CN105189581A - Acrylic emulsion, water-based primer, and water-based primer composition - Google Patents
Acrylic emulsion, water-based primer, and water-based primer composition Download PDFInfo
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- CN105189581A CN105189581A CN201480025960.1A CN201480025960A CN105189581A CN 105189581 A CN105189581 A CN 105189581A CN 201480025960 A CN201480025960 A CN 201480025960A CN 105189581 A CN105189581 A CN 105189581A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/002—Priming paints
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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
- 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
-
- 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
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- 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
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- 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)
- Dispersion Chemistry (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
- Sealing Material Composition (AREA)
Abstract
Provided is an acrylic emulsion that exhibits excellent water-resistant adhesion. The acrylic emulsion contains acrylic particles, and the average particle size of the acrylic particles is 0.6 mum or less. The acrylic particles are polymer particles obtained by polymerizing a polymerizable monomer (A) having a (meth)acryloyl group in the presence of a persulfate (B). The polymerizable monomer (A) comprises a (meth)acrylic acid alkyl ester monomer (A1) and a hydroxy group-containing polymerizable monomer (A2). The molar ratio (B/A1) of the persulfate (B) to the (meth)acrylic acid alkyl ester monomer (A1) is 0.007 or higher. The molar ratio (OH/A1) of the hydroxy group (OH) of the hydroxy group-containing polymerizable monomer (A2) to the (meth)acrylic acid alkyl ester monomer (A1) is 0.05 or higher. The solid content of the acrylic emulsion is 15 mass% or higher but less than 40 mass%.
Description
Technical field
The present invention relates to a kind of acrylic emulsion and water system priming paint and water system paint base composition.
Background technology
Generally speaking, in order to make sealing material for building bonding with the adherend such as aluminium, Mortar Plates, primer coating on adherend is needed.
At present, priming paint is generally containing organic solvent.But, in order to reduce environmental pollution as far as possible, further improve safety and sanitation to operator, require exploitation water system priming paint (reference example is as patent documentation 1 etc.).
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2011-231274 publication
Summary of the invention
Invent problem to be solved
As existing water system priming paint, such as, there will be a known by making the emulsifying agents such as Sodium Lauryl Sulphate BP/USP be attached to the surface of acrylic particles and make the acrylic emulsion of this particle dispersion in water.
When such acrylic emulsion is coated adherend as water system priming paint and made its drying, water tolerance (water-fast cementability) is poor sometimes.Think that its reason is as follows.That is, think because in water system priming paint after the drying, acrylic particles tight clusters and form film time, if make this film impregnated in water, then the emulsifying agent being attached to acrylic particles surface can stripping, and this part becomes space, and the water capacity easily immerses film.
Therefore, the object of the invention is to, a kind of water-fast acrylic emulsion excellent in adhesion is provided.
For solving the means of problem
The present inventor etc. concentrate on studies to achieve these goals, found that, by using the emulsion of the acrylic acid series containing specific acrylic particles, the cementability of the adherends such as Mortar Plates, particularly water-fast cementability being become good, thus completes the present invention.
That is, the invention provides following (1) ~ (5).
(1) a kind of acrylic emulsion, containing acrylic particles, aforesaid propylene acid is the median size of particle is less than 0.6 μm, the aforesaid propylene acid polymerizable monomer (A) that to be particle be makes to have (methyl) acryl carries out being polymerized the polymer particle obtained under the existence of the persulphate (B) as polymerization starter, above-mentioned polymerizable monomer (A) comprises (methyl) alkyl acrylate monomer (A1) and has the polymerizable monomer (A2) of hydroxyl of hydroxyl, above-mentioned persulphate (B) is more than 0.007 relative to the mol ratio (B/A1) of above-mentioned (methyl) alkyl acrylate monomer (A1), the hydroxyl (OH) that the polymerizable monomer (A2) of above-mentioned hydroxyl has is more than 0.05 relative to the mol ratio (OH/A1) of above-mentioned (methyl) alkyl acrylate monomer (A1), solids component is more than 15 quality % and lower than 40 quality %.
(2) acrylic emulsion according to claim 1, the polymerizable monomer (A2) of above-mentioned hydroxyl comprises the polymerizable monomer (A21) of the alcoholic hydroxy with the hydroxyl being bonded to carbon atom and has the polymerizable monomer (A22) containing silicone hydroxyl of the hydroxyl being bonded to Siliciumatom.
(3) acrylic emulsion according to claim 1 and 2, aforesaid propylene acid is that particle has the hydroxyl being bonded to carbon atom and the hydroxyl being bonded to Siliciumatom.
(4) a sealing material use water system priming paint, the acrylic emulsion according to any one of claims 1 to 3 forms.
(5) a sealing material use water system paint base composition, containing the acrylic emulsion according to any one of claims 1 to 3.
Invention effect
According to the present invention, a kind of water-fast acrylic emulsion excellent in adhesion can be provided.
Embodiment
[acrylic emulsion]
Acrylic emulsion of the present invention contains acrylic particles, aforesaid propylene acid is the median size of particle is less than 0.6 μm, the aforesaid propylene acid polymerizable monomer (A) that to be particle be makes to have (methyl) acryl carries out being polymerized the polymer particle obtained under the existence of the persulphate (B) as polymerization starter, above-mentioned polymerizable monomer (A) comprises (methyl) alkyl acrylate monomer (A1) and has the polymerizable monomer (A2) of hydroxyl of hydroxyl, above-mentioned persulphate (B) is more than 0.007 relative to the mol ratio (B/A1) of above-mentioned (methyl) alkyl acrylate monomer (A1), the hydroxyl (OH) that the polymerizable monomer (A2) of above-mentioned hydroxyl has is more than 0.05 relative to the mol ratio (OH/A1) of above-mentioned (methyl) alkyl acrylate monomer (A1), solids component is more than 15 quality % and lower than 40 quality %.
In addition, in acrylic emulsion of the present invention, as dispersate acrylic particles can be liquid phase mutually, also can be solid phase.
Namely, generally speaking, be called in the system be dispersed with as the dispersate of liquid phase in the dispersion medium of liquid phase " emulsion ", be called in the system be dispersed with as the dispersate of solid phase in the dispersion medium of liquid phase " suspension liquid ", but in the present invention, " emulsion " is for comprising the concept of " suspension liquid ".
Acrylic emulsion of the present invention is like this to the cementability of the adherends such as Mortar Plates, especially water-fast excellent in adhesion.Thinking that its median size due to contained acrylic particles is less than 0.6 μm, is path, therefore, good, excellent in adhesion to the perviousness (moistening) of adherend.
In addition, as mentioned above, in existing acrylic emulsion, if make dried film impregnated in water, then the emulsifying agent on acrylic particles surface is understood stripping and forms space, and the water capacity easily immerses, but acrylic emulsion of the present invention obtains when not using the emulsifying agents such as Sodium Lauryl Sulphate BP/USP, therefore, even if think that dried film be impregnated in water also can not form space, water tolerance (water-fast cementability) is also excellent.
Below, acrylic emulsion of the present invention is described in detail.
In addition; in the following description; (methyl) acrylate refers to acrylate and/or methacrylic ester; (methyl) acrylic acid series refers to acrylic acid series and/or metha crylic, and (methyl) acryl refers to acryl and/or methacryloyl.
(acrylic particles)
Acrylic particles contained by acrylic emulsion of the present invention as dispersate dispersion (suspension), illustratively is and makes the polymerizable monomer (A) with (methyl) acryl described later carry out being polymerized under the existence of persulphate described later (B) and the polymer particle that obtains in the dispersion medium such as water.
Just be not particularly limited as long as the median size of this acrylic particles is less than 0.6 μm, but moistening from the viewpoint of to adherend, preferably less than 0.58 μm, more preferably less than 0.55 μm.
On the other hand, as the lower value of the median size of acrylic particles, from the viewpoint of water tolerance, preferably greater than 0 μm, preferably more than 0.01 μm, more preferably more than 0.1 μm.
In addition, the median size of acrylic particles is the value using particle size distribution measuring machine (NanotracUPA-EX150, Ji Zhuan Inc.) to record.
In addition, the weight-average molecular weight (Mw) of acrylic particles is not particularly limited, but considers to the viewpoint such as the moistening of adherend or low viscosity, and preferably 50,000 ~ 400,000, more preferably 70,000 ~ 300,000.
In addition, the weight-average molecular weight (Mw) of acrylic particles is the weight-average molecular weight represented with polystyrene conversion recorded by the gel permeation chromatography (GPC) using tetrahydrofuran (THF) as solvent.
In addition, the acrylic particles contained by acrylic emulsion of the present invention preferably has carboxyl (-OH), and the reason more excellent from water-fast cementability considers more preferably have the hydroxyl being bonded to carbon atom and the hydroxyl being bonded to Siliciumatom.
(polymerizable monomer (A))
The polymerizable monomer (A) used in the present invention at least comprises (methyl) alkyl acrylate monomer (A1), has the polymerizable monomer (A2) of the hydroxyl of hydroxyl (OH).
< (methyl) alkyl acrylate monomer (A1) >
As (methyl) alkyl acrylate monomer (A1), such as, can enumerate: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) Ethyl acrylate, (methyl) 2-EHA, (methyl) cyclohexyl acrylate, (methyl) t-butylcyclohexyl base ester, (methyl) isoamyl acrylate, (methyl) vinylformic acid n-pentyl ester, (methyl) isoamyl acrylate, (methyl) vinylformic acid ring pentyl ester, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid ring monooctyl ester, (methyl) vinylformic acid ester in the positive ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the positive last of the ten Heavenly stems, (methyl) isodecyl acrylate, (methyl) vinylformic acid dodecyl ester, the different myristin of (methyl) vinylformic acid, (methyl) vinylformic acid n-tridecane base ester, (methyl) n-myristyl base ester etc.Wherein, can enumerate: (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA etc., they can be used alone a kind, and also two or more kinds may be used.
Polymerizable monomer (A2) > of < hydroxyl
The polymerizable monomer (A2) of hydroxyl is for having the monomer of (methyl) acryl and hydroxyl.
In the present invention, the hydroxyl (OH) that the polymerizable monomer (A2) that the use level of the polymerizable monomer (A2) of hydroxyl is hydroxyl has is the amount of more than 0.05 relative to the mol ratio (OH/A1) of above-mentioned (methyl) alkyl acrylate monomer (A1).
If this mol ratio (OH/A1) is lower than 0.05, the median size of the acrylic particles then obtained is poor to the cementability of adherend more than 0.6 μm, if but more than 0.05, then the median size of acrylic particles is less than 0.6 μm, good, excellent in adhesion to the impregnability of adherend.
For mol ratio (OH/A1), consider from the more excellent reason of cementability, preferably 0.05 ~ 0.15, more preferably 0.05 ~ 0.10.
As the polymerizable monomer (A2) of such hydroxyl, such as can enumerate the polymerizable monomer (A21) of alcoholic hydroxy described later and/or the polymerizable monomer (A22) containing silicone hydroxyl, consider from the more excellent reason of water-fast cementability, preferably and by both scheme.
(polymerizable monomer (A21) of alcoholic hydroxy)
As the polymerizable monomer (A21) of alcoholic hydroxy, as long as the hydroxyl having (methyl) acryl and be bonded to carbon atom (conveniently, also referred to as " alcoholic extract hydroxyl group ") monomer be just not particularly limited, such as can enumerate: (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxybutyl, the own ester of (methyl) vinylformic acid 2-hydroxyl, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 8-hydroxyl monooctyl ester, (methyl) vinylformic acid 10-hydroxyl ester in the last of the ten Heavenly stems, (methyl) vinylformic acid 12-hydroxylauric base ester, (4-Hydroxymethyl-cyclo-hexyl) methacrylic ester, N-methylol (methyl) acrylamide, N-hydroxyl (methyl) acrylamide, vinyl alcohol, vinyl carbinol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl base ether etc., they can be used alone a kind, also two or more kinds may be used.
Wherein, (methyl) vinylformic acid 2-hydroxy methacrylate can preferably be used.
(polymerizable monomer (A22) containing silicone hydroxyl)
As containing the polymerizable monomer (A22) of silicone hydroxyl, as long as be just not particularly limited for the monomer of the hydroxyl (also referred to as " silicone hydroxyl ") that there is (methyl) acryl and be bonded to Siliciumatom.
As such polymerizable monomer (A22) containing silicone hydroxyl, the polymerizable monomer containing alkoxysilyl with (methyl) acryl and alkoxysilyl can be used.When using this monomer to obtain acrylic emulsion of the present invention, alkoxysilyl is hydrolyzed.
At this, as the polymerizable monomer containing alkoxysilyl, specifically, such as, can enumerate: vinyltrimethoxy silane, vinyltriethoxysilane, vinyl tripropoxy silane, vinyl methyl dimethoxysilane, vinyl methyl diethoxy silane, vinyl methyl dipropoxy silane, γ-acryloxypropyl Trimethoxy silane, γ-acryloxypropyl triethoxyl silane, γ-acryloxypropyl tripropoxy silane, γ-acryloxypropyl dimethoxysilane, γ-acryloxypropyl diethoxy silane, γ-acryloxypropyl dipropoxy silane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl, γ-methacryloxypropyl tripropoxy silane, γ-methacryloyloxypropyl methyl dimethoxysilane, γ-methacryloyloxypropyl methyl diethoxy silane, γ-methacryloyloxypropyl methyl dipropoxy silane etc., they can be used alone a kind, and also two or more kinds may be used.
Wherein, γ-methacryloxypropyl, γ-methacryloyloxypropyl methyl diethoxy silane can preferably be used.
When using such polymerizable monomer (A22) containing silicone hydroxyl, its use level is preferably 5 ~ 80 % by mole relative to the polymerizable monomer (A21) of above-mentioned alcoholic hydroxy, more preferably 5 ~ 50 % by mole, preferably 5 ~ 35 % by mole further.
The carboxylic polymerizable monomer of < (A3) >
As the polymerizable monomer used in the present invention (A), except the polymerizable monomer (A2) of above-mentioned (methyl) alkyl acrylate monomer (A1) and hydroxyl, such as carboxylic polymerizable monomer (A3) can also be enumerated.
As carboxylic polymerizable monomer (A3); as long as there is (methyl) acryl and carboxyl is just not particularly limited; such as can enumerate: vinylformic acid, methacrylic acid, (methyl) carboxyethyl acrylates, (methyl) vinylformic acid carboxyl pentyl ester, methylene-succinic acid, toxilic acid, fumaric acid, β-crotonic acid etc.; they can be used alone a kind, and also two or more kinds may be used.
Wherein, vinylformic acid, methacrylic acid can preferably be used.
When using so carboxylic polymerizable monomer (A3), its use level is preferably 2.5 ~ 20 % by mole relative to above-mentioned (methyl) alkyl acrylate monomer (A1), more preferably 2.5 ~ 15 % by mole.
(persulphate (B))
The polymerization starter (radical polymerization initiator) used in the present invention is persulphate (B), such as, can enumerate ammonium persulphate, Potassium Persulphate, Sodium Persulfate etc.
By using persulphate (B) as polymerization starter, can obtain having in water solvent when not using the emulsifying agents such as Sodium Lauryl Sulphate BP/USP (tensio-active agent) acrylic particles of mechanical stability by means of only the ionic of polymerization starter.
In the present invention, the use level of persulphate (B) is persulphate (B) is the amount of more than 0.007 relative to the mol ratio (B/A1) of above-mentioned (methyl) alkyl acrylate monomer (A1).
If this mol ratio (B/A1) is lower than 0.007, the median size of the acrylic particles then obtained is poor to the cementability of adherend more than 0.6 μm, if but more than 0.007, then the median size of acrylic particles is less than 0.6 μm, good, excellent in adhesion to the impregnability of adherend.
For mol ratio (B/A1), consider from the more excellent reason of cementability, preferably 0.007 ~ 0.05, more preferably 0.007 ~ 0.04.
As the method making polymerizable monomer (A) be polymerized under the existence of persulphate (B), be not particularly limited, such as, can be suitable for the method adopting existing known radical polymerization.Polymerization such as carries out 1 ~ 10 hours the temperature of about 60 ~ 80 DEG C under the inert gas flows such as nitrogen.
Now, in the polymerizable monomer (A) of use, the ratio of the polymerizable monomer (A2) of hydroxyl and the total of carboxylic polymerizable monomer (A3) is preferably 3 ~ 20 % by mole, is more preferably 5 ~ 15 % by mole.If in this scope, then the cementability of water system priming paint to adherends such as Mortar Plates employing acrylic emulsion of the present invention becomes better.
The manufacture method of acrylic emulsion of the present invention is not particularly limited, such as can enumerate following method: in the dispersion medium such as water, under the existence of persulphate (B), carry out high-speed stirring to polymerizable monomer (A) makes it be polymerized, and obtains the acrylic emulsion disperseed as dispersate as the acrylic particles of polymer particle thus.
In addition, preferably with persulphate (B) and with and coordinate reductive agent.As reductive agent, such as, can preferably use sodium bisulfite, sodium bicarbonate.
The use level of reductive agent is not particularly limited, relative to the persulphate (B) being also superoxide, and preferably 0.05 ~ 3 equivalent, more preferably 0.1 ~ 2 equivalent, further preferred 0.3 ~ 1.5 equivalent.
In addition, when being polymerized, from the viewpoint of the molecular weight adjusting the acrylic particles obtained, also can usage chain transfer agent.As chain-transfer agent, be not particularly limited, known chain-transfer agent can be used, specifically, such as can enumerate: lauryl mercaptan, glycidyl mercaptan, Thiovanic acid, 2 mercapto ethanol, thioglycolic acid, thioglycolic acid 2-ethylhexyl, 2,3-dimercapto-1-propyl alcohol etc., they can be used alone a kind, and also two or more kinds may be used.
The use level of chain-transfer agent can be suitable for selecting to adjust molecular weight, is not particularly limited, such as, is preferably 0.01 ~ 10 % by mole relative to the total of polymerizable monomer, more preferably 0.1 ~ 8 % by mole.
In addition, in the present invention, when having the acidic-groups such as carboxyl at acrylic particles, from the viewpoint of the mechanical stability improving particle, neutralizing agent also can be utilized to neutralize.
As neutralizing agent, if can in and acidic-group be just not particularly limited, such as can enumerate: sodium hydroxide, potassium hydroxide, Trimethylamine 99, dimethylaminoethanol, 2-methyl-2-amino-1-propyl alcohol, triethylamine, ammoniacal liquor etc.These neutralizing agents such as preferred with neutralization after pH become about 7 ~ 10 amount use.
(solids component)
Acrylic emulsion of the present invention is the emulsion using above-mentioned acrylic particles as dispersate, and the water solvent as dispersion medium is preferably distilled water, and its solids component is more than 15 quality % and lower than 40 quality %.
When solids component is lower than 15 quality %, because the concentration of effective constituent is too low, therefore, sufficient cementability cannot be obtained to adherend after the drying.On the other hand, when solids component is more than 40 quality %, viscosity is high, and become difficulty to the coating of adherend, in addition, namely allowing to be coated with also becomes very uneven film, and therefore, cementability is still insufficient.
But, if the solids component of acrylic emulsion of the present invention is in above-mentioned scope, then to the cementability of adherend, especially water-fast excellent in adhesion, the reason more excellent from this effect is considered, solids component is 15 ~ 35 quality % preferably, more preferably 15 ~ 30 quality %.
(viscosity)
The viscosity of acrylic emulsion of the present invention at 20 DEG C is not particularly limited, but preferably 200 ~ 900mPas, more preferably 300 ~ 800mPas.If viscosity is in this scope, then to the moistening excellence of adherend.
In addition, viscosity is the method according to recording in JISK7117-2:1991, the viscosity (unit: mPas) at 20 DEG C that use BL shape viscometer (No.4 rotor, 6rpm) to record at 20 DEG C.
[water system priming paint and water system paint base composition]
Sealing material use water system priming paint of the present invention is (following, referred to as " water system priming paint of the present invention ") be the water system priming paint be made up of above-mentioned acrylic emulsion of the present invention, as mentioned above, excellent in adhesion, especially water-fast excellent in adhesion to adherends such as Mortar Plates.
Equally, sealing material use water system paint base composition of the present invention (hreinafter referred to as " water system paint base composition of the present invention ") is the water system paint base composition containing above-mentioned acrylic emulsion of the present invention.
At this, water system paint base composition of the present invention, except above-mentioned acrylic emulsion of the present invention, can also contain additive further as required in the scope not damaging object of the present invention and effect.As additive, such as can enumerate: weighting agent, pigment, anti blocking agent, dispersion stabilizer, thixotropic agent, viscosity modifier, flow agent, gelation preventing agent, photostabilizer, antiaging agent, antioxidant, UV light absorber, softening agent, lubricant, static inhibitor, strongthener, fire retardant, catalyzer, defoamer, tackifier, dispersion agent, organic solvent, its amount is not particularly limited.
As the adherend can applying water system priming paint of the present invention and water system paint base composition of the present invention (following, they to be referred to as " priming paint of the present invention "), such as, can enumerate: glass; The metals such as aluminium, anodised aluminium, iron, zinc-iron plate, copper, stainless steel; The porous part such as Mortar Plates, stone material; The parts of fluorine galvanic deposit, vinylformic acid galvanic deposit, fluorine application, the application of ammonia ester, the application of acrylic acid series ammonia ester are carried out; The cured article of the sealing materials such as polysiloxane series, modified polyorganosiloxane system, ammonia ester system, polythioether system, polyisobutene system; Polyvinyl chloride (PVC) RESINS, acrylic resin; The rubber-like such as NBR, EPDM; Etc..
In addition, priming paint of the present invention such as can be preferably used as the priming paint used in the sealing material of for building or automobile.
As the using method of priming paint of the present invention, such as can enumerate: on above-mentioned adherend, be coated with priming paint of the present invention, any drying, is coated with after Encapulant composition thereon, makes priming paint of the present invention and the dry and method that makes it solidify of Encapulant composition.
In addition, as used sealing material, be not particularly limited, existing known sealing material, sealing material especially for building can be used, specifically, such as can enumerate: polysiloxane series sealing material, modified polyorganosiloxane system sealing material, polyurethane series sealing material, polythioether system sealing material etc., wherein, preferably can use polyurethane series sealing material, particularly polyurethane series sealing material for building.
Embodiment
Below, enumerate embodiment to be specifically described the present invention.But the present invention is not limited to these embodiments.
< coordinating example 1 ~ 17 >
In reaction vessel, drop into the composition shown in following table 1 with the mol ratio shown in table 1, the mode becoming the concentration (unit: quality %) shown in following table 1 with solids component adds distilled water, heats after 80 DEG C, stirs 5 hours, is polymerized thus.Thus, acrylic acid polymer disperses, and the acrylic particles obtained using corpusculed is as the acrylic emulsion of dispersate.
In addition, in coordinating example 10 ~ 12, do not obtain emulsion (non-emulsification), but conveniently, the resultant obtained is called acrylic emulsion.
In addition, each composition shown in following table 1 is as described below.
MMA: methyl methacrylate (molecular weight: 100)
2EHA: 2-EHA (molecular weight: 184)
BA: butyl acrylate (molecular weight: 128)
MAA: methacrylic acid (molecular weight: 87)
HEMA: 2-hydroxyethyl methacrylate (molecular weight: 130)
Si (OH) 3: γ-methacryloxypropyl (molecular weight: 290)
Si (OH) 2: γ-methacryloyloxypropyl methyl diethoxy silane (molecular weight: 274)
APS: ammonium persulphate (molecular weight: 228)
SBS: sodium bisulfite (molecular weight: 104)
TBHP: tertbutyl peroxide (molecular weight: 90.12)
TEPA: tetren (molecular weight: 189.30)
SH: lauryl mercaptan (molecular weight: 202)
AIBN:2,2 '-azobis isobutyronitrile (molecular weight: 164)
SLS: Sodium Lauryl Sulphate BP/USP (molecular weight: 288.4)
< weight-average molecular weight and median size >
By above-mentioned method, weight-average molecular weight (Mw) and median size (unit: μm) are measured to the acrylic particles contained by the acrylic emulsion of the coordinating example 1 ~ 17 obtained.Show the result in following table 1.
In addition, to coordinating example 10 ~ 13 undetermined median size not obtaining emulsion, therefore, be recited as "-" in following table 1.
< evaluates >
In order to evaluate the cementability of the acrylic emulsion obtained and water-fast cementability, carry out following test.Show the result in following table 1.In addition, when evaluating, in following table 1, record "-".
(normality cross cut test)
Use bristle by the acrylic emulsion of coordinating example 1 ~ 17 to become 50g/m
2the mode of thickness is coated on the Mortar Plates (50mm × 50mm, パ ルテック Inc.) as adherend, makes its dry 3 hours, be made into test body at 25 DEG C.
Then, the coated surface of test body makes the checker 100 (10 × 10) of 1mm, then adhere to scotch tape (ニ チ バ Application Inc.) completely on this checker after, stripping tape under the state keeping the angle of about 60 ° immediately in one end of adhesive tape relative to coated surface, investigation is not peeled off and residual checker number completely.
Consider from viewpoint in practical use, if the result of normality cross cut test is more than 95, then can be evaluated as excellent in adhesion.
(water-fast cross cut test)
After making the test body made as described above flood one week in the water of 25 DEG C, carry out cross cut test as described above, investigation is not peeled off and residual checker number completely.
Consider from viewpoint in practical use, if the result of water-fast cross cut test is more than 30, then can be evaluated as water-fast excellent in adhesion.
Table 1 (its 1)
Table 1 (its 2)
From the result shown in above-mentioned table 1 clearly, use persulphate (B) as polymerization starter, mol ratio (B/A1) is more than 0.007, mol ratio (OH/A1) is more than 0.05, and the median size of acrylic particles is that the cementability of the coordinating example 1 ~ 6,9 and 13 of less than 0.6 μm and water-fast cementability are all excellent.
In addition, wherein, as hydroxyl polymerizable monomer (A2) and with the coordinating example 1 ~ 6 and 9 of the polymerizable monomer (A21) of alcoholic hydroxy and the polymerizable monomer (A22) containing silicone hydroxyl with only use alcoholic hydroxy polymerizable monomer (A21) coordinating example 13 compared with, water-fast cementability is more excellent.
On the other hand, mol ratio (OH/A1) lower than 0.05 coordinating example 7 and mol ratio (B/A1) although lower than 0.007 coordinating example 8 use persulphate (B), but the median size of acrylic particles is more than 0.6 μm, cementability and water-fast cementability inequality.
In addition, the non-emulsification of coordinating example 10 ~ 12 of persulphate (B) is not used.Equally, do not use persulphate (B) although coordinating example 14 carried out emulsification, water-fast cementability is poor.
In addition, solids component is that the cementability of the coordinating example 16 of more than 40 quality % and water-fast cementability are poor lower than the coordinating example 15 of 15 quality % and solids component.
In addition, be used as the Sodium Lauryl Sulphate BP/USP (SLS) of emulsifying agent (tensio-active agent) although coordinating example 17 cementability good, water-fast cementability is poor.
Claims (5)
1. an acrylic emulsion, containing acrylic particles, the median size of described acrylic particles is less than 0.6 μm, described acrylic particles is for making the polymerizable monomer A with (methyl) acryl carry out being polymerized under the existence of the persulphate B as polymerization starter and the polymer particle obtained, described polymerizable monomer A comprises the polymerizable monomer A2 of (methyl) alkyl acrylate monomer A1 and hydroxyl, described persulphate B is more than 0.007 relative to the mol ratio of described (methyl) alkyl acrylate monomer A1 and B/A1, the hydroxyl that the polymerizable monomer A2 of described hydroxyl has and OH are more than 0.05 relative to the mol ratio of described (methyl) alkyl acrylate monomer A1 and OH/A1, solids component is more than 15 quality % and lower than 40 quality %.
2. acrylic emulsion according to claim 1, the polymerizable monomer A2 of described hydroxyl comprises the polymerizable monomer A21 of the alcoholic hydroxy with the hydroxyl being bonded to carbon atom and has the polymerizable monomer A22 containing silicone hydroxyl of the hydroxyl being bonded to Siliciumatom.
3. acrylic emulsion according to claim 1 and 2, described acrylic particles has the hydroxyl being bonded to carbon atom and the hydroxyl being bonded to Siliciumatom.
4. a sealing material use water system priming paint, the acrylic emulsion according to any one of claims 1 to 3 forms.
5. a sealing material use water system paint base composition, containing the acrylic emulsion according to any one of claims 1 to 3.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013046434A JP5664680B2 (en) | 2013-03-08 | 2013-03-08 | Water-based primer and water-based primer composition |
| JP2013-046434 | 2013-03-08 | ||
| PCT/JP2014/056008 WO2014136947A1 (en) | 2013-03-08 | 2014-03-07 | Acrylic emulsion, water-based primer, and water-based primer composition |
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| CN105189581A true CN105189581A (en) | 2015-12-23 |
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| CN201480025960.1A Pending CN105189581A (en) | 2013-03-08 | 2014-03-07 | Acrylic emulsion, water-based primer, and water-based primer composition |
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| Country | Link |
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| JP (1) | JP5664680B2 (en) |
| KR (1) | KR101606473B1 (en) |
| CN (1) | CN105189581A (en) |
| PH (1) | PH12015501986B1 (en) |
| WO (1) | WO2014136947A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3950864A4 (en) * | 2019-04-05 | 2022-06-01 | KCC Corporation | Primer composition |
| CN115725214A (en) * | 2021-08-31 | 2023-03-03 | 庞贝捷涂料(上海)有限公司 | Primer composition |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180312699A1 (en) * | 2015-10-13 | 2018-11-01 | The Yokohama Rubber Co., Ltd. | Water-Based Primer Composition for Sealant |
| JP6864430B2 (en) * | 2015-10-13 | 2021-04-28 | 横浜ゴム株式会社 | Water-based primer composition for polyurethane-based sealant |
| JP6536344B2 (en) * | 2015-10-13 | 2019-07-03 | 横浜ゴム株式会社 | Waterborne primer composition for sealing material |
| KR102362614B1 (en) * | 2021-05-24 | 2022-02-15 | (주)더서울테크 | Manufacturing method for organic-inorganic composite clear coating binder ceramic resin composition applied to the LED module of the electric sign |
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|---|---|---|---|---|
| JP2000001624A (en) * | 1998-06-17 | 2000-01-07 | Sanyo Chem Ind Ltd | Aqueous resin dispersion composition and coating agent |
| US20030045626A1 (en) * | 2000-02-16 | 2003-03-06 | Kouji Tamori | Aqueous dispersion, process for production thereof and coated substances |
| JP2008056751A (en) * | 2006-08-30 | 2008-03-13 | Asahi Kasei Chemicals Corp | Aqueous resin dispersion |
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| JPH0757805B2 (en) * | 1987-08-12 | 1995-06-21 | 日本油脂株式会社 | Method for producing polymer non-aqueous dispersion |
| JPH04372674A (en) * | 1991-06-21 | 1992-12-25 | Kansai Paint Co Ltd | Ordinary temperature drying, crosslinkable water-based coating resin composition |
| EP0553957A2 (en) * | 1992-01-31 | 1993-08-04 | Rohm And Haas Company | Solvent resistant latex paint |
| JPH06107713A (en) * | 1992-09-24 | 1994-04-19 | Showa Denko Kk | Copolymer aqueous emulsion and primer using the emulsion and used for silicone-coated paper |
| JPH10195173A (en) * | 1996-11-18 | 1998-07-28 | Takeda Chem Ind Ltd | Primer composition |
| JP2001302920A (en) * | 2000-02-16 | 2001-10-31 | Jsr Corp | Aqueous dispersion, its production method and coated product |
-
2013
- 2013-03-08 JP JP2013046434A patent/JP5664680B2/en active Active
-
2014
- 2014-03-07 KR KR1020157025285A patent/KR101606473B1/en active IP Right Grant
- 2014-03-07 CN CN201480025960.1A patent/CN105189581A/en active Pending
- 2014-03-07 WO PCT/JP2014/056008 patent/WO2014136947A1/en active Application Filing
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- 2015-09-07 PH PH12015501986A patent/PH12015501986B1/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000001624A (en) * | 1998-06-17 | 2000-01-07 | Sanyo Chem Ind Ltd | Aqueous resin dispersion composition and coating agent |
| US20030045626A1 (en) * | 2000-02-16 | 2003-03-06 | Kouji Tamori | Aqueous dispersion, process for production thereof and coated substances |
| JP2008056751A (en) * | 2006-08-30 | 2008-03-13 | Asahi Kasei Chemicals Corp | Aqueous resin dispersion |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3950864A4 (en) * | 2019-04-05 | 2022-06-01 | KCC Corporation | Primer composition |
| CN115725214A (en) * | 2021-08-31 | 2023-03-03 | 庞贝捷涂料(上海)有限公司 | Primer composition |
| CN115725214B (en) * | 2021-08-31 | 2024-05-24 | 庞贝捷涂料(上海)有限公司 | Primer composition |
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| Publication number | Publication date |
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| KR101606473B1 (en) | 2016-03-25 |
| WO2014136947A1 (en) | 2014-09-12 |
| JP2014172992A (en) | 2014-09-22 |
| JP5664680B2 (en) | 2015-02-04 |
| PH12015501986A1 (en) | 2016-01-18 |
| KR20150123261A (en) | 2015-11-03 |
| PH12015501986B1 (en) | 2016-01-18 |
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