WO2014192638A1 - 水性塗料用組成物、水性塗料用キットおよび塗膜を有する物品 - Google Patents
水性塗料用組成物、水性塗料用キットおよび塗膜を有する物品 Download PDFInfo
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- WO2014192638A1 WO2014192638A1 PCT/JP2014/063618 JP2014063618W WO2014192638A1 WO 2014192638 A1 WO2014192638 A1 WO 2014192638A1 JP 2014063618 W JP2014063618 W JP 2014063618W WO 2014192638 A1 WO2014192638 A1 WO 2014192638A1
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- 0 CCOC(C)(C)[N+](C(C)(C)*1C(C)=C1)[O-] Chemical compound CCOC(C)(C)[N+](C(C)(C)*1C(C)=C1)[O-] 0.000 description 3
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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
- C09D127/00—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 a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/284—Compounds containing ester groups, e.g. oxyalkylated monocarboxylic acids
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6275—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds
- C08G18/6279—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds containing fluorine atoms
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/703—Isocyanates or isothiocyanates transformed in a latent form by physical means
- C08G18/705—Dispersions of isocyanates or isothiocyanates in a liquid medium
- C08G18/706—Dispersions of isocyanates or isothiocyanates in a liquid medium the liquid medium being water
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- 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
- C09D151/06—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 homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C09D157/00—Coating compositions based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D157/06—Homopolymers or copolymers containing elements other than carbon and hydrogen
- C09D157/08—Homopolymers or copolymers containing elements other than carbon and hydrogen containing halogen atoms
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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- C09D201/00—Coating compositions based on unspecified macromolecular compounds
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- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C09D201/04—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms
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- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
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- 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
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- 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
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- 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
Definitions
- the present invention relates to an aqueous coating composition, an aqueous coating kit, and an article having a coating film formed using the aqueous coating composition.
- a low-staining agent capable of making the surface of the coating film hydrophilic and oil repellent is added to the coating composition.
- a self-purifying function can be realized with a water-based paint having a small organic solvent content.
- composition for water-based paints containing the low pollution agent for water-based paints containing the low pollution agent for water-based paints.
- Patent Document 1 A composition for aqueous paint containing a synthetic resin emulsion and a modified condensate of alkoxysilane as a low contamination agent for aqueous paint (Patent Document 1).
- the aqueous coating composition (1) has a problem in storage stability because it contains a modified condensation product of alkoxysilane having a relatively high reactivity.
- the aqueous coating composition of (2) has good storage stability, but when the fluororesin aqueous dispersion is included as the synthetic resin aqueous dispersion, the fluorocopolymer as a low-contamination agent is applied to the coating film. It is difficult to transfer to the surface layer, and the self-purifying function is insufficiently provided.
- the fluorine-containing copolymer reacts with the isocyanate compound in the course of transferring to the surface layer of the coating film, and the fluorine-containing copolymer further moves to the surface layer of the coating film. It becomes difficult.
- the present invention is a composition for water-based paints capable of forming a coating film having a sufficient self-cleaning function even when a fluorine-containing resin water dispersion is blended as a synthetic resin water dispersion or when an isocyanate compound is contained as a curing agent.
- An aqueous coating kit capable of obtaining the aqueous coating composition; and an article having a coating film having a sufficient self-cleaning function.
- the aqueous coating composition of the present invention contains a synthetic resin aqueous dispersion and a urethane polyol, and the urethane polyol has a polyoxyoxy group having a structure in which an oxygen atom is bonded to one end of a branched alkylene group as a unit. It is a reaction product of an alkylene diol and an aliphatic diisocyanate.
- the oxyalkylene group is preferably an oxypropylene group.
- the urethane polyol is preferably a reaction product of polypropylene glycol having 2 to 6 oxypropylene groups and alkylene diisocyanate having 4 to 10 carbon atoms of an alkylene group.
- the alkylene group of the alkylene diisocyanate is preferably a branched alkylene group.
- the urethane polyol preferably has a number average molecular weight of 1,000 to 30,000 and a hydroxyl value of 50 to 500 mgKOH / g.
- the content of the urethane polyol is preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the solid content in the synthetic resin aqueous dispersion.
- At least a part of the synthetic resin in the synthetic resin aqueous dispersion is a fluorine-containing resin.
- the fluorine-containing resin in the fluorine-containing resin aqueous dispersion is: A fluorine-containing copolymer (A1p) having a structural unit based on the following monomer (m1), a structural unit based on the following monomer (m2), and a structural unit based on the following monomer (m3), Or 40 to 60 mol% of the structural unit represented by the following formula (a1), 3 to 50 mol% of the structural unit represented by the following formula (a2), and the structural unit represented by the following formula (a3) 4 to 30 mol% and 0.4 to 7 mol% of the structural unit represented by the following formula (a4) (provided that the structural unit represented by the formula (a1) and the structural unit represented by the formula (a2)) And a fluorine-containing copolymer (A2p) having a structural unit represented by the formula (a3) and a total of structural units represented by the formula (a4) of 80 to 100 mol%. It is preferable that
- Monomer (m1) fluoroolefin.
- Monomer (m2) a macromonomer having a hydrophilic site.
- Monomer (m3) A hydroxyl group-containing monomer represented by the following formula (m3).
- R 1 -R 2 -OH (m3) R 1 is a group having a radically polymerizable unsaturated group, and R 2 is an n-nonylene group or a cyclohexane-1,4-dimethylene group.
- X 1 and X 2 are each independently a hydrogen atom, chlorine atom or fluorine atom
- X 3 is a hydrogen atom, chlorine atom, fluorine atom or —CY 1 Y 2 Y 3
- Y 1 , Y 2 , Y 3 is each independently a hydrogen atom, a chlorine atom or a fluorine atom.
- R a is a hydrogen atom or a methyl group
- R 11 is an alkyl group having 1 to 12 carbon atoms or a monovalent alicyclic group having 4 to 10 carbon atoms
- u is an integer of 0 to 8.
- V is 0 or 1.
- R b is a hydrogen atom or a methyl group
- R 12 is an alkylene group having 1 to 10 carbon atoms or a divalent alicyclic group having 4 to 10 carbon atoms
- w is an integer of 0 to 8.
- X is 0 or 1.
- R c is a hydrogen atom or a methyl group
- R 13 is an alkylene group having 1 to 10 carbon atoms or a divalent alicyclic group having 4 to 10 carbon atoms
- R 14 is an alkylene group having 2 to 10 carbon atoms.
- R 15 is a hydrogen atom or —NHZ 1 Z 2 Z 3
- Z 1 , Z 2 , and Z 3 are each independently a hydrogen atom
- An alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms, at least a part of R 15 is —NHZ 1 Z 2 Z 3
- y is an integer of 0 to 8
- z is 0 or 1.
- the fluororesin aqueous dispersion preferably further contains a curing agent.
- the curing agent is preferably an isocyanate compound.
- the article of the present invention is characterized by having a coating film formed by using the aqueous coating composition of the present invention.
- the aqueous paint kit of the present invention comprises the aqueous paint composition of the present invention and an aqueous solution or aqueous dispersion of an isocyanate compound. Furthermore, the article of the present invention is characterized by having a coating film formed by using the water-based paint kit.
- the aqueous paint preparation kit of the present invention is a kit used to prepare the aqueous paint composition, and comprises the synthetic resin aqueous dispersion and the urethane polyol aqueous solution or aqueous dispersion.
- the aqueous coating composition of the present invention forms a coating film having a sufficient self-cleaning function even when a fluorine-containing resin water dispersion is blended as a synthetic resin water dispersion or when an isocyanate compound is contained as a curing agent. it can.
- a composition for water-based paints that can exhibit the above effects can be obtained.
- the article of the present invention has a coating film having a sufficient self-cleaning function.
- Structural unit means a unit derived from a monomer formed by polymerization of the monomer. It may be a unit directly formed by a polymerization reaction, or may be a unit in which a part of the unit is converted into another structure by treating the polymer.
- “Monomer” means a compound having a radically polymerizable unsaturated group.
- (Meth) acrylate means either or both of acrylate and methacrylate.
- Aqueous medium means a liquid containing water and having an organic solvent content of 3% by mass or less.
- the “macromonomer” means a low molecular weight polymer or oligomer having a radical polymerizable unsaturated group at one end.
- the “hydrophilic part” means a part having a hydrophilic group, a part having a hydrophilic bond, or a part composed of a combination thereof.
- the composition for water-based paints of the present invention contains a synthetic resin aqueous dispersion and urethane polyol as a low-fouling agent for water-based paints.
- the aqueous coating composition of the present invention can be obtained, for example, by blending a synthetic resin aqueous dispersion and a urethane polyol.
- the urethane polyol in the present invention is a compound having a urethane bond in the molecule and having two or more hydroxyl groups.
- the urethane polyol in the present invention is considered to move to the surface of the coating film when the aqueous coating composition forms a coating film, hydrophilize the coating film surface, and impart a self-cleaning function to the coating film.
- the urethane polyol contained in the aqueous coating composition of the present invention is a polyoxy group having an oxyalkylene group having a structure in which an oxygen atom is bonded to one end of a branched alkylene group as the effect of the present invention is sufficiently exerted.
- urethane polyol in the present invention is also referred to as urethane polyol (X)
- polyoxyalkylene diol is also referred to as polyoxyalkylene diol (Y)
- the polyoxyalkylene diol (Y) is a polyoxyalkylene diol having as a unit an oxyalkylene group having a structure in which an oxygen atom is bonded to one end of a branched alkylene group.
- the oxyalkylene group in the polyoxyalkylene diol (Y) may consist only of a branched oxyalkylene group, and together with the branched oxyalkylene group, an oxyalkylene group other than the branched oxyalkylene group (hereinafter also referred to as a linear oxyalkylene group).
- the oxyalkylene group in the polyoxyalkylene diol (Y) consists only of a branched oxyalkylene group.
- the branched oxyalkylene group preferably has 3 to 6 carbon atoms, more preferably 3 or 4.
- the straight-chain oxyalkylene group preferably has 2 to 6 carbon atoms, more preferably 2 or 6.
- the oxyalkylene group is preferably formed by ring opening of a cyclic ether or formed by multimerization of an alkylene diol.
- an alkylene oxide is preferable. Examples of the alkylene oxide that forms a branched oxyalkylene group include propylene oxide (ie, 1,2-epoxypropane), 1,2-epoxybutane, 2,3-epoxybutane, and the like.
- a particularly preferred branched oxyalkylene group is an oxypropylene group formed by the ring opening of propylene oxide.
- the alkylene oxide that forms the linear oxyalkylene group include ethylene oxide
- examples of the cyclic ether other than the alkylene oxide that forms the linear oxyalkylene group include oxetane and tetrahydrofuran.
- a preferred linear oxyalkylene group is an oxyethylene group formed by ring opening of ethylene oxide.
- a polyoxyalkylene diol is a compound having two or more oxyalkylene groups and two hydroxyl groups.
- the polyoxyalkylene diol is produced by a method of reacting water with an alkylene oxide, a method of ring-opening addition of an alkylene oxide to a divalent initiator, or the like.
- polyoxyalkylene diol which is a multimer of alkane diol
- the number of oxyalkylene groups of polyoxyalkylene diol which is a multimer of alkane diol refers to the number of alkane diol residues.
- alkanediols such as propylene glycol, ethylene glycol, and 1,4-butanediol have 1 oxyalkylene group, and the multimer has 2 or more oxyalkylene groups.
- dipropylene glycol has 2 oxypropylene groups
- tripropylene glycol has 3 oxypropylene groups
- tetrapropylene glycol has 4 oxypropylene groups.
- a polyoxyalkylene diol having a divalent initiator residue and an oxyalkylene group is produced by a ring-opening addition of alkylene oxide to a divalent initiator such as a dihydric alcohol.
- the residue of the divalent initiator is an alkanediol
- the residue of the divalent initiator is an oxyalkylene group
- the residue of the divalent initiator is It shall have a number of oxyalkylene groups.
- the initiator is a propylene glycol monomer or multimer such as propylene glycol or dipropylene glycol
- a polyoxy having a structure similar to that of the propylene glycol multimer is obtained by ring-opening addition of propylene oxide to the initiator. Propylene diol is produced.
- the polyoxyalkylene diol (Y) may be a single polyoxyalkylene diol or a mixture of two or more polyoxyalkylene diols. In the case of a mixture, the ratio of the branched alkylene group and the hydroxyl value of the polyoxyalkylene diol mean an average value.
- the polyoxyalkylene diol (Y) preferably has two or more alkylene groups, and more than half of the total number of alkylene groups is preferably a branched alkylene group. In particular, 75 to 100% of the total number of alkylene groups is preferably a branched alkylene group.
- the average number of oxyalkylene groups per molecule of the polyoxyalkylene diol (Y) is preferably from 2 to 10, more preferably from 2 to 7, and particularly preferably from 2 to 5, from the viewpoint of excellent transferability to the coating film surface.
- the polyoxyalkylene diol (Y) is preferably polypropylene glycol having 2 to 6 oxypropylene groups, and more preferably polypropylene glycol having 2 to 4 oxypropylene groups.
- Specific examples of polypropylene glycol include dipropylene glycol, tripropylene glycol, and tetrapropylene glycol.
- Polypropylene glycol is usually obtained by reacting propylene oxide with water. By this reaction, the above-mentioned polypropylene glycol is produced together with propylene glycol, and if necessary, each product is separated and produced.
- the polyoxyalkylene diol (Y) may be a mixture of polypropylene glycols having different degrees of multimerization, or may be a mixture of at least one polypropylene glycol and propylene glycol.
- An aliphatic diisocyanate is a compound having a branched or linear alkylene group between two isocyanate groups.
- the alkylene group preferably has 4 to 10 carbon atoms.
- an aliphatic diisocyanate having a branched alkylene group is preferred from the viewpoint that the coating film hardness when transferred to the coating film surface is high.
- 2 or more types of aliphatic diisocyanate can be used as a raw material of urethane polyol (X).
- Examples of the aliphatic diisocyanate having a branched alkylene group include 2-methylpentane-1,5-diisocyanate, pentane-1,4-diisocyanate, hexane-1,5-diisocyanate, and trimethylhexane-1,6-diisocyanate. It is done.
- Examples of the aliphatic diisocyanate having a linear alkylene group include hexamethylene diisocyanate and tetramethylene diisocyanate.
- Urethane polyol (X) is a reaction product obtained by reacting polyoxyalkylene diol (Y) and aliphatic diisocyanate under the condition that the ratio of the number of isocyanate groups to hydroxyl groups is less than 1.
- the isocyanate index One hundred times the ratio of the number of isocyanate groups to hydroxyl groups is called the isocyanate index. Therefore, the urethane polyol (X) is a reaction product obtained by reacting the polyoxyalkylene diol (Y) with an aliphatic diisocyanate under a condition where the isocyanate index is less than 100.
- urethane polyol (X) is a reaction product of polyoxyalkylene diol (Y) and aliphatic diisocyanate, urethane polyol (X) is a urethane polyol having 2 hydroxyl groups.
- the number of aliphatic diisocyanate residues in the urethane polyol (X) is preferably from 5 to 15, more preferably from 6 to 14, from the viewpoint of excellent smoothness of the coating film and less repellency to the coating film, and from 7 to 13 Is particularly preferred.
- the number of polyoxyalkylene diol (Y) residues is usually the number of aliphatic diisocyanate residues plus one.
- the number average molecular weight of the urethane polyol (X) is preferably 1000 to 30000, more preferably 2000 to 20000. When the number average molecular weight of the urethane polyol (X) is 1000 or more, the coating film does not stick to the surface of the coating film. If the number average molecular weight of urethane polyol (X) is 30000 or less, it will be easy to transfer to the coating surface, and the impact resistance of the coating will be excellent.
- the number average molecular weight of the urethane polyol (X) is determined by calculation from the structure of the urethane polyol (X) specified by NMR analysis.
- the hydroxyl value of the urethane polyol (X) is preferably 50 to 500 mgKOH / g, more preferably 100 to 400 mgKOH / g. If the hydroxyl value of urethane polyol (X) is 50 mgKOH / g or more, the coating surface is likely to be hydrophilic. When the hydroxyl value of the urethane polyol (X) is 500 mgKOH / g or less, the urethane polyol (X) itself is unlikely to flow down due to heavy rain such as a typhoon, and the coating film is easily made hydrophilic over a long period of time. The hydroxyl value of the urethane polyol (X) can be measured by a method based on JIS K1557-1 (2007).
- the urethane polyol (X) is usually provided in the form of a solution in which the urethane polyol (X) is dissolved in an aqueous medium or a dispersion in which the urethane polyol (X) is dispersed in an aqueous medium.
- the solution or dispersion may contain components other than the urethane polyol (X) and the aqueous medium as long as the effects of the present invention are not impaired. Since the solution or dispersion is blended in the aqueous coating composition, the content of the organic solvent in the solution or dispersion is preferably 3% by mass or less, particularly preferably 1% by mass or less.
- the content of the urethane polyol (X) is preferably 0.5 to 30 parts by mass and more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the solid content in the synthetic resin aqueous dispersion. If content of urethane polyol (X) is 5 mass parts or more, the effect by urethane polyol (X) will fully be exhibited. If the quantity of urethane polyol (X) is 20 mass parts or less, the water resistance of a coating film is securable.
- Synthetic resin water dispersion examples include known acrylic resin aqueous dispersions, acrylic silicon resin aqueous dispersions, and fluorine-containing resin aqueous dispersions.
- the synthetic resin water dispersion may be a two-component type used in combination with a curing agent.
- a fluorine-containing resin aqueous dispersion is preferable from the viewpoint that the effects of the present invention are sufficiently exhibited.
- the fluororesin aqueous dispersion is obtained by dispersing or dissolving a fluoropolymer in an aqueous medium.
- the fluorinated polymer include a polymer having a structural unit based on a fluorinated monomer, or a structural unit based on a fluorinated monomer and another monomer copolymerizable with the fluorinated monomer. And a polymer having a structural unit based thereon.
- fluorine-containing monomers examples include fluoroolefins (vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, pentafluoroethylene, hexafluoropropylene, etc.), fluorine-containing (meth) acrylates (trifluoroethyl). (Meth) acrylate, pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, etc.).
- fluoroolefins are preferable as the fluorine-containing monomer, and among the fluoroolefins, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, and chlorotrifluoroethylene are more preferable.
- examples of other monomers copolymerizable with the fluorine-containing monomer include acrylic monomers, other monomers copolymerizable with acrylic monomers, and the like.
- a fluorine-containing resin water dispersion (A1), a fluorine-containing resin water dispersion (A2) or a fluorine-containing resin water dispersion (A3), which will be described later, is preferable, and cracks are unlikely to occur in the coating film.
- the fluororesin water dispersion (A1) or the fluororesin water dispersion (A2) is more preferable from the viewpoint of excellent antifungal and algae resistance during storage.
- Examples of the method for producing a fluororesin aqueous dispersion include a method of obtaining a fluororesin aqueous dispersion by emulsion polymerization, and obtaining a fluorocopolymer by solution polymerization, and then dispersing the fluorocopolymer in an aqueous medium. And a method of obtaining an aqueous dispersion of a fluororesin.
- the emulsion polymerization may be performed by batch polymerization, monomer dropping polymerization, or emulsion monomer dropping polymerization.
- the emulsifier used for emulsion polymerization include an anionic emulsifier, a cationic emulsifier, a nonionic emulsifier, an amphoteric emulsifier, a nonionic-cationic emulsifier, and a nonionic-anionic emulsifier.
- an emulsifier having a reactive group may be used.
- An emulsifier may be used individually by 1 type and may use 2 or more types together.
- Examples of the polymerization initiator used in the emulsion polymerization include known radical initiators. Specifically, a persulfate (ammonium persulfate, etc.), a redox initiator (a combination of hydrogen peroxide and sodium hydrogensulfite, etc.) ), Inorganic initiators (ferrous salt, silver nitrate, etc.), dibasic acid peroxides (disuccinic acid peroxide, diglutaric acid peroxide, etc.), organic initiators (azobisbutyronitrile) Etc.).
- the amount of the polymerization initiator is, for example, about 0.01 to 5 parts by mass with respect to 100 parts by mass of the monomer.
- an inorganic salt such as sodium carbonate, potassium carbonate, or sodium thiosulfate
- an organic base such as triethylamine or triethanolamine
- the fluorine-containing copolymer obtained by solution polymerization When the fluorine-containing copolymer obtained by solution polymerization is used after being dispersed in water, the remaining organic solvent may be distilled off.
- a hydrophilic group may be introduced into the fluorine-containing copolymer obtained by solution polymerization, and an emulsifier may be used during solution polymerization.
- the fluororesin aqueous dispersion (A1) is obtained by dispersing or dissolving a synthetic resin containing a fluorocopolymer (A1p) in an aqueous medium.
- the fluorine-containing copolymer (A1p) has a structural unit based on the monomer (m1), a structural unit based on the monomer (m2), and a structural unit based on the monomer (m3).
- the monomer (m1) is a fluoroolefin.
- the fluoroolefin include vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, pentafluoropropylene, hexafluoropropylene and the like.
- a fluoroolefin having 2 to 4 carbon atoms is preferable, and a perhaloolefin is particularly preferable.
- the monomer (m2) is a macromonomer having a hydrophilic part.
- the monomer (m2) has two or more structural units in the main chain, a radically polymerizable unsaturated group at one end, and a hydrophilic portion at the remaining end, pendant group or main chain.
- the number of structural units varies depending on the type of structural unit, but is usually preferably 100 or less from the viewpoint of polymerizability, water resistance and the like.
- the fluororesin aqueous dispersion (A1) it is important that the fluorocopolymer (A1p) has a structural unit based on the monomer (m2).
- the fluororesin aqueous dispersion (A1) contains the fluorocopolymer (A1p) having a structural unit based on the monomer (m2)
- the mechanical and chemical properties of the fluororesin aqueous dispersion (A1) In addition to improving the mechanical stability, the film-forming property of the fluororesin aqueous dispersion (A1), the water resistance of the coating film, and the like are also improved.
- the hydrophilic group constituting the hydrophilic part may be any of ionic, nonionic, amphoteric and combinations thereof. From the viewpoint of the chemical stability of the fluororesin aqueous dispersion (A1), the portion having an ionic hydrophilic group and the nonionic property or the hydrophilic portion only from the portion having an ionic hydrophilic group, or It is preferable to combine with a site having an amphoteric hydrophilic group, or to combine a site having an ionic hydrophilic group and a site having a hydrophilic bond.
- Examples of the monomer (m2) include the following macromonomers.
- Monomer (m21) a macromonomer having a polyoxyalkylene chain or a polyester chain in the main chain and a radically polymerizable unsaturated group at one end.
- Monomer (m22) a macromonomer having a chain obtained by radical polymerization of a hydrophilic ethylenically unsaturated monomer and having a radically polymerizable unsaturated group (vinyloxy group or allyloxy group) at one end.
- the polyoxyalkylene chain and the polyester chain in the monomer (m21) are sites having a nonionic hydrophilic group.
- the hydrophilic polyoxyalkylene chain is a polyoxyethylene chain.
- Polyoxyalkylene chains other than polyoxyethylene chains are hydrophobic.
- An oxyalkylene group other than the oxyethylene group may exist in the polyoxyethylene chain, but the oxyalkylene group other than the oxyethylene group is hydrophobic, and when the ratio is increased, the hydrophilicity of the polyoxyethylene chain is increased.
- the ratio of the number of oxyethylene groups to the total number of all oxyalkylene groups is preferably 70 to 100%, more preferably 90 to 100%.
- Examples of oxyalkylene groups other than oxyethylene groups include oxypropylene groups and oxybutylene groups.
- the hydrophilic polyoxyalkylene chain has an oxyalkylene group other than the oxyethylene group, the oxyalkylene group is preferably an oxypropylene group.
- a monomer (m21) As a monomer (m21), the following are mentioned, for example.
- a is an integer of 1 to 10
- k is an integer of 2 to 20
- X 1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (hereinafter referred to as a lower alkyl group).
- CH 2 CHCH 2 O—C b H 2b — (OCH 2 CH 2 ) k OX 1
- b is an integer of 1 to 10
- k is an integer of 2 to 20
- X 1 is a hydrogen atom or a lower alkyl group.
- the monomer (m21) one having a vinyl ether type structure at one end is preferable from the viewpoint of excellent copolymerizability with the monomer (m1), and from the viewpoint of excellent hydrophilicity, Particularly preferred is one in which the oxyalkylene chain portion consists only of an oxyethylene group.
- the monomer (m21) is preferably one having two or more oxyethylene groups from the viewpoint of sufficiently exhibiting various properties such as stability. In addition, when there are too many oxyethylene groups, there exists a possibility that the water resistance of a coating film, a weather resistance, etc. may fall.
- the monomer (m21) can be produced by a method of ring-opening addition of alkylene oxide to vinyl ether or allyl ether having a hydroxyl group.
- a monomer (m22) can be manufactured by the following method, for example.
- a polymer having a condensable functional group can be produced by radical polymerization of an ethylenically unsaturated monomer having a hydrophilic group in the presence of an initiator having a condensable functional group and a chain transfer agent.
- a method in which a functional group is reacted with glycidyl vinyl ether, glycidyl allyl ether or the like to introduce a radical polymerizable unsaturated group at the terminal Yamashita et al., Polym. Bull., 5.335 (1981)
- the condensable functional group include a carboxy group, a hydroxyl group, and an amino group.
- Examples of the ethylenically unsaturated monomer having a hydrophilic group include acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, diacetone acrylamide, hydroxyethyl acrylate, hydroxy
- Examples include propyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, polyhydric alcohol acrylate, polyhydric alcohol methacrylate, and vinylpyrrolidone.
- Examples of the initiator having a condensable functional group include 4,4′-azobis-4-cyanovaleric acid, 2,2′-azobis-2-amidinopropane hydrochloride, potassium persulfate, ammonium persulfate, azobisisobutyrate. Examples include rhonitrile, benzoyl peroxide, and the like.
- the monomer (m3) is a hydroxyl group-containing monomer represented by the following formula (m3).
- R 1 -R 2 -OH (m3) R 1 is a group having a radically polymerizable unsaturated group
- R 2 is an n-nonylene group or a cyclohexane-1,4-dimethylene group.
- the fluorocopolymer (A1p) has a structural unit based on the monomer (m3).
- the fluorinated copolymer (A1p) may be contained during production, storage or coating.
- the fluorine copolymer (A1p) may aggregate.
- R 1 has a radically polymerizable unsaturated group and, if necessary, a linking group that links the radically polymerizable unsaturated group and R 2 .
- the radical polymerizable unsaturated group include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, an acryloyl group, and a methacryloyl group.
- the linking group an ether bond is preferable.
- the monomer (m3) those having a vinyl ether type structure are preferred from the viewpoint of excellent alternating copolymerization with the monomer (m1) and good weather resistance of the coating film.
- Monomer (m4) The fluorinated copolymer (A1p) has structural units based on monomers (m1) to (m3) and other monomers copolymerizable with these monomers (monomer (m4)). It may be.
- Monomers (m4) include olefins (ethylene, propylene, etc.), vinyl ethers (ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, etc.), vinyl esters (butanoic acid vinyl ester, octanoic acid vinyl ester) Etc.), aromatic vinyl compounds (such as styrene and vinyl toluene), allyl compounds (such as ethyl allyl ether), acryloyl compounds (such as butyl acrylate), and methacryloyl compounds (such as ethyl methacrylate).
- the monomer (m4) olefin, vinyl ether, vinyl ester, allyl ether, and allyl ester are preferable.
- the olefin an olefin having 2 to 10 carbon atoms is preferable.
- the vinyl ethers vinyl esters, allyl ethers and allyl esters, those having a linear, branched or alicyclic alkyl group having 2 to 15 carbon atoms are preferable.
- the monomer (m4) may be one in which at least a part of hydrogen atoms bonded to carbon atoms is substituted with fluorine atoms.
- Composition unit ratio The proportion of the structural unit based on the monomer (m1) is preferably 20 to 80 mol% and more preferably 30 to 70 mol% of all the structural units. When the structural unit based on the monomer (m1) is 20 mol% or more, the weather resistance is sufficiently exhibited. If the structural unit based on the monomer (m1) is 80 mol% or less, the water-dispersibility of the fluorinated copolymer (A1p) will be good.
- the proportion of the structural unit based on the monomer (m2) is preferably from 0.1 to 25 mol%, more preferably from 0.3 to 20 mol%, among all the structural units. If the structural unit based on the monomer (m2) is 0.1 mol% or more, the water-dispersibility of the fluorinated copolymer (A1p) will be good. If the structural unit based on the monomer (m2) is 25 mol% or less, the weather resistance and water resistance of the coating film will be good. When the proportion of the structural unit based on the monomer (m2) is within the above range, the film forming property is extremely excellent.
- the proportion of the structural unit based on the monomer (m3) is preferably 1 to 40 mol% of all the structural units.
- the proportion of the structural unit based on the monomer (m3) is preferably such a proportion that the hydroxyl value of the fluorinated copolymer (A1p) is 20 mgKOH / g or more, and a proportion such that it is 40 mgKOH / g or more. It is more preferable that When the hydroxyl value of the fluorinated copolymer (A1p) is 20 mgKOH / g or more, the solvent resistance of the coating film is remarkably improved by the reaction with the curing agent.
- the fluororesin aqueous dispersion (A1) is produced by emulsion polymerization. Although a fluororesin aqueous dispersion (A1) having good dispersion stability can be obtained without using an emulsifier, it is preferable to use an emulsifier.
- Nonionic emulsifiers include alkylphenol ethylene oxide adducts, higher alcohol ethylene oxide adducts, block copolymers of ethylene oxide and propylene oxide, and the like.
- anionic emulsifier examples include alkyl benzene sulfonate, alkyl naphthalene sulfonate, higher fatty acid salt, alkyl sulfate ester salt, alkyl ether sulfate ester salt, and phosphate ester salt.
- the start of emulsion polymerization is performed by adding a polymerization initiator in the same manner as the start of normal emulsion polymerization.
- a polymerization initiator a well-known radical initiator is mentioned, A water-soluble initiator is preferable.
- persulfates such as ammonium persulfate
- redox initiators such as a combination of hydrogen peroxide and a reducing agent (sodium bisulfite, sodium thiosulfate, etc.)
- inorganic initiators iron, Ferrous salt, silver sulfate, etc.
- dibasic acid peroxide disuccinic acid peroxide, diglutaric acid peroxide, etc.
- organic initiator azobisisobutylamidine hydrochloride, azobisisobutyronitrile
- Etc. organic initiator
- the amount of the polymerization initiator can be appropriately changed according to the type, emulsion polymerization conditions and the like, and is usually about 0.005 to 0.5 parts by mass with respect to 100 parts by mass of the monomer.
- the polymerization initiator may be added all at once or in divided portions.
- a pH adjuster may be used for the purpose of increasing the pH of the emulsion.
- pH adjusters include inorganic bases (sodium carbonate, potassium carbonate, sodium hydrogen orthophosphate, sodium thiosulfate, sodium tetraborate, etc.), organic bases (triethylamine, triethanolamine, dimethylethanolamine, diethylethanolamine, etc.), etc. Can be mentioned.
- the amount of the pH adjuster is usually about 0.05 to 2 parts by weight, preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the aqueous medium used for emulsion polymerization. The higher the pH of the emulsion, the higher the polymerization rate tends to be.
- the starting temperature of the emulsion polymerization is appropriately selected according to the type of the polymerization initiator, and is usually about 0 to 100 ° C., preferably 10 to 90 ° C.
- the pressure at the time of emulsion polymerization can be appropriately selected and is usually about 0.1 to 10 MPa, preferably 0.2 to 5 MPa.
- a monomer, an aqueous medium, an emulsifier, a polymerization initiator, etc. may be charged all at once, and polymerization may be carried out.
- the particle size of the fluorine-containing copolymer (A1p) may be reduced to obtain fluorine-containing resin water.
- Pre-emulsified with a stirrer such as a homogenizer before adding the polymerization initiator, and then add the polymerization initiator for the purpose of improving the stability of the dispersion (A1) and various properties such as the gloss of the coating film. And may be polymerized.
- the monomer may be added in portions or continuously. When adding in divided or continuous, the monomer composition may be changed.
- the fluorine-containing resin aqueous dispersion (A1) may contain other synthetic resins other than the fluorine-containing copolymer (A1p) as long as the effects of the present invention are not impaired.
- examples of other synthetic resins include fluorine-containing resins, phenol resins, alkyd resins, melamine resins, urea resins, vinyl resins, epoxy resins, polyesters, polyurethanes, and acrylic resins.
- the proportion of the fluorinated copolymer (A1p) is preferably 50% by mass or more and more preferably 100% by mass among all the synthetic resins contained in the fluorinated resin aqueous dispersion (A1).
- the solid content concentration of the synthetic resin is preferably 10 to 100% by mass and more preferably 30 to 80% by mass in the fluororesin aqueous dispersion (A1).
- the fluorine-containing resin aqueous dispersion (A1) may contain other components other than the fluorine-containing copolymer (A1p), other synthetic resins, and an aqueous medium as long as the effects of the present invention are not impaired. Examples of other components include those described later. Since the fluororesin aqueous dispersion (A1) is blended in the aqueous coating composition, the content of the organic solvent in the fluororesin aqueous dispersion (A1) is preferably 3% by mass or less, preferably 1% by mass. The following are particularly preferred:
- the fluororesin aqueous dispersion (A2) is obtained by dispersing or dissolving a synthetic resin containing a fluorocopolymer (A2p) in an aqueous medium (preferably water).
- the fluorine-containing copolymer (A2p) has a structural unit (a1), a structural unit (a2), a structural unit (a3), and a structural unit (a4).
- a carboxy group is introduced into the fluorocopolymer (B) obtained by the solution polymerization method, and the carboxy group is neutralized with a basic compound. Those obtained by dispersing in water are preferred.
- Structural unit (a1) The structural unit (a1) is a structural unit based on a fluoroolefin compound represented by the following formula (a1).
- X 1 and X 2 are each independently a hydrogen atom, chlorine atom or fluorine atom
- X 3 is a hydrogen atom, chlorine atom, fluorine atom or —CY 1 Y 2 Y 3
- Y 1 , Y 2 , Y 3 is each independently a hydrogen atom, a chlorine atom or a fluorine atom.
- fluoroolefin compound examples include fluoroethylene and fluoropropene.
- CClF CF 2
- CHCl CF 2
- CCl 2 CF 2
- CClF CClF
- CHF CCl 2
- CH 2 CClF
- CCl 2 CClF
- Structural unit (a2) The structural unit (a2) is a structural unit based on an alkyl vinyl ether, an alkyl vinyl ester, an alkyl allyl ether, an alkyl allyl ester, or the like represented by the following formula (a2). Among these, a constitutional unit corresponding to desired film properties (hardness, gloss, pigment dispersibility, etc.) is appropriately selected.
- the fluorine-containing copolymer (A2 ′) may have two or more structural units (a2).
- R a is a hydrogen atom or a methyl group
- R 11 is an alkyl group having 1 to 12 carbon atoms or a monovalent alicyclic group having 4 to 10 carbon atoms
- u is an integer of 0 to 8.
- V is 0 or 1.
- the structural unit (a2) structural units based on alkyl vinyl ethers or alkyl vinyl esters in which u is 0 and v is 0 or 1 are preferred.
- alkyl vinyl ether or alkyl vinyl ester examples include ethyl vinyl ether, n-butyl vinyl ether, cyclohexyl vinyl ether, vinyl acetate, vinyl valerate, and vinyl pivalate.
- ethyl vinyl ether and cyclohexyl vinyl ether are preferable from the viewpoint of good alternating copolymerization with the structural unit (a1) and easy adjustment of the glass transition temperature of the fluorinated copolymer (A2p).
- the structural unit (a3) is a structural unit based on a hydroxyl group-containing vinyl ether, a hydroxyl group-containing vinyl ester, a hydroxyl group-containing allyl ether, a hydroxyl group-containing allyl ester, or the like represented by the following formula (a3).
- R b is a hydrogen atom or a methyl group
- R 12 is an alkylene group having 1 to 10 carbon atoms or a divalent alicyclic group having 4 to 10 carbon atoms
- w is an integer of 0 to 8.
- X is 0 or 1.
- Examples of the structural unit (a3) include structural units based on 2-hydroxyalkyl vinyl ether, 4-hydroxybutyl vinyl ether, 1-hydroxymethyl-4-vinyloxymethylcyclohexane, or 4-hydroxybutyl vinyl ester.
- a structural unit based on hydroxyalkyl vinyl ether is preferable from the viewpoints of polymerizability and crosslinkability.
- Structural unit (a4) The structural unit (a4) is a structural unit represented by the following formula (a4).
- R c is a hydrogen atom or a methyl group
- R 13 is an alkylene group having 1 to 10 carbon atoms or a divalent alicyclic group having 4 to 10 carbon atoms
- R 14 is an alkylene group having 2 to 10 carbon atoms.
- R 15 is a hydrogen atom or —NHZ 1 Z 2 Z 3
- Z 1 , Z 2 , and Z 3 are each independently a hydrogen atom
- An alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms, at least a part of R 15 is —NHZ 1 Z 2 Z 3
- y is an integer of 0 to 8
- z is 0 or 1.
- the ratio of —NHZ 1 Z 2 Z 3 in R 15 is preferably 30 to 100 mol%, and more preferably 50 to 100 mol%.
- R c , R 13 , y and z are the same as R b , R 12 , w and x in the structural unit (a3) from the viewpoint of easy production of the fluorinated copolymer (A2 ′). Is preferred.
- the fluorine-containing copolymer (A2p) may have other structural units other than the structural units (a1) to (a4).
- Examples of other structural units include structural units based on ethylenic monomers.
- Composition unit ratio The proportion of the structural unit (a1) is 40 to 60 mol%, preferably 45 to 55 mol%, among all the structural units. If the proportion of the structural unit (a1) is within the above range, the weather resistance of the coating film will be sufficient, the glass transition temperature of the fluorinated copolymer (A2p) will not be too high, and an amorphous and good coating will be achieved. A membrane is obtained.
- the proportion of the structural unit (a2) is 3 to 50 mol%, preferably 20 to 45 mol%, among all the structural units.
- the proportion of the structural unit (a2) is within the above range, it is easy to disperse in water, and the fluorinated copolymer does not easily settle during storage.
- the proportion of the structural unit (a3) is 4 to 30 mol%, preferably 8 to 25 mol%, among all the structural units.
- the proportion of the structural unit (a3) is 4 mol% or more, the crosslinking density is sufficiently high when crosslinking is performed. If the ratio of a structural unit (a3) is 30 mol% or less, the fall of water resistance when it is set as a coating film will be suppressed.
- the proportion of the structural unit (a4) is 0.4 to 7 mol%, preferably 1.4 to 6 mol%, among all the structural units.
- the proportion of the structural unit (a4) is within the above range, the dispersibility in the aqueous medium is excellent, and the stability in the aqueous medium is excellent.
- the total of the structural units (a1) to (a4) is 80 to 100 mol%, preferably 95 to 100 mol%.
- the proportion of other structural units is 20 mol% or less, preferably 5 mol% or less.
- the fluorine-containing copolymer (A2p) includes 45 to 55 mol% of the structural unit (a1), 14 to 45.6 mol% of the structural unit (a2), and 8 to 25 mol% of the structural unit (a3). And from 1.4 to 6 mol% of the structural unit (a4), and those having no other structural unit are preferable.
- the fluororesin aqueous dispersion (A2) can be produced by a method having the steps ( ⁇ ) to ( ⁇ ).
- ( ⁇ ) A step of producing the fluorine-containing copolymer (B).
- ( ⁇ ) A step of esterifying a part of hydroxyl groups in the structural unit (a3) by introducing a carboxy group by reacting the fluorinated copolymer (B) with a dibasic acid anhydride in an organic solvent.
- ( ⁇ ) A step of removing the organic solvent.
- the mole% of the structural unit (a3) in the fluorinated copolymer (B) is equal to the sum of the mole% of the structural unit (a3) and the mole% of the structural unit (a4) in the fluorinated copolymer (A2 ′). .
- the fluorine-containing copolymer (B) comprises a monomer (b1), a monomer (b2), and a monomer (b3) in the presence or absence of a polymerization catalyst, a polymerization initiator, ionizing radiation. It can manufacture by making superposition
- the monomer (b1) is a compound represented by the following formula (b1).
- X 1 and X 2 are each independently a hydrogen atom, chlorine atom or fluorine atom
- X 3 is a hydrogen atom, chlorine atom, fluorine atom or —CY 1 Y 2 Y 3
- Y 1 , Y 2 , Y 3 is each independently a hydrogen atom, a chlorine atom or a fluorine atom.
- the monomer (b2) is a monomer represented by the following formula (b2).
- R a is a hydrogen atom or a methyl group
- R 11 is an alkyl group having 1 to 12 carbon atoms or a monovalent alicyclic group having 4 to 10 carbon atoms
- u is an integer of 0 to 8.
- V is 0 or 1.
- the monomer (b3) is a compound represented by the following formula (b3).
- R b is a hydrogen atom or a methyl group
- R 12 is an alkylene group having 1 to 10 carbon atoms or a divalent alicyclic group having 4 to 10 carbon atoms
- w is an integer of 0 to 8.
- X is 0 or 1.
- the proportion (mol%) of the monomer (b1), monomer (b2), and monomer (b3) charged is the structural unit (a1) or structural unit (B) constituting the fluorinated copolymer (B). a2) and the mol% of the structural unit (a3).
- polymerization initiator examples include peroxy ester peroxides (such as t-butyl peroxyacetate), dialkyl peroxydicarbonates (such as diisopropyl peroxydicarbonate), benzoyl peroxide, azobisisobutyronitrile, and the like.
- the amount of the polymerization initiator can be appropriately changed according to the type and polymerization reaction conditions, and is usually about 0.05 to 0.5 parts by mass with respect to 100 parts by mass of the monomer.
- Examples of the basic compound include organic basic compounds and inorganic basic compounds.
- Examples of the organic basic compound include alkylamine (such as triethylamine) and alkylphosphine (such as triethylphosphine).
- Inorganic basic compounds include alkali metal or alkaline earth metal carbonates (potassium carbonate, etc.), alkali metal or alkaline earth metal hydroxides (potassium hydroxide, sodium hydroxide, etc.), alkali metals or alkaline earths. Metal oxides (magnesium oxide, etc.).
- the amount of the basic compound is preferably 0.01 to 20% by mass and more preferably 0.1 to 10% by mass with respect to 100 parts by mass of the monomer.
- a solution polymerization method is preferable.
- the organic solvent include alcohols, esters, ketones, saturated halogenated hydrocarbons having one or more fluorine atoms, and aromatic hydrocarbons (such as xylene).
- the temperature during the solution polymerization is preferably 10 to 90 ° C.
- the pressure during the solution polymerization is preferably 0 to 2 MPa, more preferably 0 to 1 MPa.
- the mass average molecular weight of the fluorinated copolymer (B) is preferably 3000 to 200000. When the mass average molecular weight of the fluorinated copolymer (B) is 3000 or more, the weather resistance when formed into a coating film is good. If the mass average molecular weight of a fluorine-containing copolymer (B) is 200000 or less, paintability will become favorable and a coating-film external appearance will become favorable.
- Dibasic acid anhydrides include succinic anhydride, glutaric anhydride, itaconic anhydride, adipic anhydride, 1,2-cyclohexanedicarboxylic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, phthalic anhydride Examples include acid, 1,8-naphthalic anhydride, maleic anhydride and the like.
- organic solvent examples include alcohol (methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, etc.), cellosolve (methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, Butyl cellosolve, secondary butyl cellosolve, etc.), propylene glycol derivatives (propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol methyl ether acetate, etc.), ethylene glycol ethyl ether acetate, ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), Aromatic hydrocarbons (toluene, xylene, etc.) etc.
- alcohol methanol, ethanol, n-propanol, isopropano
- the organic solvent is appropriately selected in consideration of the solubility of the fluoropolymer (B) and the dibasic acid anhydride. If the organic solvent used in the step ( ⁇ ) remains sufficiently, there is no need to add a new organic solvent in the step ( ⁇ ).
- a catalyst may be used in combination.
- the catalyst include carboxylic acid metal salts, alkali hydroxides, alkali metal carbonates, quaternary ammonium salts, tertiary amines and the like, and tertiary amines (triethylamine and the like) are preferable.
- the temperature of the esterification reaction is preferably room temperature to 150 ° C, more preferably 50 to 100 ° C.
- the time for the esterification reaction is about several tens of minutes to several hours.
- the amount of the dibasic acid anhydride is such that the proportion of the structural unit (a4) in the resulting fluorinated copolymer (A2p) is 0.4 to 7 mol%, and the proportion of the structural unit (a3) is It is determined by adjusting so that 4 to 30 mol% remains.
- the proportion of the structural unit (a4) after the esterification reaction can be confirmed by measuring the acid value. If the acid value after the esterification reaction is 2 to 35 mg KOH / g, it can be confirmed that the structural unit (a4) is 0.4 to 7 mol%.
- the proportion of the structural unit (a3) before the esterification reaction can be confirmed from the hydroxyl value before the esterification reaction. In order for the proportion of the structural unit (a3) to be 4 to 30 mol, the hydroxyl value before the esterification reaction is 20 to 150 mgKOH / g, and the acid value after the esterification reaction is within the above range. is necessary.
- the proportion of the structural unit (a4) that is neutralized with the basic compound is preferably 30 to 100 mol%, and more preferably 50 to 100 mol%.
- a basic compound or an aqueous solution of a basic compound is added to the organic solvent in which the fluorine-containing copolymer (B) obtained in step ( ⁇ ) is dissolved with stirring for several tens of minutes at room temperature. If it is, it will proceed sufficiently.
- Basic compounds having a boiling point of 200 ° C. or less include ammonia and alkylamines (monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, monobutylamine, dibutylamine, etc.) , Alkanolamines (monoethanolamine, monoisopropanolamine, dimethylaminoethanol, diethylaminoethanol, etc.), diamines (ethylenediamine, propylenediamine, tetramethylenediamine, hexamethylenediamine, etc.), alkylene imines (ethyleneimine, propyleneimine, etc.), piperazine , Morpholine, pyrazine, pyridine and the like.
- the organic solvent in which the polymer obtained by the reaction between the fluorine-containing copolymer (B) obtained in the step ( ⁇ ) and the dibasic acid anhydride is dissolved is basic.
- Water may be added along with the compound. Water may be added simultaneously with the basic compound, may be added separately from the basic compound, a part may be added simultaneously with the basic compound, and the remainder may be added separately from the basic compound.
- water may be added before adding a basic compound, and water may be added after adding a basic compound.
- a method of adding water after adding the basic compound and a method of adding an aqueous solution of the basic compound are preferable.
- the amount of water is preferably such that the solid concentration of the aqueous dispersion obtained in step ( ⁇ ) is 20 to 70% by mass, more preferably 30 to 60% by mass.
- the fluorine-containing resin aqueous dispersion (A2) may contain other synthetic resins other than the fluorine-containing copolymer (A2p) as long as the effects of the present invention are not impaired.
- examples of other synthetic resins include fluorine-containing resins, phenol resins, alkyd resins, melamine resins, urea resins, vinyl resins, epoxy resins, polyesters, polyurethanes, and acrylic resins.
- fluororesin the structural unit based on fluoroolefin and hydrophilicity described in Japanese Patent No. 2955336 are disclosed as the mechanical stability and chemical stability of the fluororesin aqueous dispersion (A2) are improved.
- a fluorine-containing copolymer having a constitutional unit based on a macromonomer having a functional site as an essential component is preferred.
- the ratio of the fluorinated copolymer (A2p) is preferably 10 to 100% by mass, more preferably 50 to 100% by mass among all the synthetic resins contained in the fluorinated resin aqueous dispersion (A2).
- the ratio of the fluorine-containing copolymer (A2p) is that of all the synthetic resins from the viewpoint of imparting excellent weather resistance to the coating film. Of these, 55% by mass or more is preferable.
- the solid content concentration of the synthetic resin is preferably 10 to 100% by mass, more preferably 30 to 80% by mass in the fluororesin aqueous dispersion (A2).
- the fluororesin aqueous dispersion (A2) may contain other components other than the fluorocopolymer (A2p), other synthetic resins, and an aqueous medium as long as the effects of the present invention are not impaired. Examples of other components include those described later.
- the content of the organic solvent in the fluororesin aqueous dispersion (A2) is preferably 10% by mass or less, more preferably 3% by mass or less, and particularly preferably 0% by mass.
- Examples of the organic solvent include those in which the organic solvent used in the step ( ⁇ ) remains and those in which the organic solvent used in the step ( ⁇ ) remains.
- the content of the organic solvent in the fluororesin aqueous dispersion (A2) is preferably 3% by mass or less, and preferably 1% by mass. The following are particularly preferred:
- the fluororesin aqueous dispersion (A3) is a synthetic resin containing a fluoropolymer (A3p) (excluding the fluorocopolymer (A1p) and the fluorocopolymer (A2p)) in an aqueous medium. Dispersed or dissolved.
- the fluorine-containing polymer (A3p) has a structural unit based on at least one fluorine-containing monomer selected from the group consisting of vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, and chlorotrifluoroethylene.
- the fluorine-containing polymer (A3p) is another monomer copolymerizable with the fluorine-containing monomer (for example, acrylic monomer, other monomer copolymerizable with the acrylic monomer, etc.) You may have the structural unit based on.
- the fluororesin aqueous dispersion (A3) preferably contains an acrylic resin as a synthetic resin other than the fluoropolymer (A3p) from the viewpoint of the film-forming property of the coating film and the adhesion to the substrate.
- the acrylic resin preferably has a structural unit based on at least one acrylic monomer selected from the group consisting of acrylic acid, acrylic acid ester, methacrylic acid and methacrylic acid ester.
- the acrylate ester an alkyl acrylate ester having 1 to 10 carbon atoms in the alkyl group is preferable in that a coating film having excellent transparency and film-forming property can be obtained.
- methacrylic acid ester a methacrylic acid alkyl ester having 1 to 10 carbon atoms in the alkyl group is preferable in that a coating film having excellent transparency and film-forming property can be obtained.
- the fluororesin aqueous dispersion (A3) containing an acrylic resin can be prepared by mixing a fluoropolymer (A3p) dispersion and an acrylic resin dispersion.
- the mass ratio of the fluoropolymer (A3p) to the acrylic resin (the fluoropolymer (A3p) / acrylic resin) is preferably 10/90 to 90/10, more preferably 20/80 to 80/20.
- the aqueous coating composition of the present invention may further contain a curing agent or may not contain a curing agent.
- the fluororesin aqueous dispersion is a fluororesin aqueous dispersion (A2)
- the aqueous coating composition of the present invention preferably further contains a curing agent.
- the fluororesin aqueous dispersion is the fluororesin aqueous dispersion (A3)
- the aqueous coating composition of the present invention may further contain a curing agent or may not contain a curing agent.
- the curing agent is prepared as one of the later-described aqueous coating kits, and the other liquid and the curing agent are blended immediately before use. It is preferable to prepare the aqueous coating composition of the present invention.
- the mass ratio (synthetic resin aqueous dispersion / curing agent) of the synthetic resin aqueous dispersion and the curing agent on the basis of the nonvolatile content (solid content) is 50 to 95/5 to 50 is preferable, and 65 to 90/10 to 35 is more preferable.
- a coating film can be formed by applying the mixture after mixing the synthetic resin aqueous dispersion and the curing agent.
- a coating film can be formed by further baking.
- the curing agent is preferably a water-soluble or water-dispersed curing agent having a functional group that reacts with a hydroxyl group or a carboxy group.
- Specific examples include isocyanate compounds, melamine resins, phenol resins, xylene resins, toluene resins, and the like, and isocyanate compounds are particularly preferable because a coating film excellent in weather resistance and mechanical properties can be easily obtained.
- the isocyanate compound a polyisocyanate compound (C1) that can be mechanically dispersed in water or a self-emulsifiable polyisocyanate compound (C2) is preferable.
- Polyisocyanate compound (C1) examples include aliphatic polyisocyanates (such as hexamethylene diisocyanate), aromatic polyisocyanates (m- or p-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate, diphenylmethane-4, 4'-diisocyanate, naphthalene-1,5-diisocyanate, 4,4'-diisocyanate-3,3'-dimethyldiphenyl, etc.), alicyclic polyisocyanates (bis- (isocyanatocyclohexyl) methane, isophorone diisocyanate, etc.), crude Polyisocyanate (crude tolylene diisocyanate, crude diphenylmethane diisocyanate, etc.), modified polyisocyanate (carbodiimide modified diphenylmethane diisocyanate, polyol modified diis
- the polyisocyanate compound (C1) may be a dimer or trimer, such as a burette type, isocyanurate ring type, or uretdione type, and is a block obtained by reacting an isocyanate group with a blocking agent.
- Polyisocyanate may be used.
- the blocking agent include alcohol, phenol, phenol derivatives, caprolactam, oxime, and active methylene compounds. Since the block polyisocyanate usually does not cure unless it is 140 ° C. or higher, an unblocked polyisocyanate is preferable when it is cured at a lower temperature.
- a polyisocyanate compound (C1) may be used individually by 1 type, and may use 2 or more types together.
- the polyisocyanate compound (C1) is used by being mechanically dispersed in water.
- the polyisocyanate compound (C1) preferably has a relatively low viscosity from the viewpoint of mechanically dispersing in water.
- an emulsifier is added during dispersion, a more stable dispersion can be obtained.
- the emulsifier include known emulsifiers, and the ionic group, particularly active hydrogen, is preferred because it does not increase the viscosity by reacting with the polyisocyanate compound (C1) or the dispersibility of the polyisocyanate compound (C1) does not decrease. Those having no atoms are preferred.
- a nonionic emulsifier is preferable, and an emulsifier having a polyoxyethylene chain is particularly preferable.
- Polyisocyanate compound (C2) is a self-emulsifying polyisocyanate compound that can be emulsified and dispersed in water without an emulsifier. Self-emulsifying polyisocyanate compounds are described in Japanese Patent Publication No. 4-15270.
- Examples of the polyisocyanate compound (C2) include a prepolymer obtained by reacting a polyisocyanate compound (C1) with a compound having a hydrophilic polyoxyalkylene chain.
- a compound having at least one group capable of reacting with an isocyanate and having a number average molecular weight of 200 to 4000 is preferable, and a polyoxyalkylene polyol or polyoxyalkylene monool having a molecular weight of 300 to 1500 is preferable. Is more preferable. If the number average molecular weight is 200 or more, the self-emulsifying property is sufficiently exhibited. If the number average molecular weight is 4000 or less, the stability in water will be good.
- the polyoxyalkylene chain is preferably one in which all or most of the oxyalkylene groups are oxyethylene groups from the viewpoint of hydrophilicity.
- the reaction between the polyisocyanate compound (C1) and the compound having a polyoxyalkylene chain is carried out in the presence of a catalyst (tertiary amine, alkyl-substituted ethyleneimine, tertiary alkyl phosphine, metal alkyl acetonate, organic acid metal salt, etc.). If necessary, it is carried out at 100 ° C. or lower in the presence of a cocatalyst. In the reaction, it is preferable to adjust the amount of residual isocyanate groups to be 10 to 24% by mass, and it is more preferable to adjust the amount of residual isocyanate groups to be 15 to 20% by mass.
- a catalyst tertiary amine, alkyl-substituted ethyleneimine, tertiary alkyl phosphine, metal alkyl acetonate, organic acid metal salt, etc.
- the amount of the remaining isocyanate group is 10% by mass or more, the reactivity with the fluorine-containing copolymer (A1p) or the fluorine-containing copolymer (A2p) becomes good. Moreover, even if it is a small amount of polyisocyanate compound (C2), since sufficient crosslinking degree can be achieved, the weather resistance of a coating film becomes favorable. If the amount of residual isocyanate groups is 24% by mass or less, a stable emulsion can be obtained.
- melamine resins include alkyl etherified (methyl etherified, butyl etherified, isobutyl etherified, etc.) melamine resins. From the viewpoint of water solubility, melamine resins at least partially methylated are preferred.
- urethane polyol in addition to the synthetic resin aqueous dispersion, urethane polyol, and curing agent, other components may be added to the aqueous coating composition of the present invention within a range not impairing the effects of the present invention.
- other components include known coating additives, specifically, film-forming aids, inorganic coloring pigments, organic coloring pigments, extender pigments, curing catalysts, plasticizers, preservatives, and antifungal agents. Agents, antifoaming agents, leveling agents, pigment dispersants, anti-settling agents, anti-sagging agents, matting agents, ultraviolet absorbers, antioxidants and the like. You may mix
- composition for water-based paints of the present invention described above contains a specific urethane polyol having a highly hydrophilic group (such as a hydroxyl group), a self-cleaning function can be imparted to the surface of the coating film. That is, the hydrophilicity of the surface of the coating film can be improved by the urethane polyol having a highly hydrophilic group. When the hydrophilicity of the surface of the coating film is improved, dirt attached to the surface of the coating film is easily washed away with water droplets such as rain (easy cleaning).
- a fluorine-containing resin aqueous dispersion is blended in the aqueous coating composition as a synthetic resin aqueous dispersion.
- the urethane polyol (X) easily moves to the surface layer of the coating film and can sufficiently impart a self-purifying function to the coating film.
- the urethane polyol (X) hardly reacts with the isocyanate compound on the way to the surface layer of the coating film, and the surface layer of the coating film It is considered that the self-cleaning function can be sufficiently imparted to the coating film effectively because the transfer of the urethane polyol to is not inhibited.
- the urethane polyol (X) is not highly reactive like an alkoxysilane-modified condensate, for example. Even if blended into a product, it is difficult to impair the storage stability of the aqueous coating composition.
- the aqueous coating composition of the present invention described above is environmentally preferable because it is an aqueous coating composition having a low organic solvent content.
- the aqueous paint kit of the present invention comprises the aqueous paint composition of the present invention and an aqueous solution or aqueous dispersion of an isocyanate compound in a state where they are not mixed with each other.
- An aqueous paint composition containing the compound can be prepared.
- a paint additive is blended in the aqueous paint composition, it can be appropriately contained in one or both of the two liquids.
- the aqueous coating composition combined with the isocyanate compound may contain a curing agent other than the isocyanate compound, but usually an aqueous coating composition not containing a curing agent is used.
- the aqueous coating kit of the present invention described above comprises the aqueous coating composition of the present invention and an aqueous solution or aqueous dispersion of an isocyanate compound, so that the above-described effects can be exerted.
- the composition for water-based paints of this invention containing a compound can be prepared.
- the aqueous paint preparation kit of the present invention comprises two solutions of a synthetic resin aqueous dispersion and a urethane polyol (X) solution or dispersion in a state where they are not mixed with each other. Can be prepared.
- a paint additive is blended in the aqueous paint composition, it can be appropriately contained in one or both of the two liquids.
- the synthetic resin aqueous dispersion combined with the urethane polyol (X) may be blended with a curing agent in advance, or may be blended with the curing agent after mixing both components of the aqueous coating preparation kit. Both components of the kit and the curing agent may be mixed simultaneously.
- coating when using the composition for water-based coatings which does not contain a hardening
- aqueous coating composition When the curing agent is further blended in the aqueous coating composition of the present invention, three liquids of the synthetic resin aqueous dispersion, the aqueous solution or aqueous dispersion of the curing agent, and the urethane polyol (X) solution or dispersion are mixed with each other. It is preferable to prepare in a state where it is not mixed.
- An aqueous coating composition can be prepared by mixing the three liquids.
- the paint additive When the paint additive is blended in the aqueous paint composition, it can be appropriately contained in one or more of the three liquids.
- an isocyanate compound is preferable.
- the amount of the urethane polyol (X) solution or dispersion is 0.5 to 30 parts by mass of the urethane polyol (X) in the solution or dispersion with respect to 100 parts by mass of the solid content in the synthetic resin aqueous dispersion. An amount of 5 to 20 parts by mass is more preferable.
- the above-described aqueous paint preparation kit of the present invention is provided with the synthetic resin aqueous dispersion and the urethane polyol, so that the aqueous paint composition of the present invention capable of exhibiting the above-described effects can be prepared. .
- the article of the present invention has a coating film formed using the aqueous coating composition of the present invention.
- the article of the present invention can be produced by applying the aqueous coating composition of the present invention to the surface of a substrate and drying to form a coating film on the surface of the substrate.
- the base material examples include metal, glass, porcelain tile, concrete, siding board, extruded plate, plastic, and the like, and a housing such as a building or a civil engineering structure is preferable.
- a housing such as a building or a civil engineering structure is preferable.
- the surface of the building material before being assembled into a housing may be precoated.
- the aqueous coating composition of the present invention may be applied directly to a substrate, or may be applied after a known surface treatment (such as a base treatment) is applied to the substrate. Examples of the application method include brush coating, spraying, rollers, roll coaters, flow coaters and the like.
- the article of the present invention described above has a coating film having a sufficient self-cleaning function because it has a coating film made of the aqueous coating composition of the present invention that can exhibit the above-described effects.
- Gloss retention rate of coating film The gloss of the coating film surface was measured using a gloss meter (PG-1M, manufactured by Nippon Denshoku Industries Co., Ltd.), and the weather resistance was evaluated according to the following criteria. “ ⁇ ”: The gloss retention was 80% or more. “X”: The gloss retention was less than 80%.
- urethane polyol As a urethane polyol solution, an aqueous solution of urethane diol (manufactured by King Industries, FLEXOREZ (registered trademark) UD-350W, solid content concentration: 88% by mass. Average number of aliphatic diisocyanate residues of urethane diol: 10, Number average molecular weight: 5500, hydroxyl value: 350 mgKOH / g) were prepared.
- the FLEXOREZ (registered trademark) UD-350W is considered to be a urethane diol comprising a reaction product of dipropylene glycol and 2-methylpentane-1,5-diisocyanate.
- Preparation Example 1 Preparation of fluororesin aqueous dispersion (A1-1)): In a stainless steel autoclave with a stirrer with an internal volume of 2500 mL, 1280 g of water, 415 g of CHVE, 230 g of 2-EHVE, 21 g of CM-EOVE, 34 g of CHMVE, 1280 g of ion-exchanged water, 3.0 g of potassium carbonate, 5.4 g of ammonium persulfate, 33 g of nonionic emulsifier (Nippon Emulsifier, Newcol (registered trademark) -2320) and 1.4 g of anionic emulsifier (sodium lauryl sulfate) were charged with ice and cooled with nitrogen gas.
- nonionic emulsifier Nippon Emulsifier, Newcol (registered trademark) -2320
- anionic emulsifier sodium lauryl sulfate
- CTFE units / EVE units / CHVE units / 4-HBVE units / esterified 4-HBVE units 50/15/15/17/3 ( Molar ratio).
- esterified 4-HBVE units the proportion neutralized with triethylamine was 70 mol%.
- pigment composition 210 parts by mass of titanium oxide (manufactured by Sakai Chemical Industry Co., Ltd., D-918), pigment dispersant (manufactured by Big Chemie, Disperbyk (registered trademark) 190, copolymer having affinity for pigment, acid value: 10 mgKOH / g) 21 parts by mass, 4.5 parts by mass of defoaming agent (manufactured by Cognis, Dehydran (registered trademark) 1620), 64.5 parts by mass of ion-exchanged water, and 300 parts by mass of glass beads were mixed, and the disperser was mixed. And pigment beads were prepared by removing the glass beads by filtration.
- Example 1 55 g of the pigment composition obtained in Preparation Example 4, 193 g of the fluororesin aqueous dispersion (A1-1) obtained in Preparation Example 1, and 2,2,4-trimethyl-1,3- Add 15 g of pentadiol mono (2-methylpropanoate), 0.5 g of thickener (Akzo Nobel, Vermodor (registered trademark) 2150), and 15 g of urethane polyol solution, and mix. A composition was prepared. The amount of the urethane diol was 16.3 parts by mass with respect to 100 parts by mass of the solid content in the fluororesin aqueous dispersion (A1-1).
- the obtained aqueous coating composition was applied to an aluminum plate (thickness 1 mm, surface chromated) to a dry film thickness of 40 ⁇ m using a film applicator, and dried for 2 weeks at a temperature of 23 ° C. and a humidity of 50%.
- a test piece was produced. Table 1 shows the evaluation results of the obtained test pieces.
- Example 2 55 g of the pigment composition obtained in Preparation Example 4, 193 g of the fluororesin aqueous dispersion (A1-2) obtained in Preparation Example 2, 15 g of dipropylene glycol mono n-butyl ether as a film-forming aid, and thickening 25 g of an agent (manufactured by Akzo Nobel, Vermodor (registered trademark) 2150), 15 g of a solution of urethane polyol, and a water-dispersed isocyanate curing agent (manufactured by Sumika Bayer, Bihijoule (registered trademark) 3100). 9 g was added and mixed to prepare an aqueous coating composition.
- an agent manufactured by Akzo Nobel, Vermodor (registered trademark) 2150
- a solution of urethane polyol 15 g
- a water-dispersed isocyanate curing agent manufactured by Sumika Bayer, Bihijoule (registered trademark) 3100.
- the amount of the urethane diol was 16.3 parts by mass with respect to 100 parts by mass of the solid content in the fluororesin aqueous dispersion (A1-2).
- a test piece was prepared in the same manner as in Example 1. Table 1 shows the evaluation results of the obtained test pieces.
- Example 3 To 55 g of the pigment composition obtained in Preparation Example 4, 193 g of the fluororesin aqueous dispersion (A2-1) obtained in Preparation Example 3 and a surface conditioner (BYK (registered trademark) -348, manufactured by BYK Chemie) were added. 1.3 g, 0.5 g of thickener (Akzo Nobel, Vermodor (registered trademark) 2150), 15 g of urethane polyol solution, water-dispersed isocyanate curing agent (manufactured by Sumika Bayer, Bihijoule (registered trademark)) ) 25 g of 3100) was added and mixed to prepare an aqueous coating composition.
- a surface conditioner BYK (registered trademark) -348, manufactured by BYK Chemie
- the amount of the urethane diol was 16.3 parts by mass with respect to 100 parts by mass of the solid content in the fluororesin aqueous dispersion (A2-1).
- a test piece was prepared in the same manner as in Example 1. Table 1 shows the evaluation results of the obtained test pieces.
- Example 4 55 g of the pigment composition obtained in Preparation Example 4 was added to 193 g of a fluororesin aqueous dispersion (product name “Kynar Aquatec FMA-12” manufactured by Arkema), and 2,2,4-trimethyl- Add 15 g of 1,3-pentadiol mono (2-methylpropanoate), 0.5 g of thickener (Akzo Nobel, Vermodor (registered trademark) 2150) and 15 g of urethane polyol solution and mix. Then, an aqueous coating composition was prepared. The amount of the urethane diol was 16.3 parts by mass with respect to 100 parts by mass of the solid content in the fluororesin aqueous dispersion.
- a fluororesin aqueous dispersion product name “Kynar Aquatec FMA-12” manufactured by Arkema
- the obtained aqueous coating composition was applied to an aluminum plate (thickness 1 mm, surface chromated) to a dry film thickness of 40 ⁇ m using a film applicator, and dried for 2 weeks at a temperature of 23 ° C. and a humidity of 50%.
- a test piece was produced. Table 1 shows the evaluation results of the obtained test pieces.
- Example 1 A water-based paint composition was prepared in the same manner as in Example 1 except that the urethane polyol solution was not added. A test piece was prepared in the same manner as in Example 1. Table 1 shows the evaluation results of the obtained test pieces.
- Example 2 A water-based coating composition was prepared in the same manner as in Example 2 except that the urethane polyol solution was not added. A test piece was prepared in the same manner as in Example 1. Table 1 shows the evaluation results of the obtained test pieces.
- Example 3 An aqueous coating composition was prepared in the same manner as in Example 3 except that the urethane polyol solution was not added. A test piece was prepared in the same manner as in Example 1. Table 1 shows the evaluation results of the obtained test pieces.
- Example 4 An aqueous coating composition was prepared in the same manner as in Example 4 except that the urethane polyol solution was not added. A test piece was prepared in the same manner as in Example 1. Table 1 shows the evaluation results of the obtained test pieces.
- a thickener (Akzo Nobel, Vermodor (registered trademark) 2150), 25 g of a water-dispersed isocyanate curing agent (Suika Bayer, Bihijoule (registered trademark) 3100), aqueous Add 27.6 g of a low-pollution agent for paints (Asahi Glass Co., Ltd., trade name “SRAgent 2100”, solid content concentration: 40% by mass) and 6.9 g of adipic acid dihydrazide (diluted product of 10% by mass).
- a coating composition was prepared.
- the amount of the antifouling agent for water-based paints (trade name “SRAgent 2100” manufactured by Asahi Glass Co., Ltd.) was 14.3 parts by mass with respect to 100 parts by mass of the solid content in the fluororesin aqueous dispersion (A2-1). It was.
- a test piece was prepared in the same manner as in Example 1. Table 1 shows the evaluation results of the obtained test pieces.
- Examples 1 to 4 were compared with Comparative Examples 1 to 4 in which the composition for water-based paints did not contain urethane polyol and Comparative Example 5 containing a conventional low-fouling agent for water-based paints. Reduced the water contact angle. In addition, regarding the soiled state of the exposed plate, the test plate of Examples 1 to 4 was hardly soiled. From this, it can be seen that Examples 1 to 4 improved the hydrophilicity of the coating film and improved the self-cleaning function of the coating film surface as compared with Comparative Examples 1 to 5.
- the water-based paint composition of the present invention is useful as a paint for exteriors of buildings and the like which are exposed to rain and wind and easily adhere to dirt such as dust.
- the entire contents of the specification, claims and abstract of Japanese Patent Application No. 2013-11085 filed on May 27, 2013 are incorporated herein as the disclosure of the specification of the present invention. It is.
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Abstract
Description
(1)合成樹脂エマルジョンと、水性塗料用低汚染化剤として、アルコキシシランの変性縮合物とを含む水性塗料用組成物(特許文献1)。
(2)合成樹脂水分散体と、水性塗料用低汚染化剤として、炭素数1~6のペルフルオロアルキル基を有する(メタ)アクリレート単位と、ポリ(アルキレンオキシド)鎖を有する(メタ)アクリレート単位と、ジアルキルアミノ基を有する(メタ)アクリレート単位とを有する含フッ素共重合体とを含む水性塗料用組成物(特許文献2)。
(2)の水性塗料用組成物は、貯蔵安定性が良好であるものの、合成樹脂水分散体として含フッ素樹脂水分散体を含む場合、低汚染化剤である含フッ素共重合体が塗膜の表層に移行しにくく、自己浄化機能の付与が不充分となる。特に、硬化剤としてイソシアネート系化合物を含む場合、含フッ素共重合体が塗膜の表層に移行する途中でイソシアネート系化合物と反応してしまい、含フッ素共重合体が塗膜の表層にさらに移行しにくくなる。
前記ウレタンポリオールは、オキシプロピレン基数が2~6のポリプロピレングリコールとアルキレン基の炭素数が4~10のアルキレンジイソシアネートとの反応生成物であることが好ましい。
前記アルキレンジイソシアネートのアルキレン基は分岐アルキレン基であることが好ましい。
前記ウレタンポリオールの含有量は、前記合成樹脂水分散体中の固形分100質量部に対して、0.5~30質量部であることが好ましい。
下記単量体(m1)に基づく構成単位と、下記単量体(m2)に基づく構成単位と、下記単量体(m3)に基づく構成単位とを有する含フッ素共重合体(A1p)、
または、
下式(a1)で表される構成単位の40~60モル%と、下式(a2)で表される構成単位の3~50モル%と、下式(a3)で表される構成単位の4~30モル%と、下式(a4)で表される構成単位の0.4~7モル%(ただし、式(a1)で表される構成単位、式(a2)で表される構成単位、式(a3)で表される構成単位、式(a4)で表される構成単位の合計は80~100モル%である。)を有する含フッ素共重合体(A2p)
であることが好ましい。
単量体(m2):親水性部位を有するマクロモノマー。
単量体(m3):下式(m3)で表される水酸基含有単量体。
R1-R2-OH ・・・(m3)
ただし、R1はラジカル重合性不飽和基を有する基であり、R2はn-ノニレン基またはシクロヘキサン-1,4-ジメチレン基である。
前記硬化剤はイソシアネート系化合物であることが好ましい。
さらに、また、本発明の物品は、前記水性塗料用キットを用いて形成された塗膜を有することを特徴とする。
本発明の水性塗料用キットによれば、前記効果を発揮できる水性塗料用組成物を得ることができる。
本発明の物品は、充分な自己浄化機能を有する塗膜を有するものとなる。
「構成単位」とは、単量体が重合することによって形成された該単量体に由来する単位を意味する。重合反応によって直接形成された単位であってもよく、重合体を処理することによって該単位の一部が別の構造に変換された単位であってもよい。
「単量体」とは、ラジカル重合性不飽和基を有する化合物を意味する。
「(メタ)アクリレート」とは、アクリレートおよびメタクリレートのいずれか一方または両方を意味する。
「水性媒体」とは、水を含み、有機溶媒の含有量が3質量%以下である液体を意味する。
「マクロモノマー」とは、片末端にラジカル重合性不飽和基を有する低分子量のポリマーまたはオリゴマーを意味する。
「親水性部位」とは、親水性基を有する部位、親水性の結合を有する部位、またはこれらの組み合わせからなる部位を意味する。
本発明の水性塗料用組成物は、合成樹脂水分散体と、水性塗料用低汚染化剤としてウレタンポリオールとを含有するものである。
本発明の水性塗料用組成物は、たとえば、合成樹脂水分散体とウレタンポリオールとを配合することによって得られる。
本発明におけるウレタンポリオールは、分子内にウレタン結合を有し、かつ水酸基を2つ以上有する化合物である。
本発明におけるウレタンポリオールは、水性塗料用組成物が塗膜を形成する際に塗膜の表面に移行して、塗膜表面を親水化して塗膜に自己浄化機能を付与すると考えられる。
本発明の水性塗料用組成物が含有するウレタンポリオールは、本発明の効果が充分に発揮される点から、分岐アルキレン基の一端に酸素原子が結合した構造のオキシアルキレン基を単位として有するポリオキシアルキレンジオールと脂肪族ジイソシアネートの反応生成物である。
以下、本発明における上記ウレタンポリオールをウレタンポリオール(X)ともいい、上記ポリオキシアルキレンジオールをポリオキシアルキレンジオール(Y)ともいい、分岐アルキレン基の一端に酸素原子が結合した構造のオキシアルキレン基を分岐オキシアルキレン基ともいう。
分岐オキシアルキレン基の炭素数は3~6が好ましく、3または4がより好ましい。直鎖オキシアルキレン基の炭素数は2~6が好ましく、2または6がより好ましい。
オキシアルキレン基は、環状エーテルの開環により形成されるか、または、アルキレンジオールの多量化により形成されるものが好ましい。環状エーテルとしてはアルキレンオキシドが好ましい。
分岐オキシアルキレン基を形成するアルキレンオキシドとしては、プロピレンオキシド(すなわち、1,2-エポキシプロパン)、1,2-エポキシブタン、2,3-エポキシブタンなどが挙げられる。特に好ましい分岐オキシアルキレン基は、プロピレンオキシドが開環して形成されるオキシプロピレン基である。
直鎖オキシアルキレン基を形成するアルキレンオキシドとしてはエチレンオキシドが挙げられ、直鎖オキシアルキレン基を形成するアルキレンオキシド以外の環状エーテルとしては、オキセタン、テトラヒドロフランなどが挙げられる。好ましい直鎖オキシアルキレン基は、エチレンオキシドが開環して形成されるオキシエチレン基である。
アルキレンオキシドに水を反応させる方法により、アルカンジオールの多量体であるポリオキシアルキレンジオールが生成する。本発明において、アルカンジオールの多量体であるポリオキシアルキレンジオールのオキシアルキレン基数は、アルカンジオール残基の数をいう。たとえば、プロピレングリコール、エチレングリコール、1,4-ブタンジオールなどのアルカンジオールのオキシアルキレン基数は1であり、その多量体のオキシアルキレン基数は2以上である。具体的には、たとえば、ジプロピレングリコールのオキシプロピレン基数は2、トリプロピレングリコールのオキシプロピレン基数は3、テトラプロピレングリコールのオキシプロピレン基数は4である。
2価アルコールなどの2価の開始剤にアルキレンオキシドを開環付加させる方法により、2価の開始剤の残基とオキシアルキレン基を有するポリオキシアルキレンジオールが生成する。2価の開始剤がアルカンジオールの場合、2価の開始剤の残基はオキシアルキレン基とし、2価の開始剤がアルカンジオールの多量体の場合、2価の開始剤の残基は上記の数のオキシアルキレン基を有するものとする。開始剤がプロピレングリコールやジプロピレングリコールなどのプロピレングリコール単量体や多量体である場合、その開始剤にプロピレンオキシドを開環付加させることにより、上記プロピレングリコールの多量体と同様の構造のポリオキシプロピレンジオールが生成する。
ポリオキシアルキレンジオール(Y)は、2個以上のアルキレン基を有し、かつアルキレン基の総数の半数以上が分岐アルキレン基からなることが好ましい。特に、アルキレン基の総数の数にして75~100%が分岐アルキレン基からなることが好ましい。
ポリオキシアルキレンジオール(Y)の1分子あたり平均のオキシアルキレン基数は、塗膜表面への移行性に優れる点から、2~10が好ましく、2~7がより好ましく、2~5が特に好ましい。
ポリプロピレングリコールは、通常、プロピレンオキシドに水を反応させて得られる。この反応により、プロピレングリコールとともに上記のようなポリプロピレングリコールが生成し、必要により各生成物を分離して製造される。ポリオキシアルキレンジオール(Y)としては、多量化度の異なるポリプロピレングリコールの混合物であってもよく、ポリプロピレングリコールの1種以上とプロピレングリコールの混合物であってもよい。
分岐状アルキレン基を有する脂肪族ジイソシアネートとしては、2-メチルペンタン-1,5-ジイソシアネート、ペンタン-1,4-ジイソシアネート、ヘキサン-1,5-ジイソシアネート、トリメチルヘキサン-1,6-ジイソシアネートなどが挙げられる。直鎖状アルキレン基を有する脂肪族ジイソシアネートとしては、ヘキサメチレンジイソシアネート、テトラメチレンジイソシアネートなどが挙げられる。
通常、イソシアネートインデックスが100により近い条件で反応させて得られる反応生成物ほど、高分子量のウレタンポリオールが得られ、逆にイソシアネートインデックスが100からより離れた条件で反応させて得られる反応生成物ほど、低分子量のウレタンポリオールが得られる。したがって、イソシアネートインデックスを制御することにより、得られるウレタンポリオールの平均分子量を調整することができる。また、ウレタンポリオール(X)は、ポリオキシアルキレンジオール(Y)と脂肪族ジイソシアネートの反応生成物であることより、ウレタンポリオール(X)は水酸基数2のウレタンポリオールとなる。
ウレタンポリオール(X)における脂肪族ジイソシアネート残基の数は5~15が好ましく、塗膜の平滑性に優れ、塗膜にはじきが発生しにくいという点から、6~14がより好ましく、7~13が特に好ましい。その場合のポリオキシアルキレンジオール(Y)の残基の数は、通常、脂肪族ジイソシアネート残基の数プラス1となる。
ウレタンポリオール(X)の数平均分子量は、NMR分析によって特定されたウレタンポリオール(X)の構造から、計算によって求める。
ウレタンポリオール(X)の水酸基価は、JIS K 1557-1(2007)に準拠した方法で測定できる。
ウレタンポリオール(X)は、通常、ウレタンポリオール(X)が水性媒体に溶解した溶液またはウレタンポリオール(X)が水性媒体に分散した分散液の状態で提供される。
該溶液または分散液は、本発明の効果を損なわない範囲で、ウレタンポリオール(X)、水性媒体以外の他の成分を含んでいてもよい。
該溶液または分散液は、水性塗料用組成物に配合されることから、該溶液または分散液中の有機溶媒の含有量は、3質量%以下が好ましく、1質量%以下が特に好ましい。
ウレタンポリオール(X)の含有量は、合成樹脂水分散体中の固形分100質量部に対して、0.5~30質量部が好ましく、5~20質量部がより好ましい。ウレタンポリオール(X)の含有量が5質量部以上であれば、ウレタンポリオール(X)による効果が充分に発揮される。ウレタンポリオール(X)の量が20質量部以下であれば、塗膜の耐水性を確保できる。
合成樹脂水分散体としては、たとえば、公知のアクリル樹脂水分散体、アクリルシリコン樹脂水分散体、含フッ素樹脂水分散体等が挙げられる。合成樹脂水分散体は、硬化剤と組み合わせて使用される二液型であってもよい。
合成樹脂水分散体としては、本発明の効果が充分に発揮される点から、含フッ素樹脂水分散体が好ましい。
含フッ素樹脂水分散体は、水性媒体に含フッ素重合体が分散または溶解したものである。
含フッ素重合体としては、含フッ素単量体に基づく構成単位を有する重合体、または、含フッ素単量体に基づく構成単位と、含フッ素単量体と共重合可能な他の単量体に基づく構成単位とを有する重合体が挙げられる。
含フッ素単量体としては、これらの中でもフルオロオレフィンが好ましく、フルオロオレフィンの中でも、フッ化ビニリデン、テトラフルオロエチレン、ヘキサフルオロプロピレン、クロロトリフルオロエチレンがより好ましい。
含フッ素単量体と共重合可能な他の単量体としては、たとえば、アクリル系単量体、アクリル系単量体と共重合可能な他の単量体等が挙げられる。
乳化重合に用いる乳化剤としては、アニオン性乳化剤、カチオン性乳化剤、ノニオン性乳化剤、両性乳化剤、ノニオン-カチオン性乳化剤、ノニオン-アニオン性乳化剤等が挙げられる。耐水性の向上を目的として、反応性基を有する乳化剤を用いてもよい。乳化剤は、1種を単独で用いてもよく、2種以上を併用してもよい。
重合開始剤の量は、たとえば、単量体100質量部に対して0.01~5質量部程度である。
含フッ素樹脂水分散体(A1)は、水性媒体に含フッ素共重合体(A1p)を含む合成樹脂が分散または溶解したものである。
含フッ素共重合体(A1p)は、単量体(m1)に基づく構成単位と、単量体(m2)に基づく構成単位と、単量体(m3)に基づく構成単位とを有する。
単量体(m1)は、フルオロオレフィンである。
フルオロオレフィンとしては、フッ化ビニリデン、トリフルオロエチレン、クロロトリフルオロエチレン、テトラフルオロエチレン、ペンタフルオロプロピレン、ヘキサフルオロプロピレン等が挙げられる。
フルオロオレフィンとしては、炭素数2~4のフルオロオレフィンが好ましく、ペルハロオレフィンが特に好ましい。
単量体(m2)は、親水性部位を有するマクロモノマーである。
単量体(m2)としては、主鎖に2つ以上の構成単位を有し、片末端にラジカル重合性不飽和基を有し、残りの末端、ペンダント基または主鎖に親水性部位を有する化合物が挙げられる。構成単位の数は、構成単位の種類によって異なるが、重合性、耐水性等の点から、通常、100以下が好ましい。
単量体(m21):主鎖にポリオキシアルキレン鎖またはポリエステル鎖を有し、片末端にラジカル重合性不飽和基を有するマクロモノマー。
単量体(m22):親水性のエチレン性不飽和モノマーがラジカル重合した鎖を有し、片末端にラジカル重合性不飽和基(ビニルオキシ基またはアリルオキシ基)を有するマクロモノマー。
親水性のポリオキシアルキレン鎖はポリオキシエチレン鎖である。ポリオキシエチレン鎖以外のポリオキシアルキレン鎖は疎水性である。ポリオキシエチレン鎖中にはオキシエチレン基以外のオキシアルキレン基が存在していてもよいが、オキシエチレン基以外のオキシアルキレン基は疎水性であり、その割合が高くなるとポリオキシエチレン鎖の親水性を低下させる。親水性のポリオキシアルキレン鎖としては、全オキシアルキレン基の総数に対するオキシエチレン基の数の割合は70~100%が好ましく、90~100%がより好ましい。
オキシエチレン基以外のオキシアルキレン基としては、オキシプロピレン基、オキシブチレン基等が挙げられる。親水性のポリオキシアルキレン鎖がオキシエチレン基以外のオキシアルキレン基が存在する場合、そのオキシアルキレン基としてはオキシプロピレン基が好ましい。
(1)CH2=CHO-CaH2a-(OCH2CH2)kOX1
ただし、aは1~10の整数であり、kは2~20の整数であり、X1は水素原子または炭素数1~10のアルキル基(以下、低級アルキル基と記す。)である。
(2)CH2=CHCH2O-CbH2b-(OCH2CH2)kOX1
ただし、bは1~10の整数であり、kは2~20の整数であり、X1は水素原子または低級アルキル基である。
(3)CH2=CHO-CcH2c-O(CO-CdH2d-O)eH
ただし、cは1~10の整数であり、dは1~10の整数であり、eは1~30の整数である。
(4)CH2=CHOCH2-cycloC6H10-CH2(OCH2CH2)kOX1
ただし、cycloC6H10はシクロへキシレン基であり、kは2~20の整数であり、X1は水素原子または低級アルキル基である。
なお、上記式中の(OCH2CH2)kで表されるポリオキシエチレン鎖は、前記のように少数のオキシエチレン基以外のオキシアルキレン基を有していてもよい。その場合、(OCH2CH2)kは、k個のオキシエチレン基の一部がオキシエチレン基以外のオキシアルキレン基で置換された構造となる。
単量体(m21)としては、安定性等の諸性質を十分に発揮させる点から、オキシエチレン基を2つ以上有するものが好ましい。なお、オキシエチレン基の数が多すぎると、塗膜の耐水性、耐候性等が低下するおそれがある。
縮合可能な官能基を有する開始剤および連鎖移動剤の存在下に親水性基を有するエチレン性不飽和モノマーをラジカル重合させることにより、縮合可能な官能基を有する重合体を製造し、縮合可能な官能基にグリシジルビニルエーテル、グリシジルアリルエーテル等を反応させ、末端にラジカル重合性不飽和基を導入する方法(山下ら,Polym.Bull.,5.335(1981))。縮合可能な官能基としては、カルボキシ基、水酸基、アミノ基などが挙げられる。
単量体(m3)は、下式(m3)で表される水酸基含有単量体である。
R1-R2-OH ・・・(m3)
ただし、R1はラジカル重合性不飽和基を有する基であり、R2はn-ノニレン基またはシクロヘキサン-1,4-ジメチレン基である。
(1)CH2=CHOCH2-cycloC6H10-CH2OH
(2)CH2=CHCH2OCH2-cycloC6H10-CH2OH
(3)CH2=CHOC9H18OH
(4)CH2=CHCH2OC9H18OH
含フッ素共重合体(A1p)は、単量体(m1)~(m3)の他に、これらと共重合可能な他の単量体(単量体(m4))に基づく構成単位を有していてもよい。
単量体(m4)としては、オレフィン(エチレン、プロピレン等)、ビニルエーテル(エチルビニルエーテル、プロピルビニルエーテル、ブチルビニルエーテル、シクロヘキシルビニルエーテル、2-エチルヘキシルビニルエーテル等)、ビニルエステル(ブタン酸ビニルエステル、オクタン酸ビニルエステル等)、芳香族ビニル化合物(スチレン、ビニルトルエン等)、アリル化合物(エチルアリルエーテル等)、アクリロイル化合物(ブチルアクリレート等)、メタクリロイル化合物(エチルメタクリレート等)等が挙げられる。
オレフィンとしては、炭素数2~10のオレフィンが好ましい。
ビニルエーテル類、ビニルエステル類、アリルエーテル類、アリルエステル類としては、炭素数2~15の直鎖状、分岐状または脂環状のアルキル基を有するものが好ましい。
単量体(m4)は、炭素原子に結合した水素原子の少なくとも一部がフッ素原子に置換されたものであってもよい。
単量体(m1)に基づく構成単位の割合は、すべての構成単位のうち、20~80モル%が好ましく、30~70モル%がより好ましい。単量体(m1)に基づく構成単位が20モル%以上であれば、耐候性が充分に発揮される。単量体(m1)に基づく構成単位が80モル%以下であれば、含フッ素共重合体(A1p)の水分散性が良好となる。
単量体(m3)に基づく構成単位の割合は、含フッ素共重合体(A1p)の水酸基価が20mgKOH/g以上となるような割合であることが好ましく、40mgKOH/g以上となるような割合であることがより好ましい。含フッ素共重合体(A1p)の水酸基価が20mgKOH/g以上であれば、硬化剤との反応によって、塗膜の耐溶剤性等が格段に向上する。
含フッ素樹脂水分散体(A1)は、乳化重合によって製造される。
乳化剤を用いなくても分散安定性が良好な含フッ素樹脂水分散体(A1)が得られるが、乳化剤を用いることが好ましい。ノニオン性乳化剤としては、アルキルフェノールエチレンオキシド付加物、高級アルコールエチレンオキシド付加物、エチレンオキシドとプロピレンオキシドのブロックコポリマー等が挙げられる。アニオン性乳化剤としては、アルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩、高級脂肪酸塩、アルキル硫酸エステル塩、アルキルエーテル硫酸エステル塩、リン酸エステル塩等が挙げられる。
重合開始剤としては、公知のラジカル開始剤が挙げられ、水溶性開始剤が好ましい。具体的には、過硫酸塩(過硫酸アンモニウム塩等)、レドックス開始剤(過酸化水素と還元剤(亜硫酸水素ナトリウム、チオ硫酸ナトリウム等)との組み合わせ等)、これらに無機系開始剤(鉄、第一鉄塩、硫酸銀等)を共存させた系、二塩基酸過酸化物(ジコハク酸ペルオキシド、ジグルタル酸ペルオキシド等)、有機系開始剤(アゾビスイソブチルアミジン塩酸塩、アゾビスイソブチロニトリル等)等が挙げられる。
重合開始剤の量は、その種類、乳化重合条件等に応じて適宜変更でき、通常、単量体100質量部に対して0.005~0.5質量部程度である。
重合開始剤は、一括添加してもよく、分割添加してもよい。
pH調整剤の量は、乳化重合に用いる水性媒体100質量部に対して、通常、0.05~2質量部程度であり、0.1~2質量部が好ましい。乳化物のpHが高い方が、重合速度が速くなる傾向にある。
乳化重合の際の圧力は、適宜選定でき、通常、0.1~10MPa程度であり、0.2~5MPaが好ましい。
含フッ素樹脂水分散体(A1)は、本発明の効果を損なわない範囲で、含フッ素共重合体(A1p)以外の他の合成樹脂を含んでいてもよい。他の合成樹脂としては、含フッ素樹脂、フェノール樹脂、アルキド樹脂、メラミン樹脂、ユリア樹脂、ビニル系樹脂、エポキシ樹脂、ポリエステル、ポリウレタン、アクリル系樹脂等が挙げられる。
含フッ素共重合体(A1p)の割合は、含フッ素樹脂水性分散体(A1)に含まれるすべての合成樹脂のうち、50質量%以上が好ましく、100質量%がより好ましい。
合成樹脂の固形分濃度は、含フッ素樹脂水分散体(A1)中、10~100質量%が好ましく、30~80質量%がより好ましい。
含フッ素樹脂水分散体(A1)は、本発明の効果を損なわない範囲で、含フッ素共重合体(A1p)、他の合成樹脂、水性媒体以外の他の成分を含んでいてもよい。
他の成分としては、後述するものが挙げられる。
含フッ素樹脂水分散体(A1)は水性塗料用組成物に配合されることから、含フッ素樹脂水分散体(A1)中の有機溶媒の含有量は、3質量%以下が好ましく、1質量%以下が特に好ましい。
含フッ素樹脂水分散体(A2)は、水性媒体(好ましくは水)に含フッ素共重合体(A2p)を含む合成樹脂が分散または溶解したものである。
含フッ素共重合体(A2p)は、構成単位(a1)と、構成単位(a2)と、構成単位(a3)と、構成単位(a4)とを有する。
含フッ素樹脂水分散体(A2)としては、後述のとおり、溶液重合法により得られた含フッ素共重合体(B)にカルボキシ基を導入し、該カルボキシ基を塩基性化合物で中和して、水に分散させて得られたものが好ましい。
構成単位(a1)は、下式(a1)で表される、フルオロオレフィン系化合物に基づく構成単位である。
フルオロエチレンとしては、CF2=CF2、CClF=CF2、CHCl=CF2、CCl2=CF2、CClF=CClF、CHF=CCl2、CH2=CClF、CCl2=CClF、CF2=CH2等が挙げられる。
フルオロプロペンとしては、CF2ClCF=CF2、CF3CCl=CF2、CF3CF=CFCl、CF2ClCCl=CF2、CF2ClCF=CFCl、CFCl2CF=CF2、CF3CCl=CClF、CF3CCl=CCl2、CClF2CF=CCl2、CCl3CF=CF2、CF2ClCCl=CCl2、CFCl2CCl=CCl2、CF3CF=CHCl、CClF2CF=CHCl等が挙げられる。
フルオロオレフィン系化合物としては、塗膜の耐候性が優れる点で、CF2=CF2、CClF=CF2が好ましい。
構成単位(a2)は、下式(a2)で表される、アルキルビニルエーテル、アルキルビニルエステル、アルキルアリルエーテル、アルキルアリルエステル等に基づく構成単位である。これらの中から所望の塗膜物性(硬度、光沢、顔料分散性等)に応じた構成単位が適宜選択される。含フッ素共重合体(A2’)は、2種以上の構成単位(a2)を有していてもよい。
構成単位(a2)としては、構成単位(a1)との交互共重合性がよく、含フッ素共重合体(A2p)のガラス転移温度を調整しやすい点から、エチルビニルエーテル、シクロヘキシルビニルエーテルが好ましい。
構成単位(a3)は、下式(a3)で表される、水酸基含有ビニルエーテル、水酸基含有ビニルエステル、水酸基含有アリルエーテル、水酸基含有アリルエステル等に基づく構成単位である。
構成単位(a3)としては、重合性、架橋性等の点から、ヒドロキシアルキルビニルエーテルに基づく構成単位が好ましい。
構成単位(a4)は、下式(a4)で表される構成単位である。
R15のうち、-NHZ1Z2Z3である割合は、30~100モル%が好ましく、50~100モル%がより好ましい。
Rc、R13、yおよびzは、含フッ素共重合体(A2’)の製造のしやすさの点から、構成単位(a3)のRb、R12、wおよびxと同じであることが好ましい。
含フッ素共重合体(A2p)は、構成単位(a1)~(a4)以外の他の構成単位を有していてもよい。
他の構成単位としては、エチレン性単量体に基づく構成単位が挙げられる。
構成単位(a1)の割合は、すべての構成単位のうち、40~60モル%であり、45~55モル%が好ましい。構成単位(a1)の割合が前記範囲内であれば、塗膜の耐候性が充分になり、含フッ素共重合体(A2p)のガラス転移温度が高くなりすぎず、非晶質で良好な塗膜が得られる。
他の構成単位の割合は、20モル%以下であり、5モル%以下が好ましい。
含フッ素樹脂水分散体(A2)は、工程(α)~工程(δ)を有する方法により製造できる。
(α)含フッ素共重合体(B)を製造する工程。
(β)含フッ素共重合体(B)と二塩基性酸無水物とを有機溶媒中で反応させることにより、構成単位(a3)における水酸基の一部をエステル化し、カルボキシ基を導入する工程。
(γ)エステル化反応によって導入されたカルボキシ基の少なくとも一部を塩基性化合物で中和する工程。
(δ)有機溶媒を除去する工程。
含フッ素共重合体(B)は、構成単位(a1)の40~60モル%と、構成単位(a2)の3~50モル%と、構成単位(a3)の4.4~37モル%(ただし、構成単位(a1)~(a3)の合計は80~100モル%である。)を有する。
含フッ素共重合体(B)における構成単位(a3)のモル%は、含フッ素共重合体(A2’)における構成単位(a3)のモル%と構成単位(a4)のモル%の合計に等しい。
重合開始剤の量は、その種類、重合反応条件に応じて適宜変更でき、通常、単量体100質量部に対して、0.05~0.5質量部程度である。
塩基性化合物の量は、単量体100質量部に対して、0.01~20質量%が好ましく、0.1~10質量%がより好ましい。
溶液重合の際の温度は、10~90℃が好ましい。
溶液重合の際の圧力は、0~2MPaが好ましく、0~1MPaがより好ましい。
含フッ素共重合体(B)と二塩基性酸無水物とを有機溶媒中で反応させることにより、構成単位(a3)における水酸基の一部をエステル化し、カルボキシ基を導入する。
二塩基性酸無水物としては、無水コハク酸、無水グルタル酸、無水イタコン酸、無水アジピン酸、無水1,2-シクロヘキサンジカルボン酸、無水cis-4-シクロヘキセン-1,2-ジカルボン酸、無水フタル酸、無水1,8-ナフタル酸、無水マレイン酸等が挙げられる。
有機溶媒は、含フッ素重合体(B)および二塩基性酸無水物の溶解性等を勘案して適宜選定される。なお、工程(α)で用いた有機溶媒が充分に残留していれば、工程(β)において新たに有機溶媒を添加する必要はない。
エステル化反応の温度は、室温~150℃が好ましく、50~100℃がより好ましい。エステル化反応の時間は、数10分から数時間程度である。
エステル化反応後の構成単位(a4)の割合は、酸価を測定することによって確認できる。エステル化反応後の酸価が2~35mgKOH/gであれば、構成単位(a4)が0.4~7モル%であることが確認できる。
エステル化反応前の構成単位(a3)の割合は、エステル化反応前の水酸基価から確認できる。構成単位(a3)の割合が4~30モルであるためには、エステル化反応前の水酸基価が20~150mgKOH/gであって、エステル化反応後の酸価が前記範囲内であることが必要である。
工程(β)で得られた含フッ素共重合体(B)と二塩基性酸無水物との反応により得られた重合体に塩基性化合物を加え、工程(β)で導入されたカルボキシ基の少なくとも一部を塩基性化合物で中和する。
構成単位(a4)のうち、塩基性化合物で中和する割合は、30~100モル%が好ましく、50~100モル%がより好ましい。
中和反応は、塩基性化合物または塩基性化合物の水溶液を、工程(β)で得られた含フッ素共重合体(B)が溶解した有機溶媒に対して、室温で数10分撹拌しながら加えれば、充分に進行する。
沸点が200℃以下の塩基性化合物としては、アンモニア、アルキルアミン(モノメチルアミン、ジメチルアミン、トリメチルアミン、モノエチルアミン、ジエチルアミン、トリエチルアミン、モノイソプロピルアミン、ジイソプロピルアミン、トリイソプロピルアミン、モノブチルアミン、ジブチルアミン等)、アルカノールアミン(モノエタノールアミン、モノイソプロパノールアミン、ジメチルアミノエタノール、ジエチルアミノエタノール等)、ジアミン(エチレンジアミン、プロピレンジアミン、テトラメチレンジアミン、ヘキサメチレンジアミン等)、アルキレンイミン(エチレンイミン、プロピレンイミン等)、ピペラジン、モルホリン、ピラジン、ピリジン等が挙げられる。
水の量は、工程(γ)で得られる水分散体の固形分濃度が20~70質量%となる量が好ましく、30~60質量%となる量がより好ましい。
工程(γ)の後、有機溶媒を除去する。これにより、有機溶媒が全質量に対して10質量%以下である含フッ素樹脂水分散体(A2)が得られる。有機溶媒は全て除去することが好ましい。
ここで除去すべき有機溶媒としては、工程(α)で用いた有機溶媒が残留したもの、工程(β)で用いた有機溶媒が残留したものが挙げられる。
有機溶媒の除去は、減圧留去により行うことができる。
工程(γ)において必要量の水を加えていない場合、有機溶媒を除去した後に、水を加えてもよい。
水の量は、工程(δ)で得られる水分散体の固形分濃度が20~70質量%となる量が好ましく、30~60質量%となる量がより好ましい。
含フッ素樹脂水分散体(A2)は、本発明の効果を損なわない範囲で、含フッ素共重合体(A2p)以外の他の合成樹脂を含んでいてもよい。他の合成樹脂としては、含フッ素樹脂、フェノール樹脂、アルキド樹脂、メラミン樹脂、ユリア樹脂、ビニル系樹脂、エポキシ樹脂、ポリエステル、ポリウレタン、アクリル系樹脂等が挙げられる。
含フッ素樹脂としては、含フッ素樹脂水分散体(A2)の機械的安定性および化学的安定性が改良される点から、特許第2955336号公報に記載された、フルオロオレフィンに基づく構成単位および親水性部位を有するマクロモノマーに基づく構成単位を必須とする含フッ素共重合体が好ましい。
他の合成樹脂として、含フッ素樹脂以外の他の合成樹脂を用いる場合は、塗膜に優れた耐候性を付与する点から、含フッ素共重合体(A2p)の割合は、すべての合成樹脂のうち、55質量%以上が好ましい。
合成樹脂の固形分濃度は、含フッ素樹脂水分散体(A2)中、10~100質量%が好ましく、30~80質量%がより好ましい。
含フッ素樹脂水分散体(A2)は、本発明の効果を損なわない範囲で、含フッ素共重合体(A2p)、他の合成樹脂、水性媒体以外の他の成分を含んでいてもよい。他の成分としては後述するものが挙げられる。
含フッ素樹脂水分散体(A2)中の有機溶媒の含有量は、10質量%以下が好ましく、3質量%以下がより好ましく、0質量%が特に好ましい。
有機溶媒としては、たとえば、工程(α)で用いた有機溶媒が残留したもの、工程(β)で用いた有機溶媒が残留したものが挙げられる。
含フッ素樹脂水分散体(A2)は水性塗料用組成物に配合されることから、含フッ素樹脂水分散体(A2)中の有機溶媒の含有量は、3質量%以下が好ましく、1質量%以下が特に好ましい。
含フッ素樹脂水分散体(A3)は、水性媒体に含フッ素重合体(A3p)(ただし、含フッ素共重合体(A1p)および含フッ素共重合体(A2p)を除く。)を含む合成樹脂が分散または溶解したものである。
含フッ素重合体(A3p)は、フッ化ビニリデン、テトラフルオロエチレン、ヘキサフルオロプロピレン、クロロトリフルオロエチレンからなる群より選ばれる少なくとも1種の含フッ素単量体に基づく構成単位を有する。
含フッ素重合体(A3p)は、含フッ素単量体と共重合可能な他の単量体(たとえば、アクリル系単量体、アクリル系単量体と共重合可能な他の単量体等)に基づく構成単位を有していてもよい。
アクリル樹脂は、アクリル酸、アクリル酸エステル、メタクリル酸およびメタクリル酸エステルからなる群より選ばれる少なくとも1種のアクリルモノマーに基づく構成単位を有することが好ましい。
アクリル酸エステルとしては、透明性、造膜性に優れる塗膜が得られるという点で、アルキル基の炭素数が1~10のアクリル酸アルキルエステルが好ましい。
メタクリル酸エステルとしては、透明性、造膜性に優れる塗膜が得られるという点で、アルキル基の炭素数が1~10のメタクリル酸アルキルエステルが好ましい。
含フッ素重合体(A3p)とアクリル樹脂との質量比(含フッ素重合体(A3p)/アクリル樹脂)は、10/90~90/10が好ましく、20/80~80/20がより好ましい。含フッ素重合体(A3p)が多すぎると、塗膜の造膜性や基材への密着性が低下する。アクリル樹脂が多すぎると、塗膜の耐候性が低下する。
アクリル樹脂を含む含フッ素樹脂水分散体(A3)としては、Arkema社製、製品名「Kynar Aquatec FMA-12」(フッ化ビニリデン系重合体/アクリル樹脂=50/50(質量比)、アクリル樹脂=メタクリル酸メチル単位/メタクリル酸エチル単位/メタクリル酸ブチル単位=60/20/20(質量比))が挙げられる。
含フッ素樹脂水分散体が含フッ素樹脂水分散体(A1)の場合、本発明の水性塗料用組成物は、硬化剤をさらに含有してもよく、硬化剤を含有しなくてもよい。
含フッ素樹脂水分散体が含フッ素樹脂水分散体(A2)の場合、本発明の水性塗料用組成物は、硬化剤をさらに含有することが好ましい。
含フッ素樹脂水分散体が含フッ素樹脂水分散体(A3)の場合、本発明の水性塗料用組成物は、硬化剤をさらに含有してもよく、硬化剤を含有しなくてもよい。
イソシアネート系化合物としては、機械的に水に分散し得るポリイソシアネート化合物(C1)、または自己乳化性のポリイソシアネート化合物(C2)が好ましい。
ポリイソシアネート化合物(C1)としては、脂肪族ポリイソシアネート(ヘキサメチレンジイソシアネート等)、芳香族ポリイソシアネート(m-またはp-フェニレンジイソシアネート、2,4-または2,6-トリレンジイソシアネート、ジフェニルメタン-4,4’-ジイソシアネート、ナフタレン-1,5-ジイソシアネート、4,4’-ジイソシアネート-3,3’-ジメチルジフェニル等)、脂環式ポリイソシアネート(ビス-(イソシアネートシクロヘキシル)メタン、イソホロンジイソシアネート等)、クルードポリイソシアネート(クルードトリレンジイソシアネート、クルードジフェニルメタンジイソシアネート等)、変性ポリイソシアネート(カルボジイミド変性ジフェニルメタンジイソシアネート、ポリオール変性ジフェニルメタンジイソシアネート、ポリオール変性ヘキサメチレンジイソシアネート等)等が挙げられる。
ブロックポリイソシアネートは、通常、140℃以上でないと硬化しないため、それより低い温度で硬化させる場合には、ブロック化されていないポリイソシアネートが好ましい。
ポリイソシアネート化合物(C1)は、機械的に水に分散させて用いられる。
ポリイソシアネート化合物(C1)は、機械的に水に分散させる点から、比較的低粘度のものが好ましい。分散の際に乳化剤を添加すると、より安定な分散体が得られる。乳化剤としては、公知の乳化剤が挙げられ、ポリイソシアネート化合物(C1)と反応して増粘したり、ポリイソシアネート化合物(C1)の分散性が低下したりしない点から、イオン性基、特に活性水素原子を有しないものが好ましい。乳化剤としては、非イオン性乳化剤が好ましく、ポリオキシエチレン鎖を有する乳化剤が特に好ましい。
ポリイソシアネート化合物(C2)は、乳化剤なしに水に乳化分散できる自己乳化性のポリイソシアネート化合物である。自己乳化性のポリイソシアネート化合物は、特公平4-15270号公報等に記載されている。
ポリオキシアルキレン鎖としては、親水性の点から、オキシアルキレン基のすべてまたは多くがオキシエチレン基であるものが好ましい。
メラミン樹脂としては、アルキルエーテル化(メチルエーテル化、ブチルエーテル化、イソブチルエーテル化等)されたメラミン樹脂が挙げられ、水溶性の点から、少なくとも一部がメチルエーテル化されたメラミン樹脂が好ましい。
本発明の水性塗料用組成物には、本発明の効果を損なわない範囲内で、合成樹脂水分散体、ウレタンポリオール、硬化剤の他に、他の成分を配合してもよい。
他の成分としては、公知の塗料用添加剤が挙げられ、具体的には、造膜助剤、無機系着色顔料、有機系着色顔料、体質顔料、硬化触媒、可塑剤、防腐剤、防黴剤、消泡剤、レベリング剤、顔料分散剤、沈降防止剤、たれ防止剤、艶消し剤、紫外線吸収剤、酸化防止剤等が挙げられる。本発明の水性塗料用組成物には、他の成分を2種以上配合してもよい。
以上説明した本発明の水性塗料用組成物にあっては、親水性の高い基(水酸基等)を有する特定のウレタンポリオールを含有するため、塗膜の表面に自己浄化機能を付与できる。すなわち、親水性の高い基を有するウレタンポリオールによって、塗膜の表面の親水性を向上できる。塗膜の表面の親水性が向上すると、塗膜の表面に付着した汚れが降雨等の水滴で洗い流され易くなる(易洗浄性)。
また、以上説明した本発明の水性塗料用組成物にあっては、ウレタンポリオール(X)を含有するため、水性塗料用組成物に合成樹脂水分散体として含フッ素樹脂水分散体を配合した場合に、ウレタンポリオール(X)が塗膜の表層に移行しやすく、塗膜に自己浄化機能を充分に付与できると考えられる。また、水性塗料用組成物に硬化剤としてイソシアネート系化合物を配合した場合であっても、ウレタンポリオール(X)が塗膜の表層に移行する途中でイソシアネート系化合物と反応しにくく、塗膜の表層へのウレタンポリオールの移行が阻害されないため、効果的に塗膜に自己浄化機能を充分に付与できると考えられる。
また、以上説明した本発明の水性塗料用組成物にあっては、ウレタンポリオール(X)がたとえばアルコキシシラン変性縮合物のように反応性が高くないため、ウレタンポリオール(X)を水性塗料用組成物に配合しても、水性塗料用組成物の貯蔵安定性を損ないにくい。
また、以上説明した本発明の水性塗料用組成物にあっては、有機溶媒の含有量が少ない水性塗料用組成物であるため、環境上好ましい。
本発明の水性塗料用キットは、本発明の水性塗料用組成物と、イソシアネート系化合物の水溶液または水分散液の2液を、互いに混合されない状態で備えており、これらを混合することによりイソシアネート系化合物を含有する水性塗料用組成物を調製できる。塗料用添加剤を水性塗料用組成物に配合する場合は、該2液の一方または両方に適宜含有させることができる。
イソシアネート系化合物と組み合わされる水性塗料用組成物は、イソシアネート系化合物以外の硬化剤を含有していてもよいが、通常は硬化剤を含有しない水性塗料用組成物が用いられる。
以上説明した本発明の水性塗料用キットにあっては、本発明の水性塗料用組成物と、イソシアネート系化合物の水溶液または水分散液を備えたものであるため、上述した効果を発揮できる、イソシアネート系化合物を含有する本発明の水性塗料用組成物を調製できる。
本発明の水性塗料調整用キットは、合成樹脂水分散体とウレタンポリオール(X)の溶液または分散液の2液を、互いに混合されない状態で備えており、これらを混合することにより水性塗料用組成物を調製できる。塗料用添加剤を水性塗料用組成物に配合する場合は、該2液の一方または両方に適宜含有させることができる。
ウレタンポリオール(X)と組み合わされる合成樹脂水分散体は、あらかじめ硬化剤が配合されてもよく、水性塗料調整用キットの両成分を混合した後に硬化剤を配合してもよく、水性塗料調整用キットの両成分と硬化剤を同時に混合してもよい。また、硬化剤を含有しない水性塗料用組成物を塗布に使用する場合は、水性塗料調整用キットの両成分を混合して硬化剤を含有しない水性塗料用組成物とし、それを塗布に使用することができる。
以上説明した本発明の水性塗料調整用キットにあっては、合成樹脂水分散体と、ウレタンポリオールを備えたものであるため、上述した効果を発揮できる本発明の水性塗料用組成物を調製できる。
本発明の物品は、本発明の水性塗料用組成物を用いて形成された塗膜を有する。
本発明の物品は、基材の表面に本発明の水性塗料用組成物を塗布し、乾燥させて、基材の表面に塗膜を形成することによって製造できる。
本発明の水性塗料用組成物は、基材に直接塗布してもよく、基材に公知の表面処理(下地処理等)を施した上に塗布してもよい。塗布方法としては、ハケ塗り、スプレー、ローラー、ロールコーター、フローコーター等が挙げられる。
以上説明した本発明の物品にあっては、上述した効果を発揮できる本発明の水性塗料用組成物からなる塗膜を有するため、充分な自己浄化機能を有する塗膜を有するものとなる。
空気中にて塗膜に水の液滴を落とした際の接触角を接触角計(協和界面科学社製、CA-X型)を用いて測定した。水の接触角が小さいほど親水性が高いことを示す。
沖縄県那覇市の屋外に、得られた試験板を設置し、設置直前と1年後を比較して、塗膜の光沢保持率、塗膜の汚れについて評価した。
塗膜表面の光沢を光沢計(日本電色工業社製、PG-1M)を用いて測定し、以下の基準に従って耐候性を評価した。
「○」:光沢保持率が80%以上であった。
「×」:光沢保持率が80%未満であった。
以下の基準に従って、目視により、汚れの付着度合いを確認した。
「○」:塗膜の表面に目立った汚れの付着は確認されなかった。
「×」:塗膜の表面の全体に汚れが付着していた。
単量体(m1):
CTFE:クロロトリフルオロエチレン
単量体(m2):
CM-EOVE:CH2=CHOCH2-cycloC6H10-CH2(OCH2CH2)kOH(数平均分子量830)
単量体(m3):
CHMVE:CH2=CHOCH2-cycloC6H10-CH2OH
単量体(m4):
CHVE:シクロヘキシルビニルエーテル
2-EHVE:2-エチルヘキシルビニルエーテル
EVE:エチルビニルエーテル
CTFE:クロロトリフルオロエチレン
単量体(b2):
EVE:エチルビニルエーテル
CHVE:シクロヘキシルビニルエーテル
単量体(b3):
4-HBVE:4-ヒドロキシブチルビニルエーテル
ウレタンポリオールの溶液として、ウレタンジオールの水溶液(キングインダストリーズ社製、FLEXOREZ(登録商標)UD-350W、固形分濃度:88質量%。ウレタンジオールの脂肪族ジイソシアネートの残基の数の平均値:10、数平均分子量:5500、水酸基価:350mgKOH/g)を用意した。
上記FLEXOREZ(登録商標)UD-350Wは、ジプロピレングリコールと2-メチルペンタン-1,5-ジイソシアネートの反応生成物からなるウレタンジオールと考えられる。
含フッ素樹脂水分散体(A1-1))の調製:
内容積2500mLの撹拌機付きステンレス製オートクレーブ中に、水の1280g、CHVEの415g、2-EHVEの230g、CM-EOVEの21g、CHMVEの34g、イオン交換水の1280g、炭酸カリウムの3.0g、過硫酸アンモニウムの5.4g、ノニオン性乳化剤(日本乳化剤社製、Newcol(登録商標)-2320)の33g、アニオン性乳化剤(ラウリル硫酸ナトリウム)の1.4gを仕込み、氷で冷却して、窒素ガスで0.4MPaGになるよう加圧し脱気した。この加圧脱気を2回繰り返した。0.095MPaGまで脱気して溶存空気を除去した後、CTFEの580gを仕込み、50℃で24時間反応を行った。24時間反応を行った後、オートクレーブを水冷して反応を停止した。この反応液を室温まで冷却した後、未反応単量体をパージし、固形分濃度50質量%の含フッ素樹脂水分散体(A1-1)を得た。これに含まれる含フッ素共重合体(A1p-1)の水酸基価は10mgKOH/gであった。含フッ素共重合体(A1p-1)の構成単位の比は、CTFE単位/CM-EOVE単位/CHMVE単位/CHVE単位/2-EHVE単位=50/0.25/2/33/14.75(モル比)であった。
含フッ素樹脂水分散体(A1-2)の調製:
内容積2500mLの撹拌機付きステンレス製オートクレーブ中に、水の1280g、EVEの185g、CHVEの244g、CM-EOVEの47g、CHMVEの194g、イオン交換水の1280g、炭酸カリウムの2.0g、過硫酸アンモニウムの1.3g、ノニオン性乳化剤(日本乳化剤社製、Newcol(登録商標)-2320)の33g、アニオン性乳化剤(ラウリル硫酸ナトリウム)の1.4gを仕込み、氷で冷却して、窒素ガスで0.4MPaGになるよう加圧し脱気した。この加圧脱気を2回繰り返した。0.095MPaGまで脱気して溶存空気を除去した後、CTFEの664gを仕込み、50℃で24時間反応を行った。24時間反応を行った後、オートクレーブを水冷して反応を停止した。この反応液を室温まで冷却した後、未反応単量体をパージし、固形分濃度50質量%の含フッ素樹脂水分散体(A1-2)を得た。これに含まれる含フッ素共重合体(A1p-2)の水酸基価は55mgKOH/gであった。含フッ素共重合体(A1p-2)の構成単位の比は、CTFE単位/CM-EOVE単位/CHMVE単位/EVE単位/CHVE単位=50/0.5/10/17/22.5(モル比)であった。
含フッ素樹脂水分散体(A2-1)の調製:
含フッ素共重合体(B)(旭硝子社製、ルミフロン(登録商標)フレーク、CTFE単位/EVE単位/CHVE単位/4-HBVE単位=50/15/15/20(モル比)、水酸基価:100mgKOH/g、質量平均分子量:7000)を、メチルエチルケトン(MEK)に溶解させて固形分60質量%のワニスを得た。
このワニスの300gに、無水こはく酸の4.8g、触媒としてトリエチルアミンの0.072gを加え、70℃で6時間反応させエステル化した。反応液の赤外吸収スペクトルを測定したところ、反応前に観測された無水酸の特性吸収(1850cm-1、1780cm-1)が反応後では消失しており、カルボキシ基(1710cm-1)およびエステル結合(1735cm-1)の吸収が観測された。エステル化後の含フッ素共重合体(B)の水酸基価は85mg/KOH、酸価は15mgKOH/gであった。
次に、エステル化後の含フッ素共重合体(B)に、トリエチルアミンの4.9gを加え室温で20分撹拌してカルボキシ基を中和し、イオン交換水の180gを徐々に加えた。
最後に、アセトンおよびメチルエチルケトンを減圧留去した。イオン交換水を用いて、固形分濃度50質量%の含フッ素樹脂水分散体(A2-1)を調製した。含フッ素共重合体(A2p-1)の構成単位の比は、CTFE単位/EVE単位/CHVE単位/4-HBVE単位/エステル化された4-HBVE単位=50/15/15/17/3(モル比)であった。エステル化された4-HBVE単位のうち、トリエチルアミンで中和された割合は70モル%であった。
顔料組成物の調製:
酸化チタン(堺化学工業社製、D-918)の210質量部、顔料分散剤(ビックケミー社製、Disperbyk(登録商標)190、顔料に親和性のある共重合物、酸価:10mgKOH/g)の21質量部、消泡剤(コグニス社製、デヒドラン(登録商標)1620)の4.5質量部、イオン交換水の64.5質量部、ガラスビーズの300質量部を混合し、分散機を用いて分散し、ガラスビーズを濾過により除去して顔料組成物を調製した。
調製例4で得た顔料組成物の55gに、調製例1で得た含フッ素樹脂水分散体(A1-1)の193g、造膜助剤として2,2,4-トリメチル-1,3-ペンタジオールモノ(2-メチルプロパネート)の15g、増粘剤(アクゾノーベル社製、ベルモドール(登録商標)2150)の0.5g、ウレタンポリオールの溶液の15gを加えて混合し、水性塗料用組成物を調製した。ウレタンジオールの量は、含フッ素樹脂水分散体(A1-1)中の固形分100質量部に対して16.3質量部であった。
得られた水性塗料用組成物をフィルムアプリケータを用いてアルミニウム板(厚さ1mm、表面をクロメート処理)に乾燥膜厚40μmになるよう塗布し、温度23℃、湿度50%にて2週間乾燥し、試験片を作製した。得られた試験片の評価結果を表1に示す。
調製例4で得た顔料組成物の55gに、調製例2で得た含フッ素樹脂水分散体(A1-2)の193g、造膜助剤としてジプロピレングリコールモノn-ブチルエーテルの15g、増粘剤(アクゾノーベル社製、ベルモドール(登録商標)2150)の0.5g、ウレタンポリオールの溶液の15g、水分散型イソシアネート硬化剤(住化バイエル社製、バイヒジュール(登録商標)3100)の22.9gを加えて混合し、水性塗料用組成物を調製した。ウレタンジオールの量は、含フッ素樹脂水分散体(A1-2)中の固形分100質量部に対して16.3質量部であった。
実施例1と同様にして試験片を作製した。得られた試験片の評価結果を表1に示す。
調製例4で得た顔料組成物の55gに、調製例3で得た含フッ素樹脂水分散体(A2-1)の193g、表面調整剤(ビックケミー社製、BYK(登録商標)-348)の1.3g、増粘剤(アクゾノーベル社製、ベルモドール(登録商標)2150)の0.5g、ウレタンポリオールの溶液の15g、水分散型イソシアネート硬化剤(住化バイエル社製、バイヒジュール(登録商標)3100)の25gを加えて混合し、水性塗料用組成物を調製した。ウレタンジオールの量は、含フッ素樹脂水分散体(A2-1)中の固形分100質量部に対して16.3質量部であった。
実施例1と同様にして試験片を作製した。得られた試験片の評価結果を表1に示す。
調製例4で得た顔料組成物の55gに、含フッ素樹脂水分散体(Arkema社製、製品名「Kynar Aquatec FMA-12」)の193g、造膜助剤として2,2,4-トリメチル-1,3-ペンタジオールモノ(2-メチルプロパネート)の15g、増粘剤(アクゾノーベル社製、ベルモドール(登録商標)2150)の0.5g、ウレタンポリオールの溶液の15gを加えて混合し、水性塗料用組成物を調製した。ウレタンジオールの量は、含フッ素樹脂水分散体中の固形分100質量部に対して16.3質量部であった。
得られた水性塗料用組成物をフィルムアプリケータを用いてアルミニウム板(厚さ1mm、表面をクロメート処理)に乾燥膜厚40μmになるよう塗布し、温度23℃、湿度50%にて2週間乾燥し、試験片を作製した。得られた試験片の評価結果を表1に示す。
ウレタンポリオールの溶液を添加しない以外は、実施例1と同様にして水性塗料用組成物を調製した。
実施例1と同様にして試験片を作製した。得られた試験片の評価結果を表1に示す。
ウレタンポリオールの溶液を添加しない以外は、実施例2と同様にして水性塗料用組成物を調製した。
実施例1と同様にして試験片を作製した。得られた試験片の評価結果を表1に示す。
ウレタンポリオールの溶液を添加しない以外は、実施例3と同様にして水性塗料用組成物を調製した。
実施例1と同様にして試験片を作製した。得られた試験片の評価結果を表1に示す。
ウレタンポリオールの溶液を添加しない以外は、実施例4と同様にして水性塗料用組成物を調製した。
実施例1と同様にして試験片を作製した。得られた試験片の評価結果を表1に示す。
調製例4で得た顔料組成物の55gに、調製例3で得た含フッ素樹脂水分散体(A2-1)の193g、表面調整剤(ビックケミー社製、BYK(登録商標)-348)の1.3g、増粘剤(アクゾノーベル社製、ベルモドール(登録商標)2150)の0.5g、水分散型イソシアネート硬化剤(住化バイエル社製、バイヒジュール(登録商標)3100)の25g、水性塗料用低汚染化剤(旭硝子社製、商品名「SRAgent2100」、固形分濃度40質量%)の27.6g、アジピン酸ジヒドラジド(10質量%希釈品)の6.9gを加えて混合し、水性塗料用組成物を調製した。
水性塗料用低汚染化剤(旭硝子社製、商品名「SRAgent2100」)の量は、含フッ素樹脂水分散体(A2-1)中の固形分100質量部に対して14.3質量部であった。
実施例1と同様にして試験片を作製した。得られた試験片の評価結果を表1に示す。
なお、2013年5月27日に出願された日本特許出願2013-110885号の明細書、特許請求の範囲および要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
Claims (15)
- 合成樹脂水分散体とウレタンポリオールとを含有し、該ウレタンポリオールが、分岐アルキレン基の一端に酸素原子が結合した構造のオキシアルキレン基を単位として有するポリオキシアルキレンジオールと脂肪族ジイソシアネートの反応生成物であることを特徴とする水性塗料用組成物。
- 前記オキシアルキレン基がオキシプロピレン基である、請求項1に記載の水性塗料用組成物。
- 前記ウレタンポリオールが、オキシプロピレン基数が2~6のポリプロピレングリコールとアルキレン基の炭素数が4~10のアルキレンジイソシアネートとの反応生成物である、請求項1または2に記載の水性塗料用組成物。
- 前記アルキレンジイソシアネートのアルキレン基が分岐アルキレン基である、請求項3に記載の水性塗料用組成物。
- 前記ウレタンポリオールの数平均分子量が1000~30000であり、水酸基価が50~500mgKOH/gである、請求項1~4のいずれか一項に記載の水性塗料用組成物。
- 前記ウレタンポリオールの含有量が、前記合成樹脂水分散体中の固形分100質量部に対して、0.5~30質量部である、請求項1~5のいずれか一項に記載の水性塗料用組成物。
- 前記合成樹脂水分散体中の合成樹脂の少なくとも一部が含フッ素樹脂である、請求項1~6のいずれか一項に記載の水性塗料用組成物。
- 前記含フッ素樹脂が、下記単量体(m1)に基づく構成単位と、下記単量体(m2)に基づく構成単位と、下記単量体(m3)に基づく構成単位とを有する含フッ素共重合体(A1p)である、請求項7に記載の水性塗料用組成物。
単量体(m1):フルオロオレフィン。
単量体(m2):親水性部位を有するマクロモノマー。
単量体(m3):下式(m3)で表される水酸基含有単量体。
R1-R2-OH ・・・(m3)
ただし、R1はラジカル重合性不飽和基を有する基であり、R2はn-ノニレン基またはシクロヘキサン-1,4-ジメチレン基である。 - 前記含フッ素樹脂水分散体中の含フッ素樹脂が、下式(a1)で表される構成単位の40~60モル%と、下式(a2)で表される構成単位の3~50モル%と、下式(a3)で表される構成単位の4~30モル%と、下式(a4)で表される構成単位の0.4~7モル%(ただし、式(a1)で表される構成単位、式(a2)で表される構成単位、式(a3)で表される構成単位、式(a4)で表される構成単位の合計は80~100モル%である。)を有する含フッ素共重合体(A2p)である、請求項7に記載の水性塗料用組成物。
- 硬化剤をさらに含有する、請求項1~9のいずれか一項に記載の水性塗料用組成物。
- 前記硬化剤がイソシアネート系化合物である、請求項10に記載の水性塗料用組成物。
- 請求項1~11のいずれか一項に記載の水性塗料用組成物を用いて形成された塗膜を有することを特徴とする物品。
- 請求項1~9のいずれか一項に記載の水性塗料用組成物と、イソシアネート系化合物の水溶液または水分散液とからなることを特徴とする水性塗料用キット。
- 請求項13に記載の水性塗料用キットを用いて形成された塗膜を有することを特徴とする物品。
- 請求項1~11のいずれか一項に記載の水性塗料用組成物を調製するのに用いられるキットであって、
前記合成樹脂水分散体と、前記ウレタンポリオールの水溶液または水分散液とからなることを特徴とする水性塗料調整用キット。
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WO2017110926A1 (ja) * | 2015-12-25 | 2017-06-29 | 旭硝子株式会社 | 防汚コーティング材 |
JP2018145375A (ja) * | 2017-03-09 | 2018-09-20 | Agc株式会社 | フッ素系水性塗料 |
KR20190067160A (ko) * | 2016-10-05 | 2019-06-14 | 에이지씨 가부시키가이샤 | 함불소 중합체 함유 조성물 및 함불소 중합체막이 형성된 기재의 제조 방법 |
CN112517025A (zh) * | 2020-12-10 | 2021-03-19 | 万华化学集团股份有限公司 | 一种用于酯交换反应的固体酸催化剂及其制备方法、维生素a棕榈酸酯的制备方法 |
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CN111410902B (zh) * | 2019-01-08 | 2022-09-06 | 关西涂料株式会社 | 水性多组分聚氨酯涂料组合物 |
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SG11201509097TA (en) | 2015-12-30 |
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