CN108300090A - Water-based paint compositions and coating film - Google Patents
Water-based paint compositions and coating film Download PDFInfo
- Publication number
- CN108300090A CN108300090A CN201710694260.7A CN201710694260A CN108300090A CN 108300090 A CN108300090 A CN 108300090A CN 201710694260 A CN201710694260 A CN 201710694260A CN 108300090 A CN108300090 A CN 108300090A
- Authority
- CN
- China
- Prior art keywords
- water
- core
- based paint
- emulsion resin
- paint compositions
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- 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
-
- 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
- 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- 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
-
- 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
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
-
- 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
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1637—Macromolecular compounds
- C09D5/165—Macromolecular compounds containing hydrolysable groups
-
- 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
- C09D5/1668—Vinyl-type polymers
-
- 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
- C09D5/1687—Use of special additives
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
-
- 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
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Dispersion Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention provides a kind of water-based paint compositions, the water-based paint compositions include hud typed organo-mineral complexing copolymer emulsion resin, and the hud typed organo-mineral complexing copolymer emulsion resin includes：Core, the core are made of acrylic emulsion resin, and with 30 DEG C to 10 DEG C of glass transition temperature (Tg)；And shell, the shell are made of the acrylic emulsion resin containing alkoxysilyl or epoxy group silicyl, and with 30 DEG C to 100 DEG C of glass transition temperature (Tg).The invention further relates to by the obtained coating film of the coating composition.
Description
Technical field
The present invention relates to a kind of water-based paint compositions.
Background technology
Recently, the interest of water-based paint compositions environmentally friendly and with superior workability increasingly increases.It is aqueous
Coating composition generally includes acrylic emulsion resin, and when acrylic emulsion resin is dried at room temperature for shows opposite order
The durability of people's satisfaction.However, with the film that acrylic emulsion resin coats object can be contaminated, such as sand, dust, tail gas and
The pollution of exhaust gas etc., so that coating film cannot keep satisfactory appearance.In addition, rain, dew or heat etc. may cause
Coating film bleaches or weakens, therefore prevents coating film from keeping satisfactory appearance.
The acrylic emulsion resin with relatively high Tg can be used in this pollution of coating film in order to prevent.However, propylene
Sour emulsion resin has the flexibility of difference, therefore after forming coating film or when film is subjected to long-term exposure, coating film may
Directly rupture.
As described above, Conventional acrylic emulsion resin while meeting weatherability, may cannot be satisfied two kinds it is opposite
Characteristic, that is, i.e. resistance to soiling and flexibility.Therefore, it is necessary to a kind of water-based paint compositions, which includes having to change
The acrylic emulsion resin of kind physical property.
[prior art document]
[patent document]
(patent document 1) Korean Patent Application Publication No.10-2005-0071167.
Invention content
The present invention provides a kind of water-based paint compositions, the water-based paint compositions can form such coating
Film：While the coating film has excellent weather resistance, resistance to soiling and flexibility are had both.
Meanwhile the present invention provides a kind of water-based paint compositions, the water-based paint compositions, which include core-shell type, to be had
Machine-inorganic compounding copolymer emulsion resin, the core-shell type Organic-inorganic composite copolymer emulsion resin include：Core, the core
It is made of acrylic emulsion resin, and with -30 DEG C to -10 DEG C of glass transition temperature (Tg)；And shell, the shell by
It is formed containing the acrylic emulsion resin of alkoxysilyl or epoxy group silicyl, and with 30 DEG C to 100 DEG C of glass
Glass conversion temperature (Tg).
In embodiments of the present invention, the water-based paint compositions further comprise：Total water relative to 100wt%
Property coating composition, the core-shell type Organic-inorganic composite copolymer emulsion resin of 40wt% to 60wt%, 5wt% is extremely
The extender pigment of 20wt%, the water of the coloring pigment and 5wt% of 1wt% to 20wt% to 40wt%.
In embodiments of the present invention, described in the core-shell type Organic-inorganic composite copolymer emulsion resin
The content of core can be 30wt% to 80wt%, and the content of the shell can be 20wt% to 70wt%.
In embodiments of the present invention, the water-based paint compositions can further comprise：At least one type adds
Agent, the additive of at least one type is added to be selected from by film forming agent, dispersant, surfactant, thixotropic modifier and disappear
The group that infusion is formed.
Meanwhile the invention further relates to a kind of coating film, the coating film is formed using the water-based paint compositions.
By using including core with -30 DEG C to -10 DEG C of glass transition temperature and with 30 DEG C to 100 DEG C of glass
The core-shell type acrylic acid Organic-inorganic composite copolymer emulsion resin of the shell of glass conversion temperature is as adhesive, according to the present invention
Water-based paint compositions, can be formed with weatherability and have both resistance to soiling and coating film flexible simultaneously.In addition, by using
For emulsion resin as adhesive, water-based paint compositions according to the present invention, can be to the maximum extent compared with existing finish coating
Therefore the use for reducing volatile organic compounds is environmental-friendly.
Specific implementation mode
Hereinafter, the present invention will be described in further detail.
Embodiments of the present invention are related to a kind of water-based paint compositions, and the water-based paint compositions include core-shell type
Organic-inorganic composite copolymer emulsion resin, the core-shell type Organic-inorganic composite copolymer emulsion resin include：Core, institute
It states core to be made of acrylic emulsion resin, and with -30 DEG C to -10 DEG C of glass transition temperature (Tg)；And shell, it is described
Shell is made of the acrylic emulsion resin containing alkoxysilyl or epoxy group silicyl, and has 30 DEG C to 100 DEG C
Glass transition temperature (Tg).
Water-based paint compositions can be the coating composition of single-component room-temperature drying, and can be used in finishing coat.
The core-shell type Organic-inorganic composite copolymer emulsion resin is such resin：It is adjusted by multi-step emulsion polymerization
The resin is saved, so that the glass transition temperature (Tg) of core and shell is respectively -30 DEG C to -10 DEG C and 30 DEG C to 100 DEG C.Example
Such as, the Tg of core can be -20 DEG C to -10 DEG C, and the Tg of shell can be 30 DEG C to 80 DEG C.
The core-shell type Organic-inorganic composite copolymer emulsion resin can in water-based paint compositions according to the present invention
As adhesive.
When the glass transition temperature (Tg) of core is less than -30 DEG C, it may be desirable to be dried for a long time；And when Tg is more than -10
DEG C when, the flexibility of coating film can be poor.In addition, when the glass transition temperature (Tg) of shell is less than 30 DEG C, resistance to soiling can be poor；And
When Tg is more than 100 DEG C, there is the risk cracked in coating film, and therefore may require that a large amount of film forming agent to solve this
Risk.
In embodiments of the present invention, monomer type, the monomer of the adjusting in core and/or shell can usually be passed through
Weight ratio be adjusted come the glass transition temperature (Tg) to core and shell.
The acrylic emulsion resin of core can be formed by the mixture including one or more acrylic monomers, described one kind
Or a variety of acrylic monomers are selected from by methyl methacrylate, butyl methacrylate, butyl acrylate, methacrylic acid hexamethylene
The group that ester and methacrylic acid are formed.
The acrylic emulsion resin containing alkoxy silicane or epoxy group silicyl of shell can be by including one or more
The mixture of acrylic monomers and one or more monomers containing alkoxysilyl or epoxy group silicyl is formed,
One or more acrylic monomers are selected from by methyl methacrylate, butyl methacrylate, butyl acrylate, methyl-prop
The group that olefin(e) acid cyclohexyl and methacrylic acid are formed, it is described one or more containing alkoxysilyl or epoxy group first silicon
The monomer of alkyl is selected from by epoxy silane, methacryloxypropyl silane, methyltrimethoxysilane and methacryloxypropyl
The group that base propyl trimethoxy silicane is formed.
In the core-shell type Organic-inorganic composite copolymer emulsion resin, relative to the content of monomer of 100wt%, institute
The content for stating core can be 30wt% to 80wt%, and the content of the shell can be 20wt% to 70wt%.When containing for core and shell
When measuring outside the above range, polymerization stability can be poor.
The Tg of core-shell type Organic-inorganic composite copolymer emulsion resin can be 0 DEG C to 40 DEG C.When core-shell type it is organic-nothing
When the Tg of machine compound copolymer emulsion resin is less than 0 DEG C, coating film can not be formed at room temperature, and when Tg is more than 40 DEG C, it is resistance to
Impact can be poor.
According to the embodiment of the present invention, relative to total water-based paint compositions of 100wt%, the core-shell type used has
The range of machine-inorganic compounding copolymer emulsion resin can be 40wt% to 60wt%.When core-shell type Organic-inorganic composite is copolymerized
When the content of object emulsion resin is less than 40wt%, the adhesiveness and durability of coating film can be poor, and when content is more than 60wt%
When, coating film can excessive flexibility or peeling.
In embodiments of the present invention, the solid content of core-shell type Organic-inorganic composite copolymer emulsion resin can be
40wt% to 50wt%.When the solid content of core-shell type Organic-inorganic composite copolymer emulsion resin is less than 40wt%, meeting
Limit the design of coating compound；And when solid content is more than 50wt%, the stability of lotion itself can be unfavorable for.
As described above, core-shell type Organic-inorganic composite copolymer emulsion resin can be prepared by multi-step emulsion polymerization.
In embodiments of the present invention, core-shell type Organic-inorganic composite copolymer emulsion resin can be prepared as follows.
First, include the first pre-emulsion of acrylic monomers, water and emulsifier by preparing, and then by polymerization initiator
The part for being added to the first pre-emulsion of the amount for example corresponding to 1wt% to 30wt% carries out pre-emulsion polymerization, to form seed
Emulsion resin.
By the way that remaining first pre-emulsion is added to progress first emulsion polymerization in seed emulsion resin, to form core
Emulsion resin.
Finally, by prepare include acrylic monomers, the monomer containing alkoxysilyl or epoxy group silicyl,
Second pre-emulsion of water, emulsifier and polymerization initiator, and then the second pre-emulsion is added in the emulsion resin of core
Second emulsion polymerization is carried out, to prepare core-shell type Organic-inorganic composite copolymer emulsion resin.
Reactive emulsifier can be used as emulsifier.Specifically, alpha-sulfo-ω-(1- alkoxies) methyl -2- (2- allyl oxygen
Base) ethyoxyl)-the ammonium salt etc. of poly- (- two-yl of oxygen -1,2- ethane) (SR1025, Adeka) can be used as emulsifier.
Typical polymerization initiator for emulsion polymerization can be used as polymerization initiator.Specifically, persulfate, such as over cure
Sour potassium, ammonium persulfate, sodium peroxydisulfate etc. can be used as polymerization initiator.
During the second emulsion polymerization for being used to form the shell of core-shell type Organic-inorganic composite copolymer emulsion resin, shape
At the propenoic acid main chain containing silicyl, and during the second emulsion polymerize, by being reacted with water so that being bound to this
The silicyl of propenoic acid main chain hydrolyzes, to form silanol.Therefore, core-shell type Organic-inorganic composite copolymer breast is formed
The propenoic acid main chain of the shell of liquid resin may include the silanol that can form silicone cross-linked body.Silanol can carry out being condensed anti-
It answers, to be crosslinked by stable siloxanes key.This crosslinking can carry out at room temperature.Therefore, silanol is in the room of coat
Silicone cross-linked body can be formed during the lower drying of temperature.The bond energy of siloxanes key can be 443KJ/mol, corresponding to 484KJ/mol's
Carbon-fluorine bond energy, so as to show excellent weatherability.Including core-shell type Organic-inorganic composite copolymer emulsion tree therefore,
The water-based paint compositions of fat even can also form the coating film of height weatherability when being dried at room temperature for.
Further, since the core that Tg is -30 DEG C to -10 DEG C in emulsion resin, including the copolymerization of core-shell type Organic-inorganic composite
The water-based paint compositions of object emulsion resin have excellent flexibility.Simultaneously as the shell that Tg is 30 DEG C to 100 DEG C, this is aqueous
Coating composition can form the coating film with excellent resistance to soiling.
In embodiments of the present invention, water-based paint compositions may include the core-shell type of 40wt% to 60wt%
Organic-inorganic composite copolymer emulsion resin, the extender pigment of 5wt% to 20wt%, the coloring pigment of 1wt% to 20wt%,
And the water of 5wt% to 40wt%.
In embodiments of the present invention, the extender pigment is to lack covering power and colorability, but can assign painting
Overlay film is with ontology (bulk) or the pigment of engineering properties.
It can be not limited to as extender pigment commonly used in the pigment in water-based paint compositions.Specifically, barium sulfate, carbonic acid
Calcium, silica, dolomite, talcum, barium sulfate, kaolin, mica, wollastonite, chlorite, aluminosilicate and aluminium hydroxide etc. are all
It can be used as extender pigment.Extender pigment can be used alone or extender pigment can be used as a part for mixture to adjust coating
Hardness or physical property of film etc..
Relative to total water-based paint compositions of 100wt%, used extender pigment can be in the model of 5wt% to 20wt%
In enclosing.When the content of extender pigment is less than 5wt%, the hardness of coating film can reduce, and when content is more than 20wt%, in conjunction with
It can significantly deteriorate or cured coating film will produce blind crack, and have an adverse effect to water resistance.
In embodiments of the present invention, colorant is such pigment：Since colorant is by insoluble on Colored fine particles
It is formed in the inorganic or organic compound of water or solvent, assigns coating film with covering power and colorability.
It can be not limited to as coloring pigment commonly used in the pigment in water-based paint compositions.Specifically, titanium oxide, charcoal
Black, phthalocyanine and ferriferous oxide etc. are used as coloring pigment.Coloring pigment can be used alone or coloring pigment can be used as mixing
A part for object is to adjust the color of coating film.
Relative to total water-based paint compositions of 100wt%, used coloring pigment can be in the model of 1wt% to 20wt%
In enclosing.When the content of coloring pigment is less than 1wt%, the covering sex chromosome mosaicism of difference is generated, and when content is more than 20wt%, it may
There are coating film physical property and increased cost problems.
In water-based paint compositions according to the present invention, water is used as main solvent.Water is used as various in water-based paint compositions
The decentralized medium of particle, and as the solvent of various compounds in water-based paint compositions.In addition, water also serves as water paint
The diluent of various components in composition.Water be in the water-based paint compositions of the present invention bring it is environmental-friendly extremely important
Factor.
In embodiments of the present invention, the water used can be clean water or deionized water.
Relative to total water-based paint compositions of 100wt%, used water can be in the range of 5wt% to 40wt%.
When the content of water is less than 5wt%, machinability can be poor, and when content is more than 40wt%, coloring can be poor.
Water-based paint compositions according to the embodiment of the present invention can further comprise required various additives.
For example, water-based paint compositions according to the embodiment of the present invention may include film forming agent to form the coating film phase
Between so that coating film is densified by the fusion of auxiliary binder, and increased by improving the wetting effectiveness relative to substrate
Strongly adherent.Film forming agent is applied by reducing the minimum of core-shell type Organic-inorganic composite copolymer emulsion resin according to the present invention
Overlay film forms temperature to assist the cryogenic film of water-based paint compositions to be formed.
For example, the Texanol produced by Eastman, the Butyl Carbitol and Butyl produced by Dow
Cellosolve etc. can serve as film, but film forming agent is not limited to this.
Relative to total water-based paint compositions of 100wt%, used film forming agent can be in the range of 3wt% to 10wt%
It is interior.When the content of film forming agent is less than 3wt%, cryogenic film is formed can be poor；And when content is more than 10wt%, rate of drying meeting
It is extremely slow.
In addition, water-based paint compositions according to the embodiment of the present invention may include dispersant and surfactant with true
Protect the stably dispersing and compatibility with emulsion resin and the like.In addition, water paint according to the embodiment of the present invention
Composition may include thixotropic modifier, to prevent from settling during coating stores, and ensure machinability, and can wrap
It is foam stabilising to prevent to include antifoaming agent.
The example of these additives includes：Dispersant, such as Disperbyk-190 (BYK) and Orotan-1850E (DOW)
Deng；Surfactant, such as Surfynol 104 (Air Products) are free of alkylphenol ethoxylate (APEO)；It touches
Become modifying agent, such as Natrosol+330 (Hercules) and the like；And silicone antifoams agent, such as BYK011 and BYK
012 (BYK) and the like；But it is not limited to this.
Water-based paint compositions according to the present invention can be applied to building body or container by brush, sprayer or roller etc.
Deng inner and outer wall, and be then dried at room temperature for form coating film.
Therefore, embodiments of the present invention are related to a kind of coating film, the coating film using the water-based paint compositions come
It is formed.
Hereinafter, describing the present invention in detail by embodiment, comparative example and experimental example.Embodiment, comparative example and experiment
Example is only used for the description present invention, and it is apparent to a person skilled in the art that the scope of the present invention is not limited to this.
Preparation example 1：Prepare core-shell type Organic-inorganic composite copolymer emulsion resin (core Tg：- 20 DEG C, shell Tg：78℃)
Core-shell type Organic-inorganic composite is prepared according to methods described below and using being formed shown in the following table 1
Copolymer emulsion resin.
First operation：The formation of seed
By alpha-sulfo-ω-(1- alkoxies) methyl -2- (2- allyloxys) ethoxy of the deionized water of 179g and 12g
Base)-the ammonium salt (SR1025, Adeka) of poly- (- two-yl of oxygen -1,2- ethane) be introduced into be equipped with blender, temperature sensor and
In the reactor of condenser, and elevate the temperature to 80 DEG C.
In independent reaction vessel, by deionized water, alpha-sulfo-ω-(1- alkoxies) first of 12g for stirring 99g
Base -2- (2- allyloxys) ethyoxyl)-poly- (- two-yl of oxygen -1,2- ethane) (SR1025, Adeka), 86g methacrylic acid
The 2- ethylhexyl acrylates of methyl esters, the butyl acrylate of 151g and 14g prepare pre-emulsion, and by by 18.1g
The pre-emulsion of (5wt%) is put into reactor, and potassium peroxydisulfate and the holding of the deionized water and 1g of 13g are added dropwise in 10 minutes
20 minutes, to prepare seed emulsion.
Second operation：The formation of core
By the way that the remaining 95wt% pre-emulsions prepared in the first operation are continually introduced into reaction within 2 hours
It in device, and is then kept for 1 hour at 80 DEG C, to prepare the emulsion resin of core.
Third operates：The formation of shell
By by alpha-sulfo-ω-(1- alkoxies) methyl -2- (2- allyloxys) ethoxy of the deionized water of 99g, 12g
Base)-poly- (- two-yl of oxygen -1,2- ethane) (SR1025, Adeka), the methyl methacrylate of 154g, 24g butyl acrylate,
The methacrylic acid of 14g, the methyltrimethoxysilane of 21g, the methacryloxypropyl trimethoxy silane of 2g and
The potassium peroxydisulfate of 1g is put into independent reactor and after preparing pre-emulsion, which is continuously drawn in 2 hours for stirring
Enter into the reactor of the second operation, and then keeps at 80 DEG C 1 hour to prepare nuclear-shell emulsion resin.
After by the holding period, by being cooled to 40 DEG C, the deionized water of 103g and the ammonium hydroxide of 3g is added
(25%) and keep 1 hour after, obtain stable nuclear-shell emulsion resin.
In obtained nuclear-shell emulsion resin, the Tg of core is -20 DEG C, and the Tg of shell is 78 DEG C, and the Tg of core-shell structure copolymer entirety is
15 DEG C, particle diameter 100nm, solid content 46.1%, and viscosity is 300cps.
Preparation example 2：Prepare core-shell type Organic-inorganic composite copolymer emulsion resin (core Tg：- 15 DEG C, shell Tg：60℃)
Other than showing composition in using the following table 1, core-is prepared according to identical method in such as above-mentioned preparation example 1
Shell mould Organic-inorganic composite copolymer emulsion resin.
In obtained nuclear-shell emulsion resin, the Tg of core is -15 DEG C, and the Tg of shell is 60 DEG C, and the Tg of core-shell structure copolymer entirety is
15 DEG C, particle diameter 110nm, solid content 46.1%, and viscosity is 500cps.
Preparation example 3：Prepare core-shell type Organic-inorganic composite copolymer emulsion resin (core Tg：- 10 DEG C, shell Tg：40℃)
Other than showing composition in using the following table 1, core-is prepared according to identical method in such as above-mentioned preparation example 1
Shell mould Organic-inorganic composite copolymer emulsion resin.
In obtained nuclear-shell emulsion resin, the Tg of core is -10 DEG C, and the Tg of shell is 40 DEG C, and the Tg of core-shell structure copolymer entirety is
15 DEG C, particle diameter 120nm, solid content 46.1%, and viscosity is 200cps.
Preparation example 4：Prepare core-shell type Organic-inorganic composite copolymer emulsion resin (core Tg：- 10 DEG C, shell Tg：30℃)
Other than showing composition in using the following table 1, core-is prepared according to identical method in such as above-mentioned preparation example 1
Shell mould Organic-inorganic composite copolymer emulsion resin.
In obtained core-shell emulsion resin, the Tg of core is -10 DEG C, and the Tg of shell is 30 DEG C, and the Tg of nucleocapsid entirety is 15
DEG C, particle diameter 100nm, solid content 46.1%, and viscosity is 100cps.
Preparation example 5：Prepare core-shell type Organic-inorganic composite copolymer emulsion resin (core Tg：- 35 DEG C, shell Tg：109℃)
Other than showing composition in using the following table 1, core-is prepared according to identical method in such as above-mentioned preparation example 1
Shell mould Organic-inorganic composite copolymer emulsion resin.
In obtained nuclear-shell emulsion resin, the Tg of core is -35 DEG C, and the Tg of shell is 109 DEG C, and the Tg of core-shell structure copolymer entirety is
15 DEG C, particle diameter 100nm, solid content 46.1%, and viscosity is 800cps.
Preparation example 6：Prepare homogeneous Organic-inorganic composite copolymer emulsion resin
First operation：The formation of seed
By alpha-sulfo-ω-(1- alkoxies) methyl -2- (2- allyloxys) ethoxy of the deionized water of 179g and 12g
Base)-the ammonium salt (SR1025, Adeka) of poly- (- two-yl of oxygen -1,2- ethane) be introduced into be equipped with blender, temperature sensor and
In the reactor of condenser, and elevate the temperature to 80 DEG C.
By by alpha-sulfo-ω-(1- alkoxies) methyl -2- (2- allyloxys) ethoxy of the deionized water of 198g, 24g
Base)-poly- (- two-yl of oxygen -1,2- ethane) (SR1025, Adeka), the methyl methacrylate of 240g, 175g acrylic acid fourth
The methacryl of ester, the 2- ethylhexyl acrylates of 14g, the methacrylic acid of 14g, the methyltrimethoxysilane of 21g, 2g
The potassium peroxydisulfate of oxygroup propyl trimethoxy silicane and 1g be put into independent reaction vessel and stir prepare pre-emulsion it
Afterwards, the pre-emulsion of 34.4g (5wt%) is put into reactor, the persulfuric acid of the deionized water and 1g of 13g is added dropwise in 10 minutes
Potassium and keep 20 minutes, to prepare seed emulsion.
Second operation：Formation (the Tg of homogeneous emulsion resin：15℃)
By the way that the remaining 95wt% pre-emulsions prepared in the first operation are continually introduced into reaction within 4 hours
It in device, and is then kept for 1 hour at 80 DEG C, to prepare the homogeneous emulsion resin that Tg is 15 DEG C.
After by the holding period, by being cooled to 40 DEG C, the ammonium hydroxide (25%) of 103g deionized waters and 3g is added
And after being kept for 1 hour, obtain stable homogeneous emulsion resin.
In obtained homogeneous emulsion resin, Tg is 15 DEG C, particle diameter 140nm, solid content 46.1%, and
Viscosity is 200cps.
Preparation example 7：Prepare core-shell type Organic-inorganic composite copolymer emulsion resin (core Tg：- 20 DEG C, shell Tg：26℃)
Other than showing composition in using the following table 1, core-is prepared according to identical method in such as above-mentioned preparation example 1
Shell mould Organic-inorganic composite copolymer emulsion resin.
In obtained nuclear-shell emulsion resin, the Tg of core is -20 DEG C, and the Tg of shell is 26 DEG C, and the Tg of core-shell structure copolymer entirety is
15 DEG C, particle diameter 120nm, solid content 46.1%, and viscosity is 300cps.
Preparation example 8：Prepare core-shell type Organic-inorganic composite copolymer emulsion resin (core Tg：- 1 DEG C, shell Tg：78℃)
Other than showing composition in using the following table 1, core-is prepared according to identical method in such as above-mentioned preparation example 1
Shell mould Organic-inorganic composite copolymer emulsion resin.
In obtained nuclear-shell emulsion resin, the Tg of core is -1 DEG C, and the Tg of shell is 78 DEG C, and the Tg of core-shell structure copolymer entirety is 15
DEG C, particle diameter 140nm, solid content 46.1%, and viscosity is 350cps.
[table 1]
Embodiment and comparative example：Prepare water-based paint compositions
It is formed using shown in the following table 2, water-based paint compositions is prepared according to methods described below.
By the surfactant (be free of APEO, Surfynol 104, Air Products) of the deionized water of 18g, 1g,
The thixotropic modifier (Natrosol+330, Ashland) of 0.2g and the antifoaming agent (BYK011, BYK) of 0.3g are put into and are not given birth to
In the container of rust and stir about is after 30 minutes, introduces the dispersant (Disperbyk-190, BYK) of 0.5g and futher stirs 5
Minute.Next, while being slowly stirred, the coloring face of extender pigment (silica, the S-SIL 5, SAC) and 15g of 10g are introduced
Expect (TiO2, Ti-Pure R-706, Chemoours), and pass through the increase revolution per minute (linear speed of blender at the end of making
Degree reaches 18m/s to 21m/s) carry out dispersion in 15 minutes.
While the mill base for being slowly stirred dispersion, the reactive adhesive of 50g is slowly introduced, and carry out 10 minutes
Stirring, after this, introduces the film forming agent (Texanol, Eastman) of 5g and carries out stirring in about 10 minutes.To obtain
The water-based paint compositions of 100g.
[table 2]
Experimental example：Assess the physical property of coating film
The water-based paint compositions prepared according to examples and comparative examples are painted into thickness in the overhead gas blowout of 1.5T cold-rolled steel sheets
Degree is 80 microns of dry-coated overlay film, and then under conditions of 23 ± 2 DEG C of temperature and 50 ± 10% relative humidity, drying is at least
7 days.Here, during the ventilation of drying equipment, the holding of coating film surface is made to be not directly exposed to high wind.
The physical property of each coating film is assessed according to appraisal procedure hereafter, and result is shown in the following table 3.
(1) weatherability
According to ASTM G53, assessed using QUV-B testers (Q-LAQ) and by observing coating film after 600 hours
Weatherability (Δ E is color value).
(2) resistance to soiling
In the case of resistance to soiling, differentiation is carried out using the method example of independent research, and the specific method is as follows.
First, the charcoal blacks of 10g are soaked using the water of 90g, and are then stirred to prepare suspension.Then,
Using surface plate, it will place and covered in the film sample of preparation as the charcoal blacks suspension of pollutant, and with viscous
The sealing such as attached dose or adhesive tape is revealed to prevent stopping leak.Next, by sample in 50 DEG C of baking oven indwelling 1 hour.After completion, it moves
It is cleaned except surface plate, and by gently being rubbed with brush in the flowing water, after this, observes coating film
Pollute removal state.
(3) adhesiveness
Adhesiveness is assessed by strength disbonded test using scraper.
(4) flexible
It is flexible according to ASTM D522 assessments.
[table 3]
By the formed coating film of water-based paint compositions in embodiment 1 to embodiment 4 it can be seen from the result of table 3
Not only there is fabulous weatherability, also there is excellent resistance to soiling and flexibility, it can be seen that being used for when as finishing coat application
When applications, appearance beautiful and generous is kept for a long time.On the contrary, by comparative example 1 to the water-based paint compositions of comparative example 4
Resistance to soiling and flexibility cannot be realized simultaneously by being formed by coating film.
The specific aspect of the present invention is described in detail above.This detailed description is only technology neck belonging to the present invention
The illustrative embodiment of the those of ordinary skill in domain, it is therefore evident that the scope of the present invention is not limited to this implementation
Mode.In the scope of the present invention based on foregoing description, general technical staff of the technical field of the invention will be into
The various modifications and changes of row.
It is understood, therefore, that the actual scope of the present invention is limited by appended claims and equivalency range.
Claims (7)
1. a kind of water-based paint compositions, the water-based paint compositions include core-shell type Organic-inorganic composite copolymer emulsion
Resin, the core-shell type Organic-inorganic composite copolymer emulsion resin include：
Core, the core are made of acrylic emulsion resin, and with -30 DEG C to -10 DEG C of glass transition temperature (Tg)；With
And
Shell, the shell is made of the acrylic emulsion resin containing alkoxysilyl or epoxy group silicyl, and is had
30 DEG C to 100 DEG C of glass transition temperature (Tg).
2. water-based paint compositions according to claim 1, wherein the water-based paint compositions further comprise：Phase
For total water-based paint compositions of 100wt%, the core-shell type Organic-inorganic composite copolymer of 40wt% to 60wt%
Emulsion resin, the extender pigment of 5wt% to 20wt%, the coloring pigment and 5wt% of 1wt% to 20wt% is to 40wt%'s
Water.
3. water-based paint compositions according to claim 1, wherein the acrylic emulsion resin of the core is by including one kind
Or the mixture of a variety of acrylic monomers is formed, one or more acrylic monomers be selected from by methyl methacrylate,
The group that butyl methacrylate, butyl acrylate, cyclohexyl methacrylate and methacrylic acid are formed.
4. water-based paint compositions according to claim 1, wherein the shell contains alkoxy silicane or epoxy group first
The acrylic emulsion resin of silylation by include one or more acrylic monomers and it is one or more contain alkoxy silicane
The mixture of the monomer of base or epoxy group silicyl is formed, and one or more acrylic monomers are selected from by metering system
The group that sour methyl esters, butyl methacrylate, butyl acrylate, cyclohexyl methacrylate and methacrylic acid are formed, institute
One or more monomers containing alkoxysilyl or epoxy group silicyl are stated to be selected from by epoxy silane, methacryloxypropyl
The group that base silane, methyltrimethoxysilane and methacryloxypropyl trimethoxy silane are formed.
5. water-based paint compositions according to claim 1, wherein in the core-shell type Organic-inorganic composite copolymer
In emulsion resin, the content of the core is 30wt% to 80wt%, and the content of the shell is 20wt% to 70wt%.
6. water-based paint compositions according to claim 1, further comprise：The additive of at least one type, it is described
The additive of at least one type is selected from and is made of film forming agent, dispersant, surfactant, thixotropic modifier and antifoaming agent
Group.
7. a kind of coating film, the coating film using water-based paint compositions according to any one of claim 1 to 6 come
It is formed.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020160103011A KR101800969B1 (en) | 2016-08-12 | 2016-08-12 | Aqueous Paint Composition |
| KR10-2016-0103011 | 2016-08-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108300090A true CN108300090A (en) | 2018-07-20 |
Family
ID=60809499
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710694260.7A Pending CN108300090A (en) | 2016-08-12 | 2017-08-11 | Water-based paint compositions and coating film |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR101800969B1 (en) |
| CN (1) | CN108300090A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113597372A (en) * | 2019-04-01 | 2021-11-02 | Dic油墨株式会社 | Composition for paper exterior coating and adhesive, and coated article, water-and oil-resistant paper laminate, paper straw, and paper tableware using the same |
| CN116589644A (en) * | 2023-05-18 | 2023-08-15 | 青岛爱尔家佳新材料股份有限公司 | Damping emulsion with double-core-shell structure, water-based damping paint with anti-condensation function and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115124657B (en) * | 2022-08-08 | 2023-03-10 | 湖南聚仁化工新材料科技有限公司 | Acrylate emulsion with core-shell structure and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0565244A1 (en) * | 1992-04-10 | 1993-10-13 | Rohm And Haas Company | Polymeric particles |
| CN102153932A (en) * | 2010-02-01 | 2011-08-17 | 株式会社Kcc | Monocomponent aqueous top coating composition cured at room temperature |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002012601A (en) | 2000-06-30 | 2002-01-15 | Saiden Chemical Industry Co Ltd | Method for manufacturing aqueous polymer dispersion for coating material and the dispersion |
| JP4695829B2 (en) | 2002-12-27 | 2011-06-08 | エスケー化研株式会社 | Water-based paint composition |
| JP6041740B2 (en) | 2012-09-28 | 2016-12-14 | 関西ペイント株式会社 | Water-based coating composition and coating film forming method |
-
2016
- 2016-08-12 KR KR1020160103011A patent/KR101800969B1/en active IP Right Grant
-
2017
- 2017-08-11 CN CN201710694260.7A patent/CN108300090A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0565244A1 (en) * | 1992-04-10 | 1993-10-13 | Rohm And Haas Company | Polymeric particles |
| CN102153932A (en) * | 2010-02-01 | 2011-08-17 | 株式会社Kcc | Monocomponent aqueous top coating composition cured at room temperature |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113597372A (en) * | 2019-04-01 | 2021-11-02 | Dic油墨株式会社 | Composition for paper exterior coating and adhesive, and coated article, water-and oil-resistant paper laminate, paper straw, and paper tableware using the same |
| CN113597372B (en) * | 2019-04-01 | 2022-05-06 | Dic油墨株式会社 | Composition for paper exterior coating and adhesive, and coated article, water-and oil-resistant paper laminate, paper straw, and paper tableware using the same |
| CN116589644A (en) * | 2023-05-18 | 2023-08-15 | 青岛爱尔家佳新材料股份有限公司 | Damping emulsion with double-core-shell structure, water-based damping paint with anti-condensation function and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101800969B1 (en) | 2017-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109868026B (en) | Organic silicon modified acrylate resin, preparation method thereof and hydrophobic weather-resistant slow-release modified acrylic resin coating | |
| JP2625480B2 (en) | Cationic electrodeposition gelled fine particle polymer and cationic electrodeposition coating composition containing the same | |
| DE69724224T2 (en) | Anti-fouling interface composition and coated articles | |
| JP3298891B2 (en) | Paint composition, method for producing paint composition, and method for producing dispersion of inorganic oxide sol | |
| CN103602193A (en) | Priming paint for water-borne heavy anti-corrosion coating and preparation method thereof | |
| DE60110212T2 (en) | COATING COMPOSITIONS HARDENING IN ROOM TEMPERATURE | |
| JP4034579B2 (en) | High durability multi-layer coating film, method for forming the same and exterior building material | |
| CN103627286B (en) | A kind of aqueous heavy anti-corrosion paint finish paint and preparation method thereof | |
| CN107418277B (en) | A kind of water nano long-effective corrosion finishing coat and preparation method thereof | |
| CN111285960B (en) | Acrylic emulsion and application thereof | |
| CN101899251B (en) | Paint for coating surface of sanitary ware made of composite materials and preparation method thereof | |
| JP6899702B2 (en) | Room temperature curable weather resistant paint composition | |
| CN109370411A (en) | A kind of acrylic resin modified aqueous industrial coating of fluorine-silicon polyurethane | |
| CN108300090A (en) | Water-based paint compositions and coating film | |
| CN107033296A (en) | Extra-weather-proof polysiloxane-modified acrylic resin and finish paint preparation method | |
| WO2020056542A1 (en) | Two-part coating composition | |
| CN102408808B (en) | Aqueous fluorocarbon coating for painting metal base materials | |
| WO2001060920A1 (en) | Aqueous dispersion, process for production thereof and coated substances | |
| US7943698B2 (en) | Moisture cure alpha-silane modified acrylic coatings | |
| KR101183892B1 (en) | One-component type, room-temperature curing and water-soluble top coating composition | |
| CN108084828A (en) | A kind of high durable for lamp stand plates spelter coating and preparation method thereof | |
| CN105860823A (en) | Ultraviolet cured varnish with high barrier property and preparation method thereof | |
| JP6068178B2 (en) | Method for producing polymer dispersion, method for producing aqueous coating material, and method for producing coated product | |
| KR100566548B1 (en) | Resin composition comprising silicone intermediate and paints containing it | |
| JP3374885B2 (en) | Method for producing inorganic decorative board |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180720 |