its mixture.The example of the monomer of these types be alkene system not
Saturated carboxylic acid or dicarboxylic acids, especially acrylic or methacrylic acid, itaconic acid (itaconic acid), maleic acid (maleic
Acid) or amide, the N- alkylolamides or hydroxy alkyl ester of carboxylic acid especially mentioned above, such as (methyl) acrylamide,
N- methylol (methyl) acrylamide, 2- ethoxy (methyl) acrylamide, (methyl) hydroxy-ethyl acrylate and (methyl) third
Olefin(e) acid hydroxypropyl acrylate.It is highly preferred that functional monomer is methacrylic acid, acrylic acid, acrylamide, Methacrylamide.It is optimal
Selection of land, functional monomer are methacrylic acids.
Optionally, aqueous emulsion polymers can further include total weight 0wt% to the 0.5wt% by polymer, excellent
At least one of 0.05 weight % of selection of land to 0.4 weight %, more preferably 0.1 weight % to 0.3 weight % have at least one
The alkene system unsaturated monomer of alkoxysilane-functional degree is as combined polymerization unit.It preferably, is hydrolyzable alkoxy silane
Degree of functionality.For example, the monomer of functionalized with alkoxysilane includes vinyl trialkyl oxysilane, such as vinyl trimethoxy
Base silane；Alkyl vinyl dialkoxy silicane；(methyl) acryloxyalkyl trialkoxy-silane；Such as (methyl) third
Alkene trimethylammonium trimethoxy silane and (methyl) acryloxypropyl-trimethoxy silane；And its derivative.
Adhesive composition of the invention is further included to be arrived by the overall dry weight 2wt.% of adhesive composition
10wt.%, preferably 3 dry weight % are to 10 dry weight %, and second polymer of the more preferably 5 dry weight % to 10 dry weight %, institute
Stating second polymer includes sodium styrene sulfonate, 2- acrylamide-2-methyl propane sulfonic or combinations thereof.
Suitable second polymer is including but not limited to poly- (4- styrene/sodium sulfonate), such as in Sigma-Alder
Commercially available from odd Co., Ltd (Sigma-Aldrich Co.LLC)；Poly- (2- styrene/sodium sulfonate), poly- (3- styrene-sulphur
Sour sodium), poly- (2- acrylamide-2-methyl propane sulfonic), poly- (4- styrene/sodium sulfonate -co- 2- acrylamide -2- methyl-prop sulphur
Acid), poly- (2- styrene/sodium sulfonate -co- 2- acrylamide-2-methyl propane sulfonic) and poly- (3- styrene/sodium sulfonate -co-
2- acrylamide-2-methyl propane sulfonic).
In an embodiment of the present invention, comprising sodium styrene sulfonate, 2- acrylamide-2-methyl propane sulfonic or combinations thereof
The molecular weight of second polymer is 10,000 to 70,000.In a preferred embodiment, the molecular weight of second polymer is 11,
000 to 25,000.It most preferably, is 13,000 to 20,000.
In one particular embodiment of the present invention, second polymer is sodium styrene sulfonate homopolymer or itself and other alkene
It is the copolymer of unsaturated non-ionic monomer.In this embodiment, by the total dry of the second polymer comprising sodium styrene sulfonate
Restatement, sodium styrene sulfonate is in 80 dry weight % to 100 dry weight %, and preferably 90 dry weight % are to 100 dry weight %, and most preferably
In the content range of 95 dry weight % to 100 dry weight %.Preferably second polymer be sodium styrene sulfonate homopolymer.
In another embodiment of the present invention, second polymer be 2- acrylamide-2-methyl propane sulfonic homopolymer or
The copolymer of itself and other alkene system unsaturation non-ionic monomers.In this embodiment, by the overall dry weight of second polymer, 2- third
Acrylamide -2- methyl propane sulfonic acid is in 80 dry weight % to 100 dry weight %, and preferably 90 dry weight % are to 100 dry weight %, and most preferably
In the content range of 95 dry weight % of ground to 100 dry weight %.Preferably second polymer is 2- acrylamide-2-methyl propane sulfonic
Homopolymer.
In still another embodiment of the invention, second polymer is sodium styrene sulfonate and 2- acrylamide -2- first
The copolymer of base propane sulfonic acid or copolymer with other alkene system unsaturation non-ionic monomers.In this embodiment, in this copolymer
In sodium styrene sulfonate and the weight ratio of 2- acrylamide-2-methyl propane sulfonic be 1: 99 to 99: 1, and by the second polymerization
The total weight of the total weight of object, sodium styrene sulfonate and 2- acrylamide-2-methyl propane sulfonic is 80 weight % to 100 weights
% is measured, preferably 90 weight % are to 100 weight %, and most preferably 95 weight % to 100 weight %.
Optionally, second polymer of the invention can further include 0.1 weight of total weight by second polymer
% to 20 weight % is measured, preferably 0.1 weight % is to 10 weight %, and most preferably methyl of the 0.1 weight % to 5 weight %
Or mixtures thereof acrylic acid acetoacetoxyethyl (AAEM), diacetone acrylamide (DAAM).
The polymerization technique for being used to prepare copolymer is well-known in the art, such as emulsion polymerization.In lotion
In polymerization, conventional surfactant includes anion and nonionic surfactant, and illustrative example includes (but not
Be limited to) alkyl, the sulfuric ester of aryl or alkylaryl, sulphonic acid ester or phosphate alkali metal salts or ammonium salt；Alkyl sulfonic acid；Sulfo group
Succinate；Fatty acid；Alkene system unsaturation surfactant monomer；And the alcohol or phenols of ethoxylation.Press the weight of monomer
Meter, the amount of surfactant used is usually 0.1 weight % to 6 weight %.Heat or Redox Initiator method can be used.Reaction
Temperature is maintained at a below at 100 DEG C in entire reaction process.Reaction temperature is preferably between 30 DEG C and 95 DEG C, more preferably
Between 50 DEG C and 90 DEG C.Monomer mixture can be added by respective pure form or by the form of lotion in water.Monomer mixture can
With added one or more times after reaction period or continuously, linearly or non-linearly, or combinations thereof addition.
Based on the weight of total monomer, conventional free radical usually can be used with the content of 0.01 weight % to 3.0 weight %
Initiator, such as hydrogen peroxide, sodium peroxide, potassium peroxide, t-butyl hydroperoxide, cumene hydroperoxide (cumene
Hydroperoxide), ammonium persulfate and/or alkali metal salt, sodium perborate, peroxophosphoric acid and its salt, potassium permanganate and peroxide two
Ammonium sulfate or alkali metal salt.The oxidation-reduction system of initiator identical as the coupling use of suitable reducing agent can be used, it is described
Reducing agent such as sodium sulfoxylate formaldehyde, ascorbic acid, arabo-ascorbic acid (IAA), the alkali metal of sulfur acid and ammonium salt (such as sulfurous
Sour sodium, sodium hydrogensulfite, sodium thiosulfate, sodium hydrosulfide (sodium hydrosulfite), vulcanized sodium, sodium bisuflide or company
Sodium sulfite (sodium dithionite)), methyl sulfinate (formadinesulfinic acid), methylol sulfonic acid,
Acetone bisulfites, amine (such as ethanol amine), glycolic, glyoxylic acid, lactic acid, glyceric acid, malic acid, tartaric acid and
The salt of aforementioned acid.The metal salt of catalytic oxidation-reduction reaction: iron, copper, manganese, silver, platinum, vanadium, nickel, chromium, palladium or cobalt can be used.It can
Optionally using the chelating agent for being used for metal.
Buffer is optionally used in the present invention.It is a kind of salt, and for the control process during polymerization reaction
Interior pH value.General buffer salt includes phosphate, citrate, acetate, bicarbonate and carbonate.Relative ion can be
Sodium, potassium and ammonium ion.Buffer can be after entire reaction period largely or entirely, or in the limited of reaction period
During part with add one or more times or continuously, linearly or non-linearly, or combinations thereof addition.Buffer can be used to incite somebody to action
PH value control is between 2 to 7 in journey, preferably between 2 to 5, more preferably between 2 to 4.
Chain-transferring agent includes but is not limited to halogen compounds, such as tetrabromomethane；Allyl compound；Or mercaptan, example
Such as thioglycolic acid alkyl ester, sulfydryl alkanoic acid Arrcostab and C4-C22Straight chain or branched-chain alkyl mercaptan, can be used for reducing
The molecular weight of emulsion polymer and/or the molecular weight that provides and will be obtained in other ways with any initiator generated free radicals
It is distributed different molecular weight distribution.Chain-transferring agent can be after entire reaction period largely or entirely, or anti-
Answer during the finite part of period (for example, being fed in pot and in the reduction residual monomer stage) to add one or more times or
Continuously, it linearly or non-linearly adds.By the total monomer weight for being used to form aqueous copolymer dispersion liquid, usually with
The amount of 0wt% to 5wt% uses chain-transferring agent.Based on the total moles monomer for being used to form aqueous copolymer dispersion liquid, preferably
Chain transfer agent content be 0.01 to 0.5 mole of %, more preferably 0.02 to 0.4 mole of %, and most preferably 0.05 to 0.2
Mole %.
It is contained in the embodiment in second polymer in DAAM, adhesive composition of the invention is further included by institute
The 0.1 weight % of total weight to 20 weight % of adhesive composition is stated, preferably 0.5 weight % is to 10 weight %, and most
The adipic dihydrazide (ADH) of preferably 1 weight % to 5 weight %.
Adhesive composition of the invention can further include 0.005 weight of total weight by described adhesive composition
Measure % to 0.3 weight %, ZnO of the preferably 0.05 weight % to 0.2 weight %.
Adhesive composition of the invention is made in one of its application of stable coating composition.
Coating composition of the invention can further include at least one conventional coating additive, including but not limited to
Coalescent, cosolvent, surfactant, buffer, neutralizer, thickener, non-thickening rheology modifier, dispersing agent, moisturizer,
Wetting agent, mould inhibitor, biocide, plasticiser, antifoaming agent, anti-foaming agent, anti skinning agent, flowable, crosslinking agent and anti-oxidant
Agent.
Thickener used herein includes but is not limited to polyvinyl alcohol (PVA), through hydrophobic modified alkali-soluble emulsion
(HASE), alkali solubility or the swellable lotion of alkali (ASE), (affiliated through hydrophobic modified ethylene oxide-urethane polymer
HEUR is known as in field), cellulose thickener, such as hydroxymethyl cellulose (HMC), hydroxyethyl cellulose (HEC), through hydrophobic
Property modified hydroxyethyl cellulose (HMHEC), sodium carboxymethylcellulose (SCMC), carboxymethyl 2- sodium hydroxyethyl cellulose, 2- hydroxyl
Propyl methocel, 2- hydroxyethylmethylcellulose, 2- hydroxy butyl methyl cellulose, 2- hydroxyethyl ethylcellulose and 2-
Hydroxypropyl cellulose.Being also suitable make thickener is smoke-like silica, attapulgite clay (attapulgite clay)
With other types of clay and titanate chelating agent.
Dispersing agent used herein includes nonionic, anion and cation dispersing agent, such as with suitable molecular weight
Polyacid, 2-amino-2-methyl-1-propanol (AMP), dimethylaminoethanol (DMAE), potassium tripolyphosphate (KTPP), poly- phosphorus
Sour trisodium (TSPP), citric acid and other carboxylic acids.Preferred dispersing agent is the polyacid with suitable molecular weight.It is used herein
Polyacid include but is not limited to homopolymer and copolymer based on polycarboxylic acids, including hydrophobicity or hydrophilically modified
Those, such as polyacrylic acid or polymethylacrylic acid or maleic anhydride and various monomers, such as styrene, acrylate
Or the salt and its mixing of methacrylate, diisobutylene and other hydrophilies or hydrophobic monomer and foregoing dispersant
Object.The molecular weight of such polyprotic dispersing agents is 400 to 50,000, preferably 400 to 30,000, preferably 500 to 10,000,
Preferably 1,000 to 5,000, and preferably 1,500 to 3,000.
Antifoaming agent and/or anti-foaming agent used herein are including but not limited to based on silicone and based on the defoaming agent of mineral oil
(defoamer).Surfactant used herein includes anion, nonionic, cationic surfactant and amphipathic surface
Activating agent.Anion and nonionic surfactant is preferably used, and more preferred with nonionic surfactant.
The biocide that can be used in the present invention is organic or inorganic biocide.Example is described in E.I.Du Pont Company
(DuPont) U.S. Patent No. 4898895 of U.S. Patent No. 4127687, beneficial ridge (Masuoka) et al. and
In WO1995032862A1.Preferably, biocide has diiodomethyl-to toluene sulfone, 4,5-, the bis- different thiophene of chloro- 2- octyl -2H-
The active structure of or mixtures thereof azoles -3- ketone (DCOIT), chlormethylisothiazo,ine ketone, methylisothiazolinone.
The preparation of coating composition is related to following methods: selecting and mixes appropriate paint ingredient with appropriate ratio to provide
Coating with particular process and treatment characteristic and the final dry paint film with required characteristic.
Water-based paint compositions can be coated by conventional application method, and the coating method is including but not limited to brushed
Painting, roller coating and spray coating method, such as air atomizing spraying, the spraying of air auxiliary, airless spraying, the spraying of high volume low pressure and sky
The airless spraying of gas auxiliary.
Suitable substrate includes but is not limited to concrete, cement plate, medium-density fiberboard (MDF) and particle board, stone
Cream plate, timber, stone, metal, plastics, wallpaper and textile fabric.Preferably, all substrates are precoated by aqueous or solvent bottom paint
Cloth.
Example
It is expected that the experimental method in example follows fields when not described in detail, (such as polymerization is learned to do
Volume) in normal condition, follow by chemistry or apparatus manufacturer suggestion condition.
I. raw material
II. the test method of Anti-dew performance
According to TT-C-492C, coating compound, paint anti-condensation Federation specification (on May 31st, 1974) are carrying out some repair
Anti-dew performance is assessed in the case where changing.Two steel toots of different applying coatings of 20g (wet paint weight) are used respectively.
The height of circular cone is 98mm, and the bottom radius of circular cone is 53mm.By toot be dried at room temperature for 24 hours it
Afterwards, 0 DEG C of ice water is added into the toot.The temperature of external environment is 23 DEG C and 45% relative humidity.By bottle
It is placed below toot to collect moisture condensation drop.First droplet dew water is dropped into the timing definition in bottle downwards as knot
Reveal the time, is used to quantify Anti-dew performance.Condensing, the time is longer, and Anti-dew performance is better.
III. experiment embodiment
Example 1: preparation poly(sodium styrene sulfonate) (PSSS) homopolymer and copolymer
I. PSSS-1 to PSSS-5
50g sodium styrene sulfonate (SSS) is dissolved in 200g deionized water, and by the two loading with stirring simultaneously
And in 1 liter of four-neck flask reactor with condenser.The heating response device in the case where being blown into nitrogen.When the temperature of reactor
When degree reaches 80 DEG C, initiator sodium peroxydisulfate (SPS) is fitted into reactor.The amount of sodium peroxydisulfate is calculated to control final product
The molecular weight of poly(sodium styrene sulfonate) (PSSS).When temperature increases to 86 DEG C, reaction is kept for 2 hours at this temperature.
Reaction product is filtered by 100M and 325M filter, and obtains final product, 20wt.% solid PSSS aqueous solution.PSSS
Weight molecular weight be listed in Table 1.
The average molecular weight of table 1.PSSS sample
| Sample | Mw |
| PSSS-1 | 7,500 |
| PSSS-2 | 10,700 |
| PSSS-3 | 13,000 |
| PSSS-4 | 18,600 |
| PSSS-5 | 23,100 |
Ii. PSSS-6 (being purchased from Sigma-Aldrich Co., Ltd) is poly- (the 4- styrene-sulphur of 30wt.%
Sour sodium) aqueous solution, and its weight average molecular weight is 70,000.
iii. P(SSS-AAEM)
40g SSS is dissolved in 183g deionized water, and by the two loading with stirring and have condenser
1 liter of four-neck flask reactor in.10g AAEM is dissolved in 6g 25%NaOH aqueous solution to obtain AAEM water under stiring
Solution.AAEM aqueous solution is fitted into reactor.It is being blown into N2In the case where reactor is heated to 88 DEG C after, by 1.1g
SPS and 0.5g 3- mercaptopropionic acid (MPA) is fitted into reactor to start to polymerize.Reaction temperature is kept at 88 DEG C 1 hour with
Obtain SSS-AAEM copolymer.The weight average molecular weight of P (SSS-AAEM) is 207,000.
iv. P(SSS-DAAM)
40g SSS and 2g DAAM are dissolved in 183g deionized water, and with stirring and will be had at the two loading
Have in 1 liter of four-neck flask reactor of condenser.It is being blown into N2In the case where reactor is heated to 88 DEG C after, by 3g
SPS and 1g MPA is fitted into reactor to start to polymerize.Reaction temperature is kept for 2 hours at 86 DEG C.At the end of polymerization, lead to
It crosses addition ammonium hydroxide and the pH of solution is adjusted to 9.0.1.64gADH is added into reaction system to obtain SSS-DAAM copolymer.
The weight average molecular weight of P (SSS-DAAM) is 12,000.
v. P(SSS/St)
269g sodium styrene sulfonate (SSS) is dissolved in 1076g deionized water to form monomer emulsions 1# (ME 1#).
1g SLS (28% solid), 29.89g styrene and 2.99g MPA are dissolved in 10g deionized water to prepare monomer emulsions 2
(ME 2#).By at 110g deionized water loading with stirring and with condenser 1 liter of four-neck flask reactor in；Then
The heating response device in the case where being blown into nitrogen.When temperature of reactor reaches 90 DEG C, by 2g initiator sodium peroxydisulfate (SPS)
It is fitted into reactor, and observes that 1 DEG C -2 DEG C of temperature increases.When temperature begins to decline 1 DEG C, by ME 1# and ME 2# mono-
Play charging, and the feed for duration 120 minutes.Meanwhile the co-feeding catalyst containing 0.82g SPS and 22g deionized water
Solution, and the feed for duration 120 minutes.When all chargings are completed, temperature of reactor is cooled to 65 DEG C, and to anti-
Answer injection tracking promotor (9ppm FeSO in device4·7H2O and 6ppm versene (Versene)), then by 0.2%t-BHP and
0.15%IAA is co-fed in reactor, and the feed for duration 30 minutes.All chargings are based on monomer.Pass through 100M
Reaction product is filtered with 325M filter, and obtains final product, poly- (the co- St of the SSS-) lotion of 20wt.% solid.Its weight
Average molecular weight is 33,000.
vi. P(SSS/BA)
Using be prepared as above the identical method of P (SSS/St-2), but replace all styrene with BA.Its weight average point
Son amount is 42,800.
vii. PAMPS
All SSS are replaced using method identical with PSSS-5 is prepared as above, but with AMPS.Its weight average molecular weight is
10,000。
ix. P(SSS/AMPS)
Using method identical with PSSS-5 is prepared as above, but with AMPS replacement 20% SSS.Its weight average molecular weight
It is 9,000.
Example 2: water-based paint compositions are prepared
Paint 1- paint 5:
Via blending 500g PRIMALTMSF-018 adhesive and 20% poly(sodium styrene sulfonate) of 100g are (respectively
PSSS-1 to PSSS-5) aqueous solution prepares latex 1 to latex 5.It is prepared using following procedure respectively containing latex 1 to latex
5 paint 1 arrives paint 5.Use high speed Kao Leisi disperser (Cowles disperser) mixing such as grinding ingredient listed in table 2.
Diluted composition listed in such as table 2 is mixed with grinding ingredient using Routine Test Lab mixer.The pigment volume concentration of gained paint is dense
Spending (PVC) is 40% (PVC40).The volume solid amount of gained paint is 35.5%.Weight amount of solid is 50.7%.
The PVC40 water-based paint compositions of the paint of table 2. 1 to 5
Paint 6
Via blending 500g PRIMALTMPoly- (the sodium styrene sulfonate -co- methacrylic acid second of SF-018 and 125g 20%
Acyl acetoxyethyl (P (SSS-AAEM)) aqueous solution prepares latex 6.Sodium styrene sulfonate and methacrylic acid acetoacetyl
The weight ratio of oxygroup ethyl ester is 4: 1.The program of manufacture paint 1 is followed to prepare the paint 6 containing latex 6.The PVC of gained paint is
40%.The volume solid amount of gained paint is 35.5%.Weight amount of solid is 50.7%.
Paint 7
Via blending 500g PRIMALTMSF-018 and 125g 20%P (SSS-DAAM) aqueous solution prepares latex 7.Benzene
The weight ratio of vinyl sulfonic acid sodium and DAAM are 20: 1.The program of manufacture paint 1 is followed to prepare the paint 7 containing latex 7.Gained paint
PVC is 40%.The volume solid amount of gained paint is 35.5%.Weight amount of solid is 50.7%.
Paint 8
Via blending 500g PRIMALTMSF-018 and 20% poly(sodium styrene sulfonate) of 125g (PSSS-6) aqueous solution
To prepare latex 8.The program of manufacture paint 1 is followed to prepare the paint 8 containing latex 8.The PVC of gained paint is 40%.Gained paint
Volume solid amount is 35.5%.Weight amount of solid is 50.7%.
Paint 9
Via blending 500g PRIMALTMSF-018 and 20% poly(sodium styrene sulfonate) of 87.5g (PSSS-3) aqueous solution
To prepare latex 9.The program of manufacture paint 1 is followed to prepare the paint 9 containing latex 9.The PVC of gained paint is 40%.Gained paint
Volume solid amount is 35.5%.Weight amount of solid is 50.7%.
Paint 10
Via blending 500g PRIMALTMSF-018 and 20% poly(sodium styrene sulfonate) of 62.5g (PSSS-3) aqueous solution
To prepare latex 10.The program of manufacture paint 1 is followed to prepare the paint 10 containing latex 10.The PVC of gained paint is 40%.Gained paint
Volume solid amount be 35.5%.Weight amount of solid is 50.7%.
Paint the comparative paint of 11-
The program for following manufacture paint 1 only contains PRIMAL to prepareTMPaint 11 of the SF-018 as adhesive.Gained paint
PVC is 40%.The volume solid amount of gained paint is 35.5%.Weight amount of solid is 50.7%.
Paint the comparative paint of 12-
Only contain PRIMAL using following procedureTMPaint 12 of the AS-380 as adhesive.Preparation uses high speed Kao Leisi
Listed grinding ingredient in disperser (Cowles disperser) mixture table 3.Using Routine Test Lab mixer by institute in table 3
The diluted composition of column is mixed with grinding ingredient.The PVC of gained paint is 80% (PVC80).The volume solid amount of gained paint is
53.8%.Weight amount of solid is 48%.
The PVC80 water-based paint compositions of the paint of table 3. 12
Paint 13
Via blending 500g PRIMALTM20% poly(sodium styrene sulfonate) of SF-018,125g (PSSS-3) aqueous solution with
And 3.0g 25% Zinc oxide water slurry prepares latex 13.The program of manufacture paint 1 is followed to prepare the paint 13 containing latex 13.
The PVC of gained paint is 40%.The volume solid amount of gained paint is 35.5%.Weight amount of solid is 50.7%.
Paint 14
Via blending 500g PRIMALTMPoly- (the sodium styrene sulfonate -co- styrene) (P (SSS/ of SF-018,125g 20%
St)) aqueous solution prepares latex 14.The weight ratio of SSS and styrene is 90 to 10 in P (SSS/St).Follow the journey of manufacture paint 1
Sequence prepares the paint 14 containing latex 14.The PVC of gained paint is 40%.The volume solid amount of gained paint is 35.5%.Weight is solid
The scale of construction is 50.7%.
Paint 15
Via blending 500g PRIMALTMPoly- (sodium styrene sulfonate -co- the butyl acetate) (P of SF-018,125g 20%
(SSS/BA)) aqueous solution prepares latex 15.The weight ratio of SSS and styrene is 90 to 10 in P (SSS/BA).Follow manufacture paint
1 program prepares the paint 15 containing latex 15.The PVC of gained paint is 40%.The volume solid amount of gained paint is 35.5%.Weight
Measuring amount of solid is 50.7%.
Paint 16
Via blending 500g PRIMALTMSF-018,125g 20% poly- (2- acrylamide-2-methyl propane sulfonic)
(PAMPS) aqueous solution prepares latex 16.The program of manufacture paint 1 is followed to prepare the paint 16 containing latex 16.The PVC of gained paint
It is 40%.The volume solid amount of gained paint is 35.5%.Weight amount of solid is 50.7%.
IV. result:
According to brave et al. the CN 102072921A of ancient architecture, moisture condensation is related to the PVC painted in building coats region.PVC is lower,
It condenses more serious.There is serious moisture condensation lower than the paint of critical pigment volume concentration (CPVC), and the paint higher than CPVC seldom has
Condensation trouble.
Experiment of the invention is carried out in common 40PVC paint and comparative 80PVC paint.In the present invention, PVC40 is painted
CPVC value is calculated as 59, therefore PVC40 paint is lower than CPVC.The CPVC value of PVC80 paint is calculated as 64.9, therefore PVC80 paint is higher than
CPVC。
The present invention relates to adhesive compositions and its application in Anti-dew building coating.Adhesive composition of the invention
Homopolymer and/or main copolymer comprising sodium styrene sulfonate (SSS) are combined with reducing by described adhesive as additive
The moisture condensation painted made of object.
The main copolymer of " A " means that the content range of " A " in the copolymer is higher than 80%, preferably higher than 90%,
And more preferably above 95%.
Detailed test result is shown in table 4.
The general introduction of 4. Anti-dew test result of table
* paint 1,11 and 12 is comparative example.Paint 11 and 12 is used as benchmark.There is paint 11 serious dew to be formed, and paint 12 tools
There is few dew to be formed.The moisture condensation time of paint 1 does not have notable difference compared with the moisture condensation time of paint 11.
Paint 11 is common 40PVC paint, that is, is lower than CPVC, there is serious dew to be formed in practical applications.According to repairing
The TT-C-492C standard changed, the moisture condensation time for painting 11 is 32 minutes.Paint 12 is common 80PVC paint, that is, is higher than CPVC, in reality
It is seldom formed with dew in the application of border.The test moisture condensation time of paint 12 is 55 minutes, and thinks that it is present invention moisture condensation property
The target of energy.As a result it shows, when adding PSSS into composite, the moisture condensation time of 40PVC paint (representing the paint for being lower than CPVC)
It obviously increases paint 2 and arrives paint 5 and paint 8 the results show that when the Mw of PSSS is higher than 13,000, provide best Anti-dew for paint and imitate
Fruit (the moisture condensation time is within the scope of 50 to 55 minutes).When the Mw of PSSS is lower than 13000, the moisture condensation time subtracts as Mw reduces
It is few, and when it reaches 7,500 (paint 1), moisture condensation time (35 minutes) and the moisture condensation time phase for painting 11 (paints lower than CPVC)
It is more slightly higher than only.7,500 be the Mw baseline for providing the PSSS of Anti-dew performance.
In paint 9 and 10, by water-based latex PRIMALTMThe solid meter of SF-018 adhesive composition, the dosage of PSSS from
3.9% to 5.8% etc..In the case where PSSS dosage lower (paint 10), the moisture condensation time shortens.In the 3.9%PSSS of paint 10
Under dosage, the moisture condensation time is only 40 minutes.
For paint 6 and 7, the copolymer of SSS and functional monomer are added into 40PVC composite.Both all show with
Paint 11 compares preferable Anti-dew performance.
In paint 13, ZnO is added into the common 40PVC paint composite with 10% dosage PSSS-3.Its displaying has
The good Anti-dew performance of 50 minutes moisture condensation time.
In paint 14, the copolymer of SSS and styrene are added into composite.As a result it shows, contains 10% styrene
SSS copolymer p (SSS/St) is than only including PRIMALTMThe paint 11 of SF-018 is good.
Paint 15 is deployed with SSS and butyl acrylate (BA) copolymer.The ratio of SSS and BA is 9: 1.It shows preferable
40 minutes Anti-dew performances are higher than paint 11.
Paint 16 is deployed with ampere homopolymer.It shows than painting 11 good Anti-dew performances.Paint 16 has the knot with paint 11
Reveal the time and compares acceptable moisture condensation time (42 minutes).
By data it may be concluded that being played much better when second polymer is the homopolymer of sodium styrene sulfonate
Anti-dew effect.
Claims (12)
1. a kind of water-based paint compositions of coloring, the coating composition has the face lower than critical pigment volume concentration CPVC
Expect volumetric concentration, it includes adhesive composition and granules of pigments, described adhesive composition includes:
A) based on total weight in wet base of described adhesive composition, at least one aqueous emulsion polymers of the 10 weight in wet base % to 80 weight in wet base %；With
And
B) press at least one emulsion polymer and second polymer overall dry weight, the second polymer of 2 dry weight % to 10 dry weight %,
The second polymer include as the sodium styrene sulfonate of polymerized unit, 2- acrylamide-2-methyl propane sulfonic or combinations thereof,
And weight average molecular weight is 10000-70000；
The CPVC is defined as adhesive composition and is just enough to provide adhesive composition complete adsorption layer on the surface of the pigment
And fill the pigment volume concentration (PVC) in all gaps between particle in sealing system.
2. coating composition according to claim 1, wherein the weight average molecular weight of the second polymer is 11000 to arrive
25000。
3. coating composition according to claim 1, wherein the aqueous emulsion polymers include acrylate monomer, benzene second
Or mixtures thereof alkene monomer, vinyl ester monomer are used as polymerized unit.
4. coating composition according to claim 1 gathers wherein the second polymer is further included by described second
The acetoacetoxyethyl methacrylate of the 0.1 weight % of total weight to 20 weight % of object is closed as polymerized unit.
5. coating composition according to claim 1, wherein pressing the overall dry weight of the second polymer, styrene sulfonic acid
The total weight of sodium and/or 2- acrylamide-2-methyl propane sulfonic is within the scope of 80 dry weight % to 100 dry weight %.
6. coating composition as described in claim 1, wherein the second polymer includes poly- (styrene sulfonate -co- benzene
Ethylene) or it is poly- (styrene sulfonate -co- butyl acrylate).
7. coating composition as described in claim 1, wherein the second polymer include poly- (4- styrene/sodium sulfonate),
Poly- (2- styrene/sodium sulfonate), poly- (3- styrene/sodium sulfonate), poly- (2- acrylamide-2-methyl propane sulfonic), poly- (4- benzene second
Alkene-sodium sulfonate -co- 2- acrylamide-2-methyl propane sulfonic), poly- (2- styrene/sodium sulfonate -co- 2- acrylamide -2- methyl
Propane sulfonic acid) and it is poly- (3- styrene/sodium sulfonate -co- 2- acrylamide-2-methyl propane sulfonic).
8. coating composition according to claim 1, wherein the second polymer is the homopolymer of sodium styrene sulfonate.
9. coating composition according to claim 1 gathers wherein the second polymer is further included by described second
The diacetone acrylamide of the 0.1 weight % of total weight to 20 weight % of object is closed as polymerized unit, and described adhesive group
Close the adipic dihydrazide that object further includes the 0.1 weight % of total weight to 20 weight % by described adhesive composition.
10. coating composition according to claim 1, wherein described adhesive composition is further included by the bonding
The ZnO of the 0.005 weight % of total weight to 0.3 weight % of agent composition.
11. coating composition according to claim 1, wherein the pigment includes titanium dioxide.
12. coating composition according to claim 1, wherein the coating composition further includes incremental agent.
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| PCT/CN2013/072398 WO2014139074A1 (en) | 2013-03-11 | 2013-03-11 | Binder composition and its application in anti-dewing coating composition |
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| EP3434701A1 (en) | 2017-07-25 | 2019-01-30 | Arkema France | Stable aqueous polymer dispersions |
| CN111234108B (en) * | 2020-02-18 | 2021-05-25 | 上海交通大学 | Preparation method of hydrogel material for facial mask |
| US11286232B2 (en) | 2020-07-29 | 2022-03-29 | Saudi Arabian Oil Company | Preparation of cationic surfactants |
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| CN1576335A (en) * | 2003-07-24 | 2005-02-09 | 赛拉尼斯乳胶有限公司 | Coating composition and process for its preparation |
| CN101679536A (en) * | 2007-06-11 | 2010-03-24 | 巴斯夫欧洲公司 | Method for producing an aqueous polymerisate dispersion |
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| US6926957B2 (en) * | 2001-06-29 | 2005-08-09 | 3M Innovative Properties Company | Water-based ink-receptive coating |
| JP4083029B2 (en) * | 2003-02-04 | 2008-04-30 | 株式会社クラレ | Acrylic polymer powder, acrylic sol and molded product |
| BRPI0508934A (en) * | 2004-03-17 | 2007-08-14 | Ciba Sc Holding Ag | liquid thickener dispersion polymer for aqueous systems |
| WO2009147126A1 (en) * | 2008-06-03 | 2009-12-10 | Basf Se | Titanium dioxide composition comprising titanium dioxide nanoparticles, and preparation and use thereof |
| US9238747B2 (en) * | 2008-11-17 | 2016-01-19 | Basf Se | Stain blocking compositions |
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| CN1576335A (en) * | 2003-07-24 | 2005-02-09 | 赛拉尼斯乳胶有限公司 | Coating composition and process for its preparation |
| CN101679536A (en) * | 2007-06-11 | 2010-03-24 | 巴斯夫欧洲公司 | Method for producing an aqueous polymerisate dispersion |
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| 聚乙烯-对苯乙烯磺酸钠接枝膜制备;俎建华等;《辐射研究与辐射工艺学报》;20000831;第18卷(第3期);第168-170页 * |
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