WO2018079539A1 - Hydrophilic polymer and aqueous resin composition for paint using said polymer - Google Patents
Hydrophilic polymer and aqueous resin composition for paint using said polymer Download PDFInfo
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- WO2018079539A1 WO2018079539A1 PCT/JP2017/038329 JP2017038329W WO2018079539A1 WO 2018079539 A1 WO2018079539 A1 WO 2018079539A1 JP 2017038329 W JP2017038329 W JP 2017038329W WO 2018079539 A1 WO2018079539 A1 WO 2018079539A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L39/00—Compositions of 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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
- C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D139/00—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
- C09D139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
Definitions
- the present invention relates to a polymer useful as a hydrophilizing material and a composition containing the polymer.
- the surface of the coating film is made hydrophilic with a hydrophilic polymer, and rainwater is contaminated with the coating film.
- a technique is known that facilitates cleaning of dirt by making it easier to reach the interface with a substance.
- Patent Document 1 JP 2001-72928 A discloses (a) an emulsion of an organic synthetic resin, (b) a coupling agent, and (c) the organic synthetic resin, other than (a) and the coupling agent.
- a resin composition for a low-contamination water-based paint comprising a hydrophilic compound having a group capable of reacting with (b) is disclosed.
- the pamphlet of International Publication No. 2008/102816 includes (meth) acrylic emulsion (A) obtained by emulsion polymerization and water-soluble resin (B) as essential components.
- An aqueous resin composition for paints in which the emulsion (A) and the water-soluble resin (B) can form a crosslinked structure is disclosed.
- An object of the present invention is to provide a novel polymer useful as a hydrophilic material (for example, a hydrophilic polymer for paint) and a composition containing the polymer.
- Another object of the present invention is to provide a polymer useful for maintaining low contamination (hydrophilicity) of a coating film over a long period of time and a composition containing this polymer.
- Still another object of the present invention is to provide a polymer useful for forming a coating film excellent in water resistance, weather resistance, stretchability, adhesion and the like and a composition containing the polymer.
- Another object of the present invention is to provide a composition capable of forming a highly glossy coating film.
- Still another object of the present invention is to provide a composition having good handleability.
- the inventors of the present invention have studied a technique for reducing contamination using a hydrophilic polymer, and found that the hydrophilicity of the coating film gradually decreases. And based on such knowledge, like the technique of patent document 2, the technique which forms a crosslinked structure with an emulsion and a hydrophilic polymer was examined, but the drop-off inhibitory effect of a water-soluble polymer may not be enough. I found that there was room for further improvement.
- N-vinyl lactam polymers among hydrophilic polymers and N-vinyl lactam monomers
- N-vinyl lactam monomers N It has been found that by copolymerizing a hindered amine monomer with vinylpyrrolidone or the like, a composition capable of maintaining the effect of reducing the contamination of the coating film (hydrophilization effect) over a long period of time in combination with the emulsion.
- the hindered amine compound is known as a light stabilizer, but in the present invention, it is unexpectedly assumed from the light resistance stabilization effect by polymerizing a hindered amine monomer in combination with an N-vinyl lactam polymer. It was found that a polymer capable of improving the long-term effect of reducing contamination was obtained.
- the polymer (copolymer) of the present invention is a polymer (polymer (B)) having a vinyl lactam monomer and a hindered amine monomer as at least a polymerization component (monomer component (b)).
- the proportion of the vinyl lactam monomer may be 50% by mass or more based on the entire polymerization component. In the polymer of the present invention, the proportion of the vinyl lactam monomer may be 80 mol% or more based on the entire polymerization component. In the polymer of the present invention, the ratio of the hindered amine monomer may be 0.01 to 15 mol with respect to 100 mol of the vinyl lactam monomer. Typically, in the polymer of the present invention, the proportion of the vinyl lactam monomer is 80 mol% or more of the entire polymerization component, and the proportion of the hindered amine monomer is 0.05 to 10 mol with respect to 100 mol of the vinyl lactam monomer. It may be.
- the polymerization component may further contain a monomer having a functional group (functional group ⁇ ), for example, a carbonyl group, an acid group, a carbonate group, an isocyanate group, an oxazoline group, an oxazolidine group.
- a monomer having at least one functional group selected from hydrazino group, epoxy group, amino group, hydroxyl group, and mercapto group for example, carbonyl group-containing monomer (for example, diacetone (meth) acrylamide)
- a monomer having a functional group containing (functional group ⁇ ) A monomer having a functional group containing (functional group ⁇ )].
- the vinyl lactam monomer contains N-vinylpyrrolidone
- the polymerization component further includes a monomer having at least one functional group selected from a carbonyl group-containing monomer, an acid group-containing monomer, and a hydroxy group-containing monomer
- the proportion of the vinyl lactam monomer is 70% by mass or more based on the entire polymerization component
- the polymer etc. whose ratio of the hindered amine-type monomer and the monomer which has a functional group are 10 mass parts (or 10 mol) or less with respect to 100 mass parts (or 100 mol) of vinyl lactam monomers, respectively are contained.
- the polymerization component contains a monomer having a functional group
- the monomer having a functional group may contain at least a carbonyl group-containing monomer (for example, diacetone (meth) acrylamide).
- the polymer of the present invention can be suitably used as a hydrophilizing material (hydrophilizing agent) and the like, for example, a polymer for use in combination with an emulsion (particularly a polymer for constituting an aqueous composition for paint). Also good. Therefore, the present invention also includes a hydrophilizing agent composed of the polymer (polymer (B)) [for example, a hydrophilizing agent for paint (particularly for water-based paint)].
- the present invention includes a composition comprising an emulsion (A) and the polymer (B).
- the emulsion (A) may in particular be an acrylic emulsion.
- the emulsion (A) may be anionic (for example, may have an anionic group).
- the emulsion (A) may be an emulsion satisfying the following (1) and / (2).
- the emulsifier constituting the emulsion (A) contains an anionic emulsifier
- the emulsion (A) is composed of a resin having a monomer component (a) containing a monomer having a functional group ⁇ as a polymerization component, and the polymerization component of the polymer (B) is functional.
- a monomer having a functional group ⁇ capable of forming a cross-linking structure with the group ⁇ may be included.
- composition of the present invention may further contain a crosslinking agent (C) capable of forming a bond by reacting between the functional group ⁇ and the functional group ⁇ .
- C crosslinking agent
- a monomer having a functional group ⁇ includes a carbonyl group-containing monomer
- a monomer having a functional group ⁇ includes a carbonyl group-containing monomer
- a hydrazine-based crosslinking agent emulsion (A) and the polymer (B) can form a crosslinked structure via (C1)
- / or the monomer having the functional group ⁇ includes a carboxyl group-containing monomer
- the functional group ⁇ The composition may contain a carboxyl group-containing monomer and the emulsion (A) and the polymer (B) can form a crosslinked structure via the oxazoline-based crosslinking agent (C1).
- composition of the present invention may be an aqueous composition for paints containing an emulsion (A) and a polymer (B), and particularly for a top coat (especially for a top coat of an exterior material).
- the present invention includes a coating film formed from the composition.
- the present invention also includes a base material (coated base material) composed of a base material (base base material) and the coating film (coating film) formed on the base material.
- the polymer (B) by combining the polymer (B) with the emulsion (A), low contamination (hydrophilicity) of the coating film can be maintained, and adhesion of dirt to the coating film (coating film) can be suppressed or prevented.
- the present invention provides a stain-proofing agent (an agent for suppressing or preventing the adhesion of dirt) to a coating film formed from a composition containing the emulsion (A), which comprises a polymer (B) (vinyl lactam). Also included are antifouling agents (contamination prevention agents) composed of (or containing the polymer (B)) at least as a polymerization component (a polymer having the monomer component (b)) with a monomer and a hindered amine monomer.
- novel polymers and compositions (especially aqueous resin compositions) of the present invention are useful as hydrophilizing materials (for example, hydrophilic or water-soluble polymers for paints). Such polymers and compositions can maintain the low contamination (hydrophilicity) of the coating film over a long period of time despite being hydrophilic or water-soluble.
- the polymer and composition of the present invention can form a coating film excellent in coating film physical properties (for example, water resistance, weather resistance, extensibility, adhesion, etc.).
- a highly glossy coating film (or a coating film with strong gloss) can be formed.
- polymer and composition of the present invention have good handleability (for example, excellent storage stability).
- the polymer and composition of the present invention can be produced by combining these excellent effects in a well-balanced manner, and are extremely useful as a paint.
- the polymer of the present invention (corresponding to the polymer (B) described later) is a polymer comprising a vinyl lactam monomer and a hindered amine monomer as at least a polymerization component (or a monomer component, corresponding to the monomer component (b) described later). It is.
- vinyl lactam monomer examples include vinyl pyrrolidone (N-vinyl pyrrolidone), vinyl caprolactam (N-vinyl caprolactam), and the like.
- vinyl pyrrolidone is preferable, and therefore the vinyl lactam monomer may be composed of at least vinyl pyrrolidone.
- the ratio of vinyl pyrrolidone to the whole vinyl lactam monomer is, for example, 50 mol% or more, preferably 70 mol% or more, Preferably, 90 mol% or more may be sufficient.
- the proportion of the vinyl lactam monomer depends on the type of other monomers, but from the viewpoint of imparting hydrophilicity (water solubility) to the polymer, for example, the polymerization component It may be 30% by mass or more, preferably 50% by mass or more, more preferably 70% by mass or more, particularly 80% by mass or more, and particularly preferably 85% by mass or more (for example, 90% by mass or more).
- the proportion of the vinyl lactam monomer depends on the type of other monomers, but from the viewpoint of imparting hydrophilicity (water solubility) to the polymer, for example, the polymerization component It may be 30 mol% or more of the whole, preferably 50 mol% or more, more preferably 70 mol% or more, particularly 80 mol% or more, particularly preferably 85 mol% or more (for example, 90 mol% or more). That is, the ratio of the vinyl lactam monomer to the entire polymerization component may be in the same range in terms of mass (mass%) and mol (mol%). Hereinafter, the same may be applied to the ratio (for example, hindered amine monomer, monomer having a functional group, etc.) in the polymerization component (for example, mass% may be mol%).
- hindered amine monomers examples include a polymerizable compound having a piperazine skeleton (particularly a 2,2,6,6-tetramethylpiperidine skeleton) (a compound having a piperazine skeleton and a polymerizable group).
- the polymerizable group is not particularly limited, and examples thereof include an alkenyl group (such as a vinyl group and an allyl group) and an alkenylcarbonyl group [such as a (meth) acryloyl group and a crotonoyl group].
- the number of polymerizable groups in the hindered amine monomer may be 1 or more, and may be 1 to 4, preferably 1 to 3, and more preferably 1.
- a preferred hindered amine monomer is a monofunctional monomer (a compound having one polymerizable group). Therefore, the hindered amine monomer may be composed of at least a monofunctional monomer.
- Typical hindered amine monomers include compounds represented by the following formula (I).
- R 1 and R 2 are hydrogen atoms or alkyl groups, R 3 , R 4 , R 5 and R 6 are alkyl groups, X is an oxygen atom (—O—) or imino group (—NH—), Y And Z represents a hydrogen atom or a substituent.
- examples of the alkyl group include C 1-20 alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a s-butyl group, and a t-butyl group.
- a C 1-10 alkyl group more preferably a C 1-4 alkyl group, particularly a methyl group.
- R 1 and R 2 are a hydrogen atom or a methyl group, and it is particularly preferable that R 1 is a hydrogen atom and R 2 is a hydrogen atom or a methyl group.
- Representative R 3 to R 6 are methyl groups.
- Examples of the substituent for Y and Z include hydrocarbon groups such as alkyl groups (for example, the above-exemplified alkyl groups such as a methyl group (C 1-20 alkyl group, preferably C 1-4 alkyl group), etc.) ], An alkoxy group (for example, a C 1-20 alkoxy group such as a methoxy group or an ethoxy group, preferably a C 1-10 alkoxy group, more preferably a C 1-4 alkoxy group, particularly a methoxy group), an acyl group (for example, C 1-10 acyl group such as acetyl group), halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom etc.), cyano group, hydroxyl group, polymerizable group (eg (meth) acryloyl group, crotonoyl group) ) And the like.
- alkyl groups for example, the above-exemplified alkyl groups such
- Y include a hydrogen atom, an alkyl group (for example, a C 1-4 alkyl group such as a methyl group), an alkoxy group (for example, a C 1-4 alkoxy group such as a methoxy group), an acyl group (for example, an acetyl group).
- a C 1-4 acyl group such as a group), a (meth) acryloyl group, a crotonoyl group, and the like.
- a hydrogen atom or a methyl group is preferable.
- representative Z includes a hydrogen atom or a cyano group, and a hydrogen atom is particularly preferable.
- a specific hindered amine monomer for example, 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine having a substituent ⁇ for example, 4- ( (Meth) acryloyloxy-2,2,6,6-tetramethyl-1-alkylpiperidine [eg 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine etc.
- 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidines for example, 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-2,2,6,6-tetramethyl-1-alkylpiperidine etc. are preferred.
- the hindered amine monomers may be used alone or in combination of two or more.
- the ratio of the hindered amine monomer is, for example, 30% by mass or less (for example, 0.001 to 25% by mass), preferably 20% by mass or less (for example, based on the entire polymerization component (monomer component (b)). 0.01 to 15% by mass), more preferably 10% by mass or less (for example, 0.05 to 8% by mass), and usually 0.05 to 10% by mass (for example, 0.1 to 5% by mass). %).
- the ratio of the hindered amine monomer is, for example, 30 mol% or less (for example, 0.001 to 25 mol%), preferably 20 mol% or less (for example, for the entire polymerization component (monomer component (b)). 0.01 to 15 mol%), more preferably 10 mol% or less (for example, 0.05 to 8 mol%), and usually 0.05 to 10 mol% (for example, 0.1 to 5 mol%). %).
- the ratio of the hindered amine monomer is, for example, 30 parts by mass or less (for example, 0.001 to 25 parts by mass), preferably 20 parts by mass or less (for example, 0.01 to 15 parts) with respect to 100 parts by mass of the vinyl lactam monomer. Part by mass), more preferably 10 parts by mass or less (eg, 0.05 to 8 parts by mass), and usually 0.05 to 10 parts by mass (eg, 0.1 to 5 parts by mass). Also good.
- the ratio of the hindered amine monomer is, for example, 30 mol or less (for example, 0.001 to 25 mol), preferably 20 mol or less (for example, 0.01 to 15 mol), relative to 100 mol of the vinyl lactam monomer, Preferably, it may be 10 mol or less (for example, 0.05 to 8 mol), and may generally be 0.05 to 10 mol (for example, 0.1 to 5 mol).
- the polymerization component (monomer component (b)) may contain a monomer (monomer) having a functional group (corresponding to a functional group ⁇ described later). By including a monomer having such a functional group in the polymerization component, it may be more advantageous in terms of long-term hydrophilicity.
- Examples of the functional group (functional group ⁇ ) include a carbonyl group (or a carbonyl group-containing group such as a ketone group, an aldehyde group, and an acyl group), an acid group (or an anionic group such as a carboxyl group, and an acid anhydride).
- a carbonyl group or a carbonyl group-containing group such as a ketone group, an aldehyde group, and an acyl group
- an acid group or an anionic group such as a carboxyl group, and an acid anhydride.
- Group, acid halide group, sulfonic acid group, etc. carbonate group, isocyanate group, oxazoline group, oxazolidine group, hydrazino group, epoxy group, amino group, hydroxyl group, mercapto group and the like.
- the monomer having a functional group may have these functional groups alone or in combination of two or more.
- a carbonyl group, an acid group (anionic group), an oxazoline group, a hydrazino group, a hydroxyl group, and the like are preferable, and a carbonyl group, a carboxyl group, and a hydroxyl group are particularly preferable.
- the functional group (functional group ⁇ ) is a functional group that can form a crosslinked structure (or bond) in combination with a functional group (functional group ⁇ ) (a monomer having a functional group ⁇ ) in an emulsion described later. There may be.
- a crosslinked structure (or bond) may be formed by a direct reaction between the functional group ⁇ and the functional group ⁇ .
- the functional group ⁇ and the functional group ⁇ are formed via a crosslinking agent.
- a crosslinked structure may be formed.
- Specific monomers having a functional group include, for example, carbonyl group-containing monomers, acid group-containing monomers (anionic group-containing monomers), hydroxyl group-containing monomers, and the like.
- Examples of the carbonyl group-containing monomer include unsaturated aldehydes [eg, alkenals (eg, C 3-10 alkenals such as acrolein, methacrolein), (meth) acryloxyalkyl alkenals (eg, acryloxyalkylpropenal).
- alkenals eg, C 3-10 alkenals such as acrolein, methacrolein
- acryloxyalkyl alkenals eg, acryloxyalkylpropenal
- Methacryloxyalkylpropenal Formylstyrene, etc.], unsaturated ketones (eg, alkenones (eg, methyl vinyl ketone, ethyl vinyl ketone, vinyl butyl ketone), (meth) acryloyloxyalkanones (eg, acetonyl acrylate) , Acetonyl methacrylate, etc.), N- (meth) acryloylaminoalkanone (eg, diacetone acrylamide, diacetone methacrylamide, etc.), alkanediol (meth) acrylate acetyl Acetoacetoxy (eg, C 2-6 alkanediol (meth) acrylate acetyl acetate such as 2-hydroxypropyl acrylate acetyl acetate, 2-hydroxypropyl methacrylate acetyl acetate, butanediol-1,4-acrylate acetyl
- Examples of the acid group-containing monomer include carboxylic acid group-containing monomers [for example, unsaturated monocarboxylic acids (for example, aliphatic acids such as acrylic acid, methacrylic acid, crotonic acid). Unsaturated monocarboxylic acid), unsaturated dicarboxylic acid (for example, aliphatic unsaturated monocarboxylic acid such as maleic acid and fumaric acid)], sulfonic acid group-containing monomer [for example, styrenic monomer (for example, Styrene sulfonic acid, etc.)] and the like.
- carboxylic acid group-containing monomers for example, unsaturated monocarboxylic acids (for example, aliphatic acids such as acrylic acid, methacrylic acid, crotonic acid). Unsaturated monocarboxylic acid), unsaturated dicarboxylic acid (for example, aliphatic unsaturated monocarboxylic acid such as maleic acid and fumaric acid)], sul
- the acid group-containing monomer may be anionized (or may form a salt or may be neutralized).
- the method for anionization is not particularly limited, and examples thereof include a method of reacting with a basic compound (neutralizing or forming a salt).
- the basic compound include inorganic bases ⁇ eg, hydroxide (eg, alkali metal or alkaline earth metal hydroxide such as sodium hydroxide), ammonia [eg, ammonia water (25% ammonia water, etc.)] Use] and the like, and organic bases [for example, amine (eg, monomethylamine, monoethanolamine, diethanolamine, dimethylethanolamine, isopropanolamine, etc.)] and the like. Two or more basic compounds may be used in combination.
- hydroxide eg, alkali metal or alkaline earth metal hydroxide such as sodium hydroxide
- ammonia eg, ammonia water (25% ammonia water, etc.
- organic bases for example, amine (eg,
- Examples of the oxazoline group-containing monomer include alkenyl oxazolines (for example, C 2-6 alkenyl oxazolines such as 2-vinyl-2-oxazoline and 2-isopropenyl-2-oxazoline, preferably vinyl or isopropenyl oxazoline), Alkenyl-alkyloxazolines (eg 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl- C 2-6 alkenyl-C 1-10 alkyl oxazoline such as 5-ethyl-2-oxazoline, preferably vinyl or isopropenyl-C 1-4 alkyl oxazoline) and the like.
- alkenyl oxazolines for example, C 2-6 alkenyl oxazolines such as 2-vinyl-2-oxazoline and 2-isopropenyl
- hydroxyl group-containing monomer examples include hydroxyalkyl (meth) acrylate [for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy Hydroxy C 2-10 alkyl (meth) acrylate such as butyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, preferably hydroxy C 2-6 alkyl (meth) acrylate, more preferably hydroxy C 2-4 alkyl ( (Meth) acrylates, etc.] (meth) acrylates of polyols having 3 or more hydroxyl groups [eg (meth) acrylates of tri to hexahydroxy C 3-10 polyols such as glycerol mono (meth) acrylate ] And other hydroxyl group-containing acrylic monomers (particularly hydroxyl group-containing (meth) acrylate).
- hydroxyalkyl (meth) acrylate for
- Monomers having a functional group may be used alone or in combination of two or more.
- unsaturated ketones unsaturated monocarboxylic acids (such as acrylic acid), and hydroxyl group-containing (meth) acrylates are preferred.
- diacetone from the point of being advantageous in coating film properties (water whitening resistance, etc.) Meth
- the monomer having a functional group may contain at least such a monomer (particularly diacetone (meth) acrylamide).
- the ratio of diacetone (meth) acrylamide to the whole monomer having a functional group is, for example, 10% by mass or more, preferably May be 20% by mass or more, more preferably 30% by mass or more.
- Monomers having a functional group may be used alone or in combination of two or more.
- the ratio of the monomer which has a functional group is 30 mass% or less (for example, 0.00%) with respect to the whole polymerization component (monomer component (b)).
- 001 to 25% by mass preferably 20% by mass or less (eg 0.01 to 15% by mass), more preferably 10% by mass or less (eg 0.05 to 8% by mass). It may be 0.05 to 10% by mass (for example, 0.1 to 5% by mass).
- the ratio of the monomer which has a functional group is 30 mol% or less (for example, 0.00%) with respect to the whole polymerization component (monomer component (b)).
- 001-25 mol%) preferably 20 mol% or less (eg, 0.01-15 mol%), more preferably 10 mol% or less (eg, 0.05-8 mol%). It may be 0.05 to 10 mol% (for example, 0.1 to 5 mol%).
- the proportion of the monomer having a functional group is, for example, 30 parts by mass or less (for example, 0.001 to 25 parts by mass) with respect to 100 parts by mass of the vinyl lactam monomer. ), Preferably 20 parts by mass or less (eg 0.01 to 15 parts by mass), more preferably 10 parts by mass or less (eg 0.05 to 8 parts by mass), and usually 0.05 to 10 parts by mass. It may be part by mass (for example, 0.1 to 5 parts by mass).
- the ratio of the monomer having a functional group is, for example, 30 mol or less (for example, 0.001 to 25 mol) with respect to 100 mol of the vinyl lactam monomer, It may be preferably 20 mol or less (for example, 0.01 to 15 mol), more preferably 10 mol or less (for example, 0.05 to 8 mol), and usually 0.05 to 10 mol (for example, 0.1 mol). 1-5 moles).
- the polymerization component may contain other monomers as long as the effects of the present invention are not impaired.
- examples of other monomers include the monomers exemplified in the monomer component (a) described later (for example, alkyl (meth) acrylates, aromatic monomers, silicon atom-containing monomers, fluorine atoms). Containing monomer, epoxy group-containing monomer, UV-absorbing monomer, etc.), but not particularly limited.
- the proportion of the other monomer in the polymerization component (monomer component (b)) is, for example, 20% by mass or less (for example, 0.01 To 18% by mass), preferably 15% by mass or less (for example, 0.1 to 12% by mass), and more preferably 10% by mass or less (for example, 0.3 to 5% by mass).
- the proportion of the other monomer in the polymerization component (monomer component (b)) is, for example, 20 mol% or less (for example, 0.01 To 18 mol%), preferably 15 mol% or less (for example, 0.1 to 12 mol%), and more preferably 10 mol% or less (for example, 0.3 to 5 mol%).
- the copolymerization mode of the polymer of the present invention may be any of random copolymer, block copolymer, graft copolymer and the like.
- the weight average molecular weight of the polymer of the present invention can be appropriately selected depending on the kind of the monomer and is not particularly limited. However, from the viewpoint of the physical properties of the coating film, for example, 1,000 to 3,000,000, more preferably 3,000 to 1,000,000, Preferably, it may be 5,000 to 500,000, particularly 7,000 to 300,000, particularly preferably 10,000 to 250,000.
- the polymer of the present invention has a relatively high molecular weight [eg, weight average molecular weight of 50,000 or more (eg, 550,000 to 500,000), preferably 60,000 or more (eg, 650,000 to 300,000), More preferably, it may be 70,000 or more (for example, 75,000 to 200,000), particularly 80,000 or more (for example, 850,000 to 180,000), and usually 50,000 to 250,000].
- the molecular weight distribution (the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn) of the polymer of the present invention is, for example, 25 or less (for example, 1.5 to 25), preferably 20 or less (for example, 2.0 to 2.0).
- a polymer having a relatively narrow molecular weight distribution may be suitably used.
- the weight average molecular weight is, for example, gel permeation chromatography (for example, manufactured by Nippon Waters Co., Ltd., product number: E-2695, column: TSKgel ⁇ -M and TSKgel ⁇ -M used in series). It may be a weight average molecular weight (in terms of polyethylene oxide) that can be used and measured.
- the polymer of the present invention may usually be water-soluble.
- the polymer of the present invention may be basic.
- the polymer of the present invention can be obtained by polymerizing a polymerization component (monomer component (b)).
- a polymerization method for example, a conventional polymerization method such as a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, or a precipitation polymerization method can be used.
- the solution polymerization method is preferable, and the solution polymerization method using water as a solvent is more preferable.
- a solvent When preparing by solution polymerization method, a solvent is used.
- the solvent include water, alcohol, ether, ketone, ester, amide, sulfoxide, hydrocarbon compound, and the like, but the present invention is not limited to such examples.
- Suitable solvents include, for example, water, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, tert-butyl alcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, acetone, methyl ethyl ketone, tetrahydrofuran, 1,4-dioxane, 1 , 3-dioxolane, toluene, ethyl acetate and the like, but the present invention is not limited to such examples.
- These solvents may be used alone or in combination of two or more.
- the solvent may contain an appropriate amount of an organic amine compound, ammonia, an alkali metal hydroxide, or the like, if necessary.
- the polymerization temperature for preparing the polymer is not particularly limited, but may be, for example, about 0 to 100 ° C., preferably 30 to 95 ° C., and more preferably about 50 to 90 ° C.
- the pressure during the polymerization reaction may be normal pressure, reduced pressure, or increased pressure.
- the atmosphere during the polymerization reaction is preferably an inert gas such as nitrogen gas, argon gas or carbon dioxide gas.
- a polymerization initiator can be used.
- the polymerization initiator include persulfates (eg, ammonium persulfate, sodium persulfate, potassium persulfate, etc.), hydrogen peroxide, organic peroxides, azo compounds [eg, 2,2′-azobis (2- Methyl propionamidine) dihydrochloride, etc.].
- the polymerization initiators may be used alone or in combination of two or more.
- the amount of the polymerization initiator per 100 parts by mass of the polymerization component (monomer component (b)) used for the polymerization is not particularly limited, but may be, for example, about 0.01 to 10 parts by mass.
- the polymerization initiator may be charged all at once at the start of the polymerization reaction, or may be sequentially added during the polymerization reaction.
- the polymerization initiator can be used in combination with an appropriate amount of a reducing agent.
- a reducing agent include iron (II) salt, sodium dithionite, sodium hydrogen sulfite, sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, etc., but the present invention is only such examples. It is not limited to.
- the polymer of the present invention has hydrophilicity (particularly water solubility) and can be suitably used as a hydrophilic material (hydrophilizing agent).
- a composition useful for forming a hydrophilic coating film can be formed by combining with an emulsion.
- emulsion (A) emulsion (A)
- polymer (B) polymer of the present invention
- the resin (polymer, polymer) constituting the emulsion (A) is not particularly limited, and examples thereof include addition polymerization resins [for example, acrylic resins, vinyl alcohol resins (for example, polyvinyl resins). Alcohol, etc.), fluorine resin, etc.], condensation resin [eg, polyamide resin, polyester resin, polyurethane resin, etc.], heat or photocurable resin (eg, alkyd resin, epoxy resin, etc.), etc. .
- addition polymerization resins for example, acrylic resins, vinyl alcohol resins (for example, polyvinyl resins). Alcohol, etc.), fluorine resin, etc.]
- condensation resin eg, polyamide resin, polyester resin, polyurethane resin, etc.
- heat or photocurable resin eg, alkyd resin, epoxy resin, etc.
- emulsion particles These resins (polymer, polymer) may be used alone or in combination of two or more to constitute the emulsion (A). Moreover, an emulsion (A) may be used independently or may combine 2 or more types of emulsion. In addition, emulsion (A) (or resin which comprises an emulsion) is a particulate form normally. Therefore, the emulsion can also be called emulsion particles.
- the resin (polymer, polymer) usually has the monomer component (a) as a polymerization component.
- the monomer component (a) may be usually an addition polymerizable monomer (or a radical polymerizable monomer, a monomer having an ethylenically unsaturated bond, etc.).
- Examples of the monomer component (a) include aliphatic (meth) acrylates, alicyclic monomers (monomers having an alicyclic structure), hydroxyl group-containing (meth) acrylates, aromatic monomers, Acid group-containing monomer (or anionic group-containing monomer), silicon atom-containing monomer, fluorine atom-containing monomer, nitrogen atom-containing monomer, epoxy group-containing monomer, UV-absorbing monomer And hindered amine monomers (ultraviolet stable monomers).
- Monomer component (a) may be used alone or in combination of two or more.
- the emulsion (A) is an acrylic (acrylic resin) emulsion, for example, as a monomer component (a) from the viewpoint of physical properties of the coating film, for example, at least aliphatic (meth) acrylate (particularly alkyl (meth) acrylate). ) Containing a resin emulsion.
- Typical acrylic emulsions include emulsions of resins containing at least an alkyl (meth) acrylate and a monomer having an alicyclic structure, preferably at least an alkyl (meth) acrylate and a single amount having an alicyclic structure And an emulsion of a resin containing a hydroxyl group-containing (meth) acrylate, more preferably at least an alkyl (meth) acrylate, a monomer having an alicyclic structure, a hydroxyl group-containing (meth) acrylate and an aromatic monomer An emulsion of a resin containing
- alkyl (meth) acrylate [for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) ) Acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, sec-butyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) ) Acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, n-lauryl (meth)
- alkyl (meth) acrylate 1-20 alkyl (meth) acrylate], alkoxyalkyl (meth) acrylate [eg, alkoxyalkyl (meth) acrylate (eg, C 1-12 alkoxy C 1-12 alkyl methacrylate of 2-methoxyethyl (meth) acrylate, etc.) Etc.].
- alkoxyalkyl (meth) acrylate eg, C 1-12 alkoxy C 1-12 alkyl methacrylate of 2-methoxyethyl (meth) acrylate, etc.
- Aliphatic (meth) acrylates may be used alone or in combination of two or more.
- C 1-12 alkyl (meth) such as methyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc.
- Acrylates eg, C 1-8 alkyl (meth) acrylate are preferred.
- the content (content) of the aliphatic (meth) acrylate in the monomer component (a) is, for example, 10 to 90% by mass,
- the amount may be preferably 20 to 90% by mass, more preferably 25 to 80% by mass, and particularly preferably about 30 to 80% by mass.
- Examples of the monomer having an alicyclic structure include monomers having an alicyclic structure (for example, a cycloalkyl group having 4 to 20 carbon atoms, preferably a cycloalkyl group having 4 to 10 carbon atoms).
- Specific examples of the monomer having an alicyclic structure include, for example, alicyclic (meth) acrylate [for example, C 4-20 cycloalkyl (meth) acrylate such as cycloalkyl (meth) acrylate (for example, cyclohexyl (meth) acrylate).
- cycloalkyl (meth) acrylate preferably C 4-10 cycloalkyl (meth) acrylate), cycloalkylalkyl (meth) acrylate (eg, cyclohexylmethyl (meth) acrylate, cyclohexylethyl (meth) acrylate, cyclohexylpropyl (meth) acrylate, 4- C 4-10 cycloalkyl C 1-4 alkyl (meth) acrylates such as methylcyclohexylmethyl (meth) acrylate), bridged cyclic (meth) acrylates (eg isobornyl (meth) acrylate, adamantyl (meth)) Acrylate etc.)] and the like.
- cycloalkylalkyl (meth) acrylate eg, cyclohexylmethyl (meth) acrylate, cyclohexylethyl (meth) acrylate, cycl
- the monomer having an alicyclic structure is a substituent (for example, alkyl group such as methyl group, tert-butyl group, nitro group, nitrile group, alkoxyl group, acyl group, sulfone group, hydroxyl group, halogen atom, etc. ).
- substituent for example, alkyl group such as methyl group, tert-butyl group, nitro group, nitrile group, alkoxyl group, acyl group, sulfone group, hydroxyl group, halogen atom, etc.
- Monomers having an alicyclic structure may be used alone or in combination of two or more.
- C 4-20 cycloalkyl (meth) acrylate is preferable, C 4-10 cycloalkyl (meth) acrylate is more preferable, and isobornyl (meth) acrylate and cyclohexyl (meth) acrylate are preferable. Further preferred.
- the content (content) of the monomer having an alicyclic structure in the monomer component (a) is, for example, 5 to It may be about 80% by mass, preferably 10 to 70% by mass, more preferably 15 to 65% by mass, particularly preferably about 20 to 60% by mass.
- the monomer component (a) contains an aliphatic (meth) acrylate and a monomer having an alicyclic structure
- these ratios are the monomer having an aliphatic (meth) acrylate / alicyclic structure.
- Mass ratio 95/5 to 5/95 (for example, 90/10 to 10/90), preferably 80/20 to 20/80, more preferably about 80/20 to 40/60. .
- the aliphatic (meth) acrylate and alicyclic structure in the monomer component (a) contains an aliphatic (meth) acrylate and a monomer having an alicyclic structure
- the aliphatic (meth) acrylate and alicyclic structure in the monomer component (a) The ratio of the total amount of the monomers having is, for example, 10% by mass or more (for example, 15 to 99.5% by mass), preferably 20% by mass or more (for example, 25 to 99% by mass), and more preferably 30% by mass. It may be about (for example, 40 to 98% by mass), particularly preferably about 50% by mass or more (for example, 60 to 97% by mass), and usually 70% by mass or more (for example, 75 to 95% by mass). May be.
- hydroxyl group-containing (meth) acrylate examples include hydroxyalkyl (meth) acrylate [for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy Hydroxy C 2-10 alkyl (meth) acrylate such as butyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, preferably C 2-6 alkyl (meth) acrylate, more preferably C 2-4 alkyl (meth) Acrylates, etc.] (meth) acrylates of polyols having 3 or more hydroxyl groups [for example, (meth) acrylates of tri to hexahydroxy C 3-10 polyols such as glycerol mono (meth) acrylate] and the like. It is.
- hydroxyalkyl (meth) acrylate for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropy
- the hydroxyl group-containing (meth) acrylate may be used alone or in combination of two or more.
- hydroxyl group-containing (meth) acrylates 2-hydroxyethyl (meth) acrylate and glycerol mono (meth) acrylate are preferable, and 2-hydroxyethyl (meth) acrylate is more preferable.
- the content ratio (content ratio) of the hydroxyl group-containing (meth) acrylate in the monomer component (a) is, for example, 0.1 to 20 mass. %, Preferably 0.3 to 10% by mass, more preferably 0.5 to 8% by mass, and particularly preferably about 1 to 5% by mass.
- the content ratio of the hydroxyl group-containing (meth) acrylate ( Content) is, for example, 0.1 to 20 parts by weight, preferably 0.3 to 15 parts by weight, based on 100 parts by weight of the monomer having an aliphatic (meth) acrylate and / or alicyclic structure, Preferably it may be about 0.5 to 10 parts by mass, particularly preferably about 1 to 8 parts by mass.
- aromatic monomers examples include styrene monomers [eg, styrene, ⁇ -alkyl styrene (eg, ⁇ -C 1-4 alkyl styrene such as ⁇ -methyl styrene), alkyl styrene (eg, vinyl toluene, etc.
- C 1-4 alkyl styrene C 1-4 alkyl styrene
- halostyrene eg, chlorostyrene, etc.
- aromatic (meth) acrylate eg, aryl (meth) acrylate (eg, C 6-10 aryl (eg, phenyl (meth) acrylate) ( (Meth) acrylates), aralkyl (meth) acrylates (eg C 6-10 aryl C 1-4 alkyl (meth) acrylates such as benzyl (meth) acrylate, phenethyl (meth) acrylate), aryloxyalkyl methacrylates (eg phenoxy) Ethyl methacrylate Over C 6-10 aryloxy C 1-4 alkyl methacrylates) such as such as preparative] and the like.
- aryl (meth) acrylate eg, C 6-10 aryl (eg, phenyl (meth
- the aromatic monomers may be used alone or in combination of two or more.
- the content (content) of the aromatic monomer in the monomer component (a) is, for example, 0.1 to 30 mass. %, Preferably 0.5 to 20% by mass, more preferably about 1 to 15% by mass.
- acid group-containing monomer examples include the above-exemplified monomers, for example, carboxylic acid group-containing monomers [for example, unsaturated monocarboxylic acids (for example, acrylic acid, methacrylic acid). , Aliphatic unsaturated monocarboxylic acids such as crotonic acid), unsaturated dicarboxylic acids (eg, aliphatic unsaturated monocarboxylic acids such as maleic acid and fumaric acid)], sulfonic acid group-containing monomers [eg, styrene Based monomers (for example, styrenesulfonic acid, etc.)] and the like.
- the acid group-containing monomer may be anionized (or may form a salt).
- the acid group-containing monomers may be used alone or in combination of two or more.
- Typical acid group-containing monomers include acrylic acid and methacrylic acid.
- the content ratio (content ratio) of the acid group-containing monomer in the monomer component (a) is For example, it may be about 0.01 to 10% by mass, preferably about 0.02 to 5% by mass, and more preferably about 0.05 to 3% by mass.
- silicon atom-containing monomer examples include vinyl group-containing silane [eg, vinyl group-containing halosilane (eg, vinyl mono to trihalosilane such as vinyltrichlorosilane), vinyl group-containing alkoxysilane [vinyl alkoxysilane (eg, Vinyl mono to trialkoxy silanes such as vinyl trimethoxy silane and vinyl triethoxy silane, preferably vinyl mono to tri C 1-4 alkoxy silanes), vinyl alkoxy alkoxy silanes (eg vinyl mono to tris ( ⁇ -methoxyethoxy) silane etc.
- vinyl group-containing silane eg, vinyl group-containing halosilane (eg, vinyl mono to trihalosilane such as vinyltrichlorosilane), vinyl group-containing alkoxysilane [vinyl alkoxysilane (eg, Vinyl mono to trialkoxy silanes such as vinyl trimethoxy silane and vinyl triethoxy silane, preferably vinyl mono to tri C 1-4 alk
- alkoxysilane having a (meth) acryloyl group eg, ⁇ - (meth) acryloyl) (Meth) acrylo
- the silicon atom-containing monomers may be used alone or in combination of two or more.
- Typical silicon atom-containing monomers include alkoxysilanes having a (meth) acryloyl group such as ⁇ - (meth) acryloyloxypropyltrimethoxysilane.
- the content ratio (content ratio) of the silicon atom-containing monomer in the monomer component (a) is, for example, 0.01 to 10 mass. %, Preferably 0.02 to 5% by mass, more preferably about 0.03 to 3% by mass.
- fluorine atom-containing monomer examples include fluorine atom-containing acrylic monomers [for example, fluoroalkyl (meth) acrylate (for example, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, octafluoropentyl).
- fluorine atom-containing acrylic monomers for example, fluoroalkyl (meth) acrylate (for example, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, octafluoropentyl).
- fluoroalkyl C 1-10 alkyl (meth) acrylates such as acrylates, preferably such as fluoro C 2-6 alkyl (meth) acrylate
- Fluorine atom-containing monomers may be used alone or in combination of two or more.
- the content ratio (content ratio) of the fluorine atom-containing monomer in the monomer component (a) is, for example, 0.01 to 10 mass. %, Preferably 0.02 to 5% by mass, more preferably about 0.03 to 3% by mass.
- nitrogen atom-containing monomer examples include (meth) acrylamide compounds ⁇ for example, (meth) acrylamide, N-substituted (meth) acrylamide [for example, N-alkyl (meth) acrylamide (for example, N, N-dimethyl).
- N, N-diC 1-4 alkyl (meth) acrylamide such as (meth) acrylamide; N, N-dimethylaminopropyl (meth) acrylamide, etc.), etc.
- nitrogen atom-containing (meth) acrylate compounds ⁇ for example, N-substituted aminoalkyl (meth) acrylate [for example, N, N-diC 1-4 alkylamino C 2-4 alkyl (meth) acrylate such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate], etc. ⁇ .
- the nitrogen atom-containing monomers may be used alone or in combination of two or more.
- the content ratio (content ratio) of the nitrogen atom-containing monomer in the monomer component (a) is, for example, 0.01 to 10 mass. %, Preferably 0.02 to 5% by mass, more preferably about 0.03 to 3% by mass.
- epoxy group-containing monomer examples include epoxy group-containing (meth) acrylate [for example, glycidyloxy such as glycidyl (meth) acrylate, glycidyloxyalkyl (meth) acrylate (for example, 2-glycidyloxyethyl (meth) acrylate), etc. C 2-4 alkyl (meth) acrylate)], and allyl glycidyl ether.
- epoxy group-containing (meth) acrylate for example, glycidyloxy such as glycidyl (meth) acrylate, glycidyloxyalkyl (meth) acrylate (for example, 2-glycidyloxyethyl (meth) acrylate), etc. C 2-4 alkyl (meth) acrylate)
- allyl glycidyl ether examples include epoxy group-containing (meth) acrylate [for example, glycidyloxy such as glycid
- the epoxy group-containing monomers may be used alone or in combination of two or more.
- the content ratio (content ratio) of the epoxy group-containing monomer in the monomer component (a) is, for example, 0.01 to 10 mass. %, Preferably 0.02 to 5% by mass, more preferably about 0.03 to 3% by mass.
- UV absorbing monomer examples include a benzotriazole ultraviolet absorbing monomer and a benzophenone ultraviolet absorbing monomer.
- benzotriazole-based UV-absorbing monomer examples include benzotriazole-based UV absorbers having a polymerizable group (for example, (meth) acryloyl group), such as 2- [2′-hydroxy-5 ′-(meth) acryloyl Oxymethylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-5 '-(meth) acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-(meth) acryloyl Oxymethylphenyl] -5-tert-butyl-2H-benzotriazole, 2- [2'-hydroxy-5 '-(meth) acryloylaminomethyl-5'-tert-octylphenyl] -2H-benzotriazole, 2 -[2'-hydroxy-5 '-(meth) acryloyloxypropylphenyl] 2H-benzotriazole, 2- [
- benzophenone-based UV-absorbing monomer examples include benzophenone-based UV absorbers having a polymerizable group (for example, (meth) acryloyl group), such as 2-hydroxy-4- (meth) acryloyloxybenzophenone, 2-hydroxy- 4- [2-hydroxy-3- (meth) acryloyloxy] propoxybenzophenone, 2-hydroxy-4- [2- (meth) acryloyloxy] ethoxybenzophenone, 2-hydroxy-4- [3- (meth) acryloyloxy -2-hydroxypropoxy] benzophenone, 2-hydroxy-3-tert-butyl-4- [2- (meth) acryloyloxy] butoxybenzophenone, and the like.
- a polymerizable group for example, (meth) acryloyl group
- 2-hydroxy-4- (meth) acryloyloxybenzophenone 2-hydroxy- 4- [2-hydroxy-3- (meth) acryloyloxy] propoxybenzophenone
- the ultraviolet absorbing monomers may be used alone or in combination of two or more.
- the content (content) of the ultraviolet absorbing monomer in the monomer component (a) is, for example, 0.01 to 10 mass. %, Preferably 0.02 to 5% by mass, more preferably about 0.03 to 3% by mass.
- hindered amine monomers examples include the hindered amine monomers exemplified above, such as 4- (meth) acryloyloxy-2.
- the hindered amine monomers may be used alone or in combination of two or more.
- the content (content) of the hindered amine monomer in the monomer component (a) is, for example, 0.01 to 20% by mass, preferably 0.8. It may be about 05 to 10% by mass, more preferably about 0.1 to 5% by mass.
- the monomer component (a) may contain a monomer having a functional group (referred to as a functional group ⁇ ). Since the resin in the emulsion (A) has a structural unit derived from a monomer having such a functional group ⁇ , an emulsion (by the functional group ⁇ described later) can be selected by selecting a functional group (functional group ⁇ described later). A bond between A) and polymer (B) can be formed efficiently. Such bond formation is a preferable form because it can suppress the outflow of the polymer (B) from the surface of the coating film and also improves the water resistance and the elastic modulus of the coating film.
- the affinity with the polymer (B) can be improved by the functional group ⁇ , the polymer (B) is more efficiently adsorbed to the coating film, and it is easy to improve long-term contamination resistance.
- the same functional group as the functional group ⁇ (functional group exemplified in the polymer (B)), for example, a carbonyl group (or a carbonyl group-containing group such as a ketone group, an aldehyde group, an acyl group, etc.), Acid group or anionic group (for example, carboxyl group, acid anhydride group, acid halide group, sulfonic acid group, etc.), carbonate group, isocyanate group, oxazoline group, oxazolidine group, hydrazino group, epoxy group, amino group, hydroxyl group And a mercapto group.
- the functional group ⁇ may be selected in combination with the functional group ⁇ .
- the monomer having the functional group ⁇ may have these functional groups alone or in combination of two or more.
- a carbonyl group, an acid group (anionic group), an oxazoline group, a hydrazino group, a hydroxyl group, and the like are preferable from the viewpoint of physical properties of the coating film, and a carbonyl group and a carboxyl group are particularly preferable.
- Specific monomers having a functional group include, for example, carbonyl group-containing monomers, acid group-containing monomers (anionic group-containing monomers), hydroxyl group-containing monomers, and the like.
- Examples of the carbonyl group-containing monomer include unsaturated aldehydes [eg, alkenals (eg, C 3-10 alkenals such as acrolein, methacrolein), (meth) acryloxyalkyl alkenals (eg, acryloxyalkylpropenal).
- alkenals eg, C 3-10 alkenals such as acrolein, methacrolein
- acryloxyalkyl alkenals eg, acryloxyalkylpropenal
- Methacryloxyalkylpropenal Formylstyrene, etc.], unsaturated ketones (eg, alkenones (eg, methyl vinyl ketone, ethyl vinyl ketone, vinyl butyl ketone), (meth) acryloyloxyalkanones (eg, acetonyl acrylate) , Acetonyl methacrylate, etc.), N- (meth) acryloylaminoalkanone (eg, diacetone acrylamide, diacetone methacrylamide, etc.), alkanediol (meth) acrylate acetyl Acetoacetoxy (eg, C 2-6 alkanediol (meth) acrylate acetyl acetate such as 2-hydroxypropyl acrylate acetyl acetate, 2-hydroxypropyl methacrylate acetyl acetate, butanediol-1,4-acrylate acetyl
- Examples of the acid group-containing monomer include the above-exemplified monomers, for example, carboxylic acid group-containing monomers [for example, unsaturated monocarboxylic acids (for example, acrylic acid, methacrylic acid). , Aliphatic unsaturated monocarboxylic acids such as crotonic acid), unsaturated dicarboxylic acids (eg, aliphatic unsaturated monocarboxylic acids such as maleic acid and fumaric acid)], sulfonic acid group-containing monomers [eg, styrene Based monomers (for example, styrenesulfonic acid, etc.)] and the like.
- carboxylic acid group-containing monomers for example, unsaturated monocarboxylic acids (for example, acrylic acid, methacrylic acid).
- Aliphatic unsaturated monocarboxylic acids such as crotonic acid
- unsaturated dicarboxylic acids eg, aliphatic unsaturated monocarboxylic acids such as maleic
- the acid group-containing monomer may be anionized (or may form a salt or be neutralized).
- the method for anionization is not particularly limited.
- the basic compound includes, for example, an inorganic base ⁇ for example, hydroxide (for example, alkali metal or alkaline earth metal hydroxide such as sodium hydroxide), Ammonia [for example, aqueous ammonia (used as 25% aqueous ammonia, etc.), etc.], organic base [eg, amine (eg, monomethylamine, monoethanolamine, diethanolamine, dimethylethanolamine, isopropanolamine, etc.), etc.] be able to. Two or more basic compounds may be used in combination.
- an inorganic base for example, hydroxide (for example, alkali metal or alkaline earth metal hydroxide such as sodium hydroxide), Ammonia [for example, aqueous ammonia (used as 25% aqueous ammonia, etc.), etc.]
- organic base eg, amine
- Examples of the oxazoline group-containing monomer include alkenyl oxazolines (for example, C 2-6 alkenyl oxazolines such as 2-vinyl-2-oxazoline and 2-isopropenyl-2-oxazoline, preferably vinyl or isopropenyl oxazoline), Alkenyl-alkyloxazolines (eg 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl- C 2-6 alkenyl-C 1-10 alkyl oxazoline such as 5-ethyl-2-oxazoline, preferably vinyl or isopropenyl-C 1-4 alkyl oxazoline) and the like.
- alkenyl oxazolines for example, C 2-6 alkenyl oxazolines such as 2-vinyl-2-oxazoline and 2-isopropenyl
- hydroxyl group-containing monomer examples include the monomers exemplified above (for example, hydroxyl group-containing (meth) acrylate).
- Monomers having a functional group ⁇ may be used alone or in combination of two or more.
- the monomer having the functional group ⁇ may contain at least such a monomer (particularly diacetone (meth) acrylamide).
- acid group-containing monomers such as (meth) acrylic acid are also preferable.
- the ratio of diacetone (meth) acrylamide to the whole monomer having the functional group ⁇ is, for example, 10% by mass or more. , Preferably 20% by mass or more, more preferably 30% by mass or more.
- the ratio of the acid group-containing monomer to the whole monomer having the functional group ⁇ is, for example, 10% by mass or more. , Preferably 20% by mass or more, more preferably 30% by mass or more.
- Monomers having a functional group ⁇ may be used alone or in combination of two or more.
- the content (content) of the monomer having a functional group ⁇ in the monomer component (a) is 30% by mass or less.
- 20% by mass or less can be selected from a range, for example, 0.01 to 10% by mass, preferably 0.02 to 5% by mass, more preferably about 0.05 to 3% by mass.
- the content ratio (content ratio) of the acid group-containing monomer in the monomer component (a) is 0.01 mass. % Or more (for example, 0.01 to 3% by mass), preferably 0.1% by mass or more (for example, 0.1 to 2% by mass), more preferably 0.3% by mass or more (for example, 0.3 to 3% by mass). 1.5% by mass).
- the monomer component (a) contains an aliphatic (meth) acrylate and / or a monomer having an alicyclic structure and a monomer having a functional group ⁇
- the monomer having the functional group ⁇ is, for example, 10 parts by mass or less (for example, 0.01 to 10 parts by mass) with respect to 100 parts by mass of the monomer having an aliphatic (meth) acrylate and / or an alicyclic structure. ), Preferably 5 parts by mass or less (eg, 0.2 to 5 parts by mass), more preferably about 3 parts by mass or less (eg, 0.3 to 3 parts by mass), particularly 2 parts by mass or less. (For example, 0.05 to 1.5 parts by mass).
- the emulsion (A) is a resin (particle) in an emulsion state, for example, a resin (resin particle) having the monomer component (a) as a polymerization component (or the resin (or resin particle) dispersed in a solvent). ). Therefore, the emulsion (A) may be composed of a resin (particles) and an emulsifier (emulsifier that coats the resin particles).
- Such an emulsion (A) may be usually obtained by emulsion polymerization of the monomer component (a) in a solvent.
- the solvent usually include aqueous solvents such as water and water-containing solvents [such as a mixed solvent of water and alcohol (such as C 1-4 alcohol such as methanol and ethanol)].
- aqueous solvents such as water and water-containing solvents [such as a mixed solvent of water and alcohol (such as C 1-4 alcohol such as methanol and ethanol)].
- the monomer component (a) As a method for emulsion polymerization of the monomer component (a), for example, the monomer component (a) (and the polymerization initiator) is mixed in a solvent (solution) containing an emulsifier (dispersant, surfactant) ( And a method of polymerizing by mixing (e.g., dropping) the monomer component (a) emulsified in advance with a solvent, but the present invention is limited only to such a method. Is not to be done.
- emulsifiers examples include anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers (for example, alkylammonium salts such as decylammonium chloride), amphoteric emulsifiers (for example, betaine ester type emulsifiers), and the like. Can be mentioned.
- anionic emulsifier examples include alkyl sulfate salts such as ammonium dodecyl sulfate and sodium dodecyl sulfate; alkyl sulfonate salts such as ammonium dodecyl sulfonate and sodium dodecyl sulfonate; alkyl aryl sulfonate salts such as ammonium dodecyl benzene sulfonate and sodium dodecyl naphthalene sulfonate; Examples include polyoxyethylene alkyl sulfate salts; polyoxyethylene alkyl aryl sulfate salts; dialkyl sulfosuccinates; aryl sulfonic acid-formalin condensates; fatty acid salts such as ammonium laurate and sodium stearate.
- alkyl sulfate salts such as ammonium dodecyl sulfate and
- Nonionic emulsifiers include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, condensate of polyethylene glycol and polypropylene glycol, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid monoglyceride, ethylene oxide and aliphatic Examples thereof include condensates with amines.
- the emulsifier includes a polymer emulsifier.
- the polymer emulsifier include anionic emulsifiers (poly (meth) acrylates such as sodium polyacrylate) and nonionic emulsifiers (polyhydroxyalkyl (meth) acrylates such as polyvinyl alcohol, polyvinyl pyrrolidone, and polyhydroxyethyl acrylate). ), Polymers having one or more monomers among these monomers as a copolymerization component.
- an emulsifier having a reactive group that is, a so-called reactive emulsifier may be suitably used.
- reactive emulsifiers non-nonylphenyl emulsifiers may be suitably used, particularly from the viewpoint of environmental protection.
- the reactive emulsifier examples include an anionic emulsifier [for example, propenyl-alkylsulfosuccinate ester salt, (meth) acrylic acid polyoxyethylene sulfonate salt, (meth) acrylic acid polyoxyethylene phosphonate salt [for example, Sanyo Kasei Co., Ltd.] Manufactured by Kogyo Co., Ltd., trade name: Eleminol RS-30, etc.], polyoxyethylene alkyl propenyl phenyl ether sulfonate salt (for example, trade name: Aqualon HS-10, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), allyloxymethyl Sulfonate salt of alkyloxypolyoxyethylene [for example, product name: Aqualon KH-10 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], sulfonate salt of allyloxymethylnonylphenoxyethylhydroxypolyoxy
- Emulsifiers may be used alone or in combination of two or more.
- anionic emulsifiers particularly anionic reactive emulsifiers
- anionic emulsifiers functions in the same manner as the acid group-containing monomer, and easily improves the affinity with the polymer (B). Therefore, the polymer (B) is more efficiently adsorbed to the coating film. Easy to improve long-term pollution resistance.
- the amount of the emulsifier per 100 parts by mass of the monomer component (a) is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more from the viewpoint of polymerization stability, etc. Therefore, it may be 10 parts by mass or less, more preferably 7 parts by mass or less, and still more preferably 5 parts by mass or less.
- the polymerization may be usually performed in the presence of a polymerization initiator.
- a polymerization initiator examples include azobisisobutyronitrile, 2,2-azobis (2-methylbutyronitrile), 2,2-azobis (2,4-dimethylvaleronitrile), 2,2-azobis ( Azo compounds such as 2-diaminopropane) hydrochloride, 4,4-azobis (4-cyananovaleric acid), 2,2-azobis (2-methylpropionamidine); persulfates such as potassium persulfate; Examples thereof include hydrogen, peroxides such as benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, and ammonium peroxide.
- the amount of the polymerization initiator per 100 parts by mass of the monomer component (a) is preferably 0.05 parts by mass or more from the viewpoint of increasing the polymerization rate and reducing the residual amount of the unreacted monomer component. More preferably, it is 0.1 part by mass or more, and from the viewpoint of physical properties of the coating film, it is preferably 1 part by mass or less, more preferably 0.5 part by mass or less.
- the method for adding the polymerization initiator is not particularly limited. Examples of the addition method include batch charging, divided charging, and continuous dripping. Further, from the viewpoint of accelerating the completion time of the polymerization reaction, a part of the polymerization initiator may be added to the reaction vessel before or after the monomer component (a) is added to the reaction system. Good.
- a reducing agent such as sodium bisulfite and a polymerization initiator decomposition agent such as transition metal salt such as ferrous sulfate are added in an appropriate amount to the reaction system. Also good.
- additives such as a chain transfer agent such as a compound having a thiol group (such as tert-dodecyl mercaptan), a pH buffering agent, a chelating agent, and a film forming aid may be present as necessary. Also good.
- the amount of the additive per 100 parts by mass of the monomer component (a) varies depending on the type of the monomer component (a) and cannot be determined unconditionally. For example, it is 0.01 to 5 parts by mass, preferably 0.1 to 3 parts. A mass part may be sufficient.
- the atmosphere for emulsion polymerization of the monomer component (a) is not particularly limited, but may be an inert gas such as nitrogen gas from the viewpoint of polymerization efficiency.
- the polymerization temperature for emulsion polymerization of the monomer component (a) is not particularly limited, but may be, for example, 50 to 100 ° C., preferably 60 to 95 ° C.
- the polymerization temperature may be constant or may be changed during the polymerization reaction.
- the polymerization time for emulsion polymerization of the monomer component (a) is not particularly limited and may be appropriately set according to the progress of the polymerization reaction, but is usually 1 hour or longer (eg, 1 to 24 hours), preferably May be about 2 to 12 hours (eg, 2 to 9 hours).
- the emulsion (A) may have a single-layer structure (consisting of only one layer) or a multilayer structure (or core-shell structure) (even if the inner layer is configured, the outer layer (outermost layer) ) And an inner layer).
- a multilayer structure (core-shell structure) may be advantageous in terms of physical properties of the coating film.
- the number of layers may be 2 or more, for example, 2 to 6, preferably 2 to 5, more preferably 2 to 4 (eg 2 to 3). In particular, it may be 3.
- the outer layer (shell) and the inner layer (core) are different resins as long as they are composed of the resin having the monomer component (a) exemplified above as a polymerization component. Also good.
- the multilayer structure may be composed (relatively composed) of a hard layer (hard layer) and a soft layer (soft layer).
- a hard layer hard layer
- a soft layer soft layer
- the inner layer is composed of a plurality of layers
- a hard layer and a soft layer may be configured between the plurality of inner layers.
- the emulsion (A) having a multilayer structure is composed of the polymer of the monomer component (a) containing a monomer having a functional group ⁇ , usually a single amount containing a monomer having a functional group ⁇
- the polymer of the body component (a) usually constitutes at least the outer layer, and may constitute the outer layer and the inner layer.
- each layer may be independently composed of a resin having the monomer component (a) as a polymerization component, and the composition of the resin in each layer is the same as described above. You can choose from a range of
- the content of the alkyl (meth) acrylate is preferably 5 to 25% by mass, more preferably 10 to 20% by mass, and the content of the alicyclic structure-containing monomer is preferably 55 to 80% by mass, more preferably 60 to 75% by mass, and hydroxyl group-containing
- the content of (meth) acrylate is preferably 0.5 to 5% by mass, more preferably 1 to 3% by mass, and the content of aromatic monomer is preferably 0 to 20% by mass, more
- the content of the silicon atom-containing monomer is preferably 5 to 15% by mass, preferably 0 to 5% by mass, more preferably 1 to 3% by mass, and the content of the carboxyl group-containing monomer is , Preferably 0-5% by mass
- the content of the UV-stable monomer is preferably 0 to 5%
- the solubility parameter (SP value) of the resin constituting the outer layer is preferably higher than the SP value of the resin constituting the inner layer from the viewpoint of improving the flexibility and film-forming property of the coating film. Moreover, it is preferable that the difference (absolute value) between the SP value of the resin constituting the inner layer and the SP value of the resin constituting the outer layer is large from the viewpoint of forming a layer separation structure in the emulsion.
- the SP value is a value defined by the regular solution theory introduced by Hildebrand, and is also a measure of the solubility of the binary solution. In general, substances having similar SP values tend to be mixed with each other. Therefore, the SP value is also a measure for judging the ease of mixing of the solute and the solvent.
- the mass ratio of the polymer (resin, polymer) constituting the inner layer to the polymer (resin, polymer) constituting the outer layer (polymer constituting the inner layer / polymer constituting the outer layer) is determined by the coating strength and the coating thickness. For example, 95/5 to 5/95 (for example, 90/10 to 10/90), preferably 88/12 to 12/88 (for example, 85/15 to 15). / 85) or 95/5 to 20/80 (for example, 90/10 to 30/70, preferably 88/12 to 40/60).
- the ratio of the first layer is 10 to 25% by mass with respect to the whole emulsion particles (A), and the ratio of the second layer is 40 to 40%.
- the ratio of the 55% by mass and the third layer may be about 20 to 45% by mass.
- the emulsion polymerization method and polymerization conditions for forming the inner layer may be the same as the method and polymerization conditions for producing the resin emulsion cake.
- the resin (polymer) constituting the emulsion (A) may have a crosslinked structure.
- the weight average molecular weight of the resin constituting the emulsion (A) is, for example, 100,000 or more, preferably 300,000 or more, more preferably 550,000 or more, particularly preferably from the viewpoint of improving the water resistance of the coating film. It may be 600,000 or more.
- the upper limit value of the weight average molecular weight of the resin constituting the emulsion (A) is not particularly limited because it is difficult to measure the weight average molecular weight of the resin having a crosslinked structure.
- the resin does not have a crosslinked structure.
- it is preferably 5 million or less from the viewpoint of improving the film forming property.
- the weight average molecular weight can be measured using, for example, gel permeation chromatography (for example, manufactured by Tosoh Corporation, product number: HLC-8120GPC, column: TSKgel G-5000HXL and TSKgel GMHXL-L in series). It may be a weight average molecular weight (polystyrene conversion).
- the glass transition temperature of the emulsion (A) is preferably ⁇ 20 ° C. or higher, more preferably ⁇ 10 ° C. or higher, and still more preferably from the viewpoint of physical properties of the coating film. May be 0 ° C. or higher, and may be preferably 50 ° C. or lower, more preferably 40 ° C. or lower, still more preferably 30 ° C. or lower, and even more preferably 20 ° C. or lower from the viewpoint of physical properties of the coating film. .
- the inner layer and the outer layer may have different glass transition temperatures.
- the emulsion (A) has a multilayer structure composed of a layer having a high glass transition temperature and a layer having a low glass transition temperature. Also good.
- the glass transition temperature of the resin constituting the layer having a high glass transition temperature is preferably 55 ° C. or higher, more preferably 60 ° C. or higher, further preferably, from the viewpoint of physical properties of the coating film. Is 65 ° C. or higher, and may be 120 ° C. or lower, more preferably 110 ° C. or lower, and even more preferably 100 ° C. or lower from the viewpoint of physical properties of the coating film.
- the glass transition temperature of the resin constituting the layer having a low glass transition temperature is preferably ⁇ 70 ° C. or higher, more preferably ⁇ 60 ° C. or higher, from the viewpoint of increasing the coating strength. In view of improving the water crack resistance, it may be preferably 0 ° C. or lower, more preferably ⁇ 10 ° C. or lower, and further preferably ⁇ 20 ° C. or lower.
- the inner layer When the inner layer is composed of a plurality of layers, all the layers may be low glass transition temperature layers or high glass transition temperature layers, and the inner layers may be a high glass transition temperature layer and a low glass transition temperature layer. You may comprise.
- the glass transition temperature of the polymer constituting the emulsion (A) may mean the glass transition temperature obtained based on the formula (I) unless otherwise specified.
- the glass transition temperature of the whole polymer constituting the emulsion (A) having a multilayer structure corresponds to the mass fraction of each monomer in all monomer components used in the multistage emulsion polymerization. It means the glass transition temperature determined from the glass transition temperature of the homopolymer of the monomer.
- the total amount of monomers with unknown glass transition temperature in the monomer component is the mass fraction. If it is 10% by mass or less, the glass transition temperature can be determined using only the monomer whose glass transition temperature is known.
- the glass transition temperature of the polymer is determined by differential scanning calorimetry (DSC) or differential calorimetry. (DTA), thermomechanical analysis (TMA), etc.
- the glass transition temperature of the polymer can be easily adjusted by adjusting the composition of the monomer component. Considering the glass transition temperature of the polymer constituting the emulsion (A), the composition of the monomer component used as the raw material for the polymer constituting the emulsion (A) can be determined.
- the glass transition temperature of the polymer is, for example, -70 ° C. for 2-ethylhexyl acrylate homopolymer, 83 ° C. for cyclohexyl methacrylate homopolymer, 100 ° C. for styrene homopolymer, ⁇ -methacryloxypropyltrimethoxysilane 70 ° C. for homopolymers of 2-hydroxyethyl methacrylate, 55 ° C. for homopolymers of 2-hydroxyethyl methacrylate, 105 ° C. for homopolymers of methyl methacrylate, 130 ° C.
- n- butyl methacrylate homopolymer for homopolymers of methacrylic acid, and for homopolymers of tert-butyl methacrylate 107 ° C., about 130 ° C. for 1,2,2,6,6-pentamethylpiperidyl methacrylate homopolymer, 77 ° C. for diacetone acrylamide homopolymer, 55 ° C. for glycerol monomethacrylate homopolymer, n- Butyl methacrylate homopolymer Is 20 ° C., a homopolymer of n- butyl acrylate is -56 ° C..
- the average particle diameter of the emulsion (A) is preferably 50 nm or more, more preferably 100 nm or more, from the viewpoint of mechanical stability of the emulsion (A) itself, preferably from the viewpoint of physical properties of the coating film, etc. May be 300 nm or less, more preferably 200 nm or less.
- the average particle size of the emulsion (A) may typically be about 50 to 300 nm (for example, 60 to 250 nm), preferably 80 to 200 nm, and more preferably about 100 to 180 nm.
- the average particle size of the emulsion (A) is measured using a particle size distribution measuring instrument (Particulate Sizing Systems, trade name: NICOMP Model 380) by a dynamic light scattering method. Means the volume average particle diameter measured by
- the content of the resin in the emulsion (A) is, for example, 20% by mass or more (for example, 25 to 100% by mass), preferably 30% by mass or more (eg 35 to 90% by mass), more preferably 40% by mass or more (eg 45 to 85% by mass).
- the solid content (non-volatile content) of the particles (or solid content) in the emulsion (A) is preferably 30% by mass or more, more preferably 40% by mass or more from the viewpoint of productivity and the like, and improves the handleability. In view of the above, it may be preferably 70% by mass or less, more preferably 60% by mass or less.
- the non-volatile content in the emulsion is, for example, weighing 1 g of the resin emulsion and drying it with a hot air dryer at a temperature of 110 ° C. for 1 hour.
- [Nonvolatile content in resin emulsion (mass%)] ([residue mass] ⁇ [resin emulsion 1 g]) ⁇ 100
- [Nonvolatile content in resin emulsion (mass%)] ([residue mass] ⁇ [resin emulsion 1 g]) ⁇ 100
- [Nonvolatile content in resin emulsion (mass%)] ([residue mass] ⁇ [resin emulsion 1 g]) ⁇ 100
- [Nonvolatile content in resin emulsion (mass%)] ([residue mass] ⁇ [resin emulsion 1 g]) ⁇ 100
- the proportion of the emulsifier is, for example, 0.1 to 30 parts by mass, preferably 0.5 to 20 parts per 100 parts by mass of the resin (or monomer component (a)) constituting the emulsion. It may be about 1 to 10 parts by mass (for example, 0.7 to 15 parts by mass).
- the minimum film-forming temperature of the emulsion is preferably 60 ° C. or lower, more preferably 50 ° C. or lower, and further preferably 40 ° C. or lower from the viewpoint of improving the film-forming property.
- the minimum film-forming temperature of the emulsion can be adjusted, for example, by adjusting the glass transition temperature of the whole emulsion particle or the glass transition temperature of the outermost layer.
- the minimum film-forming temperature of the emulsion is, for example, by applying the resin emulsion on a glass plate placed on a thermal gradient tester with an applicator so that the thickness is 0.2 mm, and cracking. It can be determined as the temperature at which this occurs.
- the emulsion (A) may particularly have an anionic group (or may be anionic).
- anionic group By having an anionic property (anionic group), the affinity with the polymer (B) can be improved, and the dropping of the polymer (B) from the coating film can be further suppressed.
- the anionic emulsion (A) is not particularly limited, but can be obtained, for example, by introducing an anionic group into the emulsion.
- An anionic group can be introduce
- the emulsion (A) having a specific anionic property (anionic group) includes an emulsion satisfying the following (1) and / or (2).
- the emulsifier constituting the emulsion (A) contains an anionic emulsifier
- composition of this invention should just contain emulsion (A), and contains emulsion (A) as an emulsion (emulsion which emulsion (A) disperse
- the ratio of the emulsion (A) to the polymer (B) solid content when a solvent is included
- the former / the latter mass ratio
- the ratio of the emulsion (A) to the polymer (B) solid content when a solvent is included
- the former / the latter mass ratio
- 99.5 / 0.5 to 40/60 for example, 99.2 / 0.8 to 50/50
- coating film properties In view of advantages (such as weather resistance and water whitening resistance), it is more preferably 99/1 to 60/40 (for example, 98.5 / 1.5 to 70/30), particularly 98
- the presence form of the emulsion (A) and the polymer (B) is not particularly limited, but may be separated from each other or may be bonded (crosslinked) to each other.
- an emulsion (A) and a polymer (B) should just couple
- a bonded or crosslinked structure may be formed afterwards or with time (for example, in a coating film or the like). Therefore, in the composition of the present invention, the emulsion (A) and the polymer (B) may be capable of forming a bond (or a crosslinked structure).
- the bonding form of the emulsion (A) and the polymer (B) is not particularly limited, and (i) the emulsion (A) and the polymer (B) are directly (Ii) a combination of emulsion (A) and polymer (B) via a crosslinking agent (C) (formation of a crosslinked structure), (iii) a combination of these The form etc. are mentioned.
- the emulsion (A) is composed of a resin having a monomer component (a) containing a monomer having a functional group ⁇ as a polymerization component, and the polymer (B) is a functional group. It is composed of a polymer having a monomer component (a) containing a monomer having ⁇ (functional group ⁇ that can react and bond with functional group ⁇ ) as a polymerization component, and between functional group ⁇ and functional group ⁇ .
- a bond or a crosslinked structure
- reaction or a bond or a crosslinked structure can be taken
- the emulsion (A) is composed of a resin having a monomer component (a) containing a monomer having a functional group ⁇ as a polymerization component, and the polymer (B) has a functional group ⁇ It is composed of a polymer having a monomer component (b) containing a monomer having a functional group ⁇ and a functional group ⁇ capable of forming a crosslinked structure via a crosslinking agent (C) as a polymerization component, and the functional group ⁇ And a mode in which the functional group ⁇ reacts with the crosslinking agent (C) to form a bond (or a crosslinked structure) (or can take a bond or a crosslinked structure).
- the combination of the functional group ⁇ and the functional group ⁇ , the combination of the functional group ⁇ and the functional group ⁇ and the functional group (functional group ⁇ ) of the crosslinking agent Not particularly limited, for example, epoxy group and hydroxyl group, epoxy group and carboxyl group, epoxy group and carboxyl group, epoxy group and amino group, epoxy group and amino group, carbonate group and carboxyl group, hydroxyl group and alkoxycarbonyl group, hydroxyl group and Isocyanate group, hydroxyl group and carboxylic anhydride group, acetoacetoxy group and isocyanate group, oxazoline group and carboxyl group, hydroxyl group and carboxylic anhydride group, oxazolidine group and isocyanate group or carboxylic anhydride group, hydrazino group and carbonyl group Can be mentioned. You may use these in combination of 1 or 2 or more.
- the combination of the representative functional group ⁇ and the functional group ⁇ is not particularly limited as long as it is a combination capable of forming a crosslinked structure or a bond by reaction with each other.
- a carboxyl group and an oxazoline group A combination of a carbonyl group and a hydrazino group, a combination of an isocyanate group and a hydroxy group, a carboxyl group, an amino group, and the like.
- the combination of the representative functional group ⁇ and the functional group ⁇ can be appropriately selected according to the type of the crosslinking agent (C), and may be the same functional group.
- Examples of such combinations include combinations in which the functional group ⁇ and the functional group ⁇ are both carboxyl groups or carbonyl groups.
- a hydrazine-based crosslinking agent or an oxazoline-based crosslinking agent described later can be suitably used as the crosslinking agent (C).
- a bond (or a cross-linked structure) can be formed by reacting between the functional group ⁇ and the functional group ⁇ (a bond or a cross-linked structure can be formed with both the functional group ⁇ and the functional group ⁇ ).
- the cross-linking agent (C) is not particularly limited and can be appropriately selected according to the type of the functional group ⁇ and the functional group ⁇ .
- the polyfunctional compound multifunctional having a plurality of functional groups ( ⁇ )) Compound).
- Examples of the functional group ⁇ include the functional groups exemplified as the functional group ⁇ and the functional group ⁇ , and examples thereof include a carboxyl group, a hydrazino group, an oxazoline group, a carbodiimide group, an epoxy group, an isocyanate group, and an amino group.
- the polyfunctional compound may have the same or different functional groups.
- the number of functional groups (functional group ⁇ ) may be two or more.
- a low molecular type (non-polymer type or non-resin type) polyfunctional compound It is 2 to 10, preferably 2 to 6, more preferably 2 to 4, particularly 2.
- Typical crosslinking agents (C) include hydrazine crosslinking agents (compounds having a plurality of hydrazino groups), oxazoline crosslinking agents, carbodiimide crosslinking agents, isocyanate crosslinking agents, amine crosslinking agents, epoxy crosslinking agents, and the like. Can be mentioned.
- the crosslinking agent (C) may be water-soluble (water-soluble crosslinking agent).
- hydrazine-based crosslinking agent examples include dicarboxylic acid dihydrazide [for example, alkane dicarboxylic acid dihydrazide (for example, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanoic acid hydride, etc.) C 2-20 alkane dicarboxylic acid dihydrazide, preferably C 2-10 alkane dicarboxylic acid dihydrazide), alkene dicarboxylic acid dihydrazide (e.g., maleic acid dihydrazide, fumaric acid dihydrazide, C 2-10 alkene dicarboxylic acid dihydrazide and itaconic acid dihydrazide ) Aliphatic dicarboxylic acid dihydrazide; isophthalic acid dihydrazide,
- oxazoline-based crosslinking agent examples include polymers having an oxazoline group-containing monomer as a polymerization component.
- examples of such a polymer include a homopolymer or a copolymer of an oxazoline group-containing monomer, a copolymer of an oxazoline group-containing monomer and another copolymerizable monomer, and the like.
- alkenyl oxazolines for example, C 2-6 alkenyl oxazolines such as 2-vinyl-2-oxazoline, 2-isopropenyl-2-oxazoline, preferably Vinyl or isopropenyl oxazoline
- alkenyl-alkyl oxazolines eg 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline
- C 2-6 alkenyl-C 1-10 alkyl oxazoline such as 2-isopropenyl-5-ethyl-2-oxazoline, preferably vinyl or isopropenyl-C 1-4 alkyl oxazoline
- alkenyl oxazolines for example, C 2-6 alkenyl oxazolines such as 2-vinyl-2-oxazoline, 2-isopropenyl-2-oxazoline, preferably Vinyl or isopropen
- the other copolymerizable monomer is not particularly limited as long as it is a copolymerizable monomer that does not react with the oxazoline group.
- (meth) acrylic acid ester for example, methyl (meth) acrylate , Alkyl (meth) acrylates as exemplified above such as ethyl (meth) acrylate; hydroxy group-containing (meth) acrylates as exemplified above such as hydroxyethyl (meth) acrylate]
- (meth) acrylic acid amide, vinyl acetate aromatic Group monomers (for example, the above-described styrene monomers such as styrene and ⁇ -methylstyrene).
- the oxazoline group equivalent may be, for example, about 200 to 5000 g / equivalent, preferably about 250 to 4000 g / equivalent, and more preferably about 300 to 3000 g / equivalent.
- Such an oxazoline-based crosslinking agent can also be obtained as an Epocross series (for example, Epocross K-2010E, K-2020E, K-2030E, WS-500, etc.) manufactured by Nippon Shokubai Co., Ltd.
- Epocross series for example, Epocross K-2010E, K-2020E, K-2030E, WS-500, etc.
- the carbodiimide-based crosslinking agent may be a compound having at least one carbodiimide group [—N ⁇ C ⁇ N—] in the molecule, may be a monocarbodiimide compound, or may be a polycarbodiimide compound. May be.
- the carbodiimide compound may be water-soluble (hydrophilic or aqueous).
- Such a water-soluble carbodiimide compound may usually have a hydrophilic group (hydrophilic skeleton, hydrophilic segment).
- the hydrophilic group (hydrophilic skeleton) is not particularly limited, and examples thereof include a hydroxy group, a carbamate group, a (poly) oxyalkylene group, and a substituted amino group (tertiary amino group).
- the hydrophilic group may form a salt (for example, an amine salt).
- Such a hydrophilic group may be located at the end of carbodiimide, for example.
- a water-soluble carbodiimide compound aqueous carbodiimide compound
- the terminal of the carbodiimide compound serving as a base may be blocked with a hydrophilic group (or a hydrophilic skeleton).
- the carbodiimide compound examples include a carbodiimide having an N, N-disubstituted amino group [eg, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide], a carbodiimide having an isocyanate group at its terminal and a hydrophilic group.
- a compound having a reactive group (such as a hydroxyl group) capable of forming a bond by reacting with a reactive segment and an isocyanate group eg, polyalkylene glycol monoalkyl ether, oxycarboxylic acid ester (such as glycolic acid ester), N, N And a reaction product with a substituted amino alcohol (such as a dialkylamino alcohol).
- Isocyanate-based crosslinking agents include polyisocyanates [for example, 1,6-hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, Aliphatic polyisocyanates such as lysine isocyanate; 1,3-diisocyanatecyclohexane, 1,4-diisocyanatecyclohexane, 1,3-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanatemethyl) cyclohexane, dicyclohexylmethane-4 , 4′-diisocyanate, isophorone diisocyanate, norbornane diisocyanate, and the like; xylylene diisocyanate, tetramethyl Le xylylene diisocyanate, 4,4-bis such araliphatic
- amine crosslinking agents examples include urea resins (eg, urea resins, thiourea resins, etc.), triazine resins (eg, melamine resins, isomelamine resins, benzoguanamine resins, acetoguanamine resins, guanylmelamine resins, etc.). Can be mentioned.
- urea resins eg, urea resins, thiourea resins, etc.
- triazine resins eg, melamine resins, isomelamine resins, benzoguanamine resins, acetoguanamine resins, guanylmelamine resins, etc.
- epoxy-based crosslinking agent examples include polyglycidyl ether, epoxy resin (for example, novolac type epoxy resin, brominated epoxy resin, alicyclic epoxy resin, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, etc.). It is done.
- the crosslinking agent (C) may be used alone or in combination of two or more.
- crosslinking agents (C) a water-soluble crosslinking agent is preferable. Also preferred are hydrazine-based crosslinking agents, oxazoline-based crosslinking agents, carbodiimide-based crosslinking agents, and the like.
- Representative forms (ii) include the following forms (ii-1) and (ii-2).
- the emulsion (A) is composed of a polymer of a monomer component (a) containing a carbonyl group-containing monomer as a monomer having a functional group ⁇ , and the polymer (B) has a functional group ⁇ It is composed of a polymer of a monomer component (b) containing a carbonyl group-containing monomer as a monomer having a structure, and the emulsion (A) and the polymer (B) are bonded via a hydrazine-based crosslinking agent (C1).
- C1 hydrazine-based crosslinking agent
- the emulsion (A) is composed of a polymer of a monomer component (a) containing a carboxyl-containing monomer as a monomer having a functional group ⁇ , and the polymer (B) has a functional group ⁇ . It is composed of a polymer of a monomer component (b) containing a carboxyl group-containing monomer as a monomer, and the emulsion particles (A) and the polymer (B) are bonded via an oxazoline-based crosslinking agent (C2).
- C2 oxazoline-based crosslinking agent
- the ratio of the total amount of the monomer having the functional group ⁇ and the monomer having the functional group ⁇ to the total amount of the monomer component (a) and the monomer component (b) is, for example, 0. It may be about 01 to 40% by mass, preferably about 0.05 to 30% by mass, and more preferably about 0.1 to 20% by mass.
- the ratio of the crosslinking agent (C) is, for example, 0.01 to 500 with respect to 100 parts by mass of the total amount of the monomer having the functional group ⁇ and the monomer having the functional group ⁇ . It may be about 1 part by mass, preferably about 0.1 to 300 parts by mass, and more preferably about 1 to 100 parts by mass.
- the composition of the present invention may be a composition containing a solvent.
- the composition of the present invention may be a composition in which the emulsion (A) and the polymer (B) are dispersed (or dissolved) in a solvent.
- a preferable solvent is an aqueous solvent such as water, a solvent containing water [for example, a mixed solvent containing water and an alcohol (a lower alcohol such as methanol or ethanol)].
- the composition of the present invention may be a composition (aqueous composition) in which the emulsion (A) and the polymer (B) are dispersed (or dissolved) in an aqueous solvent.
- the ratio of the total amount of the emulsion (A) and the polymer (B) can be appropriately selected depending on the application and the like, for example, 0.1 to 95% by mass, preferably 1 to 90% by mass, More preferably, it may be about 3 to 80% by mass.
- composition of this invention may contain the other component according to a use etc.
- the method for producing the composition of the present invention is not particularly limited, and can be produced, for example, by mixing the emulsion (A) and the polymer (B) (and, if necessary, a solvent and other components).
- the emulsion (A) and the polymer (B) may be mixed under appropriate crosslinking conditions.
- the emulsion (A), the polymer (B), and the crosslinking agent (C) may be mixed and crosslinked in a solvent (for example, in the aqueous solvent).
- composition of the present invention is particularly suitable for paint (for coating).
- a coating composition particularly, an aqueous coating composition
- Such a coating composition is used, for example, for surface finishing of a substrate formed of various materials (for example, metal, glass, porcelain, concrete, siding board, resin, etc.). May be used.
- composition of the present invention can be suitably used for a topcoat (or topcoat material, for example, a topcoat for exterior materials (building materials)), among others.
- Such a composition or paint of the present invention contains other components in addition to the above-described components (eg, emulsion (A) and polymer (B)). May be included.
- other components include pigments (pigments described later), pigment dispersants, precipitation inhibitors, ultraviolet absorbers, light stabilizers, film forming aids, thickeners, surface conditioners, antiseptic / antifungal agents, and the like. , Leveling agents, antifreezing agents, wetting agents, pH adjusting agents, antifoaming agents and the like. These components may be used alone or in combination of two or more.
- Ceramic building materials for example, flexible boards, calcium silicate boards, gypsum slag perlite boards, wood cement boards, precast concrete boards, ALC boards, gypsum boards, etc .; for example, tiles, outer wall materials, etc. Ceramic building materials). Ceramic-based building materials, for example, add inorganic fillers, fibrous materials, etc. to hydraulic glue, which is a raw material for inorganic hardened bodies, mold the resulting mixture, and cure and cure the resulting molded body Can be obtained.
- hydraulic glue which is a raw material for inorganic hardened bodies, mold the resulting mixture, and cure and cure the resulting molded body Can be obtained.
- top coating material water-based paint
- water-based paint is a paint that forms a coating film that protects the building from the external environment such as sunlight or wind and rain, or has the aesthetics and design of the building. Used as (architectural and exterior paint).
- the composition of the present invention can be suitably used for this top coat or as a top coating material (water-based paint).
- paints it is preferable to apply directly to the outer wall (exterior material) of the building and use it for the exterior paint that is dried and cured (normal temperature drying) in a natural environment.
- a coating film formed with a paint that is dry-cured at room temperature is often soft, and because of its softness, the surface of the coating film becomes sticky and causes contaminants to adhere to it.
- the paint (or paint composition) of the present invention can be used as a stain-proofing agent for such a soft coating film, and by adding it to the coating, the stain resistance is improved by the hydrophilic effect of the coating film surface. sell.
- the state of the surface coating film formed using the above-mentioned exterior coating material can be in various forms from transparent to colored translucent to colored concealment.
- the colored concealed state is particularly numerous. Therefore, the paint (coating composition) of the present invention may be a paint containing a pigment (aqueous paint, aqueous exterior paint, etc.).
- the pigment may be a colorant or an extender pigment (a bulking agent).
- Typical pigments include, for example, inorganic pigments (for example, inorganic color pigments such as titanium oxide, iron oxide, aluminum, pearl pigments), organic pigments (for example, quinacridone, anthraquinone, perylene, diketopyrrolopyrrole, And organic pigments such as benzimidazolone, isoindolinone, anthrapyrimidine, phthalocyanine, selenium, dioxazine, and carbon black) and extender pigments (eg, calcium carbonate, barium sulfate, kaolin, mica, talc, etc.) . You may use a pigment individually or in combination of 2 or more types.
- the amount of the pigment blended is, for example, 5 to 70 parts by weight, preferably 7 to 7 parts by weight with respect to 100 parts by weight of the solid content of the resin component (or emulsion (A) and polymer (B)) in the coating film after drying. It may be about 65 parts by mass, more preferably about 10 to 60 parts by mass.
- composition of the present invention When the composition of the present invention is used for paint (coating), it may be applied alone in one layer, or may be applied by recoating two or more layers. When the coating is performed by overcoating two or more layers, only a part of the layers may be formed by the composition of the present invention, or all the layers may be formed by the composition of the present invention.
- a first layer eg, undercoat layer
- the second layer eg, topcoat layer
- this invention is not limited by this method.
- spray, roller, brush, or iron can be used.
- part means “part by mass”.
- a dropping funnel 163 parts of deionized water, 80 parts of 25% aqueous solution of an anionic emulsifier (manufactured by ADEKA, trade name: Adekaria soap SR-10, a reactive anionic emulsifier), 300 parts of 2-ethylhexyl acrylate, 250 parts of cyclohexyl methacrylate, 50 parts of 2,2,6,6-tetramethylpiperidyl methacrylate (4-methacryloyloxy-2,2,6,6-tetramethylpiperidine), 50 parts of butyl acrylate, 10 parts of diacetone acrylamide, styrene
- a pre-emulsion for dripping consisting of 250 parts, hydroxyethyl methacrylate 10 parts, tert-butyl methacrylate 30 parts and methyl methacrylate 50 parts was prepared, 74 parts of which were added into the flask, and 80 ° C. while gently blowing nitrogen gas. Ma The temperature was raised,
- the obtained reaction liquid was cooled to room temperature, and then filtered through a 300 mesh (JIS mesh, hereinafter the same) wire mesh to obtain an aqueous resin dispersion having a nonvolatile content of 49% by mass.
- the emulsion particles contained in the obtained aqueous resin dispersion had a single-layer structure with an average particle diameter of 150 nm, and the glass transition temperature of the entire emulsion particles was 14.7 ° C.
- a first-stage dripping pre-treatment comprising 400 parts of cyclohexyl methacrylate, 150 parts of styrene, 80 parts of methyl methacrylate, 20 parts of tert-butyl methacrylate, 10 parts of diacetone acrylamide, 20 parts of hydroxyethyl methacrylate, 10 parts of methacrylic acid and 10 parts of acrylic acid.
- An emulsion was prepared, 74 parts thereof were added into the flask, the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and 20 parts of a 5% aqueous solution of potassium persulfate was added to initiate polymerization.
- the obtained reaction liquid was cooled to room temperature and then filtered through a 300 mesh wire netting to obtain an aqueous resin dispersion having a nonvolatile content of 49% by mass.
- the emulsion particles contained in the obtained aqueous resin dispersion had a single-layer structure with an average particle diameter of 160 nm, and the glass transition temperature of the entire emulsion particles was 20.2 ° C.
- a pre-emulsion for first-stage dropping comprising 210 parts of cyclohexyl methacrylate, 250 parts of methyl methacrylate, 5 parts of ⁇ -methacryloyloxypropyltrimethoxysilane, 10 parts of styrene, 5 parts of acrylic acid and 5 parts of hydroxyethyl methacrylate was prepared.
- Polymerization was started by adding 74 parts into the flask, raising the temperature to 80 ° C. while gently blowing nitrogen gas, and adding 20 parts of a 5% aqueous solution of potassium persulfate into the flask.
- Pre-emulsion for second-stage dropping and potassium persulfate comprising 150 parts of butyl acrylate, 105 parts of cyclohexyl methacrylate, 10 parts of hydroxyethyl methacrylate, 10 parts of 2,2,6,6-tetramethylpiperidyl methacrylate, and 10 parts of diacetone acrylamide 10 parts of a 5% aqueous solution and 10 parts of a 2.5% aqueous sodium hydrogen sulfite solution were added dropwise uniformly over 120 minutes. After completion of the dropping, the content of the flask was maintained at 80 ° C. for 60 minutes, 25% aqueous ammonia was added,
- the obtained reaction liquid was cooled to room temperature and then filtered through a 300 mesh wire netting to obtain an aqueous resin dispersion having a nonvolatile content of 49% by mass.
- the emulsion particles contained in the obtained aqueous resin dispersion have a two-layer structure with an average particle diameter of 150 nm, the glass transition temperature of the inner layer is 85.3 ° C., and the glass transition temperature of the outer layer is ⁇ 38.6 ° C. Yes, the glass transition temperature of the entire emulsion particles was 9.1 ° C.
- a dropping funnel 163 parts of deionized water, 80 parts of 25% aqueous solution of an anionic emulsifier (manufactured by ADEKA, trade name: ADEKA rear soap SR-10, a reactive anionic emulsifier), 2-ethylhexyl acrylate 330
- an anionic emulsifier manufactured by ADEKA, trade name: ADEKA rear soap SR-10, a reactive anionic emulsifier
- 2-ethylhexyl acrylate 330 For first-stage dripping comprising 50 parts of cyclohexyl methacrylate, 40 parts of styrene, 20 parts of methyl methacrylate, 15 parts of tert-butyl methacrylate, 30 parts of butyl acrylate, 5 parts of acrylic acid, 5 parts of methacrylic acid and 5 parts of hydroxyethyl methacrylate.
- a pre-emulsion was prepared, 74 parts thereof were added into the flask, the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and 20 parts of a 5% aqueous solution of potassium persulfate was added into the flask to polymerize. The reaction was started.
- the obtained reaction liquid was cooled to room temperature and then filtered through a 300 mesh wire netting to obtain an aqueous resin dispersion having a nonvolatile content of 49% by mass.
- the emulsion particles contained in the obtained aqueous resin dispersion have a two-layer structure with an average particle diameter of 150 nm, the inner layer has a glass transition temperature of ⁇ 39.9 ° C., and the outer layer has a glass transition temperature of 62.0 ° C. Yes, the glass transition temperature of the entire emulsion particles was 1.9 ° C.
- the obtained reaction liquid was cooled to room temperature, and then filtered through a 300 mesh (JIS mesh, hereinafter the same) wire mesh to obtain an aqueous resin dispersion having a nonvolatile content of 49% by mass.
- the emulsion particles contained in the obtained aqueous resin dispersion had a one-layer structure with an average particle diameter of 150 nm, and the glass transition temperature of the whole emulsion particles was 9.5 ° C.
- Example B1 594 parts of deionized water was charged into a polymerization vessel equipped with a cooling pipe, a nitrogen introduction line and a thermometer. Nitrogen gas was introduced into the flask, and the atmosphere in the flask was changed to a nitrogen gas atmosphere.
- the contents of the dropping funnel A and the dropping funnel B were dropped uniformly into the polymerization vessel over 2 hours to initiate the polymerization reaction. After the temperature in the polymerization vessel rose due to the heat of polymerization, the mixture was stirred for 2 hours at a temperature of 80 ° C.
- the dropping funnel A and the dropping funnel B were each washed with 51 parts of deionized water, and the obtained washing solution was added to the polymerization vessel and stirred at a temperature of 80 ° C. for 1 hour. After 1 hour, 2.6 parts of a 10% aqueous solution of 2,2′-azobis (2-methylpropionamidine) dihydrochloride dissolved in deionized water was added to the polymerization vessel, and further stirred at a temperature of 80 ° C. for 1 hour. As a result, a water-soluble polymer solution was obtained.
- the obtained water-soluble polymer solution had a nonvolatile content of 25.0% by mass, and the polymer obtained had a weight average molecular weight of 20000.
- Example B2 594 parts of deionized water was charged into a polymerization vessel equipped with a cooling pipe, a nitrogen introduction line and a thermometer. Nitrogen gas was introduced into the flask, and the atmosphere in the flask was changed to a nitrogen gas atmosphere.
- the contents of the dropping funnel A and the dropping funnel B were dropped uniformly into the polymerization vessel over 2 hours to initiate the polymerization reaction. After the temperature in the polymerization vessel rose due to the heat of polymerization, the mixture was stirred for 2 hours at a temperature of 80 ° C.
- the dropping funnel A and the dropping funnel B were each washed with 51 parts of deionized water, and the obtained washing solution was added to the polymerization vessel and stirred at a temperature of 80 ° C. for 1 hour. After 1 hour, 2.6 parts of a 10% aqueous solution of 2,2′-azobis (2-methylpropionamidine) dihydrochloride dissolved in deionized water was added to the polymerization vessel, and further stirred at a temperature of 80 ° C. for 1 hour. As a result, a water-soluble polymer solution was obtained.
- the obtained water-soluble polymer solution had a nonvolatile content of 25.0% by mass, and the polymer obtained had a weight average molecular weight of 20000.
- Example B3 594 parts of deionized water was charged into a polymerization vessel equipped with a cooling pipe, a nitrogen introduction line and a thermometer. Nitrogen gas was introduced into the flask, and the atmosphere in the flask was changed to a nitrogen gas atmosphere.
- the contents of the dropping funnel A and the dropping funnel B were dropped uniformly into the polymerization vessel over 2 hours to initiate the polymerization reaction. After the temperature in the polymerization vessel rose due to the heat of polymerization, the mixture was stirred for 2 hours at a temperature of 80 ° C.
- the dropping funnel A and the dropping funnel B were each washed with 51 parts of deionized water, and the obtained washing solution was added to the polymerization vessel and stirred at a temperature of 80 ° C. for 1 hour. After 1 hour, 2.6 parts of a 10% aqueous solution of 2,2′-azobis (2-methylpropionamidine) dihydrochloride dissolved in deionized water was added to the polymerization vessel, and further stirred at a temperature of 80 ° C. for 1 hour. As a result, a water-soluble polymer solution was obtained.
- the obtained water-soluble polymer solution had a nonvolatile content of 25.0% by mass, and the polymer obtained had a weight average molecular weight of 20000.
- Example B4 300 parts of deionized water was charged into a polymerization vessel equipped with a cooling pipe, a nitrogen introduction line and a thermometer. Nitrogen gas was introduced into the flask, and the atmosphere in the flask was changed to a nitrogen gas atmosphere.
- the contents of the dropping funnel A and the dropping funnel B were dropped uniformly into the polymerization vessel over 2 hours to initiate the polymerization reaction. After the temperature in the polymerization vessel rose due to the heat of polymerization, the mixture was stirred for 2 hours at a temperature of 80 ° C.
- the dropping funnel A and the dropping funnel B were each washed with 345 parts of deionized water, and the obtained washing solution was added to the polymerization vessel and stirred at a temperature of 80 ° C. for 1 hour. After 1 hour, 2.6 parts of a 10% aqueous solution of 2,2′-azobis (2-methylpropionamidine) dihydrochloride dissolved in deionized water was added to the polymerization vessel, and further stirred at a temperature of 80 ° C. for 1 hour. As a result, a water-soluble polymer solution was obtained.
- the obtained water-soluble polymer solution had a nonvolatile content of 25.0% by mass, and the obtained polymer had a weight average molecular weight of 40000.
- Example B5 198 parts of deionized water was charged into a polymerization vessel equipped with a cooling pipe, a nitrogen introduction line and a thermometer. Nitrogen gas was introduced into the flask, and the atmosphere in the flask was changed to a nitrogen gas atmosphere.
- dropping funnel A 252 parts of N-vinylpyrrolidone, 2.6 parts of diacetone acrylamide, 2.6 parts of hydroxyethyl methacrylate, 1.3 parts of 2,2,6,6-tetramethylpiperidyl methacrylate and 1,2,2 , 6,6-Pentamethylpiperidylmethacrylate 1.3 parts was added to prepare a premix.
- dropping funnel B 129 parts of deionized water and 6.5 parts of 2,2'-azobis (2-methylpropionamidine) dihydrochloride were added.
- the contents of the dropping funnel A and the dropping funnel B were dropped uniformly into the polymerization vessel over 2 hours to initiate the polymerization reaction. After the temperature in the polymerization vessel rose due to the heat of polymerization, the mixture was stirred for 2 hours at a temperature of 80 ° C.
- the dropping funnel A and the dropping funnel B were each washed with 447 parts of deionized water, and the obtained washing solution was added to the polymerization vessel and stirred at a temperature of 80 ° C. for 1 hour. After 1 hour, 2.6 parts of a 10% aqueous solution of 2,2′-azobis (2-methylpropionamidine) dihydrochloride dissolved in deionized water was added to the polymerization vessel, and further stirred at a temperature of 80 ° C. for 1 hour. As a result, a water-soluble polymer solution was obtained.
- the obtained water-soluble polymer solution had a nonvolatile content of 25.0% by mass, and the obtained polymer had a weight average molecular weight of 200,000.
- the contents of the dropping funnel A and the dropping funnel B were dropped uniformly into the polymerization vessel over 2 hours to initiate the polymerization reaction. After the temperature in the polymerization vessel rose due to the heat of polymerization, the mixture was stirred for 2 hours at a temperature of 80 ° C.
- the dropping funnel A and the dropping funnel B were each washed with 48 parts of deionized water, and the obtained washing solution was added to the polymerization vessel and stirred at a temperature of 80 ° C. for 1 hour. After 1 hour, 2.6 parts of a 10% aqueous solution of 2,2′-azobis (2-methylpropionamidine) dihydrochloride dissolved in deionized water was added to the polymerization vessel, and further stirred at a temperature of 80 ° C. for 1 hour. As a result, a water-soluble polymer solution was obtained.
- the obtained water-soluble polymer solution had a nonvolatile content of 25.0% by mass, and the polymer obtained had a weight average molecular weight of 20000.
- the contents of the dropping funnel A and the dropping funnel B were dropped uniformly into the polymerization vessel over 2 hours to initiate the polymerization reaction. After the temperature in the polymerization vessel rose due to the heat of polymerization, the mixture was stirred for 2 hours at a temperature of 80 ° C.
- the dropping funnel A and the dropping funnel B were each washed with 430 parts of deionized water, and the obtained washing solution was added to the polymerization vessel and stirred at a temperature of 80 ° C. for 1 hour. After 1 hour, 2.6 parts of a 10% aqueous solution of 2,2′-azobis (2-methylpropionamidine) dihydrochloride dissolved in deionized water was added to the polymerization vessel, and further stirred at a temperature of 80 ° C. for 1 hour. As a result, a water-soluble polymer solution was obtained.
- the obtained water-soluble polymer solution had a nonvolatile content of 25.0% by mass, and the obtained polymer had a weight average molecular weight of 200,000.
- Example B8 300 parts of deionized water was charged into a polymerization vessel equipped with a cooling pipe, a nitrogen introduction line and a thermometer. Nitrogen gas was introduced into the flask, and the atmosphere in the flask was changed to a nitrogen gas atmosphere.
- dropping funnel A 226 parts of N-vinylpyrrolidone, 26 parts of hydroxyethyl methacrylate, 4.0 parts of 25% aqueous ammonia, 4.2 parts of acrylic acid and 2.6 parts of 2,2,6,6-tetramethylpiperidyl methacrylate was added to prepare a premix.
- the dropping funnel B 129 parts of deionized water and 6.5 parts of 2,2′-azobis (2-methylpropionamidine) dihydrochloride were added.
- the contents of the dropping funnel A and the dropping funnel B were dropped uniformly into the polymerization vessel over 2 hours to initiate the polymerization reaction. After the temperature in the polymerization vessel rose due to the heat of polymerization, the mixture was stirred for 2 hours at a temperature of 80 ° C.
- the dropping funnel A and the dropping funnel B were each washed with 345 parts of deionized water, and the obtained washing solution was added to the polymerization vessel and stirred at a temperature of 80 ° C. for 1 hour. After 1 hour, 2.6 parts of a 10% aqueous solution of 2,2′-azobis (2-methylpropionamidine) dihydrochloride dissolved in deionized water was added to the polymerization vessel, and further stirred at a temperature of 80 ° C. for 1 hour. As a result, a water-soluble polymer solution was obtained.
- the obtained water-soluble polymer solution had a nonvolatile content of 25.0% by mass, and the obtained polymer had a weight average molecular weight of 40000.
- Example 1 The water-soluble polymer B1 obtained in Example B1 was added to the aqueous resin dispersion (emulsion particles) A1 obtained in Production Example A1 so that the mass ratio (A1 / B1) of both solids was 97/3 As a result, an aqueous resin composition was obtained.
- Example 2 The water-soluble polymer B1 obtained in Example B1 was added to the aqueous resin dispersion A1 obtained in Production Example A1 so that the mass ratio (A1 / B1) of both solids was 93/7.
- An aqueous resin composition was obtained by adding 10 parts of a 5% hydrazine-based crosslinking agent (adipic acid dihydrazide) aqueous solution as a crosslinking agent to 100 parts of the obtained mixture.
- a 5% hydrazine-based crosslinking agent adipic acid dihydrazide
- Example 3 The water-soluble polymer B3 obtained in Example B3 was added to the aqueous resin dispersion (emulsion particles) A1 obtained in Production Example A1 so that the mass ratio (A1 / B3) of both solids was 97/3 As a result, an aqueous resin composition was obtained.
- Example 4 The water-soluble polymer B2 obtained in Example B2 was added to the aqueous resin dispersion A1 obtained in Production Example A1 so that the mass ratio (A1 / B2) of both solids was 90/10.
- An aqueous resin composition was obtained by adding 10 parts of a 5% hydrazine-based crosslinking agent (adipic acid dihydrazide) aqueous solution as a crosslinking agent to 100 parts of the obtained mixture.
- a 5% hydrazine-based crosslinking agent adipic acid dihydrazide
- Example 5 The water-soluble polymer B1 obtained in Example B1 was added to the aqueous resin dispersion A2 obtained in Production Example A2 so that the mass ratio (A2 / B1) of both solids was 97/3. A composition was obtained.
- Example 6 The water-soluble polymer B4 obtained in Example B4 was added to the aqueous resin dispersion A2 obtained in Production Example A2 so that the mass ratio (A2 / B4) of both solids was 95/5.
- An aqueous resin composition was obtained by adding 4 parts of an oxazoline-based crosslinking agent (Epocross WS-500 [manufactured by Nippon Shokubai Co., Ltd.]) as a crosslinking agent to 100 parts of the mixture.
- an oxazoline-based crosslinking agent Epocross WS-500 [manufactured by Nippon Shokubai Co., Ltd.]
- Example 7 The water-soluble polymer B5 obtained in Example B5 was added to the aqueous resin dispersion A1 obtained in Production Example A1 so that the mass ratio (A1 / B5) of both solids was 90/10.
- An aqueous resin composition was obtained by adding 10 parts of a 5% hydrazine-based crosslinking agent (adipic acid dihydrazide) aqueous solution as a crosslinking agent to 100 parts of the obtained mixture.
- a 5% hydrazine-based crosslinking agent adipic acid dihydrazide
- Example 8 The water-soluble polymer B4 obtained in Example B4 was added to the aqueous resin dispersion A3 obtained in Production Example A3 so that the mass ratio (A3 / B4) of both solids was 95/5.
- an oxazoline-based crosslinking agent Epocross WS-500 [manufactured by Nippon Shokubai Co., Ltd.]
- a crosslinking agent a 5% aqueous solution of a hydrazine-based crosslinking agent (adipic acid dihydrazide)
- Example 9 The water-soluble polymer B1 obtained in Example B1 was added to the aqueous resin dispersion A4 obtained in Production Example A4 so that the mass ratio (A4 / B1) of both solids was 95/5.
- An aqueous resin composition was obtained by adding 10 parts of a 5% hydrazine-based crosslinking agent (adipic acid dihydrazide) aqueous solution as a crosslinking agent to 100 parts of the obtained mixture.
- a 5% hydrazine-based crosslinking agent adipic acid dihydrazide
- Example 10 The water-soluble polymer B8 obtained in Example B8 was added to the aqueous resin dispersion A5 obtained in Production Example A5 so that the mass ratio (A5 / B8) of both solids was 97/3.
- an oxazoline-based crosslinking agent Epocross WS-500 [manufactured by Nippon Shokubai Co., Ltd.]
- Example 11 The water-soluble polymer B4 obtained in Example B4 was added to the aqueous resin dispersion A3 obtained in Production Example A3 so that the mass ratio of both solids (A3 / B4) was 80/20.
- an oxazoline-based crosslinking agent Epocross WS-500 [manufactured by Nippon Shokubai Co., Ltd.]
- a hydrazine-based crosslinking agent adipic acid dihydrazide
- the white paste consists of 210 parts of deionized water, 60 parts of a dispersant (trade name: Demol EP, manufactured by Kao Corporation), and a dispersant (trade name: DISCOAT N-14, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). ] 50 parts, 10 parts of wetting agent [trade name: Emulgen LS-106], propylene glycol 60 parts, titanium oxide [product of Ishihara Sangyo Co., Ltd., product number: CR-95] 1000 parts and glass beads It was prepared by dispersing 200 parts (diameter: 1 mm) with a homodisper at a rotational speed of 3000 times / minute for 60 minutes.
- a dispersant trade name: Demol EP, manufactured by Kao Corporation
- DISCOAT N-14 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
- the sample was applied on the slate film with a 10 mil applicator and dried at 23 ° C. for 1 week, and then the side and back of the slate plate on which the sample was applied were sealed with aluminum tape, and the sample was applied.
- the 60 ° specular gloss of the surface was measured with a gloss meter (manufactured by Nippon Denshoku Industries Co., Ltd., product number: VG-7000), and the weather resistance test was repeated continuously for 1000 hours under the following conditions as one cycle.
- the L value (L 0 ) of the test plate was measured with a color difference meter [manufactured by Nippon Denshoku Industries Co., Ltd., product number: ZE-6000], and this test plate was immersed in water at 23 ° C. for 24 hours, The water content was wiped off with Kim Towel (manufactured by Nippon Paper Crecia Co., Ltd.), and the L value (L 1 ) was measured with the color difference meter within 1 minute.
- ⁇ L is less than 5 ⁇ : ⁇ L is 5 or more and less than 10 x: ⁇ L is 10 or more
- the white paste consists of 210 parts of deionized water, 60 parts of a dispersant (trade name: Demol EP, manufactured by Kao Corporation), and a dispersant (trade name: DISCOAT N-14, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). ] 50 parts, 10 parts of wetting agent [trade name: Emulgen LS-106], propylene glycol 60 parts, titanium oxide [product of Ishihara Sangyo Co., Ltd., product number: CR-95] 1000 parts and glass beads It was prepared by dispersing 200 parts (diameter: 1 mm) with a homodisper at a rotational speed of 3000 times / minute for 60 minutes.
- a dispersant trade name: Demol EP, manufactured by Kao Corporation
- DISCOAT N-14 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
- the test plate was bent so as to have an inclination of 30 degrees on the south surface at half (200 mm) in the vertical direction.
- the initial L value (L 0 ) of the sloped part of the test plate was measured with a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., product number: ZE-6000), and in accordance with JIS Z2381 (general rules for atmospheric exposure test methods)
- An outdoor exposure test was conducted under the following conditions. After 3 months and 6 months, the test plate was pulled up, and the L value (L 1 ) was measured with respect to the slope portion of the test plate with the color difference meter.
- -Test conditions South surface 30 degrees, direct exposure (exposure location: Suita City, Osaka / Nippon Catalyst Co., Ltd.)).
- Results are shown in Tables 1 and 2.
- OX represents Epocros WS-500 (oxazoline-based crosslinking agent)
- ADH represents adipic acid dihydrazide (hydrazine-based crosslinking agent).
- Example 12 The water-soluble polymer B1 obtained in Example B1 is added to the aqueous resin dispersion (emulsion particles) A1 obtained in Production Example A1 so that the mass ratio (A1 / B1) of both solids is 50/50. As a result, an aqueous resin composition was obtained. When the “stain resistance (1)” and “stain resistance (2)” of the obtained aqueous resin composition were examined by the same method as described above, both evaluations were “ ⁇ ”.
- the present invention can provide a polymer useful for coatings and the like and a composition containing this polymer.
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Abstract
Provided is a composition useful for paints and the like. The composition includes an emulsion (A) and a polymer (B) containing at least a vinyl lactam-based monomer and a hindered amine-based monomer as polymerization components.
Description
本発明は、親水化材料などとして有用なポリマー及びこのポリマーを含む組成物に関する。
The present invention relates to a polymer useful as a hydrophilizing material and a composition containing the polymer.
建築・外装用塗料には、塗膜の低汚染性(耐汚染性)が要求されるが、このような技術として、例えば、親水性ポリマーにより塗膜表面を親水化し、雨水を塗膜と汚染物質との界面に到達しやすくすることで、汚れの洗浄を促す技術が知られている。
For coatings for buildings and exteriors, low contamination (stain resistance) of the coating film is required, but as such a technology, for example, the surface of the coating film is made hydrophilic with a hydrophilic polymer, and rainwater is contaminated with the coating film. A technique is known that facilitates cleaning of dirt by making it easier to reach the interface with a substance.
特開2001-72928号公報(特許文献1)には、(a)有機合成樹脂のエマルション、(b)カップリング剤、および(c)前記有機合成樹脂、(a)以外でかつ前記カップリング剤(b)と反応し得る基を有する親水化用有機化合物からなる低汚染型水性塗料用樹脂組成物が開示されている。
JP 2001-72928 A (Patent Document 1) discloses (a) an emulsion of an organic synthetic resin, (b) a coupling agent, and (c) the organic synthetic resin, other than (a) and the coupling agent. A resin composition for a low-contamination water-based paint comprising a hydrophilic compound having a group capable of reacting with (b) is disclosed.
また、国際公開第2008/102816号パンフレット(特許文献2)には、乳化重合によって得られる(メタ)アクリルエマルション(A)と、水溶性樹脂(B)とを必須として構成され、(メタ)アクリルエマルション(A)と水溶性樹脂(B)とが架橋構造を形成し得る塗料用水性樹脂組成物が開示されている。
In addition, the pamphlet of International Publication No. 2008/102816 (Patent Document 2) includes (meth) acrylic emulsion (A) obtained by emulsion polymerization and water-soluble resin (B) as essential components. An aqueous resin composition for paints in which the emulsion (A) and the water-soluble resin (B) can form a crosslinked structure is disclosed.
このような中、親水性ポリマーを利用したさらなる塗料の低汚染化技術が望まれている。
In such circumstances, there is a demand for a technology for further reducing paint contamination using a hydrophilic polymer.
本発明の目的は、親水化材料(例えば、塗料用の親水性ポリマー)などとして有用な新規ポリマー及びこのポリマーを含む組成物を提供することにある。
An object of the present invention is to provide a novel polymer useful as a hydrophilic material (for example, a hydrophilic polymer for paint) and a composition containing the polymer.
本発明の他の目的は、長期にわたって塗膜の低汚染性(親水性)を維持するのに有用なポリマー及びこのポリマーを含む組成物を提供することにある。
Another object of the present invention is to provide a polymer useful for maintaining low contamination (hydrophilicity) of a coating film over a long period of time and a composition containing this polymer.
本発明のさらに他の目的は、耐水性、耐候性、伸長性、密着性などに優れた塗膜を形成するのに有用なポリマー及びこのポリマーを含む組成物を提供することにある。
Still another object of the present invention is to provide a polymer useful for forming a coating film excellent in water resistance, weather resistance, stretchability, adhesion and the like and a composition containing the polymer.
本発明の別の目的は、高光沢の塗膜を形成できる組成物を提供することにある。
Another object of the present invention is to provide a composition capable of forming a highly glossy coating film.
本発明のさらに別の目的は、良好な取扱性を有する組成物を提供することにある。
Still another object of the present invention is to provide a composition having good handleability.
本発明者らは、親水性ポリマーを利用した低汚染化技術を検討したところ、塗膜の親水性が徐々に低下することを見出した。
そして、このような知見に基づいて、特許文献2の技術のように、エマルションと親水性ポリマーとで架橋構造を形成する技術を検討したが、水溶性ポリマーの脱落抑制効果が十分でない場合があり、さらに改善の余地があることがわかった。 The inventors of the present invention have studied a technique for reducing contamination using a hydrophilic polymer, and found that the hydrophilicity of the coating film gradually decreases.
And based on such knowledge, like the technique of patent document 2, the technique which forms a crosslinked structure with an emulsion and a hydrophilic polymer was examined, but the drop-off inhibitory effect of a water-soluble polymer may not be enough. I found that there was room for further improvement.
そして、このような知見に基づいて、特許文献2の技術のように、エマルションと親水性ポリマーとで架橋構造を形成する技術を検討したが、水溶性ポリマーの脱落抑制効果が十分でない場合があり、さらに改善の余地があることがわかった。 The inventors of the present invention have studied a technique for reducing contamination using a hydrophilic polymer, and found that the hydrophilicity of the coating film gradually decreases.
And based on such knowledge, like the technique of patent document 2, the technique which forms a crosslinked structure with an emulsion and a hydrophilic polymer was examined, but the drop-off inhibitory effect of a water-soluble polymer may not be enough. I found that there was room for further improvement.
このような中、本発明者らは、上記課題を解決するためさらに鋭意研究を重ねた結果、親水性ポリマーの中でも、特にN-ビニルラクタム系ポリマーに着目し、N-ビニルラクタム系モノマー(N-ビニルピロリドンなど)に、ヒンダードアミン系モノマーを共重合することで、エマルションとの組み合わせにおいて、塗膜の低汚染化効果(親水化効果)を長期にわたって維持できる組成物が得られることを見出した。
Under these circumstances, as a result of further earnest studies to solve the above-mentioned problems, the present inventors have focused on N-vinyl lactam polymers among hydrophilic polymers, and N-vinyl lactam monomers (N It has been found that by copolymerizing a hindered amine monomer with vinylpyrrolidone or the like, a composition capable of maintaining the effect of reducing the contamination of the coating film (hydrophilization effect) over a long period of time in combination with the emulsion.
なお、ヒンダードアミン系化合物は、耐光安定剤として知られるが、本発明では、ヒンダードアミン系モノマーをN-ビニルラクタム系ポリマーと組み合わせて重合することで、意外なことに、耐光安定化効果からは想定しえない長期の低汚染化効果を向上できるポリマーが得られることがわかった。
The hindered amine compound is known as a light stabilizer, but in the present invention, it is unexpectedly assumed from the light resistance stabilization effect by polymerizing a hindered amine monomer in combination with an N-vinyl lactam polymer. It was found that a polymer capable of improving the long-term effect of reducing contamination was obtained.
本発明者らは、上記以外にも種々の新知見を得て、さらに鋭意検討を重ねて本発明を完成するに至った。
In addition to the above, the present inventors have obtained various new findings and have made further studies to complete the present invention.
すなわち、本発明のポリマー(コポリマー)は、ビニルラクタム系モノマー及びヒンダードアミン系モノマーを少なくとも重合成分(単量体成分(b))とするポリマー(ポリマー(B))である。
That is, the polymer (copolymer) of the present invention is a polymer (polymer (B)) having a vinyl lactam monomer and a hindered amine monomer as at least a polymerization component (monomer component (b)).
本発明のポリマーにおいて、ビニルラクタム系モノマーの割合は、重合成分全体に対して50質量%以上であってもよい。また、本発明のポリマーにおいて、ビニルラクタム系モノマーの割合は、重合成分全体に対して80モル%以上であってもよい。
本発明のポリマーにおいて、ヒンダードアミン系モノマーの割合は、ビニルラクタム系モノマー100モルに対して、0.01~15モルであってもよい。代表的には、本発明のポリマーにおいて、ビニルラクタム系モノマーの割合が重合成分全体の80モル%以上であり、ヒンダードアミン系モノマーの割合がビニルラクタム系モノマー100モルに対して0.05~10モルであってもよい。 In the polymer of the present invention, the proportion of the vinyl lactam monomer may be 50% by mass or more based on the entire polymerization component. In the polymer of the present invention, the proportion of the vinyl lactam monomer may be 80 mol% or more based on the entire polymerization component.
In the polymer of the present invention, the ratio of the hindered amine monomer may be 0.01 to 15 mol with respect to 100 mol of the vinyl lactam monomer. Typically, in the polymer of the present invention, the proportion of the vinyl lactam monomer is 80 mol% or more of the entire polymerization component, and the proportion of the hindered amine monomer is 0.05 to 10 mol with respect to 100 mol of the vinyl lactam monomer. It may be.
本発明のポリマーにおいて、ヒンダードアミン系モノマーの割合は、ビニルラクタム系モノマー100モルに対して、0.01~15モルであってもよい。代表的には、本発明のポリマーにおいて、ビニルラクタム系モノマーの割合が重合成分全体の80モル%以上であり、ヒンダードアミン系モノマーの割合がビニルラクタム系モノマー100モルに対して0.05~10モルであってもよい。 In the polymer of the present invention, the proportion of the vinyl lactam monomer may be 50% by mass or more based on the entire polymerization component. In the polymer of the present invention, the proportion of the vinyl lactam monomer may be 80 mol% or more based on the entire polymerization component.
In the polymer of the present invention, the ratio of the hindered amine monomer may be 0.01 to 15 mol with respect to 100 mol of the vinyl lactam monomer. Typically, in the polymer of the present invention, the proportion of the vinyl lactam monomer is 80 mol% or more of the entire polymerization component, and the proportion of the hindered amine monomer is 0.05 to 10 mol with respect to 100 mol of the vinyl lactam monomer. It may be.
本発明のポリマーにおいて、重合成分は、さらに、官能基(官能基β)を有する単量体を含んでいてもよく、例えば、カルボニル基、酸基、カーボネート基、イソシアネート基、オキサゾリン基、オキサゾリジン基、ヒドラジノ基、エポキシ基、アミノ基、ヒドロキシル基、及びメルカプト基から選択された少なくとも1種の官能基を有する単量体[例えば、カルボニル基含有単量体(例えば、ダイアセトン(メタ)アクリルアミド)を含有する官能基(官能基β)を有する単量体]を含んでいてもよい。
In the polymer of the present invention, the polymerization component may further contain a monomer having a functional group (functional group β), for example, a carbonyl group, an acid group, a carbonate group, an isocyanate group, an oxazoline group, an oxazolidine group. , A monomer having at least one functional group selected from hydrazino group, epoxy group, amino group, hydroxyl group, and mercapto group [for example, carbonyl group-containing monomer (for example, diacetone (meth) acrylamide) A monomer having a functional group containing (functional group β)].
代表的な本発明のポリマーには、
ビニルラクタム系モノマーがN-ビニルピロリドンを含み、
重合成分が、さらに、カルボニル基含有単量体、酸基含有単量体、及びヒドロキシ基含有単量体から選択された少なくとも1種の官能基を有する単量体を含み、
ビニルラクタム系モノマーの割合が重合成分全体に対して70質量%以上であり、
ヒンダードアミン系モノマー及び官能基を有する単量体の割合が、それぞれ、ビニルラクタム系モノマー100質量部(又は100モル)に対して10質量部(又は10モル)以下である、ポリマーなどが含まれる。 Representative polymers of the present invention include:
The vinyl lactam monomer contains N-vinylpyrrolidone,
The polymerization component further includes a monomer having at least one functional group selected from a carbonyl group-containing monomer, an acid group-containing monomer, and a hydroxy group-containing monomer,
The proportion of the vinyl lactam monomer is 70% by mass or more based on the entire polymerization component,
The polymer etc. whose ratio of the hindered amine-type monomer and the monomer which has a functional group are 10 mass parts (or 10 mol) or less with respect to 100 mass parts (or 100 mol) of vinyl lactam monomers, respectively are contained.
ビニルラクタム系モノマーがN-ビニルピロリドンを含み、
重合成分が、さらに、カルボニル基含有単量体、酸基含有単量体、及びヒドロキシ基含有単量体から選択された少なくとも1種の官能基を有する単量体を含み、
ビニルラクタム系モノマーの割合が重合成分全体に対して70質量%以上であり、
ヒンダードアミン系モノマー及び官能基を有する単量体の割合が、それぞれ、ビニルラクタム系モノマー100質量部(又は100モル)に対して10質量部(又は10モル)以下である、ポリマーなどが含まれる。 Representative polymers of the present invention include:
The vinyl lactam monomer contains N-vinylpyrrolidone,
The polymerization component further includes a monomer having at least one functional group selected from a carbonyl group-containing monomer, an acid group-containing monomer, and a hydroxy group-containing monomer,
The proportion of the vinyl lactam monomer is 70% by mass or more based on the entire polymerization component,
The polymer etc. whose ratio of the hindered amine-type monomer and the monomer which has a functional group are 10 mass parts (or 10 mol) or less with respect to 100 mass parts (or 100 mol) of vinyl lactam monomers, respectively are contained.
特に、重合成分が官能基を有する単量体を含む場合、官能基を有する単量体は、少なくともカルボニル基含有単量体(例えば、ダイアセトン(メタ)アクリルアミド)を含んでいてもよい。
In particular, when the polymerization component contains a monomer having a functional group, the monomer having a functional group may contain at least a carbonyl group-containing monomer (for example, diacetone (meth) acrylamide).
本発明のポリマーは、親水化材料(親水化剤)などとして好適に使用でき、例えば、エマルションと組み合わせて使用するためのポリマー(特に、塗料用水性組成物を構成するためのポリマー)であってもよい。そのため、本発明には、前記ポリマー(ポリマー(B))で構成された親水化剤[例えば、塗料用(特に水性塗料用)の親水化剤]も含まれる。
The polymer of the present invention can be suitably used as a hydrophilizing material (hydrophilizing agent) and the like, for example, a polymer for use in combination with an emulsion (particularly a polymer for constituting an aqueous composition for paint). Also good. Therefore, the present invention also includes a hydrophilizing agent composed of the polymer (polymer (B)) [for example, a hydrophilizing agent for paint (particularly for water-based paint)].
本発明は、エマルション(A)と、前記ポリマー(B)とを含む組成物を包含する。
このような組成物において、エマルション(A)は、特に、アクリル系エマルションであってもよい。 The present invention includes a composition comprising an emulsion (A) and the polymer (B).
In such a composition, the emulsion (A) may in particular be an acrylic emulsion.
このような組成物において、エマルション(A)は、特に、アクリル系エマルションであってもよい。 The present invention includes a composition comprising an emulsion (A) and the polymer (B).
In such a composition, the emulsion (A) may in particular be an acrylic emulsion.
本発明の組成物において、エマルション(A)は、アニオン性であってもよい(例えば、アニオン性基を有してもよい)。代表的には、エマルション(A)は、以下の(1)及び/(2)を充足するエマルションであってもよい。
(1)アニオン性基含有単量体を含む単量体成分(a)を重合成分とする樹脂で構成されている
(2)エマルション(A)を構成する乳化剤がアニオン性乳化剤を含む In the composition of the present invention, the emulsion (A) may be anionic (for example, may have an anionic group). Typically, the emulsion (A) may be an emulsion satisfying the following (1) and / (2).
(1) Consists of a resin comprising a monomer component (a) containing an anionic group-containing monomer as a polymerization component (2) The emulsifier constituting the emulsion (A) contains an anionic emulsifier
(1)アニオン性基含有単量体を含む単量体成分(a)を重合成分とする樹脂で構成されている
(2)エマルション(A)を構成する乳化剤がアニオン性乳化剤を含む In the composition of the present invention, the emulsion (A) may be anionic (for example, may have an anionic group). Typically, the emulsion (A) may be an emulsion satisfying the following (1) and / (2).
(1) Consists of a resin comprising a monomer component (a) containing an anionic group-containing monomer as a polymerization component (2) The emulsifier constituting the emulsion (A) contains an anionic emulsifier
本発明の組成物において、エマルション(A)は、官能基αを有する単量体を含む単量体成分(a)を重合成分とする樹脂で構成され、ポリマー(B)の重合成分が、官能基αと架橋構造を形成しうる官能基βを有する単量体を含んでいてもよい。
In the composition of the present invention, the emulsion (A) is composed of a resin having a monomer component (a) containing a monomer having a functional group α as a polymerization component, and the polymerization component of the polymer (B) is functional. A monomer having a functional group β capable of forming a cross-linking structure with the group α may be included.
本発明の組成物は、さらに、官能基αと官能基βとの間で反応して結合を形成可能な架橋剤(C)を含有してもよい。
The composition of the present invention may further contain a crosslinking agent (C) capable of forming a bond by reacting between the functional group α and the functional group β.
代表的には、本発明の組成物は、官能基αを有する単量体がカルボニル基含有単量体を含み、官能基βを有するモノマーがカルボニル基含有単量体を含み、ヒドラジン系架橋剤(C1)を介してエマルション(A)とポリマー(B)とが架橋構造を形成可能である、及び/又は
官能基αを有する単量体がカルボキシル基含有単量体を含み、官能基βを有するモノマーがカルボキシル基含有単量体を含み、オキサゾリン系架橋剤(C1)を介してエマルション(A)とポリマー(B)とが架橋構造を形成可能である、組成物であってもよい。 Typically, in the composition of the present invention, a monomer having a functional group α includes a carbonyl group-containing monomer, a monomer having a functional group β includes a carbonyl group-containing monomer, and a hydrazine-based crosslinking agent. The emulsion (A) and the polymer (B) can form a crosslinked structure via (C1), and / or the monomer having the functional group α includes a carboxyl group-containing monomer, and the functional group β The composition may contain a carboxyl group-containing monomer and the emulsion (A) and the polymer (B) can form a crosslinked structure via the oxazoline-based crosslinking agent (C1).
官能基αを有する単量体がカルボキシル基含有単量体を含み、官能基βを有するモノマーがカルボキシル基含有単量体を含み、オキサゾリン系架橋剤(C1)を介してエマルション(A)とポリマー(B)とが架橋構造を形成可能である、組成物であってもよい。 Typically, in the composition of the present invention, a monomer having a functional group α includes a carbonyl group-containing monomer, a monomer having a functional group β includes a carbonyl group-containing monomer, and a hydrazine-based crosslinking agent. The emulsion (A) and the polymer (B) can form a crosslinked structure via (C1), and / or the monomer having the functional group α includes a carboxyl group-containing monomer, and the functional group β The composition may contain a carboxyl group-containing monomer and the emulsion (A) and the polymer (B) can form a crosslinked structure via the oxazoline-based crosslinking agent (C1).
本発明の組成物において、エマルション(A)とポリマー(B)との割合は、例えば、前者/後者(質量比)=99/1~60/40程度であってもよい。
In the composition of the present invention, the ratio of the emulsion (A) to the polymer (B) may be, for example, the former / the latter (mass ratio) = 99/1 to 60/40.
本発明の組成物は、エマルション(A)及びポリマー(B)を含む塗料用水性組成物であってもよく、特に、トップコート用(特に、外装材のトップコート用)であってもよい。
The composition of the present invention may be an aqueous composition for paints containing an emulsion (A) and a polymer (B), and particularly for a top coat (especially for a top coat of an exterior material).
本発明には、前記組成物で形成された塗膜も含まれる。また、本発明には、基材(ベース基材)とこの基材上に形成された前記塗膜(被膜)とで構成された基材(コート基材)も含まれる。
The present invention includes a coating film formed from the composition. The present invention also includes a base material (coated base material) composed of a base material (base base material) and the coating film (coating film) formed on the base material.
本発明では、エマルション(A)に対して、ポリマー(B)を組み合わせることで、塗膜の低汚染性(親水性)を維持でき、塗膜(被膜)に対する汚れの付着を抑制又は防止できる。
In the present invention, by combining the polymer (B) with the emulsion (A), low contamination (hydrophilicity) of the coating film can be maintained, and adhesion of dirt to the coating film (coating film) can be suppressed or prevented.
そのため、本発明には、エマルション(A)を含む組成物で形成された塗膜に対する耐汚染化剤(汚れの付着を抑制又は防止するための剤)であって、ポリマー(B)(ビニルラクタム系モノマー及びヒンダードアミン系モノマーを少なくとも重合成分(単量体成分(b))とするポリマー)で構成された(又はポリマー(B)を含む)耐汚染化剤(汚れ付着防止剤)も含まれる。
Therefore, the present invention provides a stain-proofing agent (an agent for suppressing or preventing the adhesion of dirt) to a coating film formed from a composition containing the emulsion (A), which comprises a polymer (B) (vinyl lactam). Also included are antifouling agents (contamination prevention agents) composed of (or containing the polymer (B)) at least as a polymerization component (a polymer having the monomer component (b)) with a monomer and a hindered amine monomer.
本発明の新規なポリマー及び組成物(特に水性樹脂組成物)は、親水化材料(例えば、塗料用の親水性又は水溶性ポリマー)などとして有用である。
このようなポリマー及び組成物は、親水性又は水溶性であるにもかかわらず、長期にわたって塗膜の低汚染性(親水性)を維持できる。 The novel polymers and compositions (especially aqueous resin compositions) of the present invention are useful as hydrophilizing materials (for example, hydrophilic or water-soluble polymers for paints).
Such polymers and compositions can maintain the low contamination (hydrophilicity) of the coating film over a long period of time despite being hydrophilic or water-soluble.
このようなポリマー及び組成物は、親水性又は水溶性であるにもかかわらず、長期にわたって塗膜の低汚染性(親水性)を維持できる。 The novel polymers and compositions (especially aqueous resin compositions) of the present invention are useful as hydrophilizing materials (for example, hydrophilic or water-soluble polymers for paints).
Such polymers and compositions can maintain the low contamination (hydrophilicity) of the coating film over a long period of time despite being hydrophilic or water-soluble.
また、本発明のポリマー及び組成物は、塗膜物性(例えば、耐水性、耐候性、伸長性、密着性など)において優れた塗膜を形成できる。
Also, the polymer and composition of the present invention can form a coating film excellent in coating film physical properties (for example, water resistance, weather resistance, extensibility, adhesion, etc.).
さらに、本発明のポリマー及び組成物によれば、高光沢の塗膜(又はつやが強い塗膜)を形成することもできる。
Furthermore, according to the polymer and composition of the present invention, a highly glossy coating film (or a coating film with strong gloss) can be formed.
さらにまた、本発明のポリマー及び組成物は、良好な取扱性(例えば、優れた貯蔵安定性)を有している。
Furthermore, the polymer and composition of the present invention have good handleability (for example, excellent storage stability).
特に、本発明のポリマー及び組成物は、これらの優れた効果をバランス良く組み合わせて奏することもでき、塗料などとしての有用性が極めて高いものである。
In particular, the polymer and composition of the present invention can be produced by combining these excellent effects in a well-balanced manner, and are extremely useful as a paint.
<ポリマー>
本発明のポリマー(後述のポリマー(B)に対応)は、ビニルラクタム系モノマー及びヒンダードアミン系モノマーを少なくとも重合成分(又は単量体成分、後述の単量体成分(b)に対応)とするポリマーである。 <Polymer>
The polymer of the present invention (corresponding to the polymer (B) described later) is a polymer comprising a vinyl lactam monomer and a hindered amine monomer as at least a polymerization component (or a monomer component, corresponding to the monomer component (b) described later). It is.
本発明のポリマー(後述のポリマー(B)に対応)は、ビニルラクタム系モノマー及びヒンダードアミン系モノマーを少なくとも重合成分(又は単量体成分、後述の単量体成分(b)に対応)とするポリマーである。 <Polymer>
The polymer of the present invention (corresponding to the polymer (B) described later) is a polymer comprising a vinyl lactam monomer and a hindered amine monomer as at least a polymerization component (or a monomer component, corresponding to the monomer component (b) described later). It is.
(ビニルラクタム系モノマー)
ビニルラクタム系モノマーとしては、例えば、ビニルピロリドン(N-ビニルピロリドン)、ビニルカプロラクタム(N-ビニルカプロラクタム)などが挙げられる。 (Vinyl lactam monomer)
Examples of vinyl lactam monomers include vinyl pyrrolidone (N-vinyl pyrrolidone), vinyl caprolactam (N-vinyl caprolactam), and the like.
ビニルラクタム系モノマーとしては、例えば、ビニルピロリドン(N-ビニルピロリドン)、ビニルカプロラクタム(N-ビニルカプロラクタム)などが挙げられる。 (Vinyl lactam monomer)
Examples of vinyl lactam monomers include vinyl pyrrolidone (N-vinyl pyrrolidone), vinyl caprolactam (N-vinyl caprolactam), and the like.
中でも、ビニルピロリドンが好ましく、そのため、ビニルラクタム系モノマーは、少なくともビニルピロリドンで構成してもよい。
Among them, vinyl pyrrolidone is preferable, and therefore the vinyl lactam monomer may be composed of at least vinyl pyrrolidone.
なお、ビニルラクタム系モノマーを、ビニルピロリドンと他のビニルラクタム系モノマーとで構成する場合、ビニルラクタム系モノマー全体に対するビニルピロリドンの割合は、例えば、50モル%以上、好ましくは70モル%以上、さらに好ましくは90モル%以上であってもよい。
In the case where the vinyl lactam monomer is composed of vinyl pyrrolidone and another vinyl lactam monomer, the ratio of vinyl pyrrolidone to the whole vinyl lactam monomer is, for example, 50 mol% or more, preferably 70 mol% or more, Preferably, 90 mol% or more may be sufficient.
重合成分(単量体成分(b))において、ビニルラクタム系モノマーの割合は、他のモノマーの種類にもよるが、ポリマーに親水性(水溶性)を付与するという観点から、例えば、重合成分全体の30質量%以上、好ましくは50質量%以上、さらに好ましくは70質量%以上、特に80質量%以上、特に好ましくは85質量%以上(例えば、90質量%以上)であってもよい。
重合成分(単量体成分(b))において、ビニルラクタム系モノマーの割合は、他のモノマーの種類にもよるが、ポリマーに親水性(水溶性)を付与するという観点から、例えば、重合成分全体の30モル%以上、好ましくは50モル%以上、さらに好ましくは70モル%以上、特に80モル%以上、特に好ましくは85モル%以上(例えば、90モル%以上)であってもよい。すなわち、重合成分全体に対するビニルラクタム系モノマーの割合は、質量換算(質量%)及びモル換算(モル%)において同様の範囲であってもよい。以下、重合成分における割合(例えば、ヒンダードアミン系モノマー、官能基を有する単量体等)についても同様であってもよい(例えば、質量%をモル%としてもよい)。 In the polymerization component (monomer component (b)), the proportion of the vinyl lactam monomer depends on the type of other monomers, but from the viewpoint of imparting hydrophilicity (water solubility) to the polymer, for example, the polymerization component It may be 30% by mass or more, preferably 50% by mass or more, more preferably 70% by mass or more, particularly 80% by mass or more, and particularly preferably 85% by mass or more (for example, 90% by mass or more).
In the polymerization component (monomer component (b)), the proportion of the vinyl lactam monomer depends on the type of other monomers, but from the viewpoint of imparting hydrophilicity (water solubility) to the polymer, for example, the polymerization component It may be 30 mol% or more of the whole, preferably 50 mol% or more, more preferably 70 mol% or more, particularly 80 mol% or more, particularly preferably 85 mol% or more (for example, 90 mol% or more). That is, the ratio of the vinyl lactam monomer to the entire polymerization component may be in the same range in terms of mass (mass%) and mol (mol%). Hereinafter, the same may be applied to the ratio (for example, hindered amine monomer, monomer having a functional group, etc.) in the polymerization component (for example, mass% may be mol%).
重合成分(単量体成分(b))において、ビニルラクタム系モノマーの割合は、他のモノマーの種類にもよるが、ポリマーに親水性(水溶性)を付与するという観点から、例えば、重合成分全体の30モル%以上、好ましくは50モル%以上、さらに好ましくは70モル%以上、特に80モル%以上、特に好ましくは85モル%以上(例えば、90モル%以上)であってもよい。すなわち、重合成分全体に対するビニルラクタム系モノマーの割合は、質量換算(質量%)及びモル換算(モル%)において同様の範囲であってもよい。以下、重合成分における割合(例えば、ヒンダードアミン系モノマー、官能基を有する単量体等)についても同様であってもよい(例えば、質量%をモル%としてもよい)。 In the polymerization component (monomer component (b)), the proportion of the vinyl lactam monomer depends on the type of other monomers, but from the viewpoint of imparting hydrophilicity (water solubility) to the polymer, for example, the polymerization component It may be 30% by mass or more, preferably 50% by mass or more, more preferably 70% by mass or more, particularly 80% by mass or more, and particularly preferably 85% by mass or more (for example, 90% by mass or more).
In the polymerization component (monomer component (b)), the proportion of the vinyl lactam monomer depends on the type of other monomers, but from the viewpoint of imparting hydrophilicity (water solubility) to the polymer, for example, the polymerization component It may be 30 mol% or more of the whole, preferably 50 mol% or more, more preferably 70 mol% or more, particularly 80 mol% or more, particularly preferably 85 mol% or more (for example, 90 mol% or more). That is, the ratio of the vinyl lactam monomer to the entire polymerization component may be in the same range in terms of mass (mass%) and mol (mol%). Hereinafter, the same may be applied to the ratio (for example, hindered amine monomer, monomer having a functional group, etc.) in the polymerization component (for example, mass% may be mol%).
(ヒンダードアミン系モノマー)
ヒンダードアミン系モノマーとしては、例えば、ピペラジン骨格(特に、2,2,6,6-テトラメチルピペリジン骨格)を有する重合性化合物(ピペラジン骨格及び重合性基を有する化合物)が挙げられる。 (Hindered amine monomers)
Examples of the hindered amine monomer include a polymerizable compound having a piperazine skeleton (particularly a 2,2,6,6-tetramethylpiperidine skeleton) (a compound having a piperazine skeleton and a polymerizable group).
ヒンダードアミン系モノマーとしては、例えば、ピペラジン骨格(特に、2,2,6,6-テトラメチルピペリジン骨格)を有する重合性化合物(ピペラジン骨格及び重合性基を有する化合物)が挙げられる。 (Hindered amine monomers)
Examples of the hindered amine monomer include a polymerizable compound having a piperazine skeleton (particularly a 2,2,6,6-tetramethylpiperidine skeleton) (a compound having a piperazine skeleton and a polymerizable group).
ヒンダードアミン系モノマーにおいて、重合性基としては、特に限定されず、例えば、アルケニル基(ビニル基、アリル基など)、アルケニルカルボニル基[例えば、(メタ)アクリロイル基、クロトノイル基など]などが挙げられる。
In the hindered amine monomer, the polymerizable group is not particularly limited, and examples thereof include an alkenyl group (such as a vinyl group and an allyl group) and an alkenylcarbonyl group [such as a (meth) acryloyl group and a crotonoyl group].
なお、ヒンダードアミン系モノマーの重合性基の数は、1以上であればよく、1~4、好ましくは1~3、さらに好ましくは1であってもよい。好ましいヒンダードアミン系モノマーは、単官能性モノマー(重合性基を1つ有する化合物)である。そのため、ヒンダードアミン系モノマーは、少なくとも単官能性モノマーで構成してもよい。
The number of polymerizable groups in the hindered amine monomer may be 1 or more, and may be 1 to 4, preferably 1 to 3, and more preferably 1. A preferred hindered amine monomer is a monofunctional monomer (a compound having one polymerizable group). Therefore, the hindered amine monomer may be composed of at least a monofunctional monomer.
代表的なヒンダードアミン系モノマーには、下記式(I)で表される化合物などが含まれる。
Typical hindered amine monomers include compounds represented by the following formula (I).
R1~R6において、アルキル基としては、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、s-ブチル基、t-ブチル基などのC1-20アルキル基、好ましくはC1-10アルキル基、さらに好ましくはC1-4アルキル基、特にメチル基が挙げられる。
In R 1 to R 6 , examples of the alkyl group include C 1-20 alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a s-butyl group, and a t-butyl group. Preferably, a C 1-10 alkyl group, more preferably a C 1-4 alkyl group, particularly a methyl group.
代表的なR1及びR2は水素原子又はメチル基であり、特にR1が水素原子、R2が水素原子又はメチル基であるのが好ましい。また、代表的なR3~R6はメチル基である。
Typical R 1 and R 2 are a hydrogen atom or a methyl group, and it is particularly preferable that R 1 is a hydrogen atom and R 2 is a hydrogen atom or a methyl group. Representative R 3 to R 6 are methyl groups.
Y及びZにおける置換基としては、炭化水素基[例えば、アルキル基(例えば、メチル基などの前記例示のアルキル基(C1-20アルキル基、好ましくはC1-4アルキル基など)など)など]、アルコキシ基(例えば、メトキシ基、エトキシ基などのC1-20アルコキシ基、好ましくはC1-10アルコキシ基、さらに好ましくはC1-4アルコキシ基、特にメトキシ基)、アシル基(例えば、アセチル基などのC1-10アシル基など)、ハロゲン原子(フッ素原子、塩素原子、臭素原子、ヨウ素原子など)、シアノ基、ヒドロキシル基、重合性基(例えば、(メタ)アクリロイル基、クロトノイル基)などが挙げられる。
Examples of the substituent for Y and Z include hydrocarbon groups such as alkyl groups (for example, the above-exemplified alkyl groups such as a methyl group (C 1-20 alkyl group, preferably C 1-4 alkyl group), etc.) ], An alkoxy group (for example, a C 1-20 alkoxy group such as a methoxy group or an ethoxy group, preferably a C 1-10 alkoxy group, more preferably a C 1-4 alkoxy group, particularly a methoxy group), an acyl group (for example, C 1-10 acyl group such as acetyl group), halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom etc.), cyano group, hydroxyl group, polymerizable group (eg (meth) acryloyl group, crotonoyl group) ) And the like.
代表的なYとしては、水素原子、アルキル基(例えば、メチル基などのC1-4アルキル基)、アルコキシ基(例えば、メトキシ基などのC1-4アルコキシ基)、アシル基(例えば、アセチル基などのC1-4アシル基)、(メタ)アクリルロイル基、クロトノイル基などが挙げられ、特に、水素原子又はメチル基が好ましい。
Typical examples of Y include a hydrogen atom, an alkyl group (for example, a C 1-4 alkyl group such as a methyl group), an alkoxy group (for example, a C 1-4 alkoxy group such as a methoxy group), an acyl group (for example, an acetyl group). A C 1-4 acyl group such as a group), a (meth) acryloyl group, a crotonoyl group, and the like. Particularly, a hydrogen atom or a methyl group is preferable.
また、代表的なZとしては、水素原子又はシアノ基が挙げられ、特に水素原子が好ましい。
Further, representative Z includes a hydrogen atom or a cyano group, and a hydrogen atom is particularly preferable.
具体的なヒンダードアミン系モノマーとしては、例えば、
4-(メタ)アクリルロイルオキシ-2,2,6,6-テトラメチルピペリジン、置換基を有する4-(メタ)アクリロイルオキシ-2,2,6,6-テトラメチルピペリジン{例えば、4-(メタ)アクリロイルオキシ-2,2,6,6-テトラメチル-1-アルキルピペリジン[例えば、4-(メタ)アクリロイルオキシ-1,2,2,6,6-ペンタメチルピペリジンなどの4-(メタ)アクリロイルオキシ-1-C1-4アルキル-2,2,6,6-テトラメチルピペリジン]、4-(メタ)アクリロイルオキシ-2,2,6,6-テトラメチル-1-アルコキシピペリジン[例えば、4-(メタ)アクリロイル-1-メトキシ-2,2,6,6-テトラメチルピペリジンなどの4-(メタ)アクリロイルオキシ-1-C1-4アルコキシ-2,2,6,6-テトラメチルピペリジンなど]などのN-置換(メタ)アクリロイルオキシ-2,2,6,6-テトラメチルピペリジン;4-シアノ-4-(メタ)アクリロイルオキシ-2,2,6,6-テトラメチルピペリジンなどの4-置換-4-(メタ)アクリロイルオキシ-2,2,6,6-テトラメチルピペリジンなど}などの4-(メタ)アクリロイルオキシ-2,2,6,6-テトラメチルピペリジン類;
4-クロトノイルオキシ-2,2,6,6-テトラメチルピペリジンなどの4-クロトノイルオキシ-2,2,6,6-テトラメチルピペリジン類;
4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジン、置換基を有する4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジン{例えば、4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチル-1-アルキルピペリジン[例えば、4-(メタ)アクリロイルアミノ-1,2,2,6,6-ペンタメチルピペリジンなどの4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチル-1-C1-4アルキルピペリジン]などのN-置換(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジン;4-シアノ-4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジンなどの4-置換-4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジンなど}などの4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジン類;
4-クロトノイルアミノ-2,2,6,6-テトラメチルピペリジンなどの4-クロトノイルアミノ-2,2,6,6-テトラメチルピペリジン類;
1-(メタ)アクリロイル-4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジン、1-(メタ)アクリロイル-4-シアノ-4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジンなどの1-(メタ)アクリロイル-4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジン類;
1-クロトノイル-4-クロトノイルオキシ-2,2,6,6-テトラメチルピペリジンなどの1-クロトノイル-4-クロトノイルオキシ-2,2,6,6-テトラメチルピペリジン類;
などが挙げられる。 As a specific hindered amine monomer, for example,
4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine having a substituent {for example, 4- ( (Meth) acryloyloxy-2,2,6,6-tetramethyl-1-alkylpiperidine [eg 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine etc. ) Acryloyloxy-1-C 1-4 alkyl-2,2,6,6-tetramethylpiperidine], 4- (meth) acryloyloxy-2,2,6,6-tetramethyl-1-alkoxypiperidine [for example 4- (meth) acryloyl-1-methoxy-2,2,6,6-tetramethylpiperidine, such as 4- (meth) acryloyloxy -1-C 1-4 a N-substituted (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, such as 4-hydroxy-4- (meth) acryloyloxy- 4- (meth) acryloyloxy-2 such as 4-substituted-4- (meth) acryloyloxy-2, such as 2,2,6,6-tetramethylpiperidine, 2,6,6-tetramethylpiperidine, etc.} 2,6,6-tetramethylpiperidines;
4-crotonoyloxy-2,2,6,6-tetramethylpiperidines such as 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine;
4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine having a substituent {for example, 4- (meta ) Acryloylamino-2,2,6,6-tetramethyl-1-alkylpiperidine [eg 4- (meth) such as 4- (meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine N-substituted (meth) acryloylamino-2,2,6,6-tetramethylpiperidine such as acryloylamino-2,2,6,6-tetramethyl-1-C 1-4 alkylpiperidine]; 4-cyano- 4-Substituted-4- (meth) acryloylamino-2,2,6,6-teto such as 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidines such as lamethylpiperidine etc .;
4-crotonoylamino-2,2,6,6-tetramethylpiperidines such as 4-crotonoylamino-2,2,6,6-tetramethylpiperidine;
1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4-cyano-4- (meth) acryloylamino-2,2, 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidines such as 6,6-tetramethylpiperidine;
1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidines such as 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine;
Etc.
4-(メタ)アクリルロイルオキシ-2,2,6,6-テトラメチルピペリジン、置換基を有する4-(メタ)アクリロイルオキシ-2,2,6,6-テトラメチルピペリジン{例えば、4-(メタ)アクリロイルオキシ-2,2,6,6-テトラメチル-1-アルキルピペリジン[例えば、4-(メタ)アクリロイルオキシ-1,2,2,6,6-ペンタメチルピペリジンなどの4-(メタ)アクリロイルオキシ-1-C1-4アルキル-2,2,6,6-テトラメチルピペリジン]、4-(メタ)アクリロイルオキシ-2,2,6,6-テトラメチル-1-アルコキシピペリジン[例えば、4-(メタ)アクリロイル-1-メトキシ-2,2,6,6-テトラメチルピペリジンなどの4-(メタ)アクリロイルオキシ-1-C1-4アルコキシ-2,2,6,6-テトラメチルピペリジンなど]などのN-置換(メタ)アクリロイルオキシ-2,2,6,6-テトラメチルピペリジン;4-シアノ-4-(メタ)アクリロイルオキシ-2,2,6,6-テトラメチルピペリジンなどの4-置換-4-(メタ)アクリロイルオキシ-2,2,6,6-テトラメチルピペリジンなど}などの4-(メタ)アクリロイルオキシ-2,2,6,6-テトラメチルピペリジン類;
4-クロトノイルオキシ-2,2,6,6-テトラメチルピペリジンなどの4-クロトノイルオキシ-2,2,6,6-テトラメチルピペリジン類;
4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジン、置換基を有する4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジン{例えば、4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチル-1-アルキルピペリジン[例えば、4-(メタ)アクリロイルアミノ-1,2,2,6,6-ペンタメチルピペリジンなどの4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチル-1-C1-4アルキルピペリジン]などのN-置換(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジン;4-シアノ-4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジンなどの4-置換-4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジンなど}などの4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジン類;
4-クロトノイルアミノ-2,2,6,6-テトラメチルピペリジンなどの4-クロトノイルアミノ-2,2,6,6-テトラメチルピペリジン類;
1-(メタ)アクリロイル-4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジン、1-(メタ)アクリロイル-4-シアノ-4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジンなどの1-(メタ)アクリロイル-4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジン類;
1-クロトノイル-4-クロトノイルオキシ-2,2,6,6-テトラメチルピペリジンなどの1-クロトノイル-4-クロトノイルオキシ-2,2,6,6-テトラメチルピペリジン類;
などが挙げられる。 As a specific hindered amine monomer, for example,
4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine having a substituent {for example, 4- ( (Meth) acryloyloxy-2,2,6,6-tetramethyl-1-alkylpiperidine [eg 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine etc. ) Acryloyloxy-1-C 1-4 alkyl-2,2,6,6-tetramethylpiperidine], 4- (meth) acryloyloxy-2,2,6,6-tetramethyl-1-alkoxypiperidine [for example 4- (meth) acryloyl-1-methoxy-2,2,6,6-tetramethylpiperidine, such as 4- (meth) acryloyloxy -1-C 1-4 a N-substituted (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, such as 4-hydroxy-4- (meth) acryloyloxy- 4- (meth) acryloyloxy-2 such as 4-substituted-4- (meth) acryloyloxy-2, such as 2,2,6,6-tetramethylpiperidine, 2,6,6-tetramethylpiperidine, etc.} 2,6,6-tetramethylpiperidines;
4-crotonoyloxy-2,2,6,6-tetramethylpiperidines such as 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine;
4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine having a substituent {for example, 4- (meta ) Acryloylamino-2,2,6,6-tetramethyl-1-alkylpiperidine [eg 4- (meth) such as 4- (meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine N-substituted (meth) acryloylamino-2,2,6,6-tetramethylpiperidine such as acryloylamino-2,2,6,6-tetramethyl-1-C 1-4 alkylpiperidine]; 4-cyano- 4-Substituted-4- (meth) acryloylamino-2,2,6,6-teto such as 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidines such as lamethylpiperidine etc .;
4-crotonoylamino-2,2,6,6-tetramethylpiperidines such as 4-crotonoylamino-2,2,6,6-tetramethylpiperidine;
1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4-cyano-4- (meth) acryloylamino-2,2, 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidines such as 6,6-tetramethylpiperidine;
1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidines such as 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine;
Etc.
これらの中でも、特に、4-(メタ)アクリロイルオキシ-2,2,6,6-テトラメチルピペリジン類[例えば、4-(メタ)アクリルロイルオキシ-2,2,6,6-テトラメチルピペリジン、4-(メタ)アクリロイルオキシ-2,2,6,6-テトラメチル-1-アルキルピペリジンなど]が好ましい。
Among these, 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidines [for example, 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-2,2,6,6-tetramethyl-1-alkylpiperidine etc.] are preferred.
ヒンダードアミン系モノマーは、単独で又は2種以上組み合わせて使用してもよい。
The hindered amine monomers may be used alone or in combination of two or more.
ヒンダードアミン系モノマーの割合は、重合成分(単量体成分(b))全体に対して、例えば、30質量%以下(例えば、0.001~25質量%)、好ましくは20質量%以下(例えば、0.01~15質量%)、さらに好ましくは10質量%以下(例えば、0.05~8質量%)であってもよく、通常0.05~10質量%(例えば、0.1~5質量%)であってもよい。
ヒンダードアミン系モノマーの割合は、重合成分(単量体成分(b))全体に対して、例えば、30モル%以下(例えば、0.001~25モル%)、好ましくは20モル%以下(例えば、0.01~15モル%)、さらに好ましくは10モル%以下(例えば、0.05~8モル%)であってもよく、通常0.05~10モル%(例えば、0.1~5モル%)であってもよい。 The ratio of the hindered amine monomer is, for example, 30% by mass or less (for example, 0.001 to 25% by mass), preferably 20% by mass or less (for example, based on the entire polymerization component (monomer component (b)). 0.01 to 15% by mass), more preferably 10% by mass or less (for example, 0.05 to 8% by mass), and usually 0.05 to 10% by mass (for example, 0.1 to 5% by mass). %).
The ratio of the hindered amine monomer is, for example, 30 mol% or less (for example, 0.001 to 25 mol%), preferably 20 mol% or less (for example, for the entire polymerization component (monomer component (b)). 0.01 to 15 mol%), more preferably 10 mol% or less (for example, 0.05 to 8 mol%), and usually 0.05 to 10 mol% (for example, 0.1 to 5 mol%). %).
ヒンダードアミン系モノマーの割合は、重合成分(単量体成分(b))全体に対して、例えば、30モル%以下(例えば、0.001~25モル%)、好ましくは20モル%以下(例えば、0.01~15モル%)、さらに好ましくは10モル%以下(例えば、0.05~8モル%)であってもよく、通常0.05~10モル%(例えば、0.1~5モル%)であってもよい。 The ratio of the hindered amine monomer is, for example, 30% by mass or less (for example, 0.001 to 25% by mass), preferably 20% by mass or less (for example, based on the entire polymerization component (monomer component (b)). 0.01 to 15% by mass), more preferably 10% by mass or less (for example, 0.05 to 8% by mass), and usually 0.05 to 10% by mass (for example, 0.1 to 5% by mass). %).
The ratio of the hindered amine monomer is, for example, 30 mol% or less (for example, 0.001 to 25 mol%), preferably 20 mol% or less (for example, for the entire polymerization component (monomer component (b)). 0.01 to 15 mol%), more preferably 10 mol% or less (for example, 0.05 to 8 mol%), and usually 0.05 to 10 mol% (for example, 0.1 to 5 mol%). %).
ヒンダードアミン系モノマーの割合は、ビニルラクタム系モノマー100質量部に対して、例えば、30質量部以下(例えば、0.001~25質量部)、好ましくは20質量部以下(例えば、0.01~15質量部)、さらに好ましくは10質量部以下(例えば、0.05~8質量部)であってもよく、通常0.05~10質量部(例えば、0.1~5質量部)であってもよい。
ヒンダードアミン系モノマーの割合は、ビニルラクタム系モノマー100モルに対して、例えば、30モル以下(例えば、0.001~25モル)、好ましくは20モル以下(例えば、0.01~15モル)、さらに好ましくは10モル以下(例えば、0.05~8モル)であってもよく、通常0.05~10モル(例えば、0.1~5モル)であってもよい。 The ratio of the hindered amine monomer is, for example, 30 parts by mass or less (for example, 0.001 to 25 parts by mass), preferably 20 parts by mass or less (for example, 0.01 to 15 parts) with respect to 100 parts by mass of the vinyl lactam monomer. Part by mass), more preferably 10 parts by mass or less (eg, 0.05 to 8 parts by mass), and usually 0.05 to 10 parts by mass (eg, 0.1 to 5 parts by mass). Also good.
The ratio of the hindered amine monomer is, for example, 30 mol or less (for example, 0.001 to 25 mol), preferably 20 mol or less (for example, 0.01 to 15 mol), relative to 100 mol of the vinyl lactam monomer, Preferably, it may be 10 mol or less (for example, 0.05 to 8 mol), and may generally be 0.05 to 10 mol (for example, 0.1 to 5 mol).
ヒンダードアミン系モノマーの割合は、ビニルラクタム系モノマー100モルに対して、例えば、30モル以下(例えば、0.001~25モル)、好ましくは20モル以下(例えば、0.01~15モル)、さらに好ましくは10モル以下(例えば、0.05~8モル)であってもよく、通常0.05~10モル(例えば、0.1~5モル)であってもよい。 The ratio of the hindered amine monomer is, for example, 30 parts by mass or less (for example, 0.001 to 25 parts by mass), preferably 20 parts by mass or less (for example, 0.01 to 15 parts) with respect to 100 parts by mass of the vinyl lactam monomer. Part by mass), more preferably 10 parts by mass or less (eg, 0.05 to 8 parts by mass), and usually 0.05 to 10 parts by mass (eg, 0.1 to 5 parts by mass). Also good.
The ratio of the hindered amine monomer is, for example, 30 mol or less (for example, 0.001 to 25 mol), preferably 20 mol or less (for example, 0.01 to 15 mol), relative to 100 mol of the vinyl lactam monomer, Preferably, it may be 10 mol or less (for example, 0.05 to 8 mol), and may generally be 0.05 to 10 mol (for example, 0.1 to 5 mol).
(官能基を有する単量体)
重合成分(単量体成分(b))は、官能基(後述の官能基βに対応)を有する単量体(モノマー)を含んでいてもよい。このような官能基を有するモノマーを重合成分に含むことで、長期親水性などの点でより一層有利になる場合がある。 (Monomer having a functional group)
The polymerization component (monomer component (b)) may contain a monomer (monomer) having a functional group (corresponding to a functional group β described later). By including a monomer having such a functional group in the polymerization component, it may be more advantageous in terms of long-term hydrophilicity.
重合成分(単量体成分(b))は、官能基(後述の官能基βに対応)を有する単量体(モノマー)を含んでいてもよい。このような官能基を有するモノマーを重合成分に含むことで、長期親水性などの点でより一層有利になる場合がある。 (Monomer having a functional group)
The polymerization component (monomer component (b)) may contain a monomer (monomer) having a functional group (corresponding to a functional group β described later). By including a monomer having such a functional group in the polymerization component, it may be more advantageous in terms of long-term hydrophilicity.
官能基(官能基β)としては、例えば、カルボニル基(又はカルボニル基含有基、例えば、ケトン基、アルデヒド基、アシル基など)、酸基(又はアニオン性基、例えば、カルボキシル基、酸無水物基、酸ハライド基、スルホン酸基など)、カーボネート基、イソシアネート基、オキサゾリン基、オキサゾリジン基、ヒドラジノ基、エポキシ基、アミノ基、ヒドロキシル基、メルカプト基などが挙げられる。
Examples of the functional group (functional group β) include a carbonyl group (or a carbonyl group-containing group such as a ketone group, an aldehyde group, and an acyl group), an acid group (or an anionic group such as a carboxyl group, and an acid anhydride). Group, acid halide group, sulfonic acid group, etc.), carbonate group, isocyanate group, oxazoline group, oxazolidine group, hydrazino group, epoxy group, amino group, hydroxyl group, mercapto group and the like.
官能基を有する単量体は、これらの官能基を単独で又は2種以上組み合わせて有していてもよい。
The monomer having a functional group may have these functional groups alone or in combination of two or more.
これらの官能基の中でも、カルボニル基、酸基(アニオン性基)、オキサゾリン基、ヒドラジノ基、ヒドロキシル基などが好ましく、特にカルボニル基、カルボキシル基、ヒドロキシル基が好ましい。
Among these functional groups, a carbonyl group, an acid group (anionic group), an oxazoline group, a hydrazino group, a hydroxyl group, and the like are preferable, and a carbonyl group, a carboxyl group, and a hydroxyl group are particularly preferable.
また、官能基(官能基β)は、後述のエマルションにおける官能基(官能基α)(官能基αを有する単量体)との組み合わせにおいて、架橋構造(又は結合)を形成しうる官能基であってもよい。このような架橋構造(又は結合)は、官能基αと官能基βとの直接的な反応により形成してもよく、後述のように、架橋剤を介して官能基αと官能基βとが架橋構造を形成してもよい。
The functional group (functional group β) is a functional group that can form a crosslinked structure (or bond) in combination with a functional group (functional group α) (a monomer having a functional group α) in an emulsion described later. There may be. Such a crosslinked structure (or bond) may be formed by a direct reaction between the functional group α and the functional group β. As described later, the functional group α and the functional group β are formed via a crosslinking agent. A crosslinked structure may be formed.
具体的な官能基を有する単量体としては、例えば、カルボニル基含有単量体、酸基含有単量体(アニオン性基含有単量体)、ヒドロキシル基含有単量体などが含まれる。
Specific monomers having a functional group include, for example, carbonyl group-containing monomers, acid group-containing monomers (anionic group-containing monomers), hydroxyl group-containing monomers, and the like.
カルボニル基含有単量体としては、例えば、不飽和アルデヒド[例えば、アルケナール(例えば、アクロレイン、メタクロレインなどのC3-10アルケナール)、(メタ)アクリロキシアルキルアルケナール(例えば、アクリルオキシアルキルプロペナール、メタクリルオキシアルキルプロペナール)、ホルミルスチロールなど]、不飽和ケトン[例えば、アルケノン(例えば、メチルビニルケトン、エチルビニルケトン、ビニルブチルケトンなど)、(メタ)アクリロイルオキシアルカノン(例えば、アセトニルアクリレート、アセトニルメタクリレートなど)、N-(メタ)アクリロイルアミノアルカノン(例えば、ダイアセトンアクリルアミド、ダイアセトンメタクリルアミドなど)、アルカンジオール(メタ)アクリレートアセチルアセテート(例えば、2-ヒドロキシプロピルアクリレートアセチルアセテート、2-ヒドロキシプロピルメタクリレートアセチルアセテート、ブタンジオール-1,4-アクリレートアセチルアセテートなどのC2-6アルカンジオール(メタ)アクリレートアセチルアセテート)、アセトアセトキシアルキル(メタ)アクリレート(例えば、2-(アセトアセトキシ)エチルアクリレート、2-(アセトアセトキシ)エチルメタクリレート)など]などが挙げられる。
Examples of the carbonyl group-containing monomer include unsaturated aldehydes [eg, alkenals (eg, C 3-10 alkenals such as acrolein, methacrolein), (meth) acryloxyalkyl alkenals (eg, acryloxyalkylpropenal). , Methacryloxyalkylpropenal), formylstyrene, etc.], unsaturated ketones (eg, alkenones (eg, methyl vinyl ketone, ethyl vinyl ketone, vinyl butyl ketone), (meth) acryloyloxyalkanones (eg, acetonyl acrylate) , Acetonyl methacrylate, etc.), N- (meth) acryloylaminoalkanone (eg, diacetone acrylamide, diacetone methacrylamide, etc.), alkanediol (meth) acrylate acetyl Acetoacetoxy (eg, C 2-6 alkanediol (meth) acrylate acetyl acetate such as 2-hydroxypropyl acrylate acetyl acetate, 2-hydroxypropyl methacrylate acetyl acetate, butanediol-1,4-acrylate acetyl acetate), acetoacetoxyalkyl (Meth) acrylates (for example, 2- (acetoacetoxy) ethyl acrylate, 2- (acetoacetoxy) ethyl methacrylate, etc.) and the like.
酸基含有単量体(アニオン性基含有単量体)としては、例えば、カルボン酸基含有単量体[例えば、不飽和モノカルボン酸(例えば、アクリル酸、メタクリル酸、クロトン酸などの脂肪族不飽和モノカルボン酸)、不飽和ジカルボン酸(例えば、マレイン酸、フマル酸などの脂肪族不飽和モノカルボン酸)など]、スルホン酸基含有単量体[例えば、スチレン系単量体(例えば、スチレンスルホン酸など)など]などが挙げられる。
Examples of the acid group-containing monomer (anionic group-containing monomer) include carboxylic acid group-containing monomers [for example, unsaturated monocarboxylic acids (for example, aliphatic acids such as acrylic acid, methacrylic acid, crotonic acid). Unsaturated monocarboxylic acid), unsaturated dicarboxylic acid (for example, aliphatic unsaturated monocarboxylic acid such as maleic acid and fumaric acid)], sulfonic acid group-containing monomer [for example, styrenic monomer (for example, Styrene sulfonic acid, etc.)] and the like.
なお、酸基含有単量体は、アニオン化されていても(又は塩を形成していても又は中和されていても)よい。アニオン化する方法としては、特に限定されず、例えば、塩基性化合物と反応させる(中和する又は塩を形成させる)方法が挙げられる。塩基性化合物としては、例えば、無機塩基{例えば、水酸化物(例えば、水酸化ナトリウムなどのアルカリ金属又はアルカリ土類金属水酸化物)、アンモニア[例えば、アンモニア水(25%アンモニア水など)として使用]など}、有機塩基[例えば、アミン(例えば、モノメチルアミン、モノエタノールアミン、ジエタノールアミン、ジメチルエタノールアミン、イソプロパノールアミンなど)など]などを挙げることができる。塩基性化合物は、2種以上併用してもよい。
The acid group-containing monomer may be anionized (or may form a salt or may be neutralized). The method for anionization is not particularly limited, and examples thereof include a method of reacting with a basic compound (neutralizing or forming a salt). Examples of the basic compound include inorganic bases {eg, hydroxide (eg, alkali metal or alkaline earth metal hydroxide such as sodium hydroxide), ammonia [eg, ammonia water (25% ammonia water, etc.)] Use] and the like, and organic bases [for example, amine (eg, monomethylamine, monoethanolamine, diethanolamine, dimethylethanolamine, isopropanolamine, etc.)] and the like. Two or more basic compounds may be used in combination.
オキサゾリン基含有単量体としては、例えば、アルケニルオキサゾリン(例えば、2-ビニル-2-オキサゾリン、2-イソプロペニル-2-オキサゾリンなどのC2-6アルケニルオキサゾリン、好ましくはビニル又はイソプロペニルオキサゾリン)、アルケニル-アルキルオキサゾリン(例えば、2-ビニル-4-メチル-2-オキサゾリン、2-ビニル-5-メチル-2-オキサゾリン、2-イソプロペニル-4-メチル-2-オキサゾリン、2-イソプロぺニル-5-エチル-2-オキサゾリンなどのC2-6アルケニル-C1-10アルキルオキサゾリン、好ましくはビニル又はイソプロペニル-C1-4アルキルオキサゾリンなど)などが挙げられる。
Examples of the oxazoline group-containing monomer include alkenyl oxazolines (for example, C 2-6 alkenyl oxazolines such as 2-vinyl-2-oxazoline and 2-isopropenyl-2-oxazoline, preferably vinyl or isopropenyl oxazoline), Alkenyl-alkyloxazolines (eg 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl- C 2-6 alkenyl-C 1-10 alkyl oxazoline such as 5-ethyl-2-oxazoline, preferably vinyl or isopropenyl-C 1-4 alkyl oxazoline) and the like.
ヒドロキシル基含有単量体としては、例えば、ヒドロキシアルキル(メタ)アクリレート[例えば、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、3-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシブチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレートなどのヒドロキシC2-10アルキル(メタ)アクリレート、好ましくはヒドロキシC2-6アルキル(メタ)アクリレート、さらに好ましくはヒドロキシC2-4アルキル(メタ)アクリレートなど]、3以上のヒドロキシル基を有するポリオールの(メタ)アクリレート[例えば、グリセリンモノ(メタ)アクリレートなどのトリ乃至ヘキサヒドロキシC3-10ポリオールの(メタ)アクリレート]などの水酸基含有アクリル系単量体(特に水酸基含有(メタ)アクリレート)などが挙げられる。
Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth) acrylate [for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy Hydroxy C 2-10 alkyl (meth) acrylate such as butyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, preferably hydroxy C 2-6 alkyl (meth) acrylate, more preferably hydroxy C 2-4 alkyl ( (Meth) acrylates, etc.] (meth) acrylates of polyols having 3 or more hydroxyl groups [eg (meth) acrylates of tri to hexahydroxy C 3-10 polyols such as glycerol mono (meth) acrylate ] And other hydroxyl group-containing acrylic monomers (particularly hydroxyl group-containing (meth) acrylate).
官能基を有する単量体は、単独で又は2種以上組み合わせて使用してもよい。
Monomers having a functional group may be used alone or in combination of two or more.
これらのうち、不飽和ケトン、不飽和モノカルボン酸(アクリル酸など)、水酸基含有(メタ)アクリレートなどが好ましく、中でも、塗膜物性(耐水白化性など)などにおいて有利になる点からダイアセトン(メタ)アクリルアミドが好ましい。そのため、官能基を有する単量体は、少なくともこのような単量体(特に、ダイアセトン(メタ)アクリルアミド)を含んでいてもよい。
Of these, unsaturated ketones, unsaturated monocarboxylic acids (such as acrylic acid), and hydroxyl group-containing (meth) acrylates are preferred. Among them, diacetone (from the point of being advantageous in coating film properties (water whitening resistance, etc.) Meth) acrylamide is preferred. Therefore, the monomer having a functional group may contain at least such a monomer (particularly diacetone (meth) acrylamide).
なお、官能基を有する単量体として、ダイアセトン(メタ)アクリルアミドを少なくとも使用する場合、官能基を有する単量体全体に対するダイアセトン(メタ)アクリルアミドの割合は、例えば、10質量%以上、好ましくは20質量%以上、さらに好ましくは30質量%以上であってもよい。
When diacetone (meth) acrylamide is used at least as the monomer having a functional group, the ratio of diacetone (meth) acrylamide to the whole monomer having a functional group is, for example, 10% by mass or more, preferably May be 20% by mass or more, more preferably 30% by mass or more.
官能基(官能基β)を有する単量体は、単独で又は2種以上組み合わせて使用してもよい。
Monomers having a functional group (functional group β) may be used alone or in combination of two or more.
官能基を有する単量体を使用する場合、官能基を有する単量体の割合は、重合成分(単量体成分(b))全体に対して、例えば、30質量%以下(例えば、0.001~25質量%)、好ましくは20質量%以下(例えば、0.01~15質量%)、さらに好ましくは10質量%以下(例えば、0.05~8質量%)であってもよく、通常0.05~10質量%(例えば、0.1~5質量%)であってもよい。
官能基を有する単量体を使用する場合、官能基を有する単量体の割合は、重合成分(単量体成分(b))全体に対して、例えば、30モル%以下(例えば、0.001~25モル%)、好ましくは20モル%以下(例えば、0.01~15モル%)、さらに好ましくは10モル%以下(例えば、0.05~8モル%)であってもよく、通常0.05~10モル%(例えば、0.1~5モル%)であってもよい。 When using the monomer which has a functional group, the ratio of the monomer which has a functional group is 30 mass% or less (for example, 0.00%) with respect to the whole polymerization component (monomer component (b)). 001 to 25% by mass), preferably 20% by mass or less (eg 0.01 to 15% by mass), more preferably 10% by mass or less (eg 0.05 to 8% by mass). It may be 0.05 to 10% by mass (for example, 0.1 to 5% by mass).
When using the monomer which has a functional group, the ratio of the monomer which has a functional group is 30 mol% or less (for example, 0.00%) with respect to the whole polymerization component (monomer component (b)). 001-25 mol%), preferably 20 mol% or less (eg, 0.01-15 mol%), more preferably 10 mol% or less (eg, 0.05-8 mol%). It may be 0.05 to 10 mol% (for example, 0.1 to 5 mol%).
官能基を有する単量体を使用する場合、官能基を有する単量体の割合は、重合成分(単量体成分(b))全体に対して、例えば、30モル%以下(例えば、0.001~25モル%)、好ましくは20モル%以下(例えば、0.01~15モル%)、さらに好ましくは10モル%以下(例えば、0.05~8モル%)であってもよく、通常0.05~10モル%(例えば、0.1~5モル%)であってもよい。 When using the monomer which has a functional group, the ratio of the monomer which has a functional group is 30 mass% or less (for example, 0.00%) with respect to the whole polymerization component (monomer component (b)). 001 to 25% by mass), preferably 20% by mass or less (eg 0.01 to 15% by mass), more preferably 10% by mass or less (eg 0.05 to 8% by mass). It may be 0.05 to 10% by mass (for example, 0.1 to 5% by mass).
When using the monomer which has a functional group, the ratio of the monomer which has a functional group is 30 mol% or less (for example, 0.00%) with respect to the whole polymerization component (monomer component (b)). 001-25 mol%), preferably 20 mol% or less (eg, 0.01-15 mol%), more preferably 10 mol% or less (eg, 0.05-8 mol%). It may be 0.05 to 10 mol% (for example, 0.1 to 5 mol%).
官能基を有する単量体を使用する場合、官能基を有する単量体の割合は、ビニルラクタム系モノマー100質量部に対して、例えば、30質量部以下(例えば、0.001~25質量部)、好ましくは20質量部以下(例えば、0.01~15質量部)、さらに好ましくは10質量部以下(例えば、0.05~8質量部)であってもよく、通常0.05~10質量部(例えば、0.1~5質量部)であってもよい。
官能基を有する単量体を使用する場合、官能基を有する単量体の割合は、ビニルラクタム系モノマー100モルに対して、例えば、30モル以下(例えば、0.001~25質モル)、好ましくは20モル以下(例えば、0.01~15モル)、さらに好ましくは10モル以下(例えば、0.05~8モル)であってもよく、通常0.05~10モル(例えば、0.1~5モル)であってもよい。 When using a monomer having a functional group, the proportion of the monomer having a functional group is, for example, 30 parts by mass or less (for example, 0.001 to 25 parts by mass) with respect to 100 parts by mass of the vinyl lactam monomer. ), Preferably 20 parts by mass or less (eg 0.01 to 15 parts by mass), more preferably 10 parts by mass or less (eg 0.05 to 8 parts by mass), and usually 0.05 to 10 parts by mass. It may be part by mass (for example, 0.1 to 5 parts by mass).
When using a monomer having a functional group, the ratio of the monomer having a functional group is, for example, 30 mol or less (for example, 0.001 to 25 mol) with respect to 100 mol of the vinyl lactam monomer, It may be preferably 20 mol or less (for example, 0.01 to 15 mol), more preferably 10 mol or less (for example, 0.05 to 8 mol), and usually 0.05 to 10 mol (for example, 0.1 mol). 1-5 moles).
官能基を有する単量体を使用する場合、官能基を有する単量体の割合は、ビニルラクタム系モノマー100モルに対して、例えば、30モル以下(例えば、0.001~25質モル)、好ましくは20モル以下(例えば、0.01~15モル)、さらに好ましくは10モル以下(例えば、0.05~8モル)であってもよく、通常0.05~10モル(例えば、0.1~5モル)であってもよい。 When using a monomer having a functional group, the proportion of the monomer having a functional group is, for example, 30 parts by mass or less (for example, 0.001 to 25 parts by mass) with respect to 100 parts by mass of the vinyl lactam monomer. ), Preferably 20 parts by mass or less (eg 0.01 to 15 parts by mass), more preferably 10 parts by mass or less (eg 0.05 to 8 parts by mass), and usually 0.05 to 10 parts by mass. It may be part by mass (for example, 0.1 to 5 parts by mass).
When using a monomer having a functional group, the ratio of the monomer having a functional group is, for example, 30 mol or less (for example, 0.001 to 25 mol) with respect to 100 mol of the vinyl lactam monomer, It may be preferably 20 mol or less (for example, 0.01 to 15 mol), more preferably 10 mol or less (for example, 0.05 to 8 mol), and usually 0.05 to 10 mol (for example, 0.1 mol). 1-5 moles).
官能基を有する単量体を使用する場合、ヒンダードアミン系モノマーと官能基を有する単量体との割合は、前者/後者(質量比)=100/1~0.01/1、好ましくは50/1~0.02/1(例えば、30/1~0.03/1)、さらに好ましくは20/1~0.05/1(例えば、10/1~0.1/1)程度であってもよい。
官能基を有する単量体を使用する場合、ヒンダードアミン系モノマーと官能基を有する単量体との割合は、前者/後者(モル比)=100/1~0.01/1、好ましくは50/1~0.02/1(例えば、30/1~0.03/1)、さらに好ましくは20/1~0.05/1(例えば、10/1~0.1/1)程度であってもよい。 When a monomer having a functional group is used, the ratio of the hindered amine monomer to the monomer having a functional group is the former / the latter (mass ratio) = 100/1 to 0.01 / 1, preferably 50 / 1 to 0.02 / 1 (for example, 30/1 to 0.03 / 1), more preferably about 20/1 to 0.05 / 1 (for example, 10/1 to 0.1 / 1). Also good.
When using a monomer having a functional group, the ratio of the hindered amine monomer to the monomer having a functional group is the former / the latter (molar ratio) = 100/1 to 0.01 / 1, preferably 50 / 1 to 0.02 / 1 (for example, 30/1 to 0.03 / 1), more preferably about 20/1 to 0.05 / 1 (for example, 10/1 to 0.1 / 1). Also good.
官能基を有する単量体を使用する場合、ヒンダードアミン系モノマーと官能基を有する単量体との割合は、前者/後者(モル比)=100/1~0.01/1、好ましくは50/1~0.02/1(例えば、30/1~0.03/1)、さらに好ましくは20/1~0.05/1(例えば、10/1~0.1/1)程度であってもよい。 When a monomer having a functional group is used, the ratio of the hindered amine monomer to the monomer having a functional group is the former / the latter (mass ratio) = 100/1 to 0.01 / 1, preferably 50 / 1 to 0.02 / 1 (for example, 30/1 to 0.03 / 1), more preferably about 20/1 to 0.05 / 1 (for example, 10/1 to 0.1 / 1). Also good.
When using a monomer having a functional group, the ratio of the hindered amine monomer to the monomer having a functional group is the former / the latter (molar ratio) = 100/1 to 0.01 / 1, preferably 50 / 1 to 0.02 / 1 (for example, 30/1 to 0.03 / 1), more preferably about 20/1 to 0.05 / 1 (for example, 10/1 to 0.1 / 1). Also good.
なお、重合成分は、本発明の効果を害しない範囲であれば、他のモノマーを含んでいてよい。他のモノマーとしては、例えば、後述の単量体成分(a)の項で例示の単量体(例えば、アルキル(メタ)アクリレート、芳香族系単量体、ケイ素原子含有単量体、フッ素原子含有単量体、エポキシ基含有単量体、紫外線吸収性単量体など)などが挙げられるが、特に限定されない。
The polymerization component may contain other monomers as long as the effects of the present invention are not impaired. Examples of other monomers include the monomers exemplified in the monomer component (a) described later (for example, alkyl (meth) acrylates, aromatic monomers, silicon atom-containing monomers, fluorine atoms). Containing monomer, epoxy group-containing monomer, UV-absorbing monomer, etc.), but not particularly limited.
他のモノマーは、単独で又は2種以上組み合わせて使用してもよい。
Other monomers may be used alone or in combination of two or more.
重合成分(単量体成分(b))が他のモノマーを含む場合、重合成分(単量体成分(b))における他のモノマーの割合は、例えば、20質量%以下(例えば、0.01~18質量%)、好ましくは15質量%以下(例えば、0.1~12質量%)、さらに好ましくは10質量%以下(例えば、0.3~5質量%)であってもよい。
重合成分(単量体成分(b))が他のモノマーを含む場合、重合成分(単量体成分(b))における他のモノマーの割合は、例えば、20モル%以下(例えば、0.01~18モル%)、好ましくは15モル%以下(例えば、0.1~12モル%)、さらに好ましくは10モル%以下(例えば、0.3~5モル%)であってもよい。 When the polymerization component (monomer component (b)) contains another monomer, the proportion of the other monomer in the polymerization component (monomer component (b)) is, for example, 20% by mass or less (for example, 0.01 To 18% by mass), preferably 15% by mass or less (for example, 0.1 to 12% by mass), and more preferably 10% by mass or less (for example, 0.3 to 5% by mass).
When the polymerization component (monomer component (b)) contains another monomer, the proportion of the other monomer in the polymerization component (monomer component (b)) is, for example, 20 mol% or less (for example, 0.01 To 18 mol%), preferably 15 mol% or less (for example, 0.1 to 12 mol%), and more preferably 10 mol% or less (for example, 0.3 to 5 mol%).
重合成分(単量体成分(b))が他のモノマーを含む場合、重合成分(単量体成分(b))における他のモノマーの割合は、例えば、20モル%以下(例えば、0.01~18モル%)、好ましくは15モル%以下(例えば、0.1~12モル%)、さらに好ましくは10モル%以下(例えば、0.3~5モル%)であってもよい。 When the polymerization component (monomer component (b)) contains another monomer, the proportion of the other monomer in the polymerization component (monomer component (b)) is, for example, 20% by mass or less (for example, 0.01 To 18% by mass), preferably 15% by mass or less (for example, 0.1 to 12% by mass), and more preferably 10% by mass or less (for example, 0.3 to 5% by mass).
When the polymerization component (monomer component (b)) contains another monomer, the proportion of the other monomer in the polymerization component (monomer component (b)) is, for example, 20 mol% or less (for example, 0.01 To 18 mol%), preferably 15 mol% or less (for example, 0.1 to 12 mol%), and more preferably 10 mol% or less (for example, 0.3 to 5 mol%).
なお、本発明のポリマーの共重合の態様は、ランダム共重合体、ブロック共重合体、グラフト共重合体などのいずれであってもよい。
The copolymerization mode of the polymer of the present invention may be any of random copolymer, block copolymer, graft copolymer and the like.
本発明のポリマーの重量平均分子量は、モノマーの種類等に応じて適宜選択でき、特に限定されないが、塗膜物性等の観点から、例えば、1000~300万、より好ましくは3000~100万、さらに好ましくは5000~50万、特に7000~30万、特に好ましくは1万~25万であってもよい。特に、本発明のポリマーを、比較的高分子量[例えば、重量平均分子量5万以上(例えば、5.5万~50万)、好ましくは6万以上(例えば、6.5万~30万)、さらに好ましくは7万以上(例えば、7.5万~20万)、特に8万以上(例えば、8.5万~18万)、通常5万~25万]とすることもできる。
本発明のポリマーの分子量分布(重量平均分子量Mwと数平均分子量Mnの比率Mw/Mn)は、例えば、25以下(例えば、1.5~25)、好ましくは20以下(例えば、2.0~20)、さらに好ましくは(例えば、2.0~10)であってもよく、8以下(例えば、7以下、好ましくは5以下、さらに好ましくは4以下、特に好ましくは3.5以下)であってもよい。本発明では、比較的分子量分布の狭いポリマーを好適に使用してもよい。 The weight average molecular weight of the polymer of the present invention can be appropriately selected depending on the kind of the monomer and is not particularly limited. However, from the viewpoint of the physical properties of the coating film, for example, 1,000 to 3,000,000, more preferably 3,000 to 1,000,000, Preferably, it may be 5,000 to 500,000, particularly 7,000 to 300,000, particularly preferably 10,000 to 250,000. In particular, the polymer of the present invention has a relatively high molecular weight [eg, weight average molecular weight of 50,000 or more (eg, 550,000 to 500,000), preferably 60,000 or more (eg, 650,000 to 300,000), More preferably, it may be 70,000 or more (for example, 75,000 to 200,000), particularly 80,000 or more (for example, 850,000 to 180,000), and usually 50,000 to 250,000].
The molecular weight distribution (the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn) of the polymer of the present invention is, for example, 25 or less (for example, 1.5 to 25), preferably 20 or less (for example, 2.0 to 2.0). 20), more preferably (for example, 2.0 to 10), and 8 or less (for example, 7 or less, preferably 5 or less, more preferably 4 or less, particularly preferably 3.5 or less). May be. In the present invention, a polymer having a relatively narrow molecular weight distribution may be suitably used.
本発明のポリマーの分子量分布(重量平均分子量Mwと数平均分子量Mnの比率Mw/Mn)は、例えば、25以下(例えば、1.5~25)、好ましくは20以下(例えば、2.0~20)、さらに好ましくは(例えば、2.0~10)であってもよく、8以下(例えば、7以下、好ましくは5以下、さらに好ましくは4以下、特に好ましくは3.5以下)であってもよい。本発明では、比較的分子量分布の狭いポリマーを好適に使用してもよい。 The weight average molecular weight of the polymer of the present invention can be appropriately selected depending on the kind of the monomer and is not particularly limited. However, from the viewpoint of the physical properties of the coating film, for example, 1,000 to 3,000,000, more preferably 3,000 to 1,000,000, Preferably, it may be 5,000 to 500,000, particularly 7,000 to 300,000, particularly preferably 10,000 to 250,000. In particular, the polymer of the present invention has a relatively high molecular weight [eg, weight average molecular weight of 50,000 or more (eg, 550,000 to 500,000), preferably 60,000 or more (eg, 650,000 to 300,000), More preferably, it may be 70,000 or more (for example, 75,000 to 200,000), particularly 80,000 or more (for example, 850,000 to 180,000), and usually 50,000 to 250,000].
The molecular weight distribution (the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn) of the polymer of the present invention is, for example, 25 or less (for example, 1.5 to 25), preferably 20 or less (for example, 2.0 to 2.0). 20), more preferably (for example, 2.0 to 10), and 8 or less (for example, 7 or less, preferably 5 or less, more preferably 4 or less, particularly preferably 3.5 or less). May be. In the present invention, a polymer having a relatively narrow molecular weight distribution may be suitably used.
なお、重量平均分子量等は、例えば、ゲルパーミエイションクロマトグラフィー〔例えば、日本ウォーターズ(株)製、品番:E-2695、カラム:TSKgel α-MとTSKgel α-Mとを直列に使用〕を用いて測定できる重量平均分子量(ポリエチレンオキサイド換算)であってもよい。
The weight average molecular weight is, for example, gel permeation chromatography (for example, manufactured by Nippon Waters Co., Ltd., product number: E-2695, column: TSKgel α-M and TSKgel α-M used in series). It may be a weight average molecular weight (in terms of polyethylene oxide) that can be used and measured.
本発明のポリマーは、通常、水溶性であってもよい。
The polymer of the present invention may usually be water-soluble.
また、本発明のポリマーは、塩基性であってもよい。
The polymer of the present invention may be basic.
(ポリマーの製造方法)
本発明のポリマーは、重合成分(単量体成分(b))を重合することで得ることができる。重合方法としては、例えば、溶液重合法、乳化重合法、懸濁重合法、沈殿重合法などの慣用の重合方法を利用できる。これらの重合方法のなかでは、溶液重合法が好ましく、溶媒として水を用いた溶液重合法がより好ましい。 (Method for producing polymer)
The polymer of the present invention can be obtained by polymerizing a polymerization component (monomer component (b)). As the polymerization method, for example, a conventional polymerization method such as a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, or a precipitation polymerization method can be used. Among these polymerization methods, the solution polymerization method is preferable, and the solution polymerization method using water as a solvent is more preferable.
本発明のポリマーは、重合成分(単量体成分(b))を重合することで得ることができる。重合方法としては、例えば、溶液重合法、乳化重合法、懸濁重合法、沈殿重合法などの慣用の重合方法を利用できる。これらの重合方法のなかでは、溶液重合法が好ましく、溶媒として水を用いた溶液重合法がより好ましい。 (Method for producing polymer)
The polymer of the present invention can be obtained by polymerizing a polymerization component (monomer component (b)). As the polymerization method, for example, a conventional polymerization method such as a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, or a precipitation polymerization method can be used. Among these polymerization methods, the solution polymerization method is preferable, and the solution polymerization method using water as a solvent is more preferable.
溶液重合法によって調製する場合、溶媒が用いられる。溶媒としては 、例えば、水、アルコール、エーテル、ケトン、エステル、アミド、スルホキシド、炭化水素化合物などが挙げられるが、本発明は、かかる例示のみに限定されるものではない。好適な溶媒としては、例えば、水、メチルアルコール、エチルアルコール、n-プロピル アルコール、イソプロピルアルコール、tert-ブチルアルコール、メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、アセトン、メチルエチルケトン、テトラヒドロフラン、1,4-ジオキサン、1,3-ジオキソラン、トルエン、酢酸エチルなどが挙げられるが、本発明は、かかる例示のみに限定されるものではない。
これらの溶媒は、それぞれ単独で用いてもよく、2種類以上を併用してもよい。 When preparing by solution polymerization method, a solvent is used. Examples of the solvent include water, alcohol, ether, ketone, ester, amide, sulfoxide, hydrocarbon compound, and the like, but the present invention is not limited to such examples. Suitable solvents include, for example, water, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, tert-butyl alcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, acetone, methyl ethyl ketone, tetrahydrofuran, 1,4-dioxane, 1 , 3-dioxolane, toluene, ethyl acetate and the like, but the present invention is not limited to such examples.
These solvents may be used alone or in combination of two or more.
これらの溶媒は、それぞれ単独で用いてもよく、2種類以上を併用してもよい。 When preparing by solution polymerization method, a solvent is used. Examples of the solvent include water, alcohol, ether, ketone, ester, amide, sulfoxide, hydrocarbon compound, and the like, but the present invention is not limited to such examples. Suitable solvents include, for example, water, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, tert-butyl alcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, acetone, methyl ethyl ketone, tetrahydrofuran, 1,4-dioxane, 1 , 3-dioxolane, toluene, ethyl acetate and the like, but the present invention is not limited to such examples.
These solvents may be used alone or in combination of two or more.
なお、前記溶媒には、必要により、有機アミン化合物、アンモニア、アルカリ金属水酸化物などが適量で含まれていてもよい。
Note that the solvent may contain an appropriate amount of an organic amine compound, ammonia, an alkali metal hydroxide, or the like, if necessary.
ポリマーを調製する際の重合温度は、特に限定されないが、例えば、0~100℃、好ましくは30~95℃、さらに好ましくは50~90℃程度であってもよい。また、重合反応の際の圧力は、常圧であってもよく、減圧であってもよく、あるいは加圧であってもよい。重合反応の際の雰囲気は、窒素ガス、アルゴンガス、二酸化炭素ガスなどの不活性ガスであることが好ましい。
The polymerization temperature for preparing the polymer is not particularly limited, but may be, for example, about 0 to 100 ° C., preferably 30 to 95 ° C., and more preferably about 50 to 90 ° C. Further, the pressure during the polymerization reaction may be normal pressure, reduced pressure, or increased pressure. The atmosphere during the polymerization reaction is preferably an inert gas such as nitrogen gas, argon gas or carbon dioxide gas.
重合の際には、重合開始剤を用いることができる。重合開始剤としては、例えば、過硫酸塩(例えば、過硫酸アンモニウム、過硫酸ナトリウム、過硫酸カリウムなど)、過酸化水素、有機過酸化物、アゾ化合物[例えば、2,2’-アゾビス(2-メチルプロピオンアミジン)二塩酸塩など]などが挙げられる。重合開始剤は、それぞれ単独で用いてもよく、2種類以上を併用してもよい。
In the polymerization, a polymerization initiator can be used. Examples of the polymerization initiator include persulfates (eg, ammonium persulfate, sodium persulfate, potassium persulfate, etc.), hydrogen peroxide, organic peroxides, azo compounds [eg, 2,2′-azobis (2- Methyl propionamidine) dihydrochloride, etc.]. The polymerization initiators may be used alone or in combination of two or more.
重合に供する重合成分(単量体成分(b))100質量部あたりの重合開始剤の量は、特に限定されないが、例えば、0.01~10質量部程度であってもよい。なお、重合開始剤は、重合反応の開始時に一括で仕込んでもよく、重合反応中に逐次添加してもよい。
The amount of the polymerization initiator per 100 parts by mass of the polymerization component (monomer component (b)) used for the polymerization is not particularly limited, but may be, for example, about 0.01 to 10 parts by mass. The polymerization initiator may be charged all at once at the start of the polymerization reaction, or may be sequentially added during the polymerization reaction.
重合開始剤は、適量の還元剤と併用することができる。還元剤としては、例えば、鉄(II)塩、亜ジチオン酸ナトリウム、亜硫酸水素ナトリウム、亜硫酸ナトリウム、チオ硫酸ナトリウム、ホルムアルデヒドスルホキシル酸ナトリウム、アスコルビン酸などが挙げられるが、本発明は、かかる例示のみに限定されるものではない。
The polymerization initiator can be used in combination with an appropriate amount of a reducing agent. Examples of the reducing agent include iron (II) salt, sodium dithionite, sodium hydrogen sulfite, sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, etc., but the present invention is only such examples. It is not limited to.
<組成物>
本発明のポリマーは、親水性(特に水溶性)を有しており、親水化材料(親水化剤)として好適に使用できる。特に、エマルションと組み合わせることで、親水性の塗膜を形成するのに有用な組成物を形成できる。 <Composition>
The polymer of the present invention has hydrophilicity (particularly water solubility) and can be suitably used as a hydrophilic material (hydrophilizing agent). In particular, a composition useful for forming a hydrophilic coating film can be formed by combining with an emulsion.
本発明のポリマーは、親水性(特に水溶性)を有しており、親水化材料(親水化剤)として好適に使用できる。特に、エマルションと組み合わせることで、親水性の塗膜を形成するのに有用な組成物を形成できる。 <Composition>
The polymer of the present invention has hydrophilicity (particularly water solubility) and can be suitably used as a hydrophilic material (hydrophilizing agent). In particular, a composition useful for forming a hydrophilic coating film can be formed by combining with an emulsion.
以下では、エマルション(エマルション(A)という)と、本発明のポリマー(ポリマー(B)という)とを含む組成物について、詳述する。
Hereinafter, the composition containing the emulsion (referred to as emulsion (A)) and the polymer of the present invention (referred to as polymer (B)) will be described in detail.
[エマルション(A)]
エマルション(A)(樹脂エマルション(A))を構成する樹脂(重合体、ポリマー)としては、特に限定されず、例えば、付加重合系樹脂[例えば、アクリル系樹脂、ビニルアルコール系樹脂(例えば、ポリビニルアルコールなど)、フッ素系樹脂など]、縮合系樹脂[例えば、ポリアミド系樹脂、ポリエステル系樹脂、ポリウレタン系樹脂など]、熱又は光硬化性樹脂(例えば、アルキド樹脂、エポキシ樹脂など)などが挙げられる。 [Emulsion (A)]
The resin (polymer, polymer) constituting the emulsion (A) (resin emulsion (A)) is not particularly limited, and examples thereof include addition polymerization resins [for example, acrylic resins, vinyl alcohol resins (for example, polyvinyl resins). Alcohol, etc.), fluorine resin, etc.], condensation resin [eg, polyamide resin, polyester resin, polyurethane resin, etc.], heat or photocurable resin (eg, alkyd resin, epoxy resin, etc.), etc. .
エマルション(A)(樹脂エマルション(A))を構成する樹脂(重合体、ポリマー)としては、特に限定されず、例えば、付加重合系樹脂[例えば、アクリル系樹脂、ビニルアルコール系樹脂(例えば、ポリビニルアルコールなど)、フッ素系樹脂など]、縮合系樹脂[例えば、ポリアミド系樹脂、ポリエステル系樹脂、ポリウレタン系樹脂など]、熱又は光硬化性樹脂(例えば、アルキド樹脂、エポキシ樹脂など)などが挙げられる。 [Emulsion (A)]
The resin (polymer, polymer) constituting the emulsion (A) (resin emulsion (A)) is not particularly limited, and examples thereof include addition polymerization resins [for example, acrylic resins, vinyl alcohol resins (for example, polyvinyl resins). Alcohol, etc.), fluorine resin, etc.], condensation resin [eg, polyamide resin, polyester resin, polyurethane resin, etc.], heat or photocurable resin (eg, alkyd resin, epoxy resin, etc.), etc. .
これらの樹脂(ポリマー、重合体)は、単独で又は2種以上組み合わせてエマルション(A)を構成してもよい。また、エマルション(A)は、単独で使用してもよく、又は2種以上のエマルションを組み合わせてもよい。
なお、エマルション(A)(又はエマルションを構成する樹脂)は、通常、粒子状である。そのため、エマルションは、エマルション粒子ということもできる。 These resins (polymer, polymer) may be used alone or in combination of two or more to constitute the emulsion (A). Moreover, an emulsion (A) may be used independently or may combine 2 or more types of emulsion.
In addition, emulsion (A) (or resin which comprises an emulsion) is a particulate form normally. Therefore, the emulsion can also be called emulsion particles.
なお、エマルション(A)(又はエマルションを構成する樹脂)は、通常、粒子状である。そのため、エマルションは、エマルション粒子ということもできる。 These resins (polymer, polymer) may be used alone or in combination of two or more to constitute the emulsion (A). Moreover, an emulsion (A) may be used independently or may combine 2 or more types of emulsion.
In addition, emulsion (A) (or resin which comprises an emulsion) is a particulate form normally. Therefore, the emulsion can also be called emulsion particles.
以下、代表的な樹脂を説明する。
樹脂(ポリマー、重合体)は、通常、単量体成分(a)を重合成分とする。単量体成分(a)は、通常、付加重合性モノマー(又はラジカル重合性モノマー、エチレン性不飽和結合を有する単量体など)であってもよい。 Hereinafter, typical resins will be described.
The resin (polymer, polymer) usually has the monomer component (a) as a polymerization component. The monomer component (a) may be usually an addition polymerizable monomer (or a radical polymerizable monomer, a monomer having an ethylenically unsaturated bond, etc.).
樹脂(ポリマー、重合体)は、通常、単量体成分(a)を重合成分とする。単量体成分(a)は、通常、付加重合性モノマー(又はラジカル重合性モノマー、エチレン性不飽和結合を有する単量体など)であってもよい。 Hereinafter, typical resins will be described.
The resin (polymer, polymer) usually has the monomer component (a) as a polymerization component. The monomer component (a) may be usually an addition polymerizable monomer (or a radical polymerizable monomer, a monomer having an ethylenically unsaturated bond, etc.).
単量体成分(a)としては、例えば、脂肪族(メタ)アクリレート、脂環族単量体(脂環構造を有する単量体)、水酸基含有(メタ)アクリレート、芳香族系単量体、酸基含有単量体(又はアニオン性基含有単量体)、ケイ素原子含有単量体、フッ素原子含有単量体、窒素原子含有単量体、エポキシ基含有単量体、紫外線吸収性単量体、ヒンダードアミン系モノマー(紫外線安定性単量体)などが挙げられる。
Examples of the monomer component (a) include aliphatic (meth) acrylates, alicyclic monomers (monomers having an alicyclic structure), hydroxyl group-containing (meth) acrylates, aromatic monomers, Acid group-containing monomer (or anionic group-containing monomer), silicon atom-containing monomer, fluorine atom-containing monomer, nitrogen atom-containing monomer, epoxy group-containing monomer, UV-absorbing monomer And hindered amine monomers (ultraviolet stable monomers).
単量体成分(a)は単独で又は2種以上組み合わせて使用してもよい。
Monomer component (a) may be used alone or in combination of two or more.
特に、エマルション(A)は、塗膜物性などの観点から、アクリル系(アクリル系樹脂)エマルション、例えば、単量体成分(a)として、少なくとも脂肪族(メタ)アクリレート(特にアルキル(メタ)アクリレート)を含有する樹脂のエマルションであってもよい。
In particular, the emulsion (A) is an acrylic (acrylic resin) emulsion, for example, as a monomer component (a) from the viewpoint of physical properties of the coating film, for example, at least aliphatic (meth) acrylate (particularly alkyl (meth) acrylate). ) Containing a resin emulsion.
代表的なアクリル系エマルションには、少なくともアルキル(メタ)アクリレートおよび脂環構造を有する単量体を含有する樹脂のエマルションが含まれ、好ましくは少なくともアルキル(メタ)アクリレート、脂環構造を有する単量体および水酸基含有(メタ)アクリレートを含有する樹脂のエマルションが含まれ、さらに好ましくは少なくともアルキル(メタ)アクリレート、脂環構造を有する単量体、水酸基含有(メタ)アクリレートおよび芳香族系単量体を含有する樹脂のエマルションが含まれる。
Typical acrylic emulsions include emulsions of resins containing at least an alkyl (meth) acrylate and a monomer having an alicyclic structure, preferably at least an alkyl (meth) acrylate and a single amount having an alicyclic structure And an emulsion of a resin containing a hydroxyl group-containing (meth) acrylate, more preferably at least an alkyl (meth) acrylate, a monomer having an alicyclic structure, a hydroxyl group-containing (meth) acrylate and an aromatic monomer An emulsion of a resin containing
(脂肪族(メタ)アクリレート)
脂肪族(メタ)アクリレートとしては、例えば、アルキル(メタ)アクリレート[例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、n-プロピル(メタ)アクリレート、イソプロピル(メタ)アクリレート、n-ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、tert-ブチル(メタ)アクリレート、sec-ブチル(メタ)アクリレート、アミル(メタ)アクリレート、ヘキシル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、n-オクチル(メタ)アクリレート、ノニル(メタ)アクリレート、デシル(メタ)アクリレート、ドデシル(メタ)アクリレート、n-ラウリル(メタ)アクリレート、トリデシル(メタ)アクリレート、ステアリル(メタ)アクリレートなどのC1-20アルキル(メタ)アクリレート]、アルコキシアルキル(メタ)アクリレート[例えば、アルコキシアルキル(メタ)アクリレート(例えば、2-メトキシエチル(メタ)アクリレートのC1-12アルコキシC1-12アルキルメタクリレートなど)など]などが挙げられる。 (Aliphatic (meth) acrylate)
Examples of the aliphatic (meth) acrylate include alkyl (meth) acrylate [for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) ) Acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, sec-butyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) ) Acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, n-lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, etc. 1-20 alkyl (meth) acrylate], alkoxyalkyl (meth) acrylate [eg, alkoxyalkyl (meth) acrylate (eg, C 1-12 alkoxy C 1-12 alkyl methacrylate of 2-methoxyethyl (meth) acrylate, etc.) Etc.].
脂肪族(メタ)アクリレートとしては、例えば、アルキル(メタ)アクリレート[例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、n-プロピル(メタ)アクリレート、イソプロピル(メタ)アクリレート、n-ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、tert-ブチル(メタ)アクリレート、sec-ブチル(メタ)アクリレート、アミル(メタ)アクリレート、ヘキシル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、n-オクチル(メタ)アクリレート、ノニル(メタ)アクリレート、デシル(メタ)アクリレート、ドデシル(メタ)アクリレート、n-ラウリル(メタ)アクリレート、トリデシル(メタ)アクリレート、ステアリル(メタ)アクリレートなどのC1-20アルキル(メタ)アクリレート]、アルコキシアルキル(メタ)アクリレート[例えば、アルコキシアルキル(メタ)アクリレート(例えば、2-メトキシエチル(メタ)アクリレートのC1-12アルコキシC1-12アルキルメタクリレートなど)など]などが挙げられる。 (Aliphatic (meth) acrylate)
Examples of the aliphatic (meth) acrylate include alkyl (meth) acrylate [for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) ) Acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, sec-butyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) ) Acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, n-lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, etc. 1-20 alkyl (meth) acrylate], alkoxyalkyl (meth) acrylate [eg, alkoxyalkyl (meth) acrylate (eg, C 1-12 alkoxy C 1-12 alkyl methacrylate of 2-methoxyethyl (meth) acrylate, etc.) Etc.].
脂肪族(メタ)アクリレートは、単独で又は2種以上組み合わせて使用してもよい。
Aliphatic (meth) acrylates may be used alone or in combination of two or more.
これらの脂肪族(メタ)アクリレートの中でも、メチル(メタ)アクリレート、n-ブチル(メタ)アクリレート、tert-ブチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレートなどのC1-12アルキル(メタ)アクリレート(例えば、C1-8アルキル(メタ)アクリレート)が好ましい。
Among these aliphatic (meth) acrylates, C 1-12 alkyl (meth) such as methyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc. Acrylates (eg, C 1-8 alkyl (meth) acrylate) are preferred.
単量体成分(a)が脂肪族(メタ)アクリレートを含有する場合、単量体成分(a)における脂肪族(メタ)アクリレートの含有割合(含有率)は、例えば、10~90質量%、好ましくは20~90質量%、さらに好ましくは25~80質量%、特に好ましくは30~80質量%程度であってもよい。
When the monomer component (a) contains an aliphatic (meth) acrylate, the content (content) of the aliphatic (meth) acrylate in the monomer component (a) is, for example, 10 to 90% by mass, The amount may be preferably 20 to 90% by mass, more preferably 25 to 80% by mass, and particularly preferably about 30 to 80% by mass.
(脂環構造を有する単量体)
脂環構造を有する単量体としては、脂環構造(例えば、炭素数が4~20のシクロアルキル基、好ましくは炭素数が4~10のシクロアルキル基)を有する単量体が挙げられる。具体的な脂環構造を有する単量体としては、例えば、脂環式(メタ)アクリレート[例えば、シクロアルキル(メタ)アクリレート(例えば、シクロヘキシル(メタ)アクリレートなどのC4-20シクロアルキル(メタ)アクリレート、好ましくはC4-10シクロアルキル(メタ)アクリレート)、シクロアルキルアルキル(メタ)アクリレート(例えば、シクロヘキシルメチル(メタ)アクリレート、シクロヘキシルエチル(メタ)アクリレート、シクロヘキシルプロピル(メタ)アクリレート、4-メチルシクロヘキシルメチル(メタ)アクリレートなどのC4-10シクロアルキルC1-4アルキル(メタ)アクリレート)、架橋環式(メタ)アクリレート(例えば、イソボルニル(メタ)アクリレート、アダマンチル(メタ)アクリレートなど)など]などが挙げられる。 (Monomer having an alicyclic structure)
Examples of the monomer having an alicyclic structure include monomers having an alicyclic structure (for example, a cycloalkyl group having 4 to 20 carbon atoms, preferably a cycloalkyl group having 4 to 10 carbon atoms). Specific examples of the monomer having an alicyclic structure include, for example, alicyclic (meth) acrylate [for example, C 4-20 cycloalkyl (meth) acrylate such as cycloalkyl (meth) acrylate (for example, cyclohexyl (meth) acrylate). ) Acrylate, preferably C 4-10 cycloalkyl (meth) acrylate), cycloalkylalkyl (meth) acrylate (eg, cyclohexylmethyl (meth) acrylate, cyclohexylethyl (meth) acrylate, cyclohexylpropyl (meth) acrylate, 4- C 4-10 cycloalkyl C 1-4 alkyl (meth) acrylates such as methylcyclohexylmethyl (meth) acrylate), bridged cyclic (meth) acrylates (eg isobornyl (meth) acrylate, adamantyl (meth)) Acrylate etc.)] and the like.
脂環構造を有する単量体としては、脂環構造(例えば、炭素数が4~20のシクロアルキル基、好ましくは炭素数が4~10のシクロアルキル基)を有する単量体が挙げられる。具体的な脂環構造を有する単量体としては、例えば、脂環式(メタ)アクリレート[例えば、シクロアルキル(メタ)アクリレート(例えば、シクロヘキシル(メタ)アクリレートなどのC4-20シクロアルキル(メタ)アクリレート、好ましくはC4-10シクロアルキル(メタ)アクリレート)、シクロアルキルアルキル(メタ)アクリレート(例えば、シクロヘキシルメチル(メタ)アクリレート、シクロヘキシルエチル(メタ)アクリレート、シクロヘキシルプロピル(メタ)アクリレート、4-メチルシクロヘキシルメチル(メタ)アクリレートなどのC4-10シクロアルキルC1-4アルキル(メタ)アクリレート)、架橋環式(メタ)アクリレート(例えば、イソボルニル(メタ)アクリレート、アダマンチル(メタ)アクリレートなど)など]などが挙げられる。 (Monomer having an alicyclic structure)
Examples of the monomer having an alicyclic structure include monomers having an alicyclic structure (for example, a cycloalkyl group having 4 to 20 carbon atoms, preferably a cycloalkyl group having 4 to 10 carbon atoms). Specific examples of the monomer having an alicyclic structure include, for example, alicyclic (meth) acrylate [for example, C 4-20 cycloalkyl (meth) acrylate such as cycloalkyl (meth) acrylate (for example, cyclohexyl (meth) acrylate). ) Acrylate, preferably C 4-10 cycloalkyl (meth) acrylate), cycloalkylalkyl (meth) acrylate (eg, cyclohexylmethyl (meth) acrylate, cyclohexylethyl (meth) acrylate, cyclohexylpropyl (meth) acrylate, 4- C 4-10 cycloalkyl C 1-4 alkyl (meth) acrylates such as methylcyclohexylmethyl (meth) acrylate), bridged cyclic (meth) acrylates (eg isobornyl (meth) acrylate, adamantyl (meth)) Acrylate etc.)] and the like.
なお、脂環構造を有する単量体は、置換基(例えば、メチル基、tert-ブチル基などのアルキル基、ニトロ基、ニトリル基、アルコキシル基、アシル基、スルホン基、ヒドロキシル基、ハロゲン原子など)を有していてもよい。
The monomer having an alicyclic structure is a substituent (for example, alkyl group such as methyl group, tert-butyl group, nitro group, nitrile group, alkoxyl group, acyl group, sulfone group, hydroxyl group, halogen atom, etc. ).
脂環構造を有する単量体は、単独で又は2種以上組み合わせて使用してもよい。
Monomers having an alicyclic structure may be used alone or in combination of two or more.
脂環構造を有する単量体の中でも、C4-20シクロアルキル(メタ)アクリレートが好ましく、C4-10シクロアルキル(メタ)アクリレートがより好ましく、イソボルニル(メタ)アクリレートおよびシクロヘキシル(メタ)アクリレートがさらに好ましい。
Among the monomers having an alicyclic structure, C 4-20 cycloalkyl (meth) acrylate is preferable, C 4-10 cycloalkyl (meth) acrylate is more preferable, and isobornyl (meth) acrylate and cyclohexyl (meth) acrylate are preferable. Further preferred.
単量体成分(a)が脂環構造を有する単量体を含有する場合、単量体成分(a)における脂環構造を有する単量体の含有割合(含有率)は、例えば、5~80質量%、好ましくは10~70質量%、さらに好ましくは15~65質量%、特に好ましくは20~60質量%程度であってもよい。
When the monomer component (a) contains a monomer having an alicyclic structure, the content (content) of the monomer having an alicyclic structure in the monomer component (a) is, for example, 5 to It may be about 80% by mass, preferably 10 to 70% by mass, more preferably 15 to 65% by mass, particularly preferably about 20 to 60% by mass.
また、単量体成分(a)が脂肪族(メタ)アクリレート及び脂環構造を有する単量体を含有する場合、これらの割合は、脂肪族(メタ)アクリレート/脂環構造を有する単量体(質量比)=95/5~5/95(例えば、90/10~10/90)、好ましくは80/20~20/80、さらに好ましくは80/20~40/60程度であってもよい。
In addition, when the monomer component (a) contains an aliphatic (meth) acrylate and a monomer having an alicyclic structure, these ratios are the monomer having an aliphatic (meth) acrylate / alicyclic structure. (Mass ratio) = 95/5 to 5/95 (for example, 90/10 to 10/90), preferably 80/20 to 20/80, more preferably about 80/20 to 40/60. .
さらに、単量体成分(a)が脂肪族(メタ)アクリレート及び脂環構造を有する単量体を含有する場合、単量体成分(a)における、脂肪族(メタ)アクリレート及び脂環構造を有する単量体の総量の割合は、例えば、10質量%以上(例えば、15~99.5質量%)、好ましくは20質量%以上(例えば、25~99質量%)、さらに好ましくは30質量%以上(例えば、40~98質量%)、特に好ましくは50質量%以上(例えば、60~97質量%)程度であってもよく、通常70質量%以上(例えば、75~95質量%)であってもよい。
Further, when the monomer component (a) contains an aliphatic (meth) acrylate and a monomer having an alicyclic structure, the aliphatic (meth) acrylate and alicyclic structure in the monomer component (a) The ratio of the total amount of the monomers having is, for example, 10% by mass or more (for example, 15 to 99.5% by mass), preferably 20% by mass or more (for example, 25 to 99% by mass), and more preferably 30% by mass. It may be about (for example, 40 to 98% by mass), particularly preferably about 50% by mass or more (for example, 60 to 97% by mass), and usually 70% by mass or more (for example, 75 to 95% by mass). May be.
(水酸基含有(メタ)アクリレート)
水酸基含有(メタ)アクリレートとしては、例えば、ヒドロキシアルキル(メタ)アクリレート[例えば、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、3-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシブチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレートなどのヒドロキシC2-10アルキル(メタ)アクリレート、好ましくはC2-6アルキル(メタ)アクリレート、さらに好ましくはC2-4アルキル(メタ)アクリレートなど]、3以上のヒドロキシル基を有するポリオールの(メタ)アクリレート[例えば、グリセリンモノ(メタ)アクリレートなどのトリ乃至ヘキサヒドロキシC3-10ポリオールの(メタ)アクリレート]などが挙げられる。 (Hydroxyl group-containing (meth) acrylate)
Examples of the hydroxyl group-containing (meth) acrylate include hydroxyalkyl (meth) acrylate [for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy Hydroxy C 2-10 alkyl (meth) acrylate such as butyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, preferably C 2-6 alkyl (meth) acrylate, more preferably C 2-4 alkyl (meth) Acrylates, etc.] (meth) acrylates of polyols having 3 or more hydroxyl groups [for example, (meth) acrylates of tri to hexahydroxy C 3-10 polyols such as glycerol mono (meth) acrylate] and the like. It is.
水酸基含有(メタ)アクリレートとしては、例えば、ヒドロキシアルキル(メタ)アクリレート[例えば、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、3-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシブチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレートなどのヒドロキシC2-10アルキル(メタ)アクリレート、好ましくはC2-6アルキル(メタ)アクリレート、さらに好ましくはC2-4アルキル(メタ)アクリレートなど]、3以上のヒドロキシル基を有するポリオールの(メタ)アクリレート[例えば、グリセリンモノ(メタ)アクリレートなどのトリ乃至ヘキサヒドロキシC3-10ポリオールの(メタ)アクリレート]などが挙げられる。 (Hydroxyl group-containing (meth) acrylate)
Examples of the hydroxyl group-containing (meth) acrylate include hydroxyalkyl (meth) acrylate [for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy Hydroxy C 2-10 alkyl (meth) acrylate such as butyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, preferably C 2-6 alkyl (meth) acrylate, more preferably C 2-4 alkyl (meth) Acrylates, etc.] (meth) acrylates of polyols having 3 or more hydroxyl groups [for example, (meth) acrylates of tri to hexahydroxy C 3-10 polyols such as glycerol mono (meth) acrylate] and the like. It is.
水酸基含有(メタ)アクリレートは、単独で又は2種以上組み合わせて使用してもよい。
The hydroxyl group-containing (meth) acrylate may be used alone or in combination of two or more.
水酸基含有(メタ)アクリレートの中でも、2-ヒドロキシエチル(メタ)アクリレートおよびグリセリンモノ(メタ)アクリレートが好ましく、2-ヒドロキシエチル(メタ)アクリレートがより好ましい。
Among the hydroxyl group-containing (meth) acrylates, 2-hydroxyethyl (meth) acrylate and glycerol mono (meth) acrylate are preferable, and 2-hydroxyethyl (meth) acrylate is more preferable.
単量体成分(a)が水酸基含有(メタ)アクリレートを含有する場合、単量体成分(a)における水酸基含有(メタ)アクリレートの含有割合(含有率)は、例えば、0.1~20質量%、好ましくは0.3~10質量%、さらに好ましくは0.5~8質量%、特に好ましくは1~5質量%程度であってもよい。
When the monomer component (a) contains a hydroxyl group-containing (meth) acrylate, the content ratio (content ratio) of the hydroxyl group-containing (meth) acrylate in the monomer component (a) is, for example, 0.1 to 20 mass. %, Preferably 0.3 to 10% by mass, more preferably 0.5 to 8% by mass, and particularly preferably about 1 to 5% by mass.
また、単量体成分(a)が脂肪族(メタ)アクリレート及び/又は脂環構造を有する単量体、並びに水酸基含有(メタ)アクリレートを含有する場合、水酸基含有(メタ)アクリレートの含有割合(含有率)は、脂肪族(メタ)アクリレート及び/又は脂環構造を有する単量体100質量部に対して、例えば、0.1~20質量部、好ましくは0.3~15質量部、さらに好ましくは0.5~10質量部、特に好ましくは1~8質量部程度であってもよい。
When the monomer component (a) contains an aliphatic (meth) acrylate and / or a monomer having an alicyclic structure, and a hydroxyl group-containing (meth) acrylate, the content ratio of the hydroxyl group-containing (meth) acrylate ( Content) is, for example, 0.1 to 20 parts by weight, preferably 0.3 to 15 parts by weight, based on 100 parts by weight of the monomer having an aliphatic (meth) acrylate and / or alicyclic structure, Preferably it may be about 0.5 to 10 parts by mass, particularly preferably about 1 to 8 parts by mass.
(芳香族系単量体)
芳香族系単量体としては、例えば、スチレン系モノマー[例えば、スチレン、α-アルキルスチレン(例えば、α-メチルスチレンなどのα-C1-4アルキルスチレン)、アルキルスチレン(例えば、ビニルトルエンなどのC1-4アルキルスチレン)、ハロスチレン(例えば、クロロスチレンなど)など]、芳香族(メタ)アクリレート[例えば、アリール(メタ)アクリレート(例えば、フェニル(メタ)アクリレートなどのC6-10アリール(メタ)アクリレート)、アラルキル(メタ)アクリレート(例えば、ベンジル(メタ)アクリレート、フェネチル(メタ)アクリレートなどのC6-10アリールC1-4アルキル(メタ)アクリレート)、アリールオキシアルキルメタクリレート(例えば、フェノキシエチルメタクリレートなどのC6-10アリールオキシC1-4アルキルメタクリレート)など]などが挙げられる。 (Aromatic monomer)
Examples of aromatic monomers include styrene monomers [eg, styrene, α-alkyl styrene (eg, α-C 1-4 alkyl styrene such as α-methyl styrene), alkyl styrene (eg, vinyl toluene, etc. C 1-4 alkyl styrene), halostyrene (eg, chlorostyrene, etc.)], aromatic (meth) acrylate [eg, aryl (meth) acrylate (eg, C 6-10 aryl (eg, phenyl (meth) acrylate) ( (Meth) acrylates), aralkyl (meth) acrylates (eg C 6-10 aryl C 1-4 alkyl (meth) acrylates such as benzyl (meth) acrylate, phenethyl (meth) acrylate), aryloxyalkyl methacrylates (eg phenoxy) Ethyl methacrylate Over C 6-10 aryloxy C 1-4 alkyl methacrylates) such as such as preparative] and the like.
芳香族系単量体としては、例えば、スチレン系モノマー[例えば、スチレン、α-アルキルスチレン(例えば、α-メチルスチレンなどのα-C1-4アルキルスチレン)、アルキルスチレン(例えば、ビニルトルエンなどのC1-4アルキルスチレン)、ハロスチレン(例えば、クロロスチレンなど)など]、芳香族(メタ)アクリレート[例えば、アリール(メタ)アクリレート(例えば、フェニル(メタ)アクリレートなどのC6-10アリール(メタ)アクリレート)、アラルキル(メタ)アクリレート(例えば、ベンジル(メタ)アクリレート、フェネチル(メタ)アクリレートなどのC6-10アリールC1-4アルキル(メタ)アクリレート)、アリールオキシアルキルメタクリレート(例えば、フェノキシエチルメタクリレートなどのC6-10アリールオキシC1-4アルキルメタクリレート)など]などが挙げられる。 (Aromatic monomer)
Examples of aromatic monomers include styrene monomers [eg, styrene, α-alkyl styrene (eg, α-C 1-4 alkyl styrene such as α-methyl styrene), alkyl styrene (eg, vinyl toluene, etc. C 1-4 alkyl styrene), halostyrene (eg, chlorostyrene, etc.)], aromatic (meth) acrylate [eg, aryl (meth) acrylate (eg, C 6-10 aryl (eg, phenyl (meth) acrylate) ( (Meth) acrylates), aralkyl (meth) acrylates (eg C 6-10 aryl C 1-4 alkyl (meth) acrylates such as benzyl (meth) acrylate, phenethyl (meth) acrylate), aryloxyalkyl methacrylates (eg phenoxy) Ethyl methacrylate Over C 6-10 aryloxy C 1-4 alkyl methacrylates) such as such as preparative] and the like.
芳香族系単量体は、単独で又は2種以上組み合わせて使用してもよい。
The aromatic monomers may be used alone or in combination of two or more.
単量体成分(a)が芳香族系単量体を含有する場合、単量体成分(a)における芳香族系単量体の含有割合(含有率)は、例えば、0.1~30質量%、好ましくは0.5~20質量%、さらに好ましくは1~15質量%程度であってもよい。
When the monomer component (a) contains an aromatic monomer, the content (content) of the aromatic monomer in the monomer component (a) is, for example, 0.1 to 30 mass. %, Preferably 0.5 to 20% by mass, more preferably about 1 to 15% by mass.
(酸基含有単量体)
酸基含有単量体(アニオン性基含有単量体)としては、前記例示の単量体、例えば、カルボン酸基含有単量体[例えば、不飽和モノカルボン酸(例えば、アクリル酸、メタクリル酸、クロトン酸などの脂肪族不飽和モノカルボン酸)、不飽和ジカルボン酸(例えば、マレイン酸、フマル酸などの脂肪族不飽和モノカルボン酸)など]、スルホン酸基含有単量体[例えば、スチレン系単量体(例えば、スチレンスルホン酸など)など]などが挙げられる。
なお、酸基含有単量体は、アニオン化されていても(又は塩を形成していても)よい。 (Acid group-containing monomer)
Examples of the acid group-containing monomer (anionic group-containing monomer) include the above-exemplified monomers, for example, carboxylic acid group-containing monomers [for example, unsaturated monocarboxylic acids (for example, acrylic acid, methacrylic acid). , Aliphatic unsaturated monocarboxylic acids such as crotonic acid), unsaturated dicarboxylic acids (eg, aliphatic unsaturated monocarboxylic acids such as maleic acid and fumaric acid)], sulfonic acid group-containing monomers [eg, styrene Based monomers (for example, styrenesulfonic acid, etc.)] and the like.
In addition, the acid group-containing monomer may be anionized (or may form a salt).
酸基含有単量体(アニオン性基含有単量体)としては、前記例示の単量体、例えば、カルボン酸基含有単量体[例えば、不飽和モノカルボン酸(例えば、アクリル酸、メタクリル酸、クロトン酸などの脂肪族不飽和モノカルボン酸)、不飽和ジカルボン酸(例えば、マレイン酸、フマル酸などの脂肪族不飽和モノカルボン酸)など]、スルホン酸基含有単量体[例えば、スチレン系単量体(例えば、スチレンスルホン酸など)など]などが挙げられる。
なお、酸基含有単量体は、アニオン化されていても(又は塩を形成していても)よい。 (Acid group-containing monomer)
Examples of the acid group-containing monomer (anionic group-containing monomer) include the above-exemplified monomers, for example, carboxylic acid group-containing monomers [for example, unsaturated monocarboxylic acids (for example, acrylic acid, methacrylic acid). , Aliphatic unsaturated monocarboxylic acids such as crotonic acid), unsaturated dicarboxylic acids (eg, aliphatic unsaturated monocarboxylic acids such as maleic acid and fumaric acid)], sulfonic acid group-containing monomers [eg, styrene Based monomers (for example, styrenesulfonic acid, etc.)] and the like.
In addition, the acid group-containing monomer may be anionized (or may form a salt).
酸基含有単量体は、単独で又は2種以上組み合わせて使用してもよい。
The acid group-containing monomers may be used alone or in combination of two or more.
代表的な酸基含有単量体には、アクリル酸、メタクリル酸が含まれる。
Typical acid group-containing monomers include acrylic acid and methacrylic acid.
単量体成分(a)が酸基含有単量体(アニオン性基含有単量体)を含有する場合、単量体成分(a)における酸基含有単量体の含有割合(含有率)は、例えば、0.01~10質量%、好ましくは0.02~5質量%、さらに好ましくは0.05~3質量%程度であってもよい。
When the monomer component (a) contains an acid group-containing monomer (anionic group-containing monomer), the content ratio (content ratio) of the acid group-containing monomer in the monomer component (a) is For example, it may be about 0.01 to 10% by mass, preferably about 0.02 to 5% by mass, and more preferably about 0.05 to 3% by mass.
(ケイ素原子含有単量体)
ケイ素原子含有単量体としては、例えば、ビニル基含有シラン[例えば、ビニル基を有するハロシラン(例えば、ビニルトリクロロシランなどのビニルモノ乃至トリハロシラン)、ビニル基を有するアルコキシシラン[ビニルアルコキシシラン(例えば、ビニルトリメトキシシラン、ビニルトリエトキシシランなどのビニルモノ乃至トリアルコキシシラン、好ましくはビニルモノ乃至トリC1-4アルコキシシラン)、ビニルアルコキシアルコキシシラン(例えば、ビニルトリス(β-メトキシエトキシ)シランなどのビニルモノ乃至トリ(C1-4アルコキシC1-4アルコキシ)シランなど)など]、(メタ)アクリロイル基含有シラン[例えば、(メタ)アクリロイル基を有するアルコキシシラン(例えば、γ-(メタ)アクリロイルオキシプロピルトリメトキシシランなどの(メタ)アクリロイルオキシアルキルモノ乃至トリアルコキシシラン、好ましくは(メタ)アクリロイルオキシC2-4アルキルモノ乃至トリC1-4アルコキシシラン)、トリアルキルシロキシアルキル(メタ)アクリレート(例えば、トリメチルシロキシエチル(メタ)アクリレートなどのトリC1-4アルキルシロキシC2-4アルキル(メタ)アクリレートなど)など]などが挙げられる。 (Silicon atom-containing monomer)
Examples of the silicon atom-containing monomer include vinyl group-containing silane [eg, vinyl group-containing halosilane (eg, vinyl mono to trihalosilane such as vinyltrichlorosilane), vinyl group-containing alkoxysilane [vinyl alkoxysilane (eg, Vinyl mono to trialkoxy silanes such as vinyl trimethoxy silane and vinyl triethoxy silane, preferably vinyl mono to tri C 1-4 alkoxy silanes), vinyl alkoxy alkoxy silanes (eg vinyl mono to tris (β-methoxyethoxy) silane etc. (C 1-4 alkoxy C 1-4 alkoxy) silane, etc.)], (meth) acryloyl group-containing silane [eg, alkoxysilane having a (meth) acryloyl group (eg, γ- (meth) acryloyl) (Meth) acryloyloxyalkyl mono to trialkoxysilane such as oxypropyltrimethoxysilane, preferably (meth) acryloyloxy C 2-4 alkyl mono to tri C 1-4 alkoxysilane), trialkylsiloxyalkyl (meth) acrylate (For example, tri-C 1-4 alkylsiloxy C 2-4 alkyl (meth) acrylate such as trimethylsiloxyethyl (meth) acrylate)) and the like.
ケイ素原子含有単量体としては、例えば、ビニル基含有シラン[例えば、ビニル基を有するハロシラン(例えば、ビニルトリクロロシランなどのビニルモノ乃至トリハロシラン)、ビニル基を有するアルコキシシラン[ビニルアルコキシシラン(例えば、ビニルトリメトキシシラン、ビニルトリエトキシシランなどのビニルモノ乃至トリアルコキシシラン、好ましくはビニルモノ乃至トリC1-4アルコキシシラン)、ビニルアルコキシアルコキシシラン(例えば、ビニルトリス(β-メトキシエトキシ)シランなどのビニルモノ乃至トリ(C1-4アルコキシC1-4アルコキシ)シランなど)など]、(メタ)アクリロイル基含有シラン[例えば、(メタ)アクリロイル基を有するアルコキシシラン(例えば、γ-(メタ)アクリロイルオキシプロピルトリメトキシシランなどの(メタ)アクリロイルオキシアルキルモノ乃至トリアルコキシシラン、好ましくは(メタ)アクリロイルオキシC2-4アルキルモノ乃至トリC1-4アルコキシシラン)、トリアルキルシロキシアルキル(メタ)アクリレート(例えば、トリメチルシロキシエチル(メタ)アクリレートなどのトリC1-4アルキルシロキシC2-4アルキル(メタ)アクリレートなど)など]などが挙げられる。 (Silicon atom-containing monomer)
Examples of the silicon atom-containing monomer include vinyl group-containing silane [eg, vinyl group-containing halosilane (eg, vinyl mono to trihalosilane such as vinyltrichlorosilane), vinyl group-containing alkoxysilane [vinyl alkoxysilane (eg, Vinyl mono to trialkoxy silanes such as vinyl trimethoxy silane and vinyl triethoxy silane, preferably vinyl mono to tri C 1-4 alkoxy silanes), vinyl alkoxy alkoxy silanes (eg vinyl mono to tris (β-methoxyethoxy) silane etc. (C 1-4 alkoxy C 1-4 alkoxy) silane, etc.)], (meth) acryloyl group-containing silane [eg, alkoxysilane having a (meth) acryloyl group (eg, γ- (meth) acryloyl) (Meth) acryloyloxyalkyl mono to trialkoxysilane such as oxypropyltrimethoxysilane, preferably (meth) acryloyloxy C 2-4 alkyl mono to tri C 1-4 alkoxysilane), trialkylsiloxyalkyl (meth) acrylate (For example, tri-C 1-4 alkylsiloxy C 2-4 alkyl (meth) acrylate such as trimethylsiloxyethyl (meth) acrylate)) and the like.
ケイ素原子含有単量体は、単独で又は2種以上組み合わせて使用してもよい。
The silicon atom-containing monomers may be used alone or in combination of two or more.
代表的なケイ素原子含有単量体には、γ-(メタ)アクリロイルオキシプロピルトリメトキシシランなどの(メタ)アクリロイル基を有するアルコキシシランなどが含まれる。
Typical silicon atom-containing monomers include alkoxysilanes having a (meth) acryloyl group such as γ- (meth) acryloyloxypropyltrimethoxysilane.
単量体成分(a)がケイ素原子含有単量体を含有する場合、単量体成分(a)におけるケイ素原子含有単量体の含有割合(含有率)は、例えば、0.01~10質量%、好ましくは0.02~5質量%、さらに好ましくは0.03~3質量%程度であってもよい。
When the monomer component (a) contains a silicon atom-containing monomer, the content ratio (content ratio) of the silicon atom-containing monomer in the monomer component (a) is, for example, 0.01 to 10 mass. %, Preferably 0.02 to 5% by mass, more preferably about 0.03 to 3% by mass.
(フッ素原子含有単量体)
フッ素原子含有単量体としては、例えば、フッ素原子含有アクリル系単量体[例えば、フルオロアルキル(メタ)アクリレート(例えば、トリフルオロエチル(メタ)アクリレート、テトラフルオロプロピル(メタ)アクリレート、オクタフルオロペンチル(メタ)アクリレートなどのフルオロC1-10アルキル(メタ)アクリレート、好ましくはフルオロC2-6アルキル(メタ)アクリレートなど)など]などが挙げられる。 (Fluorine atom-containing monomer)
Examples of the fluorine atom-containing monomer include fluorine atom-containing acrylic monomers [for example, fluoroalkyl (meth) acrylate (for example, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, octafluoropentyl). (meth) fluoroalkyl C 1-10 alkyl (meth) acrylates such as acrylates, preferably such as fluoro C 2-6 alkyl (meth) acrylate)], and others.
フッ素原子含有単量体としては、例えば、フッ素原子含有アクリル系単量体[例えば、フルオロアルキル(メタ)アクリレート(例えば、トリフルオロエチル(メタ)アクリレート、テトラフルオロプロピル(メタ)アクリレート、オクタフルオロペンチル(メタ)アクリレートなどのフルオロC1-10アルキル(メタ)アクリレート、好ましくはフルオロC2-6アルキル(メタ)アクリレートなど)など]などが挙げられる。 (Fluorine atom-containing monomer)
Examples of the fluorine atom-containing monomer include fluorine atom-containing acrylic monomers [for example, fluoroalkyl (meth) acrylate (for example, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, octafluoropentyl). (meth) fluoroalkyl C 1-10 alkyl (meth) acrylates such as acrylates, preferably such as fluoro C 2-6 alkyl (meth) acrylate)], and others.
フッ素原子含有単量体は、単独で又は2種以上組み合わせて使用してもよい。
Fluorine atom-containing monomers may be used alone or in combination of two or more.
単量体成分(a)がフッ素原子含有単量体を含有する場合、単量体成分(a)におけるフッ素原子含有単量体の含有割合(含有率)は、例えば、0.01~10質量%、好ましくは0.02~5質量%、さらに好ましくは0.03~3質量%程度であってもよい。
When the monomer component (a) contains a fluorine atom-containing monomer, the content ratio (content ratio) of the fluorine atom-containing monomer in the monomer component (a) is, for example, 0.01 to 10 mass. %, Preferably 0.02 to 5% by mass, more preferably about 0.03 to 3% by mass.
(窒素原子含有単量体)
窒素原子含有単量体としては、例えば、(メタ)アクリルアミド系化合物{例えば、(メタ)アクリルアミド、N-置換(メタ)アクリルアミド[例えば、N-アルキル(メタ)アクリルアミド(例えば、N,N-ジメチル(メタ)アクリルアミドなどのN,N-ジC1-4アルキル(メタ)アクリルアミド;N,N-ジメチルアミノプロピル(メタ)アクリルアミドなど)など]など}、窒素原子含有(メタ)アクリレート化合物{例えば、N-置換アミノアルキル(メタ)アクリレート[例えば、ジメチルアミノエチル(メタ)アクリレート、ジエチルアミノエチル(メタ)アクリレートなどのN,N-ジC1-4アルキルアミノC2-4アルキル(メタ)アクリレート]など}などが挙げられる。 (Nitrogen atom-containing monomer)
Examples of the nitrogen atom-containing monomer include (meth) acrylamide compounds {for example, (meth) acrylamide, N-substituted (meth) acrylamide [for example, N-alkyl (meth) acrylamide (for example, N, N-dimethyl). N, N-diC 1-4 alkyl (meth) acrylamide, such as (meth) acrylamide; N, N-dimethylaminopropyl (meth) acrylamide, etc.), etc.], nitrogen atom-containing (meth) acrylate compounds {for example, N-substituted aminoalkyl (meth) acrylate [for example, N, N-diC 1-4 alkylamino C 2-4 alkyl (meth) acrylate such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate], etc. }.
窒素原子含有単量体としては、例えば、(メタ)アクリルアミド系化合物{例えば、(メタ)アクリルアミド、N-置換(メタ)アクリルアミド[例えば、N-アルキル(メタ)アクリルアミド(例えば、N,N-ジメチル(メタ)アクリルアミドなどのN,N-ジC1-4アルキル(メタ)アクリルアミド;N,N-ジメチルアミノプロピル(メタ)アクリルアミドなど)など]など}、窒素原子含有(メタ)アクリレート化合物{例えば、N-置換アミノアルキル(メタ)アクリレート[例えば、ジメチルアミノエチル(メタ)アクリレート、ジエチルアミノエチル(メタ)アクリレートなどのN,N-ジC1-4アルキルアミノC2-4アルキル(メタ)アクリレート]など}などが挙げられる。 (Nitrogen atom-containing monomer)
Examples of the nitrogen atom-containing monomer include (meth) acrylamide compounds {for example, (meth) acrylamide, N-substituted (meth) acrylamide [for example, N-alkyl (meth) acrylamide (for example, N, N-dimethyl). N, N-diC 1-4 alkyl (meth) acrylamide, such as (meth) acrylamide; N, N-dimethylaminopropyl (meth) acrylamide, etc.), etc.], nitrogen atom-containing (meth) acrylate compounds {for example, N-substituted aminoalkyl (meth) acrylate [for example, N, N-diC 1-4 alkylamino C 2-4 alkyl (meth) acrylate such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate], etc. }.
窒素原子含有単量体は、単独で又は2種以上組み合わせて使用してもよい。
The nitrogen atom-containing monomers may be used alone or in combination of two or more.
単量体成分(a)が窒素原子含有単量体を含有する場合、単量体成分(a)における窒素原子含有単量体の含有割合(含有率)は、例えば、0.01~10質量%、好ましくは0.02~5質量%、さらに好ましくは0.03~3質量%程度であってもよい。
When the monomer component (a) contains a nitrogen atom-containing monomer, the content ratio (content ratio) of the nitrogen atom-containing monomer in the monomer component (a) is, for example, 0.01 to 10 mass. %, Preferably 0.02 to 5% by mass, more preferably about 0.03 to 3% by mass.
(エポキシ基含有単量体)
エポキシ基含有単量体としては、例えば、エポキシ基含有(メタ)アクリレート[例えば、グリシジル(メタ)アクリレート、グリシジルオキシアルキル(メタ)アクリレート(例えば、2-グリシジルオキシエチル(メタ)アクリレートなどのグリシジルオキシC2-4アルキル(メタ)アクリレート)など]、アリルグリシジルエーテルなどが挙げられる。 (Epoxy group-containing monomer)
Examples of the epoxy group-containing monomer include epoxy group-containing (meth) acrylate [for example, glycidyloxy such as glycidyl (meth) acrylate, glycidyloxyalkyl (meth) acrylate (for example, 2-glycidyloxyethyl (meth) acrylate), etc. C 2-4 alkyl (meth) acrylate)], and allyl glycidyl ether.
エポキシ基含有単量体としては、例えば、エポキシ基含有(メタ)アクリレート[例えば、グリシジル(メタ)アクリレート、グリシジルオキシアルキル(メタ)アクリレート(例えば、2-グリシジルオキシエチル(メタ)アクリレートなどのグリシジルオキシC2-4アルキル(メタ)アクリレート)など]、アリルグリシジルエーテルなどが挙げられる。 (Epoxy group-containing monomer)
Examples of the epoxy group-containing monomer include epoxy group-containing (meth) acrylate [for example, glycidyloxy such as glycidyl (meth) acrylate, glycidyloxyalkyl (meth) acrylate (for example, 2-glycidyloxyethyl (meth) acrylate), etc. C 2-4 alkyl (meth) acrylate)], and allyl glycidyl ether.
エポキシ基含有単量体は、単独で又は2種以上組み合わせて使用してもよい。
The epoxy group-containing monomers may be used alone or in combination of two or more.
単量体成分(a)がエポキシ基含有単量体を含有する場合、単量体成分(a)におけるエポキシ基含有単量体の含有割合(含有率)は、例えば、0.01~10質量%、好ましくは0.02~5質量%、さらに好ましくは0.03~3質量%程度であってもよい。
When the monomer component (a) contains an epoxy group-containing monomer, the content ratio (content ratio) of the epoxy group-containing monomer in the monomer component (a) is, for example, 0.01 to 10 mass. %, Preferably 0.02 to 5% by mass, more preferably about 0.03 to 3% by mass.
(紫外線吸収性単量体)
紫外線吸収性単量体(紫外線吸収性基を有する単量体)としては、例えば、ベンゾトリアゾール系紫外線吸収性単量体、ベンゾフェノン系紫外線吸収性単量体などが挙げられる。 (UV absorbing monomer)
Examples of the ultraviolet absorbing monomer (monomer having an ultraviolet absorbing group) include a benzotriazole ultraviolet absorbing monomer and a benzophenone ultraviolet absorbing monomer.
紫外線吸収性単量体(紫外線吸収性基を有する単量体)としては、例えば、ベンゾトリアゾール系紫外線吸収性単量体、ベンゾフェノン系紫外線吸収性単量体などが挙げられる。 (UV absorbing monomer)
Examples of the ultraviolet absorbing monomer (monomer having an ultraviolet absorbing group) include a benzotriazole ultraviolet absorbing monomer and a benzophenone ultraviolet absorbing monomer.
ベンゾトリアゾール系紫外線吸収性単量体としては、重合性基(例えば、(メタ)アクリロイル基)を有するベンゾトリアゾール系紫外線吸収剤、例えば、2-〔2’-ヒドロキシ-5’-(メタ)アクリロイルオキシメチルフェニル〕-2H-ベンゾトリアゾール、2-〔2’-ヒドロキシ-5’-(メタ)アクリロイルオキシエチルフェニル〕-2H-ベンゾトリアゾール、2-〔2’-ヒドロキシ-5’-(メタ)アクリロイルオキシメチルフェニル〕-5-tert-ブチル-2H-ベンゾトリアゾール、2-〔2’-ヒドロキ シ-5’-(メタ)アクリロイルアミノメチル-5’-tert-オクチルフェニル〕-2H-ベンゾトリアゾール、2-〔2’-ヒドロキシ-5’-(メタ)アクリロイルオキシプロピルフェニル〕-2H-ベンゾトリアゾール、2-〔2’-ヒドロキシ-5’-(メタ)アクリロイルオキシヘキシルフェニル〕-2H-ベンゾトリアゾール、2-〔2’-ヒドロキシ-3’-tert-ブチル-5’-(メタ)アクリロイルオキシエチルフェニル〕-2H-ベンゾトリアゾール、2-〔2’-ヒドロキシ-3’-tert-ブチル-5’-(メタ)アクリロイルオキシエチルフェニル〕-5-クロロ-2H-ベンゾトリアゾール、2-〔2’-ヒドロキシ-5’-tert-ブチル-3’-(メタ)アクリロイルオキシエチルフェニル〕-2H-ベンゾトリアゾール、2-〔2’-ヒドロキシ-5’-(メタ)アクリロイルオキシエチルフェニル〕-5-クロロ-2H-ベンゾトリアゾール、2-〔2’-ヒドロキシ-5’-(メタ)アクリロイルオキシエチルフェニル〕-5-シアノ-2H-ベンゾトリアゾール、2-〔2’-ヒドロキシ-5’-(メタ)アクリロイルオキシエチルフェニル〕-5-tert-ブチル-2H-ベンゾトリアゾール、2-〔2’-ヒドロキシ-5’-(β-(メタ)アクリロイルオキシエトキシ)-3’-tert-ブチルフェニル〕-4-tert-ブチル-2H-ベンゾトリアゾールなどが挙げられる。
Examples of the benzotriazole-based UV-absorbing monomer include benzotriazole-based UV absorbers having a polymerizable group (for example, (meth) acryloyl group), such as 2- [2′-hydroxy-5 ′-(meth) acryloyl Oxymethylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-5 '-(meth) acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-(meth) acryloyl Oxymethylphenyl] -5-tert-butyl-2H-benzotriazole, 2- [2'-hydroxy-5 '-(meth) acryloylaminomethyl-5'-tert-octylphenyl] -2H-benzotriazole, 2 -[2'-hydroxy-5 '-(meth) acryloyloxypropylphenyl] 2H-benzotriazole, 2- [2'-hydroxy-5 '-(meth) acryloyloxyhexylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-tert-butyl-5'-(meta ) Acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2′-hydroxy-3′-tert-butyl-5 ′-(meth) acryloyloxyethylphenyl] -5-chloro-2H-benzotriazole, 2- [2′-hydroxy-5′-tert-butyl-3 ′-(meth) acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl]- 5-chloro-2H-benzotriazole, 2- [2'-hydroxy-5 '-(meth) act Liloyloxyethylphenyl] -5-cyano-2H-benzotriazole, 2- [2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl] -5-tert-butyl-2H-benzotriazole, 2- [ And 2′-hydroxy-5 ′-(β- (meth) acryloyloxyethoxy) -3′-tert-butylphenyl] -4-tert-butyl-2H-benzotriazole.
ベンゾフェノン系紫外線吸収性単量体としては、重合性基(例えば、(メタ)アクリロイル基)を有するベンゾフェノン系紫外線吸収剤、例えば、2-ヒドロキシ-4-(メタ)アクリロイルオキシベンゾフェノン、2-ヒドロキシ-4-〔2-ヒドロキシ-3-(メタ)アクリロイルオキシ〕プロポキシベンゾフェノン、2-ヒドロキシ-4-〔2-(メタ)アクリロイルオキシ〕エトキシベンゾフェノン、2-ヒドロキシ-4-〔3-(メタ)アクリロイルオキシ-2-ヒドロキシプロポキシ〕ベンゾフェノン、2-ヒドロキシ-3-tert-ブチル-4-〔2-(メタ)アクリロイルオキシ〕ブトキシベンゾフェノンなどが挙げられる。
Examples of the benzophenone-based UV-absorbing monomer include benzophenone-based UV absorbers having a polymerizable group (for example, (meth) acryloyl group), such as 2-hydroxy-4- (meth) acryloyloxybenzophenone, 2-hydroxy- 4- [2-hydroxy-3- (meth) acryloyloxy] propoxybenzophenone, 2-hydroxy-4- [2- (meth) acryloyloxy] ethoxybenzophenone, 2-hydroxy-4- [3- (meth) acryloyloxy -2-hydroxypropoxy] benzophenone, 2-hydroxy-3-tert-butyl-4- [2- (meth) acryloyloxy] butoxybenzophenone, and the like.
紫外線吸収性単量体は、単独で又は2種以上組み合わせて使用してもよい。
The ultraviolet absorbing monomers may be used alone or in combination of two or more.
単量体成分(a)が紫外線吸収性単量体を含有する場合、単量体成分(a)における紫外線吸収性単量体の含有割合(含有率)は、例えば、0.01~10質量%、好ましくは0.02~5質量%、さらに好ましくは0.03~3質量%程度であってもよい。
When the monomer component (a) contains an ultraviolet absorbing monomer, the content (content) of the ultraviolet absorbing monomer in the monomer component (a) is, for example, 0.01 to 10 mass. %, Preferably 0.02 to 5% by mass, more preferably about 0.03 to 3% by mass.
(ヒンダードアミン系モノマー)
ヒンダードアミン系モノマー(紫外線安定性単量体、重合性基を有する光安定剤、光安定性を有する単量体)としては、前記例示のヒンダードアミン系モノマー、例えば、4-(メタ)アクリロイルオキシ-2,2,6,6-テトラメチルピペリジン、4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジン、4-(メタ)アクリロイルオキシ-1,2,2,6,6-ペンタメチルピペリジン、4-(メタ)アクリロイル-1-メトキシ-2,2,6,6-テトラメチルピペリジン、4-シアノ-4-(メタ)アクリロイルオキシ-2,2,6,6-テトラメチルピペリジン、1-(メタ)アクリロイル-4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジン、4-クロトノイルアミノ-2,2,6,6-テトラメチルピペリジン、4-(メタ)アクリロイルアミノ-1,2,2,6,6-ペンタメチルピペリジン、4-シアノ-4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジン、4-クロトノイルオキシ-2,2,6,6-テトラメチルピペリジン、1-(メタ)アクリロイル-4-シアノ-4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジン、1-クロトノイル-4-クロトノイルオキシ-2,2,6,6-テトラメチルピペリジンなどが挙げられる。 (Hindered amine monomers)
Examples of hindered amine monomers (ultraviolet-stable monomers, light stabilizers having a polymerizable group, and monomers having light stability) include the hindered amine monomers exemplified above, such as 4- (meth) acryloyloxy-2. , 2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-penta Methylpiperidine, 4- (meth) acryloyl-1-methoxy-2,2,6,6-tetramethylpiperidine, 4-cyano-4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2,2 6,6-tetramethylpiperidine, 4- (meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-cyano-4- (meth) acryloylamino-2,2,6,6- Tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4-cyano-4- (meth) acryloylamino-2,2,6,6-tetra Examples include methylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine.
ヒンダードアミン系モノマー(紫外線安定性単量体、重合性基を有する光安定剤、光安定性を有する単量体)としては、前記例示のヒンダードアミン系モノマー、例えば、4-(メタ)アクリロイルオキシ-2,2,6,6-テトラメチルピペリジン、4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジン、4-(メタ)アクリロイルオキシ-1,2,2,6,6-ペンタメチルピペリジン、4-(メタ)アクリロイル-1-メトキシ-2,2,6,6-テトラメチルピペリジン、4-シアノ-4-(メタ)アクリロイルオキシ-2,2,6,6-テトラメチルピペリジン、1-(メタ)アクリロイル-4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジン、4-クロトノイルアミノ-2,2,6,6-テトラメチルピペリジン、4-(メタ)アクリロイルアミノ-1,2,2,6,6-ペンタメチルピペリジン、4-シアノ-4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジン、4-クロトノイルオキシ-2,2,6,6-テトラメチルピペリジン、1-(メタ)アクリロイル-4-シアノ-4-(メタ)アクリロイルアミノ-2,2,6,6-テトラメチルピペリジン、1-クロトノイル-4-クロトノイルオキシ-2,2,6,6-テトラメチルピペリジンなどが挙げられる。 (Hindered amine monomers)
Examples of hindered amine monomers (ultraviolet-stable monomers, light stabilizers having a polymerizable group, and monomers having light stability) include the hindered amine monomers exemplified above, such as 4- (meth) acryloyloxy-2. , 2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-penta Methylpiperidine, 4- (meth) acryloyl-1-methoxy-2,2,6,6-tetramethylpiperidine, 4-cyano-4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2,2 6,6-tetramethylpiperidine, 4- (meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-cyano-4- (meth) acryloylamino-2,2,6,6- Tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4-cyano-4- (meth) acryloylamino-2,2,6,6-tetra Examples include methylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine.
ヒンダードアミン系モノマーは、単独で又は2種以上組み合わせて使用してもよい。
The hindered amine monomers may be used alone or in combination of two or more.
単量体成分(a)がヒンダードアミン系モノマーを含有する場合、単量体成分(a)におけるヒンダードアミン系モノマーの含有割合(含有率)は、例えば、0.01~20質量%、好ましくは0.05~10質量%、さらに好ましくは0.1~5質量%程度であってもよい。
When the monomer component (a) contains a hindered amine monomer, the content (content) of the hindered amine monomer in the monomer component (a) is, for example, 0.01 to 20% by mass, preferably 0.8. It may be about 05 to 10% by mass, more preferably about 0.1 to 5% by mass.
(官能基αを有する単量体)
単量体成分(a)は、官能基(官能基αという)を有する単量体を含んでいてもよい。
エマルション(A)中の樹脂が、このような官能基αを有する単量体由来の構造単位を有することで、ポリマー(B)が有する官能基(後述の官能基β)の選択により、エマルション(A)とポリマー(B)との間での結合を効率よく形成できる。このような結合形成は、塗膜表面からポリマー(B)の流出を抑制できる他に、耐水性や塗膜の弾性率が向上することからも、好ましい形態である。 (Monomer having functional group α)
The monomer component (a) may contain a monomer having a functional group (referred to as a functional group α).
Since the resin in the emulsion (A) has a structural unit derived from a monomer having such a functional group α, an emulsion (by the functional group β described later) can be selected by selecting a functional group (functional group β described later). A bond between A) and polymer (B) can be formed efficiently. Such bond formation is a preferable form because it can suppress the outflow of the polymer (B) from the surface of the coating film and also improves the water resistance and the elastic modulus of the coating film.
単量体成分(a)は、官能基(官能基αという)を有する単量体を含んでいてもよい。
エマルション(A)中の樹脂が、このような官能基αを有する単量体由来の構造単位を有することで、ポリマー(B)が有する官能基(後述の官能基β)の選択により、エマルション(A)とポリマー(B)との間での結合を効率よく形成できる。このような結合形成は、塗膜表面からポリマー(B)の流出を抑制できる他に、耐水性や塗膜の弾性率が向上することからも、好ましい形態である。 (Monomer having functional group α)
The monomer component (a) may contain a monomer having a functional group (referred to as a functional group α).
Since the resin in the emulsion (A) has a structural unit derived from a monomer having such a functional group α, an emulsion (by the functional group β described later) can be selected by selecting a functional group (functional group β described later). A bond between A) and polymer (B) can be formed efficiently. Such bond formation is a preferable form because it can suppress the outflow of the polymer (B) from the surface of the coating film and also improves the water resistance and the elastic modulus of the coating film.
また、官能基αによって、ポリマー(B)との親和性を向上できるため、より一層効率よくポリマー(B)が塗膜に吸着し、長期耐汚染性を向上させやすい。
Moreover, since the affinity with the polymer (B) can be improved by the functional group α, the polymer (B) is more efficiently adsorbed to the coating film, and it is easy to improve long-term contamination resistance.
官能基αとしては、官能基β(ポリマー(B)において例示の官能基)と同様の官能基、例えば、カルボニル基(又はカルボニル基含有基、例えば、ケトン基、アルデヒド基、アシル基など)、酸基又はアニオン性基(例えば、カルボキシル基、酸無水物基、酸ハライド基、スルホン酸基など)、カーボネート基、イソシアネート基、オキサゾリン基、オキサゾリジン基、ヒドラジノ基、エポキシ基、アミノ基、ヒドロキシル基、メルカプト基などが挙げられる。なお、官能基βとの結合形成を所望又は意図する場合には、官能基βとの組み合わせにより、官能基αを選択してもよい。
As the functional group α, the same functional group as the functional group β (functional group exemplified in the polymer (B)), for example, a carbonyl group (or a carbonyl group-containing group such as a ketone group, an aldehyde group, an acyl group, etc.), Acid group or anionic group (for example, carboxyl group, acid anhydride group, acid halide group, sulfonic acid group, etc.), carbonate group, isocyanate group, oxazoline group, oxazolidine group, hydrazino group, epoxy group, amino group, hydroxyl group And a mercapto group. When bond formation with the functional group β is desired or intended, the functional group α may be selected in combination with the functional group β.
官能基αを有する単量体は、これらの官能基を単独で又は2種以上組み合わせて有していてもよい。
The monomer having the functional group α may have these functional groups alone or in combination of two or more.
これらの官能基の中でも、塗膜物性等の観点から、カルボニル基、酸基(アニオン性基)、オキサゾリン基、ヒドラジノ基、ヒドロキシル基などが好ましく、特にカルボニル基、カルボキシル基が好ましい。
また、これらの中でも、酸基(アニオン性基)を有する単量体を好適に使用してもよい。酸基(又はアニオン性基)は、ポリマー(B)のヒンダードアミン骨格に対して高い親和性を発揮するため、ポリマー(B)が効率よく塗膜に吸着し、長期耐汚染性を向上させやすい。 Among these functional groups, a carbonyl group, an acid group (anionic group), an oxazoline group, a hydrazino group, a hydroxyl group, and the like are preferable from the viewpoint of physical properties of the coating film, and a carbonyl group and a carboxyl group are particularly preferable.
Moreover, among these, you may use suitably the monomer which has an acid group (anionic group). Since the acid group (or anionic group) exhibits high affinity for the hindered amine skeleton of the polymer (B), the polymer (B) is efficiently adsorbed on the coating film, and it is easy to improve long-term stain resistance.
また、これらの中でも、酸基(アニオン性基)を有する単量体を好適に使用してもよい。酸基(又はアニオン性基)は、ポリマー(B)のヒンダードアミン骨格に対して高い親和性を発揮するため、ポリマー(B)が効率よく塗膜に吸着し、長期耐汚染性を向上させやすい。 Among these functional groups, a carbonyl group, an acid group (anionic group), an oxazoline group, a hydrazino group, a hydroxyl group, and the like are preferable from the viewpoint of physical properties of the coating film, and a carbonyl group and a carboxyl group are particularly preferable.
Moreover, among these, you may use suitably the monomer which has an acid group (anionic group). Since the acid group (or anionic group) exhibits high affinity for the hindered amine skeleton of the polymer (B), the polymer (B) is efficiently adsorbed on the coating film, and it is easy to improve long-term stain resistance.
具体的な官能基を有する単量体としては、例えば、カルボニル基含有単量体、酸基含有単量体(アニオン性基含有単量体)、ヒドロキシル基含有単量体などが含まれる。
Specific monomers having a functional group include, for example, carbonyl group-containing monomers, acid group-containing monomers (anionic group-containing monomers), hydroxyl group-containing monomers, and the like.
カルボニル基含有単量体としては、例えば、不飽和アルデヒド[例えば、アルケナール(例えば、アクロレイン、メタクロレインなどのC3-10アルケナール)、(メタ)アクリロキシアルキルアルケナール(例えば、アクリルオキシアルキルプロペナール、メタクリルオキシアルキルプロペナール)、ホルミルスチロールなど]、不飽和ケトン[例えば、アルケノン(例えば、メチルビニルケトン、エチルビニルケトン、ビニルブチルケトンなど)、(メタ)アクリロイルオキシアルカノン(例えば、アセトニルアクリレート、アセトニルメタクリレートなど)、N-(メタ)アクリロイルアミノアルカノン(例えば、ダイアセトンアクリルアミド、ダイアセトンメタクリルアミドなど)、アルカンジオール(メタ)アクリレートアセチルアセテート(例えば、2-ヒドロキシプロピルアクリレートアセチルアセテート、2-ヒドロキシプロピルメタクリレートアセチルアセテート、ブタンジオール-1,4-アクリレートアセチルアセテートなどのC2-6アルカンジオール(メタ)アクリレートアセチルアセテート)、アセトアセトキシアルキル(メタ)アクリレート(例えば、2-(アセトアセトキシ)エチルアクリレート、2-(アセトアセトキシ)エチルメタクリレート)など]などが挙げられる。
Examples of the carbonyl group-containing monomer include unsaturated aldehydes [eg, alkenals (eg, C 3-10 alkenals such as acrolein, methacrolein), (meth) acryloxyalkyl alkenals (eg, acryloxyalkylpropenal). , Methacryloxyalkylpropenal), formylstyrene, etc.], unsaturated ketones (eg, alkenones (eg, methyl vinyl ketone, ethyl vinyl ketone, vinyl butyl ketone), (meth) acryloyloxyalkanones (eg, acetonyl acrylate) , Acetonyl methacrylate, etc.), N- (meth) acryloylaminoalkanone (eg, diacetone acrylamide, diacetone methacrylamide, etc.), alkanediol (meth) acrylate acetyl Acetoacetoxy (eg, C 2-6 alkanediol (meth) acrylate acetyl acetate such as 2-hydroxypropyl acrylate acetyl acetate, 2-hydroxypropyl methacrylate acetyl acetate, butanediol-1,4-acrylate acetyl acetate), acetoacetoxyalkyl (Meth) acrylates (for example, 2- (acetoacetoxy) ethyl acrylate, 2- (acetoacetoxy) ethyl methacrylate, etc.) and the like.
酸基含有単量体(アニオン性基含有単量体)としては、前記例示の単量体、例えば、カルボン酸基含有単量体[例えば、不飽和モノカルボン酸(例えば、アクリル酸、メタクリル酸、クロトン酸などの脂肪族不飽和モノカルボン酸)、不飽和ジカルボン酸(例えば、マレイン酸、フマル酸などの脂肪族不飽和モノカルボン酸)など]、スルホン酸基含有単量体[例えば、スチレン系単量体(例えば、スチレンスルホン酸など)など]などが挙げられる。
なお、酸基含有単量体は、アニオン化されていても(又は塩を形成していても又は中和されていても)よい。アニオン化する方法としては、特に限定されず、例えば、塩基性化合物としては、例えば、無機塩基{例えば、水酸化物(例えば、水酸化ナトリウムなどのアルカリ金属又はアルカリ土類金属水酸化物)、アンモニア[例えば、アンモニア水(25%アンモニア水など)として使用]など}、有機塩基[例えば、アミン(例えば、モノメチルアミン、モノエタノールアミン、ジエタノールアミン、ジメチルエタノールアミン、イソプロパノールアミンなど)など]などを挙げることができる。塩基性化合物は、2種以上併用してもよい。 Examples of the acid group-containing monomer (anionic group-containing monomer) include the above-exemplified monomers, for example, carboxylic acid group-containing monomers [for example, unsaturated monocarboxylic acids (for example, acrylic acid, methacrylic acid). , Aliphatic unsaturated monocarboxylic acids such as crotonic acid), unsaturated dicarboxylic acids (eg, aliphatic unsaturated monocarboxylic acids such as maleic acid and fumaric acid)], sulfonic acid group-containing monomers [eg, styrene Based monomers (for example, styrenesulfonic acid, etc.)] and the like.
The acid group-containing monomer may be anionized (or may form a salt or be neutralized). The method for anionization is not particularly limited. For example, the basic compound includes, for example, an inorganic base {for example, hydroxide (for example, alkali metal or alkaline earth metal hydroxide such as sodium hydroxide), Ammonia [for example, aqueous ammonia (used as 25% aqueous ammonia, etc.), etc.], organic base [eg, amine (eg, monomethylamine, monoethanolamine, diethanolamine, dimethylethanolamine, isopropanolamine, etc.), etc.] be able to. Two or more basic compounds may be used in combination.
なお、酸基含有単量体は、アニオン化されていても(又は塩を形成していても又は中和されていても)よい。アニオン化する方法としては、特に限定されず、例えば、塩基性化合物としては、例えば、無機塩基{例えば、水酸化物(例えば、水酸化ナトリウムなどのアルカリ金属又はアルカリ土類金属水酸化物)、アンモニア[例えば、アンモニア水(25%アンモニア水など)として使用]など}、有機塩基[例えば、アミン(例えば、モノメチルアミン、モノエタノールアミン、ジエタノールアミン、ジメチルエタノールアミン、イソプロパノールアミンなど)など]などを挙げることができる。塩基性化合物は、2種以上併用してもよい。 Examples of the acid group-containing monomer (anionic group-containing monomer) include the above-exemplified monomers, for example, carboxylic acid group-containing monomers [for example, unsaturated monocarboxylic acids (for example, acrylic acid, methacrylic acid). , Aliphatic unsaturated monocarboxylic acids such as crotonic acid), unsaturated dicarboxylic acids (eg, aliphatic unsaturated monocarboxylic acids such as maleic acid and fumaric acid)], sulfonic acid group-containing monomers [eg, styrene Based monomers (for example, styrenesulfonic acid, etc.)] and the like.
The acid group-containing monomer may be anionized (or may form a salt or be neutralized). The method for anionization is not particularly limited. For example, the basic compound includes, for example, an inorganic base {for example, hydroxide (for example, alkali metal or alkaline earth metal hydroxide such as sodium hydroxide), Ammonia [for example, aqueous ammonia (used as 25% aqueous ammonia, etc.), etc.], organic base [eg, amine (eg, monomethylamine, monoethanolamine, diethanolamine, dimethylethanolamine, isopropanolamine, etc.), etc.] be able to. Two or more basic compounds may be used in combination.
オキサゾリン基含有単量体としては、例えば、アルケニルオキサゾリン(例えば、2-ビニル-2-オキサゾリン、2-イソプロペニル-2-オキサゾリンなどのC2-6アルケニルオキサゾリン、好ましくはビニル又はイソプロペニルオキサゾリン)、アルケニル-アルキルオキサゾリン(例えば、2-ビニル-4-メチル-2-オキサゾリン、2-ビニル-5-メチル-2-オキサゾリン、2-イソプロペニル-4-メチル-2-オキサゾリン、2-イソプロぺニル-5-エチル-2-オキサゾリンなどのC2-6アルケニル-C1-10アルキルオキサゾリン、好ましくはビニル又はイソプロペニル-C1-4アルキルオキサゾリンなど)などが挙げられる。
Examples of the oxazoline group-containing monomer include alkenyl oxazolines (for example, C 2-6 alkenyl oxazolines such as 2-vinyl-2-oxazoline and 2-isopropenyl-2-oxazoline, preferably vinyl or isopropenyl oxazoline), Alkenyl-alkyloxazolines (eg 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl- C 2-6 alkenyl-C 1-10 alkyl oxazoline such as 5-ethyl-2-oxazoline, preferably vinyl or isopropenyl-C 1-4 alkyl oxazoline) and the like.
ヒドロキシル基含有単量体としては、前記例示の単量体(例えば、水酸基含有(メタ)アクリレート)などが挙げられる。
Examples of the hydroxyl group-containing monomer include the monomers exemplified above (for example, hydroxyl group-containing (meth) acrylate).
官能基αを有する単量体は、単独で又は2種以上組み合わせて使用してもよい。
Monomers having a functional group α may be used alone or in combination of two or more.
これらのうち、カルボニル基含有単量体(不飽和ケトンなど)、不飽和モノカルボン酸(アクリル酸など)、水酸基含有(メタ)アクリレートなどが好ましく、中でも、ダイアセトン(メタ)アクリルアミドが好ましい。そのため、官能基αを有する単量体は、少なくともこのような単量体(特に、ダイアセトン(メタ)アクリルアミド)を含んでいてもよい。
Of these, carbonyl group-containing monomers (such as unsaturated ketones), unsaturated monocarboxylic acids (such as acrylic acid), and hydroxyl group-containing (meth) acrylates are preferred, with diacetone (meth) acrylamide being preferred. Therefore, the monomer having the functional group α may contain at least such a monomer (particularly diacetone (meth) acrylamide).
また、前記のように、ポリマー(B)との親和性などの観点から、(メタ)アクリル酸などの酸基含有単量体(アニオン性基含有単量体)も好ましい。
Also, as mentioned above, from the viewpoint of affinity with the polymer (B), acid group-containing monomers (anionic group-containing monomers) such as (meth) acrylic acid are also preferable.
なお、官能基αを有する単量体として、ダイアセトン(メタ)アクリルアミドを少なくとも使用する場合、官能基αを有する単量体全体に対するダイアセトン(メタ)アクリルアミドの割合は、例えば、10質量%以上、好ましくは20質量%以上、さらに好ましくは30質量%以上であってもよい。
When at least diacetone (meth) acrylamide is used as the monomer having the functional group α, the ratio of diacetone (meth) acrylamide to the whole monomer having the functional group α is, for example, 10% by mass or more. , Preferably 20% by mass or more, more preferably 30% by mass or more.
また、官能基αを有する単量体として、酸基含有単量体を少なくとも使用する場合、官能基αを有する単量体全体に対する酸基含有単量体の割合は、例えば、10質量%以上、好ましくは20質量%以上、さらに好ましくは30質量%以上であってもよい。
Further, when at least an acid group-containing monomer is used as the monomer having a functional group α, the ratio of the acid group-containing monomer to the whole monomer having the functional group α is, for example, 10% by mass or more. , Preferably 20% by mass or more, more preferably 30% by mass or more.
官能基αを有する単量体は、単独で又は2種以上組み合わせて使用してもよい。
Monomers having a functional group α may be used alone or in combination of two or more.
単量体成分(a)が官能基αを有する単量体を含有する場合、単量体成分(a)における官能基αを有する単量体の含有割合(含有率)は、30質量%以下(例えば、20質量%以下)程度範囲から選択でき、例えば、0.01~10質量%、好ましくは0.02~5質量%、さらに好ましくは0.05~3質量%程度であってもよく、0.1~10質量%(例えば、0.1~5質量%)程度であってもよい。
When the monomer component (a) contains a monomer having a functional group α, the content (content) of the monomer having a functional group α in the monomer component (a) is 30% by mass or less. (For example, 20% by mass or less) can be selected from a range, for example, 0.01 to 10% by mass, preferably 0.02 to 5% by mass, more preferably about 0.05 to 3% by mass. About 0.1 to 10% by mass (for example, 0.1 to 5% by mass).
特に、官能基αを有する単量体として、酸基含有単量体を使用する場合、単量体成分(a)における酸基含有単量体の含有割合(含有率)は、0.01質量%以上(例えば、0.01~3質量%)、好ましくは0.1質量%以上(例えば、0.1~2質量%)、さらに好ましくは0.3質量%以上(例えば、0.3~1.5質量%)であってもよい。
In particular, when an acid group-containing monomer is used as the monomer having a functional group α, the content ratio (content ratio) of the acid group-containing monomer in the monomer component (a) is 0.01 mass. % Or more (for example, 0.01 to 3% by mass), preferably 0.1% by mass or more (for example, 0.1 to 2% by mass), more preferably 0.3% by mass or more (for example, 0.3 to 3% by mass). 1.5% by mass).
また、単量体成分(a)が、脂肪族(メタ)アクリレート及び/又は脂環構造を有する単量体、並びに官能基αを有する単量体を含有する場合、官能基αを有する単量体の含有割合(含有率)は、脂肪族(メタ)アクリレート及び/又は脂環構造を有する単量体100質量部に対して、例えば、10質量部以下(例えば、0.01~10質量部)、好ましくは5質量部以下(例えば、0.2~5質量部)、さらに好ましくは3質量部以下(例えば、0.3~3質量部)程度であってもよく、特に2質量部以下(例えば、0.05~1.5質量部)であってもよい。
In addition, when the monomer component (a) contains an aliphatic (meth) acrylate and / or a monomer having an alicyclic structure and a monomer having a functional group α, the monomer having the functional group α The content ratio (content ratio) of the body is, for example, 10 parts by mass or less (for example, 0.01 to 10 parts by mass) with respect to 100 parts by mass of the monomer having an aliphatic (meth) acrylate and / or an alicyclic structure. ), Preferably 5 parts by mass or less (eg, 0.2 to 5 parts by mass), more preferably about 3 parts by mass or less (eg, 0.3 to 3 parts by mass), particularly 2 parts by mass or less. (For example, 0.05 to 1.5 parts by mass).
(エマルション(A)及びその製造方法)
エマルション(A)は、エマルション状態にある樹脂(粒子)、例えば、単量体成分(a)を重合成分とする樹脂(樹脂粒子)(又は当該樹脂(又は樹脂粒子)が溶媒中に分散したもの)である。そのため、エマルション(A)は、樹脂(粒子)と乳化剤(樹脂粒子を被覆する乳化剤)とで構成されていてもよい。 (Emulsion (A) and production method thereof)
The emulsion (A) is a resin (particle) in an emulsion state, for example, a resin (resin particle) having the monomer component (a) as a polymerization component (or the resin (or resin particle) dispersed in a solvent). ). Therefore, the emulsion (A) may be composed of a resin (particles) and an emulsifier (emulsifier that coats the resin particles).
エマルション(A)は、エマルション状態にある樹脂(粒子)、例えば、単量体成分(a)を重合成分とする樹脂(樹脂粒子)(又は当該樹脂(又は樹脂粒子)が溶媒中に分散したもの)である。そのため、エマルション(A)は、樹脂(粒子)と乳化剤(樹脂粒子を被覆する乳化剤)とで構成されていてもよい。 (Emulsion (A) and production method thereof)
The emulsion (A) is a resin (particle) in an emulsion state, for example, a resin (resin particle) having the monomer component (a) as a polymerization component (or the resin (or resin particle) dispersed in a solvent). ). Therefore, the emulsion (A) may be composed of a resin (particles) and an emulsifier (emulsifier that coats the resin particles).
このようなエマルション(A)は、通常、溶媒中で、単量体成分(a)を乳化重合することにより得てもよい。
Such an emulsion (A) may be usually obtained by emulsion polymerization of the monomer component (a) in a solvent.
溶媒としては、通常、水、水を含む溶媒[水とアルコール(メタノール、エタノールなどのC1-4アルコールなど)との混合溶媒など]などの水性溶媒が挙げられる。
Examples of the solvent usually include aqueous solvents such as water and water-containing solvents [such as a mixed solvent of water and alcohol (such as C 1-4 alcohol such as methanol and ethanol)].
単量体成分(a)を乳化重合させる方法としては、例えば、乳化剤(分散剤、界面活性剤)を含む溶媒(溶液)に、単量体成分(a)(および重合開始剤)を混合(滴下など)して重合する方法、予め乳化させておいた単量体成分(a)を溶媒に混合(滴下など)して重合する方法などが挙げられるが、本発明は、かかる方法のみに限定されるものではない。
As a method for emulsion polymerization of the monomer component (a), for example, the monomer component (a) (and the polymerization initiator) is mixed in a solvent (solution) containing an emulsifier (dispersant, surfactant) ( And a method of polymerizing by mixing (e.g., dropping) the monomer component (a) emulsified in advance with a solvent, but the present invention is limited only to such a method. Is not to be done.
なお、溶媒(媒体)の量は、得られる樹脂エマルションに含まれる不揮発分量等を考慮して適宜設定すればよい。
In addition, what is necessary is just to set the quantity of a solvent (medium) suitably considering the non volatile matter amount etc. which are contained in the resin emulsion obtained.
乳化剤(分散剤、界面活性剤)としては、例えば、アニオン性乳化剤、ノニオン性乳化剤、カチオン性乳化剤(例えば、デシルアンモニウムクロライドなどのアルキルアンモニウム塩)、両性乳化剤(例えば、ベタインエステル型乳化剤)などが挙げられる。
Examples of emulsifiers (dispersing agents, surfactants) include anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers (for example, alkylammonium salts such as decylammonium chloride), amphoteric emulsifiers (for example, betaine ester type emulsifiers), and the like. Can be mentioned.
アニオン性乳化剤としては、例えば、アンモニウムドデシルサルフェート、ナトリウムドデシルサルフェートなどのアルキルサルフェート塩;アンモニウムドデシルスルホネート、ナトリウムドデシルスルホネートなどのアルキルスルホネート塩;アンモニウムドデシルベンゼンスルホネート、ナトリウムドデシルナフタレンスルホネートなどのアルキルアリールスルホネート塩;ポリオキシエチレンアルキルサルフェート塩;ポリオキシエチレンアルキルアリールサルフェート塩;ジアルキルスルホコハク酸塩;アリールスルホン酸-ホルマリン縮合物;アンモニウムラウリレート、ナトリウムステアリレートなどの脂肪酸塩などが挙げられる。
Examples of the anionic emulsifier include alkyl sulfate salts such as ammonium dodecyl sulfate and sodium dodecyl sulfate; alkyl sulfonate salts such as ammonium dodecyl sulfonate and sodium dodecyl sulfonate; alkyl aryl sulfonate salts such as ammonium dodecyl benzene sulfonate and sodium dodecyl naphthalene sulfonate; Examples include polyoxyethylene alkyl sulfate salts; polyoxyethylene alkyl aryl sulfate salts; dialkyl sulfosuccinates; aryl sulfonic acid-formalin condensates; fatty acid salts such as ammonium laurate and sodium stearate.
ノニオン性乳化剤としては、例えば、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルアリールエーテル、ポリエチレングリコールとポリプロピレングリコールとの縮合体、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、脂肪酸モノグリセライド、エチレンオキサイドと脂肪族アミンとの縮合体などが挙げられる。
Nonionic emulsifiers include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, condensate of polyethylene glycol and polypropylene glycol, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid monoglyceride, ethylene oxide and aliphatic Examples thereof include condensates with amines.
また、乳化剤には、高分子乳化剤が含まれる。高分子乳化剤としては、例えば、アニオン性乳化剤(ポリアクリル酸ナトリウムなどのポリ(メタ)アクリル酸塩)、ノニオン性乳化剤(ポリビニルアルコール、ポリビニルピロリドン、ポリヒドロキシエチルアクリレートなどのポリヒドロキシアルキル(メタ)アクリレート)、これらの重合体を構成する単量体のうちの1種類以上の単量体を共重合成分とする重合体などが挙げられる。
Further, the emulsifier includes a polymer emulsifier. Examples of the polymer emulsifier include anionic emulsifiers (poly (meth) acrylates such as sodium polyacrylate) and nonionic emulsifiers (polyhydroxyalkyl (meth) acrylates such as polyvinyl alcohol, polyvinyl pyrrolidone, and polyhydroxyethyl acrylate). ), Polymers having one or more monomers among these monomers as a copolymerization component.
また、乳化剤としては、塗膜物性などの観点から、反応性基を有する乳化剤、すなわち、いわゆる反応性乳化剤を好適に使用してもよい。このような反応性乳化剤の中でも、特に、環境保護などの観点から、非ノニルフェニル型の乳化剤を好適に使用してもよい。
Also, as the emulsifier, from the viewpoint of physical properties of the coating film, an emulsifier having a reactive group, that is, a so-called reactive emulsifier may be suitably used. Among such reactive emulsifiers, non-nonylphenyl emulsifiers may be suitably used, particularly from the viewpoint of environmental protection.
反応性乳化剤としては、例えば、アニオン性乳化剤[例えば、プロペニル-アルキルスルホコハク酸エステル塩、(メタ)アクリル酸ポリオキシエチレンスルホネート塩、(メタ)アクリル酸ポリオキシエチレンホスフォネート塩〔例えば、三洋化成工業(株)製、商品名:エレミノールRS-30など〕、ポリオキシエチレンアルキルプロペニルフェニルエーテルスルホネート塩〔例えば、第一工業製薬(株)製、商品名:アクアロンHS-10など〕、アリルオキシメチルアルキルオキシポリオキシエチレンのスルホネート塩〔例えば、第一工業製薬(株)製、商品名:アクアロンKH-10など〕、アリルオキシメチルノニルフェノキシエチルヒドロキシポリオキシエチレンのスルホネート塩〔例えば、(株)ADEKA製、商品名 :アデカリアソープSE-10など〕、アリルオキシメチルアルコキシエチルヒドロキシポリオキシエチレン硫酸エステル塩〔例えば、(株)ADEKA製、商品名:アデカリアソープSR-10、SR-30など〕、ビス(ポリオキシエチレン多環フェニルエーテル)メタクリレート化スルホネート塩〔例えば、日本乳化剤(株)製、商品名:アントックスMS-60など〕など]、ノニオン性乳化剤[例えば、アリルオキシメチルアルコキシエチルヒドロキシポリオキシエチレン〔例えば、(株)ADEKA製、商品名:アデカリアソープER-20など〕、ポリオキシエチレンアルキルプロペニルフェニルエーテル〔例えば、第一工業製薬(株)製、商品名:アクアロンRN-20など〕、アリルオキシメチルノニルフェノキシエチルヒドロキシポリオキシエチレン〔例えば、(株)ADEKA製、商品名:アデカリアソープNE-10など〕など]などが挙げられる。
Examples of the reactive emulsifier include an anionic emulsifier [for example, propenyl-alkylsulfosuccinate ester salt, (meth) acrylic acid polyoxyethylene sulfonate salt, (meth) acrylic acid polyoxyethylene phosphonate salt [for example, Sanyo Kasei Co., Ltd.] Manufactured by Kogyo Co., Ltd., trade name: Eleminol RS-30, etc.], polyoxyethylene alkyl propenyl phenyl ether sulfonate salt (for example, trade name: Aqualon HS-10, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), allyloxymethyl Sulfonate salt of alkyloxypolyoxyethylene [for example, product name: Aqualon KH-10 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], sulfonate salt of allyloxymethylnonylphenoxyethylhydroxypolyoxyethylene [for example, ADEKA Corporation Product name : Adekaria soap SE-10, etc.], allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate salts (for example, ADEKA Corporation, trade names: Adeka soaps SR-10, SR-30, etc.), bis (poly Oxyethylene polycyclic phenyl ether) methacrylated sulfonate salts [for example, manufactured by Nippon Emulsifier Co., Ltd., trade name: Antox MS-60, etc.], nonionic emulsifiers [for example, allyloxymethylalkoxyethylhydroxypolyoxyethylene [ For example, ADEKA Co., Ltd., trade name: ADEKA rear soap ER-20, etc.], polyoxyethylene alkylpropenyl phenyl ether [eg, Daiichi Kogyo Seiyaku Co., Ltd., trade name: AQUALON RN-20, etc.], allyl Oxymethylnonylphenoxyethyl Hydroxypolyoxyethylene [for example, product name: ADEKA rear soap NE-10 manufactured by ADEKA Corporation] and the like.
乳化剤は、それぞれ単独で用いてもよく、2種類以上を併用してもよい。
Emulsifiers may be used alone or in combination of two or more.
これらの乳化剤の中でも、アニオン性乳化剤、特に、アニオン性の反応性乳化剤を好適に使用してもよい。このようなアニオン性乳化剤は、前記酸基含有単量体と同様に機能し、ポリマー(B)との親和性を向上しやすく、そのため、より一層効率よく塗膜にポリマー(B)が吸着し、長期耐汚染性を向上しやすい。
Among these emulsifiers, anionic emulsifiers, particularly anionic reactive emulsifiers, may be preferably used. Such an anionic emulsifier functions in the same manner as the acid group-containing monomer, and easily improves the affinity with the polymer (B). Therefore, the polymer (B) is more efficiently adsorbed to the coating film. Easy to improve long-term pollution resistance.
単量体成分(a)100質量部あたりの乳化剤の量は、重合安定性等の観点から、好ましくは0.5質量部以上、さらに好ましくは1質量部以上であり、塗膜物性等の観点から、好ましくは10質量部以下、より好ましくは7質量部以下、さらに好ましくは5質量部以下であってもよい。
The amount of the emulsifier per 100 parts by mass of the monomer component (a) is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more from the viewpoint of polymerization stability, etc. Therefore, it may be 10 parts by mass or less, more preferably 7 parts by mass or less, and still more preferably 5 parts by mass or less.
重合は、通常、重合開始剤の存在下で行ってもよい。
重合開始剤としては、例えば、アゾビスイソブチロニトリル、2,2-アゾビス(2- メチルブチロニトリル)、2,2-アゾビス(2,4-ジメチルバレロニトリル)、2, 2-アゾビス(2―ジアミノプロパン)ハイドロクロライド、4,4-アゾビス(4-シ アノ吉草酸)、2,2-アゾビス(2-メチルプロピオンアミジン)などのアゾ化合物;過硫酸カリウムなどの過硫酸塩;過酸化水素、ベンゾイルパーオキサイド、パラクロロベンゾイルパーオキサイド、ラウロイルパーオキサイド、過酸化アンモニウムなどの過酸化物などが挙げられる。 The polymerization may be usually performed in the presence of a polymerization initiator.
Examples of the polymerization initiator include azobisisobutyronitrile, 2,2-azobis (2-methylbutyronitrile), 2,2-azobis (2,4-dimethylvaleronitrile), 2,2-azobis ( Azo compounds such as 2-diaminopropane) hydrochloride, 4,4-azobis (4-cyananovaleric acid), 2,2-azobis (2-methylpropionamidine); persulfates such as potassium persulfate; Examples thereof include hydrogen, peroxides such as benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, and ammonium peroxide.
重合開始剤としては、例えば、アゾビスイソブチロニトリル、2,2-アゾビス(2- メチルブチロニトリル)、2,2-アゾビス(2,4-ジメチルバレロニトリル)、2, 2-アゾビス(2―ジアミノプロパン)ハイドロクロライド、4,4-アゾビス(4-シ アノ吉草酸)、2,2-アゾビス(2-メチルプロピオンアミジン)などのアゾ化合物;過硫酸カリウムなどの過硫酸塩;過酸化水素、ベンゾイルパーオキサイド、パラクロロベンゾイルパーオキサイド、ラウロイルパーオキサイド、過酸化アンモニウムなどの過酸化物などが挙げられる。 The polymerization may be usually performed in the presence of a polymerization initiator.
Examples of the polymerization initiator include azobisisobutyronitrile, 2,2-azobis (2-methylbutyronitrile), 2,2-azobis (2,4-dimethylvaleronitrile), 2,2-azobis ( Azo compounds such as 2-diaminopropane) hydrochloride, 4,4-azobis (4-cyananovaleric acid), 2,2-azobis (2-methylpropionamidine); persulfates such as potassium persulfate; Examples thereof include hydrogen, peroxides such as benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, and ammonium peroxide.
これらの重合開始剤は、それぞれ単独で用いてもよく、2種類以上を併用してもよい。
単量体成分(a)100質量部あたりの重合開始剤の量は、重合速度を高め、未反応の単量体成分の残存量を低減させる等の観点から、好ましくは0.05質量部以上、さらに好ましくは0.1質量部以上であり、塗膜物性等の観点から、好ましくは1質量部以下、さらに好ましくは0.5質量部以下である。 These polymerization initiators may be used alone or in combination of two or more.
The amount of the polymerization initiator per 100 parts by mass of the monomer component (a) is preferably 0.05 parts by mass or more from the viewpoint of increasing the polymerization rate and reducing the residual amount of the unreacted monomer component. More preferably, it is 0.1 part by mass or more, and from the viewpoint of physical properties of the coating film, it is preferably 1 part by mass or less, more preferably 0.5 part by mass or less.
単量体成分(a)100質量部あたりの重合開始剤の量は、重合速度を高め、未反応の単量体成分の残存量を低減させる等の観点から、好ましくは0.05質量部以上、さらに好ましくは0.1質量部以上であり、塗膜物性等の観点から、好ましくは1質量部以下、さらに好ましくは0.5質量部以下である。 These polymerization initiators may be used alone or in combination of two or more.
The amount of the polymerization initiator per 100 parts by mass of the monomer component (a) is preferably 0.05 parts by mass or more from the viewpoint of increasing the polymerization rate and reducing the residual amount of the unreacted monomer component. More preferably, it is 0.1 part by mass or more, and from the viewpoint of physical properties of the coating film, it is preferably 1 part by mass or less, more preferably 0.5 part by mass or less.
重合開始剤の添加方法は、特に限定されない。その添加方法としては、例えば、一括仕込み、分割仕込み、連続滴下などが挙げられる。また、重合反応の終了時期を早める等の観点から、単量体成分(a)を反応系内に添加する終了前またはその終了後に、重合開始剤の一部を反応容器内に添加してもよい。
The method for adding the polymerization initiator is not particularly limited. Examples of the addition method include batch charging, divided charging, and continuous dripping. Further, from the viewpoint of accelerating the completion time of the polymerization reaction, a part of the polymerization initiator may be added to the reaction vessel before or after the monomer component (a) is added to the reaction system. Good.
なお、重合開始剤の分解を促進するために、例えば、亜硫酸水素ナトリウムなどの還元剤、硫酸第一鉄などの遷移金属塩などの重合開始剤の分解剤を反応系内に適量で添加してもよい。
In order to accelerate the decomposition of the polymerization initiator, for example, a reducing agent such as sodium bisulfite and a polymerization initiator decomposition agent such as transition metal salt such as ferrous sulfate are added in an appropriate amount to the reaction system. Also good.
また、反応系内には、必要により、例えば、チオール基を有する化合物(tert-ドデシルメルカプタンなど)などの連鎖移動剤、pH緩衝剤、キレート剤、造膜助剤などの添加剤を存在させてもよい。
Further, in the reaction system, additives such as a chain transfer agent such as a compound having a thiol group (such as tert-dodecyl mercaptan), a pH buffering agent, a chelating agent, and a film forming aid may be present as necessary. Also good.
単量体成分(a)100質量部あたりの添加剤の量は、その種類によって異なるので一概には決定することができないが、例えば、0.01~5質量部、好ましくは0.1~3質量部であってもよい。
The amount of the additive per 100 parts by mass of the monomer component (a) varies depending on the type of the monomer component (a) and cannot be determined unconditionally. For example, it is 0.01 to 5 parts by mass, preferably 0.1 to 3 parts. A mass part may be sufficient.
単量体成分(a)を乳化重合させる際の雰囲気は、特に限定されないが、重合効率などの観点から、窒素ガスなどの不活性ガスであってもよい。
The atmosphere for emulsion polymerization of the monomer component (a) is not particularly limited, but may be an inert gas such as nitrogen gas from the viewpoint of polymerization efficiency.
単量体成分(a)を乳化重合させる際の重合温度は、特に限定がないが、例えば、50~100℃、好ましくは60~95℃であってもよい。重合温度は、一定であってもよく、重合反応の途中で変化させてもよい。
The polymerization temperature for emulsion polymerization of the monomer component (a) is not particularly limited, but may be, for example, 50 to 100 ° C., preferably 60 to 95 ° C. The polymerization temperature may be constant or may be changed during the polymerization reaction.
単量体成分(a)を乳化重合させる重合時間は、特に限定がなく、重合反応の進行状況に応じて適宜設定すればよいが、通常、1時間以上(例えば、1~24時間)、好ましくは2~12時間(例えば、2~9時間)程度であってもよい。
The polymerization time for emulsion polymerization of the monomer component (a) is not particularly limited and may be appropriately set according to the progress of the polymerization reaction, but is usually 1 hour or longer (eg, 1 to 24 hours), preferably May be about 2 to 12 hours (eg, 2 to 9 hours).
エマルション(A)は、単層構造であっても(1層のみで構成されていても)よく、多層構造(又はコアシェル構造)であっても(内層が構成されていても、外層(最外層)と内層とで構成されていても)よい。多層構造(コアシェル構造)であることで、塗膜の物性等の点で有利になる場合がある。
The emulsion (A) may have a single-layer structure (consisting of only one layer) or a multilayer structure (or core-shell structure) (even if the inner layer is configured, the outer layer (outermost layer) ) And an inner layer). A multilayer structure (core-shell structure) may be advantageous in terms of physical properties of the coating film.
エマルション(A)が多層構造である場合、層の数は2以上であればよく、例えば、2~6、好ましくは2~5、さらに好ましくは2~4(例えば、2~3)であってもよく、特に3であってもよい。
When the emulsion (A) has a multilayer structure, the number of layers may be 2 or more, for example, 2 to 6, preferably 2 to 5, more preferably 2 to 4 (eg 2 to 3). In particular, it may be 3.
エマルション(A)が多層構造である場合、外層(シェル)及び内層(コア)は、それぞれ、前記例示の単量体成分(a)を重合成分とする樹脂で構成する限り、異なる樹脂であってもよい。
When the emulsion (A) has a multi-layer structure, the outer layer (shell) and the inner layer (core) are different resins as long as they are composed of the resin having the monomer component (a) exemplified above as a polymerization component. Also good.
例えば、単量体成分(a)を重合成分とする限り、多層構造を、硬質層(ハード層)と軟質層(ソフト層)とで構成(相対的に構成)してもよい。このような場合、外層及び内層のいずれをハード層としてもよく、すなわち、外層がハード層及び内層がソフト層の層構成であってもよく、外層がソフト層及び内層がハード層の層構成であってもよい。また、内層が複数の層で構成されている場合、複数の内層間で、ハード層及びソフト層を構成してもよい。
For example, as long as the monomer component (a) is a polymerization component, the multilayer structure may be composed (relatively composed) of a hard layer (hard layer) and a soft layer (soft layer). In such a case, either the outer layer or the inner layer may be a hard layer, that is, the outer layer may be a hard layer and the inner layer may be a soft layer, and the outer layer may be a soft layer and the inner layer may be a hard layer. There may be. When the inner layer is composed of a plurality of layers, a hard layer and a soft layer may be configured between the plurality of inner layers.
また、多層構造を有するエマルション(A)が官能基αを有する単量体を含む単量体成分(a)のポリマーで構成される場合、通常、官能基αを有する単量体を含む単量体成分(a)のポリマーは、通常、少なくとも外層を構成する場合が多く、外層及び内層を構成してもよい。
In addition, when the emulsion (A) having a multilayer structure is composed of the polymer of the monomer component (a) containing a monomer having a functional group α, usually a single amount containing a monomer having a functional group α The polymer of the body component (a) usually constitutes at least the outer layer, and may constitute the outer layer and the inner layer.
このように多層構造のエマルション(A)は、それぞれの層が独立して単量体成分(a)を重合成分とする樹脂で構成されていればよく、各層の樹脂の組成などは前記と同様の範囲から選択できる。
As described above, in the emulsion (A) having a multilayer structure, each layer may be independently composed of a resin having the monomer component (a) as a polymerization component, and the composition of the resin in each layer is the same as described above. You can choose from a range of
エマルション(A)が内層を有する場合、塗膜物性等の観点から、例えば、内層を構成する樹脂の原料である単量体成分(a)において、アルキル(メタ)アクリレートの含有率は、好ましくは5~25質量%、より好ましくは10~20質量%であり、脂環構造含有単量体の含有率は、好ましくは55~80質量%、より好ましくは60~75質量%であり、水酸基含有(メタ)アクリレートの含有率は、好ましくは0.5~5質量%、より好ましくは1~3質量%であり、芳香族系単量体の含有率は、好ましくは0~20質量%、より好ましくは5~15質量%であり、ケイ素原子含有単量体の含有率は、好ましくは0~5質量%、より好ましくは1~3質量%であり、カルボキシル基含有単量体の含有率は、好ましくは0~5質量%であり、紫外線安定性単量体の含有率は、好ましくは0~5質量%であり、カルボニル基含有単量体の含有率は、好ましくは0~5質量%、より好ましくは0~3質量%であってもよい。
When the emulsion (A) has an inner layer, from the viewpoint of physical properties of the coating film, for example, in the monomer component (a) that is a raw material of the resin constituting the inner layer, the content of the alkyl (meth) acrylate is preferably 5 to 25% by mass, more preferably 10 to 20% by mass, and the content of the alicyclic structure-containing monomer is preferably 55 to 80% by mass, more preferably 60 to 75% by mass, and hydroxyl group-containing The content of (meth) acrylate is preferably 0.5 to 5% by mass, more preferably 1 to 3% by mass, and the content of aromatic monomer is preferably 0 to 20% by mass, more The content of the silicon atom-containing monomer is preferably 5 to 15% by mass, preferably 0 to 5% by mass, more preferably 1 to 3% by mass, and the content of the carboxyl group-containing monomer is , Preferably 0-5% by mass The content of the UV-stable monomer is preferably 0 to 5% by mass, and the content of the carbonyl group-containing monomer is preferably 0 to 5% by mass, more preferably 0 to 3% by mass. It may be.
外層を構成する樹脂の溶解パラメーター(SP値)は、内層を構成する樹脂のSP値よりも高いことが、塗膜の可撓性および造膜性を向上させる等の観点から好ましい。また、内層を構成する樹脂のSP値と外層を構成する樹脂のSP値の差(絶対値)は、エマルション内で層分離構造を形成させる観点から、大きいことが好ましい。
The solubility parameter (SP value) of the resin constituting the outer layer is preferably higher than the SP value of the resin constituting the inner layer from the viewpoint of improving the flexibility and film-forming property of the coating film. Moreover, it is preferable that the difference (absolute value) between the SP value of the resin constituting the inner layer and the SP value of the resin constituting the outer layer is large from the viewpoint of forming a layer separation structure in the emulsion.
なお、SP値は、ヒルデブラント(Hildebrand)によって導入された正則溶液論により定義される値であり、2成分系溶液の溶解度の目安にもなっている。一般に、SP値が近い物質同士は互いに混ざりやすい傾向がある。したがって、SP値は、溶質と溶媒との混ざりやすさを判断する目安にもなっている。
The SP value is a value defined by the regular solution theory introduced by Hildebrand, and is also a measure of the solubility of the binary solution. In general, substances having similar SP values tend to be mixed with each other. Therefore, the SP value is also a measure for judging the ease of mixing of the solute and the solvent.
内層を構成する重合体(樹脂、ポリマー)と外層を構成する重合体(樹脂、ポリマー)との質量比(内層を構成する重合体/外層を構成する重合体)は、塗膜強度および塗膜の耐透水性を向上させる等の観点から、例えば、95/5~5/95(例えば、90/10~10/90)、好ましくは88/12~12/88(例えば、85/15~15/85)であってもよく、95/5~20/80(例えば、90/10~30/70、好ましくは88/12~40/60)であってもよい。
The mass ratio of the polymer (resin, polymer) constituting the inner layer to the polymer (resin, polymer) constituting the outer layer (polymer constituting the inner layer / polymer constituting the outer layer) is determined by the coating strength and the coating thickness. For example, 95/5 to 5/95 (for example, 90/10 to 10/90), preferably 88/12 to 12/88 (for example, 85/15 to 15). / 85) or 95/5 to 20/80 (for example, 90/10 to 30/70, preferably 88/12 to 40/60).
また、特に、エマルション(A)が3層構造である場合、エマルション粒子(A)全体に対して、1段目の層の割合は10~25質量%、2段目の層の割合は40~55質量%、3段目の層の割合は20~45質量%程度であってもよい。
In particular, when the emulsion (A) has a three-layer structure, the ratio of the first layer is 10 to 25% by mass with respect to the whole emulsion particles (A), and the ratio of the second layer is 40 to 40%. The ratio of the 55% by mass and the third layer may be about 20 to 45% by mass.
なお、内層を形成させる際の乳化重合の方法および重合条件は、前記樹脂エマルション を製造する際の方法および重合条件と同様であればよい。
Note that the emulsion polymerization method and polymerization conditions for forming the inner layer may be the same as the method and polymerization conditions for producing the resin emulsion cake.
エマルション(A)を構成する樹脂(重合体)は、架橋構造を有していてもよい。
The resin (polymer) constituting the emulsion (A) may have a crosslinked structure.
エマルション(A)を構成する樹脂の重量平均分子量は、塗膜の耐透水性を向上させる等の観点から、例えば、10万以上、好ましくは30万以上、さらに好ましくは55万以上、特に好ましくは60万以上であってもよい。
The weight average molecular weight of the resin constituting the emulsion (A) is, for example, 100,000 or more, preferably 300,000 or more, more preferably 550,000 or more, particularly preferably from the viewpoint of improving the water resistance of the coating film. It may be 600,000 or more.
また、エマルション(A)を構成する樹脂の重量平均分子量の上限値は、架橋構造を有する場合、その重量平均分子量を測定することが困難なため、特に限定されないが、例えば、架橋構造を有しない樹脂である場合には、造膜性を向上させる等の観点から、500万以下であることが好ましい。
Further, the upper limit value of the weight average molecular weight of the resin constituting the emulsion (A) is not particularly limited because it is difficult to measure the weight average molecular weight of the resin having a crosslinked structure. For example, the resin does not have a crosslinked structure. In the case of a resin, it is preferably 5 million or less from the viewpoint of improving the film forming property.
重量平均分子量は、例えば、ゲルパーミエイションクロマトグラフィー〔例えば、東ソー(株)製、品番:HLC-8120GPC、カラム:TSKgel G-5000HXLとTSKgel GMHXL-Lとを直列に使用〕を用いて測定できる重量平均分子量(ポリスチレン換算)であってもよい。
The weight average molecular weight can be measured using, for example, gel permeation chromatography (for example, manufactured by Tosoh Corporation, product number: HLC-8120GPC, column: TSKgel G-5000HXL and TSKgel GMHXL-L in series). It may be a weight average molecular weight (polystyrene conversion).
エマルション(A)(多層構造のエマルション粒子である場合には、粒子全体)のガラス転移温度は、塗膜物性等の観点から、好ましくは-20℃以上、より好ましくは-10℃以上、さらに好ましくは0℃以上であってもよく、塗膜物性等の観点から、好ましくは50℃以下、より好ましくは40℃以下、さらに好ましくは30℃以下、さらに一層好ましくは20℃以下であってもよい。
The glass transition temperature of the emulsion (A) (in the case of a multi-layer emulsion particle) is preferably −20 ° C. or higher, more preferably −10 ° C. or higher, and still more preferably from the viewpoint of physical properties of the coating film. May be 0 ° C. or higher, and may be preferably 50 ° C. or lower, more preferably 40 ° C. or lower, still more preferably 30 ° C. or lower, and even more preferably 20 ° C. or lower from the viewpoint of physical properties of the coating film. .
エマルション(A)が、多層構造を有する場合、内層と外層とで異なるガラス転移温度であってもよく、例えば、高ガラス転移温度の層と低ガラス転移温度の層とで多層構造を形成してもよい。
When the emulsion (A) has a multilayer structure, the inner layer and the outer layer may have different glass transition temperatures. For example, the emulsion (A) has a multilayer structure composed of a layer having a high glass transition temperature and a layer having a low glass transition temperature. Also good.
例えば、高ガラス転移温度の層(例えば、内層又は外層)を構成する樹脂のガラス転移温度は、塗膜物性等の等の観点から、好ましくは55℃以上、より好ましくは60℃以上、さらに好ましくは65℃以上であり、塗膜物性等の観点から、好ましくは120℃以下、より好ましくは110℃以下、さらに好ましくは100℃以下であってもよい。
For example, the glass transition temperature of the resin constituting the layer having a high glass transition temperature (for example, the inner layer or the outer layer) is preferably 55 ° C. or higher, more preferably 60 ° C. or higher, further preferably, from the viewpoint of physical properties of the coating film. Is 65 ° C. or higher, and may be 120 ° C. or lower, more preferably 110 ° C. or lower, and even more preferably 100 ° C. or lower from the viewpoint of physical properties of the coating film.
また、低ガラス転移温度の層(例えば、外層又は内層)を構成する樹脂のガラス転移温度は、塗膜強度を高める等の観点から、好ましくは-70℃以上、より好ましくは-60℃以上であり、耐水クラック性を向上させる等の観点から、好ましくは0℃以下、より好ましくは-10℃以下、さらに好ましくは-20℃以下であってもよい。
The glass transition temperature of the resin constituting the layer having a low glass transition temperature (for example, the outer layer or the inner layer) is preferably −70 ° C. or higher, more preferably −60 ° C. or higher, from the viewpoint of increasing the coating strength. In view of improving the water crack resistance, it may be preferably 0 ° C. or lower, more preferably −10 ° C. or lower, and further preferably −20 ° C. or lower.
なお、内層が複数の層で構成されている場合、すべての層を低ガラス転移温度の層又は高ガラス転移温度の層としてもよく、内層を高ガラス転移温度の層と低ガラス転移温度の層とで構成してもよい。
When the inner layer is composed of a plurality of layers, all the layers may be low glass transition temperature layers or high glass transition temperature layers, and the inner layers may be a high glass transition temperature layer and a low glass transition temperature layer. You may comprise.
なお、本明細書において、樹脂のガラス転移温度は、当該樹脂(重合体)を構成する単量体成分に使用されている単量体の単独重合体のガラス転移温度を用いて、
式(I): 1/Tg=Σ(Wm/Tgm)/100 (I)
〔式中、Wmは重合体を構成する単量体成分における単量体mの含有率(質量%)、Tgmは単量体mの単独重合体のガラス転移温度(絶対温度:K)を示す〕
で表されるフォックス(Fox)の式に基づいて求められた温度を意味してもよい。 In addition, in this specification, the glass transition temperature of resin uses the glass transition temperature of the homopolymer of the monomer currently used for the monomer component which comprises the said resin (polymer),
Formula (I): 1 / Tg = Σ (Wm / Tgm) / 100 (I)
[Wherein Wm represents the content (% by mass) of the monomer m in the monomer component constituting the polymer, and Tgm represents the glass transition temperature (absolute temperature: K) of the homopolymer of the monomer m. ]
It may mean a temperature determined based on a Fox equation represented by:
式(I): 1/Tg=Σ(Wm/Tgm)/100 (I)
〔式中、Wmは重合体を構成する単量体成分における単量体mの含有率(質量%)、Tgmは単量体mの単独重合体のガラス転移温度(絶対温度:K)を示す〕
で表されるフォックス(Fox)の式に基づいて求められた温度を意味してもよい。 In addition, in this specification, the glass transition temperature of resin uses the glass transition temperature of the homopolymer of the monomer currently used for the monomer component which comprises the said resin (polymer),
Formula (I): 1 / Tg = Σ (Wm / Tgm) / 100 (I)
[Wherein Wm represents the content (% by mass) of the monomer m in the monomer component constituting the polymer, and Tgm represents the glass transition temperature (absolute temperature: K) of the homopolymer of the monomer m. ]
It may mean a temperature determined based on a Fox equation represented by:
本明細書においては、エマルション(A)を構成する重合体のガラス転移温度は、特に断りがない限り、式(I)に基づいて求められたガラス転移温度を意味してもよい。
例えば、多層構造を有するエマルション(A)を構成する重合体全体のガラス転移温度は、多段乳化重合の際に用いられたすべての単量体成分における各単量体の質量分率とこれに対応する単量体の単独重合体のガラス転移温度から求められたガラス転移温度を意味する。なお、特殊単量体、多官能単量体などのようにガラス転移温度が不明の単量体については、単量体成分における当該ガラス転移温度が不明の単量体の合計量が質量分率で10質量%以下である場合、ガラス転移温度が判明している単量体のみを用いてガラス転移温度が求められる。 In the present specification, the glass transition temperature of the polymer constituting the emulsion (A) may mean the glass transition temperature obtained based on the formula (I) unless otherwise specified.
For example, the glass transition temperature of the whole polymer constituting the emulsion (A) having a multilayer structure corresponds to the mass fraction of each monomer in all monomer components used in the multistage emulsion polymerization. It means the glass transition temperature determined from the glass transition temperature of the homopolymer of the monomer. For monomers with unknown glass transition temperature, such as special monomers and polyfunctional monomers, the total amount of monomers with unknown glass transition temperature in the monomer component is the mass fraction. If it is 10% by mass or less, the glass transition temperature can be determined using only the monomer whose glass transition temperature is known.
例えば、多層構造を有するエマルション(A)を構成する重合体全体のガラス転移温度は、多段乳化重合の際に用いられたすべての単量体成分における各単量体の質量分率とこれに対応する単量体の単独重合体のガラス転移温度から求められたガラス転移温度を意味する。なお、特殊単量体、多官能単量体などのようにガラス転移温度が不明の単量体については、単量体成分における当該ガラス転移温度が不明の単量体の合計量が質量分率で10質量%以下である場合、ガラス転移温度が判明している単量体のみを用いてガラス転移温度が求められる。 In the present specification, the glass transition temperature of the polymer constituting the emulsion (A) may mean the glass transition temperature obtained based on the formula (I) unless otherwise specified.
For example, the glass transition temperature of the whole polymer constituting the emulsion (A) having a multilayer structure corresponds to the mass fraction of each monomer in all monomer components used in the multistage emulsion polymerization. It means the glass transition temperature determined from the glass transition temperature of the homopolymer of the monomer. For monomers with unknown glass transition temperature, such as special monomers and polyfunctional monomers, the total amount of monomers with unknown glass transition temperature in the monomer component is the mass fraction. If it is 10% by mass or less, the glass transition temperature can be determined using only the monomer whose glass transition temperature is known.
単量体成分におけるガラス転移温度が不明の単量体の合計量が質量分率で10質量%を超える場合には、重合体のガラス転移温度は、示差走査熱量分析(DSC)、示差熱量分析(DTA)、熱機械分析(TMA)などによって求められる。
When the total amount of monomers with unknown glass transition temperature in the monomer component exceeds 10% by mass, the glass transition temperature of the polymer is determined by differential scanning calorimetry (DSC) or differential calorimetry. (DTA), thermomechanical analysis (TMA), etc.
重合体のガラス転移温度は、単量体成分の組成を調整することにより、容易に調節することができる。エマルション(A)を構成する重合体のガラス転移温度を考慮して、当該エマルション(A)を構成する重合体の原料として用いられる単量体成分の組成を決定することができる。
The glass transition temperature of the polymer can be easily adjusted by adjusting the composition of the monomer component. Considering the glass transition temperature of the polymer constituting the emulsion (A), the composition of the monomer component used as the raw material for the polymer constituting the emulsion (A) can be determined.
重合体のガラス転移温度は、例えば、2-エチルヘキシルアクリレートの単独重合体では-70℃、シクロヘキシルメタクリレートの単独重合体では83℃、スチレンの単独重合体では100℃、γ-メタクリロキシプロピルトリメトキシシランの単独重合体では70℃、2-ヒドロキシエチルメタクリレートの単独重合体では55℃、メチルメタクリレートの単独重合体では105℃、メタクリル酸の単独重合体では130℃、tert-ブチルメタクリレートの単独重合体では107℃、1,2,2,6,6-ペンタメチルピペリジルメタクリレートの単独重合体では約130℃、ダイアセトンアクリルアミドの単独重合体では77℃、グリセリンモノメタクリレートの単独重合体では55℃、n-ブチルメタクリレートの単独重合体では20℃、n-ブチルアクリレートの単独重合体では-56℃である。
The glass transition temperature of the polymer is, for example, -70 ° C. for 2-ethylhexyl acrylate homopolymer, 83 ° C. for cyclohexyl methacrylate homopolymer, 100 ° C. for styrene homopolymer, γ-methacryloxypropyltrimethoxysilane 70 ° C. for homopolymers of 2-hydroxyethyl methacrylate, 55 ° C. for homopolymers of 2-hydroxyethyl methacrylate, 105 ° C. for homopolymers of methyl methacrylate, 130 ° C. for homopolymers of methacrylic acid, and for homopolymers of tert-butyl methacrylate 107 ° C., about 130 ° C. for 1,2,2,6,6-pentamethylpiperidyl methacrylate homopolymer, 77 ° C. for diacetone acrylamide homopolymer, 55 ° C. for glycerol monomethacrylate homopolymer, n- Butyl methacrylate homopolymer Is 20 ° C., a homopolymer of n- butyl acrylate is -56 ° C..
エマルション(A)の平均粒子径は、エマルション(A)自体の機械的安定性等の観点から、好ましくは50nm以上、より好ましくは100nm以上であってもよく、塗膜物性等の観点から、好ましくは300nm以下、より好ましくは200nm以下であってもよい。エマルション(A)の平均粒子径は、代表的には、50~300nm(例えば、60~250nm)、好ましくは80~200nm、さらに好ましくは100~180nm程度であってもよい。
なお、本明細書において、エマルション(A)の平均粒子径は、動的光散乱法による粒度分布測定器〔パーティクル・サイジング・システムズ(Particle Sizing Systems)社製、商品名:NICOMP Model 380〕を用いて測定された体積平均粒子径を意味する。 The average particle diameter of the emulsion (A) is preferably 50 nm or more, more preferably 100 nm or more, from the viewpoint of mechanical stability of the emulsion (A) itself, preferably from the viewpoint of physical properties of the coating film, etc. May be 300 nm or less, more preferably 200 nm or less. The average particle size of the emulsion (A) may typically be about 50 to 300 nm (for example, 60 to 250 nm), preferably 80 to 200 nm, and more preferably about 100 to 180 nm.
In the present specification, the average particle size of the emulsion (A) is measured using a particle size distribution measuring instrument (Particulate Sizing Systems, trade name: NICOMP Model 380) by a dynamic light scattering method. Means the volume average particle diameter measured by
なお、本明細書において、エマルション(A)の平均粒子径は、動的光散乱法による粒度分布測定器〔パーティクル・サイジング・システムズ(Particle Sizing Systems)社製、商品名:NICOMP Model 380〕を用いて測定された体積平均粒子径を意味する。 The average particle diameter of the emulsion (A) is preferably 50 nm or more, more preferably 100 nm or more, from the viewpoint of mechanical stability of the emulsion (A) itself, preferably from the viewpoint of physical properties of the coating film, etc. May be 300 nm or less, more preferably 200 nm or less. The average particle size of the emulsion (A) may typically be about 50 to 300 nm (for example, 60 to 250 nm), preferably 80 to 200 nm, and more preferably about 100 to 180 nm.
In the present specification, the average particle size of the emulsion (A) is measured using a particle size distribution measuring instrument (Particulate Sizing Systems, trade name: NICOMP Model 380) by a dynamic light scattering method. Means the volume average particle diameter measured by
エマルション(A)における樹脂の含有率(多層構造である場合には、内層及び外層を構成する樹脂の合計の含有率)は、塗膜物性等の観点から、例えば、20質量%以上(例えば、25~100質量%)、好ましくは30質量%以上(例えば、35~90質量%)、さらに好ましくは40質量%以上(例えば、45~85質量%)であってもよい。
The content of the resin in the emulsion (A) (in the case of a multilayer structure, the total content of resins constituting the inner layer and the outer layer) is, for example, 20% by mass or more (for example, 25 to 100% by mass), preferably 30% by mass or more (eg 35 to 90% by mass), more preferably 40% by mass or more (eg 45 to 85% by mass).
エマルション(A)における粒子(又は固形分)の固形分(不揮発分)量は、生産性等の観点から、好ましくは30質量%以上、より好ましくは40質量%以上であり、取り扱い性を向上させる等の観点から、好ましくは70質量%以下、より好ましくは60質量%以下であってもよい。
The solid content (non-volatile content) of the particles (or solid content) in the emulsion (A) is preferably 30% by mass or more, more preferably 40% by mass or more from the viewpoint of productivity and the like, and improves the handleability. In view of the above, it may be preferably 70% by mass or less, more preferably 60% by mass or less.
なお、エマルションにおける不揮発分量は、例えば、樹脂エマルション1gを秤量し、熱風乾燥機で110℃の温度で1時間乾燥させ、得られた残渣を不揮発分とし、
式:〔樹脂エマルションにおける不揮発分量(質量%)〕=(〔残渣の質量〕÷〔樹脂エマルション1g〕)×100
に基づいて求めることができる。 The non-volatile content in the emulsion is, for example, weighing 1 g of the resin emulsion and drying it with a hot air dryer at a temperature of 110 ° C. for 1 hour.
Formula: [Nonvolatile content in resin emulsion (mass%)] = ([residue mass] ÷ [resin emulsion 1 g]) × 100
Can be determined based on
式:〔樹脂エマルションにおける不揮発分量(質量%)〕=(〔残渣の質量〕÷〔樹脂エマルション1g〕)×100
に基づいて求めることができる。 The non-volatile content in the emulsion is, for example, weighing 1 g of the resin emulsion and drying it with a hot air dryer at a temperature of 110 ° C. for 1 hour.
Formula: [Nonvolatile content in resin emulsion (mass%)] = ([residue mass] ÷ [resin emulsion 1 g]) × 100
Can be determined based on
エマルション(A)において、乳化剤の割合は、エマルションを構成する樹脂(又は単量体成分(a))100質量部に対して、例えば、0.1~30質量部、好ましくは0.5~20質量部(例えば、0.7~15質量部)、さらに好ましくは1~10質量部程度であってもよい。
In the emulsion (A), the proportion of the emulsifier is, for example, 0.1 to 30 parts by mass, preferably 0.5 to 20 parts per 100 parts by mass of the resin (or monomer component (a)) constituting the emulsion. It may be about 1 to 10 parts by mass (for example, 0.7 to 15 parts by mass).
また、エマルションの最低造膜温度は、造膜性を向上させる等の観点から、好ましくは60℃以下、より好ましくは50℃以下、さらに好ましくは40℃以下である。エマルションの最低造膜温度は、例えば、エマルション粒子全体のガラス転移温度や最外層のガラス転移温度を調節することによって調整することができる。
The minimum film-forming temperature of the emulsion is preferably 60 ° C. or lower, more preferably 50 ° C. or lower, and further preferably 40 ° C. or lower from the viewpoint of improving the film-forming property. The minimum film-forming temperature of the emulsion can be adjusted, for example, by adjusting the glass transition temperature of the whole emulsion particle or the glass transition temperature of the outermost layer.
なお、本明細書において、エマルションの最低造膜温度は、例えば、熱勾配試験機の上に置いたガラス板上に樹脂エマルションを厚さが0.2mmとなるようにアプリケーターで塗工し、クラックが生じたときの温度などとして求めることができる。
In this specification, the minimum film-forming temperature of the emulsion is, for example, by applying the resin emulsion on a glass plate placed on a thermal gradient tester with an applicator so that the thickness is 0.2 mm, and cracking. It can be determined as the temperature at which this occurs.
エマルション(A)は、特に、アニオン性基を有していてもよい(又はアニオン性であってもよい)。アニオン性(アニオン性基)を有することで、ポリマー(B)との親和性を向上でき、より一層、塗膜からのポリマー(B)の脱落を抑制しやすい。
The emulsion (A) may particularly have an anionic group (or may be anionic). By having an anionic property (anionic group), the affinity with the polymer (B) can be improved, and the dropping of the polymer (B) from the coating film can be further suppressed.
アニオン性を有するエマルション(A)は、特に限定されないが、例えば、エマルションにアニオン性基を導入することにより得ることができる。アニオン性基は、例えば、前記のように、エマルションを構成するモノマーや乳化剤を利用して導入できる。
具体的なアニオン性(アニオン性基)を有するエマルション(A)としては、以下の(1)及び/又は(2)を充足するエマルションなどが含まれる。
(1)アニオン性基含有単量体を含む単量体成分(a)を重合成分とする樹脂で構成されている
(2)エマルション(A)を構成する乳化剤がアニオン性乳化剤を含む The anionic emulsion (A) is not particularly limited, but can be obtained, for example, by introducing an anionic group into the emulsion. An anionic group can be introduce | transduced using the monomer and emulsifier which comprise an emulsion as mentioned above, for example.
The emulsion (A) having a specific anionic property (anionic group) includes an emulsion satisfying the following (1) and / or (2).
(1) Consists of a resin comprising a monomer component (a) containing an anionic group-containing monomer as a polymerization component (2) The emulsifier constituting the emulsion (A) contains an anionic emulsifier
具体的なアニオン性(アニオン性基)を有するエマルション(A)としては、以下の(1)及び/又は(2)を充足するエマルションなどが含まれる。
(1)アニオン性基含有単量体を含む単量体成分(a)を重合成分とする樹脂で構成されている
(2)エマルション(A)を構成する乳化剤がアニオン性乳化剤を含む The anionic emulsion (A) is not particularly limited, but can be obtained, for example, by introducing an anionic group into the emulsion. An anionic group can be introduce | transduced using the monomer and emulsifier which comprise an emulsion as mentioned above, for example.
The emulsion (A) having a specific anionic property (anionic group) includes an emulsion satisfying the following (1) and / or (2).
(1) Consists of a resin comprising a monomer component (a) containing an anionic group-containing monomer as a polymerization component (2) The emulsifier constituting the emulsion (A) contains an anionic emulsifier
なお、本発明の組成物は、エマルション(A)を含んでいればよく、エマルション(A)を、溶媒(又は媒体)を含むエマルション(エマルション(A)が溶媒に分散したエマルション)として含んでいてもよい。
In addition, the composition of this invention should just contain emulsion (A), and contains emulsion (A) as an emulsion (emulsion which emulsion (A) disperse | distributed to the solvent) containing a solvent (or medium). Also good.
(組成物及びその用途)
本発明の組成物において、エマルション(A)とポリマー(B)との割合(溶媒を含む場合には固形分)は、例えば、前者/後者(質量比)=99.9/0.1~20/80(例えば、99.8/0.2~30/70)、好ましくは99.5/0.5~40/60(例えば、99.2/0.8~50/50)、塗膜物性(耐候性、耐水白化性など)などにおいて有利になる点から、さらに好ましくは99/1~60/40(例えば、98.5/1.5~70/30)、特に98/2~80/20(例えば、97/3~85/15)程度であってもよく、99.5/0.5~90/10であってもよい。 (Composition and its use)
In the composition of the present invention, the ratio of the emulsion (A) to the polymer (B) (solid content when a solvent is included) is, for example, the former / the latter (mass ratio) = 99.9 / 0.1 to 20 / 80 (for example, 99.8 / 0.2 to 30/70), preferably 99.5 / 0.5 to 40/60 (for example, 99.2 / 0.8 to 50/50), coating film properties In view of advantages (such as weather resistance and water whitening resistance), it is more preferably 99/1 to 60/40 (for example, 98.5 / 1.5 to 70/30), particularly 98/2 to 80 /. It may be about 20 (for example, 97/3 to 85/15), or 99.5 / 0.5 to 90/10.
本発明の組成物において、エマルション(A)とポリマー(B)との割合(溶媒を含む場合には固形分)は、例えば、前者/後者(質量比)=99.9/0.1~20/80(例えば、99.8/0.2~30/70)、好ましくは99.5/0.5~40/60(例えば、99.2/0.8~50/50)、塗膜物性(耐候性、耐水白化性など)などにおいて有利になる点から、さらに好ましくは99/1~60/40(例えば、98.5/1.5~70/30)、特に98/2~80/20(例えば、97/3~85/15)程度であってもよく、99.5/0.5~90/10であってもよい。 (Composition and its use)
In the composition of the present invention, the ratio of the emulsion (A) to the polymer (B) (solid content when a solvent is included) is, for example, the former / the latter (mass ratio) = 99.9 / 0.1 to 20 / 80 (for example, 99.8 / 0.2 to 30/70), preferably 99.5 / 0.5 to 40/60 (for example, 99.2 / 0.8 to 50/50), coating film properties In view of advantages (such as weather resistance and water whitening resistance), it is more preferably 99/1 to 60/40 (for example, 98.5 / 1.5 to 70/30), particularly 98/2 to 80 /. It may be about 20 (for example, 97/3 to 85/15), or 99.5 / 0.5 to 90/10.
このような組成物において、エマルション(A)及びポリマー(B)の存在形態は、特に限定されないが、互いに分離していてもよく、互いに結合(架橋)していてもよい。なお、結合する場合、エマルション(A)とポリマー(B)とが、少なくとも一部において、結合していればよい。
なお、組成物においては、結合(又は架橋構造)していなくても、事後的に又は経時的に(例えば、塗膜等において)結合又は架橋構造を形成してもよい。そのため、本発明の組成物において、エマルション(A)とポリマー(B)とが、結合(又は架橋構造)を形成可能であってもよい。 In such a composition, the presence form of the emulsion (A) and the polymer (B) is not particularly limited, but may be separated from each other or may be bonded (crosslinked) to each other. In addition, when couple | bonding, an emulsion (A) and a polymer (B) should just couple | bond together in at least one part.
In addition, in the composition, even if it is not bonded (or a crosslinked structure), a bonded or crosslinked structure may be formed afterwards or with time (for example, in a coating film or the like). Therefore, in the composition of the present invention, the emulsion (A) and the polymer (B) may be capable of forming a bond (or a crosslinked structure).
なお、組成物においては、結合(又は架橋構造)していなくても、事後的に又は経時的に(例えば、塗膜等において)結合又は架橋構造を形成してもよい。そのため、本発明の組成物において、エマルション(A)とポリマー(B)とが、結合(又は架橋構造)を形成可能であってもよい。 In such a composition, the presence form of the emulsion (A) and the polymer (B) is not particularly limited, but may be separated from each other or may be bonded (crosslinked) to each other. In addition, when couple | bonding, an emulsion (A) and a polymer (B) should just couple | bond together in at least one part.
In addition, in the composition, even if it is not bonded (or a crosslinked structure), a bonded or crosslinked structure may be formed afterwards or with time (for example, in a coating film or the like). Therefore, in the composition of the present invention, the emulsion (A) and the polymer (B) may be capable of forming a bond (or a crosslinked structure).
結合している(又は結合形成可能である)場合、エマルション(A)とポリマー(B)との結合形態としては、特に限定されず、(i)エマルション(A)とポリマー(B)とが直接的に結合(架橋構造を形成)した形態、(ii)エマルション(A)とポリマー(B)とが架橋剤(C)を介して結合(架橋構造を形成)した形態、(iii)これらを組み合わせた形態などが挙げられる。
In the case of bonding (or bond formation is possible), the bonding form of the emulsion (A) and the polymer (B) is not particularly limited, and (i) the emulsion (A) and the polymer (B) are directly (Ii) a combination of emulsion (A) and polymer (B) via a crosslinking agent (C) (formation of a crosslinked structure), (iii) a combination of these The form etc. are mentioned.
形態(i)としては、例えば、エマルション(A)が、官能基αを有する単量体を含む単量体成分(a)を重合成分とする樹脂で構成され、ポリマー(B)が、官能基β(官能基αと反応して結合しうる官能基β)を有する単量体を含む単量体成分(a)を重合成分とするポリマーで構成され、官能基αと官能基βとの間で反応して結合(又は架橋構造)を形成している(又は結合又は架橋構造を取り得る)態様などが含まれる。
As the form (i), for example, the emulsion (A) is composed of a resin having a monomer component (a) containing a monomer having a functional group α as a polymerization component, and the polymer (B) is a functional group. It is composed of a polymer having a monomer component (a) containing a monomer having β (functional group β that can react and bond with functional group α) as a polymerization component, and between functional group α and functional group β. In which a bond (or a crosslinked structure) is formed by reaction (or a bond or a crosslinked structure can be taken) is included.
また、形態(ii)としては、エマルション(A)が官能基αを有する単量体を含む単量体成分(a)を重合成分とする樹脂で構成され、ポリマー(B)が、官能基β(官能基αと架橋剤(C)を介して架橋構造を形成しうる官能基β)を有する単量体を含む単量体成分(b)を重合成分とするポリマーで構成され、官能基α及び官能基βが架橋剤(C)と反応して結合(又は架橋構造)を形成している(又は結合又は架橋構造を取り得る)態様などが含まれる。
Further, as the form (ii), the emulsion (A) is composed of a resin having a monomer component (a) containing a monomer having a functional group α as a polymerization component, and the polymer (B) has a functional group β It is composed of a polymer having a monomer component (b) containing a monomer having a functional group α and a functional group β capable of forming a crosslinked structure via a crosslinking agent (C) as a polymerization component, and the functional group α And a mode in which the functional group β reacts with the crosslinking agent (C) to form a bond (or a crosslinked structure) (or can take a bond or a crosslinked structure).
このような形態(i)及び形態(ii)において、官能基αと官能基βとの組み合わせ、官能基α及び官能基βと架橋剤が有する官能基(官能基γ)との組み合わせとしては、特に限定されず、例えば、エポキシ基と水酸基、エポキシ基とカルボキシル基、エポキシ基とカルボキシル基、エポキシ基とアミノ基、エポキシ基とアミノ基、カーボネート基とカルボキシル基、水酸基とアルコキシカルボニル基、水酸基とイソシアネート基、水酸基とカルボン酸無水物基、アセトアセトキシ基とイソシアネート基、オキサゾリン基とカルボキシル基、水酸基とカルボン酸無水基、オキサゾリジン基とイソシアネート基又はカルボン酸無水物基、ヒドラジノ基とカルボニル基などが挙げられる。これらは1又は2以上組み合わせて使用してもよい。
In such a form (i) and form (ii), the combination of the functional group α and the functional group β, the combination of the functional group α and the functional group β and the functional group (functional group γ) of the crosslinking agent, Not particularly limited, for example, epoxy group and hydroxyl group, epoxy group and carboxyl group, epoxy group and carboxyl group, epoxy group and amino group, epoxy group and amino group, carbonate group and carboxyl group, hydroxyl group and alkoxycarbonyl group, hydroxyl group and Isocyanate group, hydroxyl group and carboxylic anhydride group, acetoacetoxy group and isocyanate group, oxazoline group and carboxyl group, hydroxyl group and carboxylic anhydride group, oxazolidine group and isocyanate group or carboxylic anhydride group, hydrazino group and carbonyl group Can be mentioned. You may use these in combination of 1 or 2 or more.
形態(i)において、代表的な官能基αと官能基βとの組み合わせとしては、互いに反応により架橋構造又は結合を形成可能な組み合わせであれば特に限定されず、例えば、カルボキシル基とオキサゾリン基との組み合わせ、カルボニル基とヒドラジノ基との組み合わせ、イソシアナート基とヒドロキシ基、カルボキシル基、アミノ基などとの組み合わせなどが挙げられる。
In the form (i), the combination of the representative functional group α and the functional group β is not particularly limited as long as it is a combination capable of forming a crosslinked structure or a bond by reaction with each other. For example, a carboxyl group and an oxazoline group A combination of a carbonyl group and a hydrazino group, a combination of an isocyanate group and a hydroxy group, a carboxyl group, an amino group, and the like.
また、形態(ii)において、代表的な官能基αと官能基βとの組み合わせとしては、架橋剤(C)の種類に応じて適宜選択でき、同じ官能基であってもよい。このような組み合わせとしては、例えば、官能基α及び官能基βがいずれもカルボキシル基又はカルボニル基である組み合わせなどが含まれる。なお、このような組み合わせでは、架橋剤(C)として、後述のヒドラジン系架橋剤やオキサゾリン系架橋剤を好適に使用できる。
In the form (ii), the combination of the representative functional group α and the functional group β can be appropriately selected according to the type of the crosslinking agent (C), and may be the same functional group. Examples of such combinations include combinations in which the functional group α and the functional group β are both carboxyl groups or carbonyl groups. In such a combination, a hydrazine-based crosslinking agent or an oxazoline-based crosslinking agent described later can be suitably used as the crosslinking agent (C).
架橋剤(C)としては、官能基αと官能基βとの間で反応して結合(又は架橋構造)を形成可能(官能基α及び官能基βの双方と結合又は架橋構造を形成可能)な架橋剤(C)であれば特に限定されず、官能基α及び官能基βの種類等に応じて適宜選択できるが、通常、多官能性化合物(官能基(γ)を複数有する多官能性化合物)であってもよい。官能基γとしては、官能基α及び官能基βで例示した官能基が挙げられ、例えば、カルボキシル基、ヒドラジノ基、オキサゾリン基、カルボジイミド基、エポキシ基、イソシアネート基、アミノ基などが挙げられる。
As the cross-linking agent (C), a bond (or a cross-linked structure) can be formed by reacting between the functional group α and the functional group β (a bond or a cross-linked structure can be formed with both the functional group α and the functional group β). The cross-linking agent (C) is not particularly limited and can be appropriately selected according to the type of the functional group α and the functional group β. Usually, the polyfunctional compound (multifunctional having a plurality of functional groups (γ)) Compound). Examples of the functional group γ include the functional groups exemplified as the functional group α and the functional group β, and examples thereof include a carboxyl group, a hydrazino group, an oxazoline group, a carbodiimide group, an epoxy group, an isocyanate group, and an amino group.
多官能性化合物は、同一又は異なる官能基を有していてもよい。なお、多官能性化合物において、官能基(官能基γ)の数は、2以上であればよく、例えば、低分子型(非ポリマー型又は非樹脂型)の多官能性化合物などの場合では、2~10、好ましくは2~6、さらに好ましくは2~4であり、特に2である。
The polyfunctional compound may have the same or different functional groups. In the polyfunctional compound, the number of functional groups (functional group γ) may be two or more. For example, in the case of a low molecular type (non-polymer type or non-resin type) polyfunctional compound, It is 2 to 10, preferably 2 to 6, more preferably 2 to 4, particularly 2.
代表的な架橋剤(C)としては、ヒドラジン系架橋剤(ヒドラジノ基を複数有する化合物)、オキサゾリン系架橋剤、カルボジイミド系架橋剤、イソシアネート系架橋剤、アミン系架橋剤、エポキシ系架橋剤などが挙げられる。特に、架橋剤(C)は、水溶性(水溶性架橋剤)であってもよい。
Typical crosslinking agents (C) include hydrazine crosslinking agents (compounds having a plurality of hydrazino groups), oxazoline crosslinking agents, carbodiimide crosslinking agents, isocyanate crosslinking agents, amine crosslinking agents, epoxy crosslinking agents, and the like. Can be mentioned. In particular, the crosslinking agent (C) may be water-soluble (water-soluble crosslinking agent).
ヒドラジン系架橋剤としては、例えば、ジカルボン酸ジヒドラジド[例えば、アルカンジカルボン酸ジヒドラジド(例えば、シュウ酸ジヒドラジド、マロン酸ジヒドラジド、コハク酸ジヒドラジド、グルタル酸ジヒドラジド、アジピン酸ジヒドラジド、セバシン酸ジヒドラジド、ドデカン酸ジヒドラジドなどのC2-20アルカンジカルボン酸ジヒドラジド、好ましくはC2-10アルカンジカルボン酸ジヒドラジド)、アルケンジカルボン酸ジヒドラジド(例えば、マレイン酸ジヒドラジド、フマル酸ジヒドラジド、イタコン酸ジヒドラジドなどのC2-10アルケンジカルボン酸ジヒドラジド)などの脂肪族ジカルボン酸ジヒドラジド;イソフタル酸ジヒドラジドなどの芳香族ジカルボン酸ヒドラジドなど]、ジヒドラジン類[例えば、エチレン-1,2-ジヒドラジン、プロピレン-1,3-ジヒドラジン、ブチレン-1,4-ジヒドラジンなどの脂肪族ジヒドラジン、好ましくはC2-4脂肪族ジヒドラジン]などが挙げられる。
Examples of the hydrazine-based crosslinking agent include dicarboxylic acid dihydrazide [for example, alkane dicarboxylic acid dihydrazide (for example, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanoic acid hydride, etc.) C 2-20 alkane dicarboxylic acid dihydrazide, preferably C 2-10 alkane dicarboxylic acid dihydrazide), alkene dicarboxylic acid dihydrazide (e.g., maleic acid dihydrazide, fumaric acid dihydrazide, C 2-10 alkene dicarboxylic acid dihydrazide and itaconic acid dihydrazide ) Aliphatic dicarboxylic acid dihydrazide; isophthalic acid dihydrazide and other aromatic dicarboxylic acid hydrazide], dihydrazines [for example Ethylene-1,2-dihydrazine, propylene-1,3-dihydrazine, aliphatic dihydrazine, such as butylene-1,4-dihydrazine, preferably like C 2-4 aliphatic dihydrazine.
オキサゾリン系架橋剤としては、例えば、オキサゾリン基含有単量体を重合成分とするポリマーなどが挙げられる。このようなポリマーとしては、例えば、オキサゾリン基含有単量体の単独又は共重合体、オキサゾリン基含有単量体と他の共重合性単量体との共重合体などが挙げられる。
Examples of the oxazoline-based crosslinking agent include polymers having an oxazoline group-containing monomer as a polymerization component. Examples of such a polymer include a homopolymer or a copolymer of an oxazoline group-containing monomer, a copolymer of an oxazoline group-containing monomer and another copolymerizable monomer, and the like.
オキサゾリン基含有単量体としては、前記例示の単量体、例えば、アルケニルオキサゾリン(例えば、2-ビニル-2-オキサゾリン、2-イソプロペニル-2-オキサゾリンなどのC2-6アルケニルオキサゾリン、好ましくはビニル又はイソプロペニルオキサゾリン)、アルケニル-アルキルオキサゾリン(例えば、2-ビニル-4-メチル-2-オキサゾリン、2-ビニル-5-メチル-2-オキサゾリン、2-イソプロペニル-4-メチル-2-オキサゾリン、2-イソプロペニル-5-エチル-2-オキサゾリンなどのC2-6アルケニル-C1-10アルキルオキサゾリン、好ましくはビニル又はイソプロペニル-C1-4アルキルオキサゾリンなど)などが挙げられる。
As the oxazoline group-containing monomer, the above-exemplified monomers, for example, alkenyl oxazolines (for example, C 2-6 alkenyl oxazolines such as 2-vinyl-2-oxazoline, 2-isopropenyl-2-oxazoline, preferably Vinyl or isopropenyl oxazoline), alkenyl-alkyl oxazolines (eg 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline) C 2-6 alkenyl-C 1-10 alkyl oxazoline such as 2-isopropenyl-5-ethyl-2-oxazoline, preferably vinyl or isopropenyl-C 1-4 alkyl oxazoline) and the like.
また、他の共重合性単量体としては、オキサゾリン基と反応しない共重合可能な単量体であれば特に限定されず、例えば、(メタ)アクリル酸エステル[例えば、(メタ)アクリル酸メチル、(メタ)アクリル酸エチルなどの前記例示のアルキル(メタ)アクリレート;ヒドロキシエチル(メタ)アクリレートなどの前記例示のヒドロキシ基含有(メタ)アクリレートなど]、(メタ)アクリル酸アミド、酢酸ビニル、芳香族系単量体(例えば、スチレン、α-メチルスチレンなどの前記例示のスチレン系モノマーなど)などが挙げられる。
The other copolymerizable monomer is not particularly limited as long as it is a copolymerizable monomer that does not react with the oxazoline group. For example, (meth) acrylic acid ester [for example, methyl (meth) acrylate , Alkyl (meth) acrylates as exemplified above such as ethyl (meth) acrylate; hydroxy group-containing (meth) acrylates as exemplified above such as hydroxyethyl (meth) acrylate], (meth) acrylic acid amide, vinyl acetate, aromatic Group monomers (for example, the above-described styrene monomers such as styrene and α-methylstyrene).
オキサゾリン系架橋剤において、オキサゾリン基当量は、例えば、200~5000g/当量、好ましくは250~4000g/当量、さらに好ましくは300~3000g/当量程度であってもよい。
In the oxazoline-based crosslinking agent, the oxazoline group equivalent may be, for example, about 200 to 5000 g / equivalent, preferably about 250 to 4000 g / equivalent, and more preferably about 300 to 3000 g / equivalent.
このようなオキサゾリン系架橋剤は、日本触媒(株)製のエポクロスシリーズ(例えば、エポクロスK-2010E、K-2020E、K-2030E、WS-500など)などとして入手することもできる。
Such an oxazoline-based crosslinking agent can also be obtained as an Epocross series (for example, Epocross K-2010E, K-2020E, K-2030E, WS-500, etc.) manufactured by Nippon Shokubai Co., Ltd.
カルボジイミド系架橋剤(カルボジイミド化合物)としては、分子内にカルボジイミド基[-N=C=N-]を少なくとも1つ有する化合物であればよく、モノカルボジイミド化合物であってもよく、ポリカルボジイミド化合物であってもよい。
特に、カルボジイミド化合物は、水溶性(親水性、水性)であってもよい。このような水溶性のカルボジイミド化合物は、通常、親水性基(親水性骨格、親水性セグメント)を有していてもよい。親水性基(親水性骨格)は、特に限定されず、例えば、ヒドロキシ基、カーバメート基、(ポリ)オキシアルキレン基、置換アミノ基(第3級アミノ基)などが挙げられる。親水性基は、塩(例えば、アミン塩など)を形成していてもよい。 The carbodiimide-based crosslinking agent (carbodiimide compound) may be a compound having at least one carbodiimide group [—N═C═N—] in the molecule, may be a monocarbodiimide compound, or may be a polycarbodiimide compound. May be.
In particular, the carbodiimide compound may be water-soluble (hydrophilic or aqueous). Such a water-soluble carbodiimide compound may usually have a hydrophilic group (hydrophilic skeleton, hydrophilic segment). The hydrophilic group (hydrophilic skeleton) is not particularly limited, and examples thereof include a hydroxy group, a carbamate group, a (poly) oxyalkylene group, and a substituted amino group (tertiary amino group). The hydrophilic group may form a salt (for example, an amine salt).
特に、カルボジイミド化合物は、水溶性(親水性、水性)であってもよい。このような水溶性のカルボジイミド化合物は、通常、親水性基(親水性骨格、親水性セグメント)を有していてもよい。親水性基(親水性骨格)は、特に限定されず、例えば、ヒドロキシ基、カーバメート基、(ポリ)オキシアルキレン基、置換アミノ基(第3級アミノ基)などが挙げられる。親水性基は、塩(例えば、アミン塩など)を形成していてもよい。 The carbodiimide-based crosslinking agent (carbodiimide compound) may be a compound having at least one carbodiimide group [—N═C═N—] in the molecule, may be a monocarbodiimide compound, or may be a polycarbodiimide compound. May be.
In particular, the carbodiimide compound may be water-soluble (hydrophilic or aqueous). Such a water-soluble carbodiimide compound may usually have a hydrophilic group (hydrophilic skeleton, hydrophilic segment). The hydrophilic group (hydrophilic skeleton) is not particularly limited, and examples thereof include a hydroxy group, a carbamate group, a (poly) oxyalkylene group, and a substituted amino group (tertiary amino group). The hydrophilic group may form a salt (for example, an amine salt).
このような親水性基は、例えば、カルボジイミドの末端に位置してもよい。このような水溶性のカルボジイミド化合物(水性カルボジイミド化合物)は、例えば、ベースとなるカルボジイミド化合物の末端が親水基(又は親水性骨格)で封鎖されていてもよい。
Such a hydrophilic group may be located at the end of carbodiimide, for example. In such a water-soluble carbodiimide compound (aqueous carbodiimide compound), for example, the terminal of the carbodiimide compound serving as a base may be blocked with a hydrophilic group (or a hydrophilic skeleton).
具体的なカルボジイミド化合物としては、例えば、N,N-二置換アミノ基を有するカルボジイミド[例えば、1-(3-ジメチルアミノプロピル)-3-エチルカルボジイミドなど]、イソシアネート基を末端に有するカルボジイミドと親水性セグメント及びイソシアネート基と反応して結合形成可能な反応性基(ヒドロキシル基など)を有する化合物[例えば、ポリアルキレングリコールモノアルキルエーテル、オキシカルボン酸エステル(グリコール酸エステルなど)、N,N-二置換アミノアルコール(ジアルキルアミノアルコールなど)など]との反応物などが挙げられる。
Specific examples of the carbodiimide compound include a carbodiimide having an N, N-disubstituted amino group [eg, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide], a carbodiimide having an isocyanate group at its terminal and a hydrophilic group. A compound having a reactive group (such as a hydroxyl group) capable of forming a bond by reacting with a reactive segment and an isocyanate group [eg, polyalkylene glycol monoalkyl ether, oxycarboxylic acid ester (such as glycolic acid ester), N, N And a reaction product with a substituted amino alcohol (such as a dialkylamino alcohol).
イソシアネート系架橋剤としては、ポリイソシアネート[例えば、1,6-ヘキサメチレンジイソシアネート、1,4-テトラメチレンジイソシアネート、2,2,4-トリメチルヘキサメチレンジイソシアネート、2,4,4-トリメチルヘキサメチレンジイソシアネート、リジンイソシアネートなどの脂肪族ポリイソシアネート類;1,3-ジイソシアネートシクロヘキサン、1,4-ジイソシアネートシクロヘキサン、1,3-ビス(イソシアネートメチル)シクロヘキサン、1,4-ビス(イソシアネートメチル)シクロヘキサン、ジシクロヘキシルメタン-4,4’-ジイソシアネート、イソホロンジイソシアネート、ノルボルナンジイソシアネートなどの脂環族ポリイソシアネート類;キシリレンジイソシアネート、テトラメチルキシリレンジイソシアネート、4,4-ビス(イソシアネートメチル)ジフェニルメタンなどの芳香脂肪族ポリイソシアネート類など]、ポリイソシアネートとポリオールとの反応物などが挙げられる。
Isocyanate-based crosslinking agents include polyisocyanates [for example, 1,6-hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, Aliphatic polyisocyanates such as lysine isocyanate; 1,3-diisocyanatecyclohexane, 1,4-diisocyanatecyclohexane, 1,3-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanatemethyl) cyclohexane, dicyclohexylmethane-4 , 4′-diisocyanate, isophorone diisocyanate, norbornane diisocyanate, and the like; xylylene diisocyanate, tetramethyl Le xylylene diisocyanate, 4,4-bis such araliphatic polyisocyanates such as (isocyanatomethyl) diphenylmethane], reaction products of polyisocyanate and polyol.
アミン系架橋剤としては、尿素系樹脂(例えば、尿素樹脂、チオ尿素樹脂など)、トリアジン系樹脂(例えば、メラミン樹脂、イソメラミン樹脂、ペンゾグアナミン樹脂、アセトグアナミン樹脂、グアニルメラミン樹脂など)などが挙げられる。
Examples of amine crosslinking agents include urea resins (eg, urea resins, thiourea resins, etc.), triazine resins (eg, melamine resins, isomelamine resins, benzoguanamine resins, acetoguanamine resins, guanylmelamine resins, etc.). Can be mentioned.
エポキシ系架橋剤としては、例えば、ポリグリシジルエーテル、エポキシ樹脂(例えば、ノボラック型エポキシ樹脂、臭素化エポキシ樹脂、脂環式エポキシ樹脂、グリシジルエーテル型エポキシ樹脂、グリシジルエステル型エポキシ樹脂など)などが挙げられる。
Examples of the epoxy-based crosslinking agent include polyglycidyl ether, epoxy resin (for example, novolac type epoxy resin, brominated epoxy resin, alicyclic epoxy resin, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, etc.). It is done.
架橋剤(C)は、単独で又は2種以上組み合わせて使用してもよい。
The crosslinking agent (C) may be used alone or in combination of two or more.
これらの架橋剤(C)の中でも、水溶性架橋剤が好ましい。また、ヒドラジン系架橋剤、オキサゾリン系架橋剤、カルボジイミド系架橋剤などが好ましい。
Among these crosslinking agents (C), a water-soluble crosslinking agent is preferable. Also preferred are hydrazine-based crosslinking agents, oxazoline-based crosslinking agents, carbodiimide-based crosslinking agents, and the like.
代表的な形態(ii)には、下記(ii-1)及び(ii-2)の形態などが含まれる。
Representative forms (ii) include the following forms (ii-1) and (ii-2).
(ii-1)エマルション(A)が、官能基αを有する単量体としてカルボニル基含有単量体を含む単量体成分(a)のポリマーで構成され、ポリマー(B)が、官能基βを有する単量体としてカルボニル基含有単量体を含む単量体成分(b)のポリマーで構成され、ヒドラジン系架橋剤(C1)を介してエマルション(A)とポリマー(B)とが結合している(又は結合可能な)形態
(Ii-1) The emulsion (A) is composed of a polymer of a monomer component (a) containing a carbonyl group-containing monomer as a monomer having a functional group α, and the polymer (B) has a functional group β It is composed of a polymer of a monomer component (b) containing a carbonyl group-containing monomer as a monomer having a structure, and the emulsion (A) and the polymer (B) are bonded via a hydrazine-based crosslinking agent (C1). Form (or connectable)
(ii-2)エマルション(A)が、官能基αを有する単量体としてカルボキシル含有単量体を含む単量体成分(a)のポリマーで構成され、ポリマー(B)が、官能基βを有する単量体としてカルボキシル基含有単量体を含む単量体成分(b)のポリマーで構成され、オキサゾリン系架橋剤(C2)を介してエマルション粒子(A)とポリマー(B)とが結合している(又は結合可能な)形態
(Ii-2) The emulsion (A) is composed of a polymer of a monomer component (a) containing a carboxyl-containing monomer as a monomer having a functional group α, and the polymer (B) has a functional group β. It is composed of a polymer of a monomer component (b) containing a carboxyl group-containing monomer as a monomer, and the emulsion particles (A) and the polymer (B) are bonded via an oxazoline-based crosslinking agent (C2). Form (or connectable)
形態(i)及び(ii)において、官能基αを有する単量体と官能基βを有する単量体との割合は、例えば、前者/後者(質量比)=0.1/1~1000/1、好ましくは0.5/1~500/1、さらに好ましくは1/1~300/1(例えば、1/1~240/1)程度であってもよい。
In the forms (i) and (ii), the ratio of the monomer having the functional group α and the monomer having the functional group β is, for example, the former / the latter (mass ratio) = 0.1 / 1 to 1000 / It may be about 1, preferably 0.5 / 1 to 500/1, more preferably about 1/1 to 300/1 (for example, 1/1 to 240/1).
また、単量体成分(a)及び単量体成分(b)の総量に対して、官能基αを有する単量体及び官能基βを有する単量体の総量の割合は、例えば、0.01~40質量%、好ましくは0.05~30質量%、さらに好ましくは0.1~20質量%程度であってもよい。
The ratio of the total amount of the monomer having the functional group α and the monomer having the functional group β to the total amount of the monomer component (a) and the monomer component (b) is, for example, 0. It may be about 01 to 40% by mass, preferably about 0.05 to 30% by mass, and more preferably about 0.1 to 20% by mass.
形態(ii)において、架橋剤(C)の割合は、例えば、官能基αを有する単量体及び官能基βを有する単量体の総量100質量部に対して、例えば、0.01~500質量部、好ましくは0.1~300質量部、さらに好ましくは1~100質量部程度であってもよい。
In the form (ii), the ratio of the crosslinking agent (C) is, for example, 0.01 to 500 with respect to 100 parts by mass of the total amount of the monomer having the functional group α and the monomer having the functional group β. It may be about 1 part by mass, preferably about 0.1 to 300 parts by mass, and more preferably about 1 to 100 parts by mass.
本発明の組成物は、溶媒を含む組成物であってもよい。特に、本発明の組成物は、エマルション(A)及びポリマー(B)が溶媒中に分散(又は溶解)した組成物であってもよい。
The composition of the present invention may be a composition containing a solvent. In particular, the composition of the present invention may be a composition in which the emulsion (A) and the polymer (B) are dispersed (or dissolved) in a solvent.
溶媒としては、前記例示の溶媒と同様の溶媒を使用できる。好ましい溶媒は、水、水を含む溶媒[例えば、水とアルコール(メタノール、エタノールなどの低級アルコール)とを含む混合溶媒]などの水性溶媒である。特に、本発明の組成物は、エマルション(A)及びポリマー(B)が水性溶媒中に分散(又は溶解)した組成物(水性組成物)であってもよい。
As the solvent, the same solvents as those exemplified above can be used. A preferable solvent is an aqueous solvent such as water, a solvent containing water [for example, a mixed solvent containing water and an alcohol (a lower alcohol such as methanol or ethanol)]. In particular, the composition of the present invention may be a composition (aqueous composition) in which the emulsion (A) and the polymer (B) are dispersed (or dissolved) in an aqueous solvent.
溶媒を含む組成物において、エマルション(A)及びポリマー(B)の総量の割合は、用途等に応じて適宜選択できるが、例えば、0.1~95質量%、好ましくは1~90質量%、さらに好ましくは3~80質量%程度であってもよい。
In the composition containing the solvent, the ratio of the total amount of the emulsion (A) and the polymer (B) can be appropriately selected depending on the application and the like, for example, 0.1 to 95% by mass, preferably 1 to 90% by mass, More preferably, it may be about 3 to 80% by mass.
なお、本発明の組成物は、用途等に応じて、他の成分を含んでいてもよい。
In addition, the composition of this invention may contain the other component according to a use etc.
本発明の組成物の製造方法は、特に限定されず、例えば、エマルション(A)とポリマー(B)と(さらに必要に応じて溶媒や他の成分と)を混合することで製造できる。
The method for producing the composition of the present invention is not particularly limited, and can be produced, for example, by mixing the emulsion (A) and the polymer (B) (and, if necessary, a solvent and other components).
エマルション(A)とポリマー(B)との間で架橋構造を形成させる場合には、適当な架橋条件下で混合すればよい。例えば、溶媒中(例えば、前記水性溶媒中)で、エマルション(A)とポリマー(B)と架橋剤(C)とを混合し、架橋させてもよい。
When a crosslinked structure is formed between the emulsion (A) and the polymer (B), they may be mixed under appropriate crosslinking conditions. For example, the emulsion (A), the polymer (B), and the crosslinking agent (C) may be mixed and crosslinked in a solvent (for example, in the aqueous solvent).
本発明の組成物(例えば、水性組成物)は、特に、塗料用(塗装用)として好適である。このような塗料用組成物(特に、塗料用水性組成物)は、例えば、各種素材(例えば、金属、ガラス、磁器、コンクリート、サイディングボード、樹脂など)で形成された基材の表面仕上げ等に使用してもよい。
The composition of the present invention (for example, an aqueous composition) is particularly suitable for paint (for coating). Such a coating composition (particularly, an aqueous coating composition) is used, for example, for surface finishing of a substrate formed of various materials (for example, metal, glass, porcelain, concrete, siding board, resin, etc.). May be used.
本発明の組成物は、中でも、トップコート(又は上塗り材、例えば、外装材(建材)のトップコート)に好適に使用することができる。
The composition of the present invention can be suitably used for a topcoat (or topcoat material, for example, a topcoat for exterior materials (building materials)), among others.
このような本発明の組成物又は塗料(塗料用組成物、例えば、水性の建築・外装用塗料)は、前記成分(例えば、エマルション(A)及びポリマー(B))以外に、その他の成分を含んでいてもよい。
その他の成分としては、例えば、顔料(後述の顔料など)、顔料分散剤、沈殿防止剤、紫外線吸収剤、光安定剤、成膜助剤、増粘剤、表面調整剤、防腐・防黴剤、レベリング剤、凍結防止剤、湿潤剤、pH調整剤、消泡剤などが挙げられる。
これらの成分は、単独で又は2種以上組み合わせて使用してもよい。 Such a composition or paint of the present invention (a paint composition, for example, an aqueous building / exterior paint) contains other components in addition to the above-described components (eg, emulsion (A) and polymer (B)). May be included.
Examples of other components include pigments (pigments described later), pigment dispersants, precipitation inhibitors, ultraviolet absorbers, light stabilizers, film forming aids, thickeners, surface conditioners, antiseptic / antifungal agents, and the like. , Leveling agents, antifreezing agents, wetting agents, pH adjusting agents, antifoaming agents and the like.
These components may be used alone or in combination of two or more.
その他の成分としては、例えば、顔料(後述の顔料など)、顔料分散剤、沈殿防止剤、紫外線吸収剤、光安定剤、成膜助剤、増粘剤、表面調整剤、防腐・防黴剤、レベリング剤、凍結防止剤、湿潤剤、pH調整剤、消泡剤などが挙げられる。
これらの成分は、単独で又は2種以上組み合わせて使用してもよい。 Such a composition or paint of the present invention (a paint composition, for example, an aqueous building / exterior paint) contains other components in addition to the above-described components (eg, emulsion (A) and polymer (B)). May be included.
Examples of other components include pigments (pigments described later), pigment dispersants, precipitation inhibitors, ultraviolet absorbers, light stabilizers, film forming aids, thickeners, surface conditioners, antiseptic / antifungal agents, and the like. , Leveling agents, antifreezing agents, wetting agents, pH adjusting agents, antifoaming agents and the like.
These components may be used alone or in combination of two or more.
外装材としては、例えば、各種建材(例えば、フレキシブルボード、珪酸カルシウム板、石膏スラグパーライト板、木片セメント板、プレキャストコンクリート板、ALC板、石膏ボードなどの無機質建材;例えば、瓦、外壁材などの窯業系建材など)などが挙げられる。窯業系建材は、例えば、無機質硬化体の原料となる水硬性膠着材に無機充填剤、繊維質材料などを添加し、得られた混合物を成形し、得られた成形体を養生し、硬化させることによって得られる。
As exterior materials, for example, various building materials (for example, flexible boards, calcium silicate boards, gypsum slag perlite boards, wood cement boards, precast concrete boards, ALC boards, gypsum boards, etc .; for example, tiles, outer wall materials, etc. Ceramic building materials). Ceramic-based building materials, for example, add inorganic fillers, fibrous materials, etc. to hydraulic glue, which is a raw material for inorganic hardened bodies, mold the resulting mixture, and cure and cure the resulting molded body Can be obtained.
このような外装材(建材)の表面には、通常、所望の意匠を付与する等のために、上塗り材(水性塗料)が塗布されている。より具体的には、トップコート又は上塗り材(水性塗料)は、太陽光や風雨などの外的環境から建築物を保護したり、建築物の美観や意匠性を持たせる塗膜を形成する塗料(建築・外装用塗料)として使用されている。本発明の組成物は、このトップコート用又は上塗り材(水性塗料)として好適に使用することができる。
The surface of such an exterior material (building material) is usually coated with a top coating material (water-based paint) in order to give a desired design. More specifically, the top coat or top coat material (water-based paint) is a paint that forms a coating film that protects the building from the external environment such as sunlight or wind and rain, or has the aesthetics and design of the building. Used as (architectural and exterior paint). The composition of the present invention can be suitably used for this top coat or as a top coating material (water-based paint).
特に塗料の中でも、建築物の外壁(外装材)に直接塗布し、自然環境下で乾燥硬化(常温乾燥)させる外装用塗料に使用することが好ましい。常温で乾燥硬化する塗料で形成した塗膜は軟質であることが多く、軟質のため塗膜表面に粘着性が生じ汚染物質を付着させることから耐汚染性が低い。本発明の塗料(又は塗料用組成物)は、このような軟質塗膜への耐汚染化剤として使用でき、塗料に配合することで塗膜表面の親水化効果等によって耐汚染性を向上しうる。
Especially, among paints, it is preferable to apply directly to the outer wall (exterior material) of the building and use it for the exterior paint that is dried and cured (normal temperature drying) in a natural environment. A coating film formed with a paint that is dry-cured at room temperature is often soft, and because of its softness, the surface of the coating film becomes sticky and causes contaminants to adhere to it. The paint (or paint composition) of the present invention can be used as a stain-proofing agent for such a soft coating film, and by adding it to the coating, the stain resistance is improved by the hydrophilic effect of the coating film surface. sell.
前記の外装用塗料を用いて形成される表面塗膜の状態としては透明~着色半透明~着色隠蔽まで、種々の形態のものであり得るが、外装材に形成した下層塗膜層もしく上塗り塗膜層を隠蔽する目的で、着色隠蔽状態のものが特に多い。
そのため、本発明の塗料(塗料用組成物)は、特に、顔料を含む塗料(水性塗料、水性の外装用塗料など)であってもよい。 The state of the surface coating film formed using the above-mentioned exterior coating material can be in various forms from transparent to colored translucent to colored concealment. For the purpose of concealing the coating layer, the colored concealed state is particularly numerous.
Therefore, the paint (coating composition) of the present invention may be a paint containing a pigment (aqueous paint, aqueous exterior paint, etc.).
そのため、本発明の塗料(塗料用組成物)は、特に、顔料を含む塗料(水性塗料、水性の外装用塗料など)であってもよい。 The state of the surface coating film formed using the above-mentioned exterior coating material can be in various forms from transparent to colored translucent to colored concealment. For the purpose of concealing the coating layer, the colored concealed state is particularly numerous.
Therefore, the paint (coating composition) of the present invention may be a paint containing a pigment (aqueous paint, aqueous exterior paint, etc.).
顔料としては、公知の顔料を広範囲に使用することができる。顔料は着色剤であってもよく、体質顔料(増量剤)であってもよい。代表的な顔料としては、例えば、無機系顔料(例えば、酸化チタン、酸化鉄、アルミニウム、パール顔料等の無機系着色顔料)、有機系顔料(例えば、キナクリドン、アントラキノン、ペリレン、ジケトピロロピロール、ベンズイミダゾロン、イソインドリノン、アンスラピリミジン、フタロシアニン、スレン、ジオキサジン、カーボンブラック等の有機系着色顔料)、体質顔料(例えば、炭酸カルシウム、硫酸バリウム、カオリン、マイカ、タルク等)を挙げることができる。
顔料は単独で又は2種以上組み合わせて使用してもよい。 As the pigment, known pigments can be used in a wide range. The pigment may be a colorant or an extender pigment (a bulking agent). Typical pigments include, for example, inorganic pigments (for example, inorganic color pigments such as titanium oxide, iron oxide, aluminum, pearl pigments), organic pigments (for example, quinacridone, anthraquinone, perylene, diketopyrrolopyrrole, And organic pigments such as benzimidazolone, isoindolinone, anthrapyrimidine, phthalocyanine, selenium, dioxazine, and carbon black) and extender pigments (eg, calcium carbonate, barium sulfate, kaolin, mica, talc, etc.) .
You may use a pigment individually or in combination of 2 or more types.
顔料は単独で又は2種以上組み合わせて使用してもよい。 As the pigment, known pigments can be used in a wide range. The pigment may be a colorant or an extender pigment (a bulking agent). Typical pigments include, for example, inorganic pigments (for example, inorganic color pigments such as titanium oxide, iron oxide, aluminum, pearl pigments), organic pigments (for example, quinacridone, anthraquinone, perylene, diketopyrrolopyrrole, And organic pigments such as benzimidazolone, isoindolinone, anthrapyrimidine, phthalocyanine, selenium, dioxazine, and carbon black) and extender pigments (eg, calcium carbonate, barium sulfate, kaolin, mica, talc, etc.) .
You may use a pigment individually or in combination of 2 or more types.
特に着色隠蔽性や塗膜表面を高光沢にすることから、酸化チタンを少なくとも使用することが好ましい。顔料の配合量としては、乾燥後の塗膜中の樹脂成分(又はエマルション(A)及びポリマー(B))の固形分100重量部に対して、例えば、5~70質量部、好ましくは7~65質量部、さらに好ましくは10~60質量部程度であってもよい。
In particular, it is preferable to use at least titanium oxide from the standpoint of color hiding and high gloss on the coating surface. The amount of the pigment blended is, for example, 5 to 70 parts by weight, preferably 7 to 7 parts by weight with respect to 100 parts by weight of the solid content of the resin component (or emulsion (A) and polymer (B)) in the coating film after drying. It may be about 65 parts by mass, more preferably about 10 to 60 parts by mass.
本発明の組成物は、塗料(塗装)に使用する場合、それ単独で1層で塗工してもよく、2層以上に重ね塗りすることによって塗工してもよい。2層以上に重ね塗りすることによって塗工する場合、その一部の層のみが本発明の組成物によって形成されてもよく、全部の層が本発明の組成物で形成されてもよい。重ね塗りは、例えば、プライマー処理やシーラー処理などを施した被塗物に、第1層(例えば、下塗り層)用塗料を塗布して乾燥させた後 、第2層(例えば、上塗り層)用塗料を上塗りし、乾燥させる方法などが挙げられるが、本発明はかかる方法によって限定されるものではない。塗料を塗布する際には、例えば、スプレー、ローラー、ハケ、コテなどを用いることができる。
When the composition of the present invention is used for paint (coating), it may be applied alone in one layer, or may be applied by recoating two or more layers. When the coating is performed by overcoating two or more layers, only a part of the layers may be formed by the composition of the present invention, or all the layers may be formed by the composition of the present invention. For overcoating, for example, a first layer (eg, undercoat layer) coating is applied to an object that has been subjected to primer treatment or sealer treatment, and then dried, and then applied to the second layer (eg, topcoat layer). Although the method of overcoating and drying a paint etc. is mentioned, this invention is not limited by this method. When applying the paint, for example, spray, roller, brush, or iron can be used.
次に本発明を実施例に基づいてさらに詳細に説明するが、本発明は、かかる実施例のみに限定されるものではない。なお、以下の実施例において、「部」は「質量部」を意味する。
Next, the present invention will be described in more detail based on examples. However, the present invention is not limited to such examples. In the following examples, “part” means “part by mass”.
(製造例A1)
滴下ロート、撹拌機、窒素導入管、温度計および還流冷却管を備えたフラスコ内に脱イオン水750部を仕込んだ。 (Production Example A1)
750 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer, and a reflux condenser.
滴下ロート、撹拌機、窒素導入管、温度計および還流冷却管を備えたフラスコ内に脱イオン水750部を仕込んだ。 (Production Example A1)
750 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer, and a reflux condenser.
滴下ロートに脱イオン水163部、アニオン性乳化剤〔(株)ADEKA製、商品名:アデカリアソープSR-10、反応性のアニオン性乳化剤〕の25%水溶液80部、2-エチルヘキシルアクリレート300部、シクロヘキシルメタクリレート250部、2,2,6,6-テトラメチルピペリジルメタクリレート(4-メタクリロイルオキシ-2,2,6,6-テトラメチルピペリジン)50部、ブチルアクリレート50部、ダイアセトンアクリルアミド10部、スチレン250部、ヒドロキシエチルメタクリレート10部、tert-ブチルメタクリレート30部およびメチルメタクリレート50部からなる滴下用プレエマルションを調製し、そのうちの74部をフラスコ内に添加し、ゆるやかに窒素ガスを吹き込みながら80℃まで昇温し、過硫酸カリウムの5%水溶液10部をフラスコ内に添加することにより、重合を開始した。
In a dropping funnel, 163 parts of deionized water, 80 parts of 25% aqueous solution of an anionic emulsifier (manufactured by ADEKA, trade name: Adekaria soap SR-10, a reactive anionic emulsifier), 300 parts of 2-ethylhexyl acrylate, 250 parts of cyclohexyl methacrylate, 50 parts of 2,2,6,6-tetramethylpiperidyl methacrylate (4-methacryloyloxy-2,2,6,6-tetramethylpiperidine), 50 parts of butyl acrylate, 10 parts of diacetone acrylamide, styrene A pre-emulsion for dripping consisting of 250 parts, hydroxyethyl methacrylate 10 parts, tert-butyl methacrylate 30 parts and methyl methacrylate 50 parts was prepared, 74 parts of which were added into the flask, and 80 ° C. while gently blowing nitrogen gas. Ma The temperature was raised, by 5% aqueous solution of 10 parts of potassium persulfate is added to the flask to initiate polymerization.
次に、滴下用プレエマルションの残部と過硫酸カリウムの5%水溶液10部と2.5%亜硫酸水素ナトリウム水溶液20部を120分間にわたり均一にフラスコ内に滴下した。滴下終了後、フラスコの内容物を80℃で60分間維持し、25%アンモニア水をフラスコ内に添加し、pHを9に調整し、重合反応を終了した。
Next, the remaining part of the pre-emulsion for dripping, 10 parts of a 5% aqueous solution of potassium persulfate and 20 parts of a 2.5% aqueous sodium hydrogen sulfite solution were uniformly dropped into the flask over 120 minutes. After completion of the dropping, the contents of the flask were maintained at 80 ° C. for 60 minutes, 25% aqueous ammonia was added into the flask, the pH was adjusted to 9, and the polymerization reaction was terminated.
得られた反応液を室温まで冷却した後、300メッシュ(JISメッシュ、以下同じ)の金網で濾過することにより、不揮発分含量が49質量%である水性樹脂分散体を得た。得られた水性樹脂分散体に含まれるエマルション粒子は、平均粒子径が150nmの1層構造を有し、エマルション粒子全体のガラス転移温度は14.7℃であった。
The obtained reaction liquid was cooled to room temperature, and then filtered through a 300 mesh (JIS mesh, hereinafter the same) wire mesh to obtain an aqueous resin dispersion having a nonvolatile content of 49% by mass. The emulsion particles contained in the obtained aqueous resin dispersion had a single-layer structure with an average particle diameter of 150 nm, and the glass transition temperature of the entire emulsion particles was 14.7 ° C.
(製造例A2)
滴下ロート、撹拌機、窒素導入管、温度計および還流冷却管を備えたフラスコ内に脱イオン水750部を仕込んだ。 (Production Example A2)
750 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer, and a reflux condenser.
滴下ロート、撹拌機、窒素導入管、温度計および還流冷却管を備えたフラスコ内に脱イオン水750部を仕込んだ。 (Production Example A2)
750 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer, and a reflux condenser.
滴下ロートに脱イオン水163部、アニオン性乳化剤〔(株)ADEKA製、商品名:アデカリアソープSR-10、反応性のアニオン性乳化剤〕の25%水溶液80部、2-エチルヘキシルアクリレート300部、シクロヘキシルメタクリレート400部、スチレン150部、メチルメタクリレート80部、tert-ブチルメタクリレート20部、ダイアセトンアクリルアミド10部、ヒドロキシエチルメタクリレート20部、メタクリル酸10部およびアクリル酸10部からなる1段目滴下用プレエマルションを調製し、そのうちの74部をフラスコ内に添加し、ゆるやかに窒素ガスを吹き込みながら80℃まで昇温し、過硫酸カリウムの5%水溶液20部を添加し重合を開始した。
In a dropping funnel, 163 parts of deionized water, 80 parts of 25% aqueous solution of an anionic emulsifier (manufactured by ADEKA, trade name: Adekaria soap SR-10, a reactive anionic emulsifier), 300 parts of 2-ethylhexyl acrylate, A first-stage dripping pre-treatment comprising 400 parts of cyclohexyl methacrylate, 150 parts of styrene, 80 parts of methyl methacrylate, 20 parts of tert-butyl methacrylate, 10 parts of diacetone acrylamide, 20 parts of hydroxyethyl methacrylate, 10 parts of methacrylic acid and 10 parts of acrylic acid. An emulsion was prepared, 74 parts thereof were added into the flask, the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and 20 parts of a 5% aqueous solution of potassium persulfate was added to initiate polymerization.
次に、滴下用プレエマルションの残部と過硫酸カリウムの5%水溶液10部と2.5%亜硫酸水素ナトリウム水溶液10部を120分間にわたり均一にフラスコ内に滴下した。滴下終了後、80℃で60分間フラスコの内容物を維持した。25%アンモニア水をフラスコ内に添加し、pHを9に調整することにより、重合反応を終了した。
Next, the remainder of the pre-emulsion for dripping, 10 parts of a 5% aqueous solution of potassium persulfate and 10 parts of a 2.5% aqueous solution of sodium hydrogen sulfite were uniformly dropped into the flask over 120 minutes. After completion of the dropping, the contents of the flask were maintained at 80 ° C. for 60 minutes. The polymerization reaction was completed by adding 25% aqueous ammonia into the flask and adjusting the pH to 9.
得られた反応液を室温まで冷却した後、300メッシュの金網で濾過することにより、不揮発分含量が49質量%である水性樹脂分散体を得た。得られた水性樹脂分散体に含まれるエマルション粒子は、平均粒子径が160nmの1層構造を有し、エマルション粒子全体のガラス転移温度は20.2℃であった。
The obtained reaction liquid was cooled to room temperature and then filtered through a 300 mesh wire netting to obtain an aqueous resin dispersion having a nonvolatile content of 49% by mass. The emulsion particles contained in the obtained aqueous resin dispersion had a single-layer structure with an average particle diameter of 160 nm, and the glass transition temperature of the entire emulsion particles was 20.2 ° C.
(製造例A3)
滴下ロート、撹拌機、窒素導入管、温度計および還流冷却管を備えたフラスコ内に脱イオン水507部を仕込んだ。 (Production Example A3)
507 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer, and a reflux condenser.
滴下ロート、撹拌機、窒素導入管、温度計および還流冷却管を備えたフラスコ内に脱イオン水507部を仕込んだ。 (Production Example A3)
507 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer, and a reflux condenser.
滴下ロートに脱イオン水163部、アニオン性乳化剤〔(株)ADEKA製、商品名:アデカリアソープSR-10、反応性のアニオン性乳化剤〕の25%水溶液80部、2-エチルヘキシルアクリレート15部、シクロヘキシルメタクリレート210部、メチルメタクリレート250部、γ-メタクリロイルオキシプロピルトリメトキシシラン5部、スチレン10部、アクリル酸5部およびヒドロキシエチルメタクリレート5部からなる1段目滴下用プレエマルションを調製し、そのうちの74部をフラスコ内に添加し、ゆるやかに窒素ガスを吹き込みながら80℃まで昇温し、過硫酸カリウムの5%水溶液20部をフラスコ内に添加することにより、重合を開始した。
In a dropping funnel, 163 parts of deionized water, 80 parts of a 25% aqueous solution of an anionic emulsifier (manufactured by ADEKA, trade name: Adekari Soap SR-10, a reactive anionic emulsifier), 15 parts of 2-ethylhexyl acrylate, A pre-emulsion for first-stage dropping comprising 210 parts of cyclohexyl methacrylate, 250 parts of methyl methacrylate, 5 parts of γ-methacryloyloxypropyltrimethoxysilane, 10 parts of styrene, 5 parts of acrylic acid and 5 parts of hydroxyethyl methacrylate was prepared. Polymerization was started by adding 74 parts into the flask, raising the temperature to 80 ° C. while gently blowing nitrogen gas, and adding 20 parts of a 5% aqueous solution of potassium persulfate into the flask.
次に、滴下用プレエマルションの残部と過硫酸カリウムの5%水溶液10部と2.5%亜硫酸水素ナトリウム水溶液10部を120分間にわたり均一にフラスコ内に滴下した。滴下終了後、80℃で60分間フラスコの内容物を維持し、25%アンモニア水5部を添加した。
Next, the remainder of the pre-emulsion for dripping, 10 parts of a 5% aqueous solution of potassium persulfate and 10 parts of a 2.5% aqueous solution of sodium hydrogen sulfite were uniformly dropped into the flask over 120 minutes. After completion of the dropping, the contents of the flask were maintained at 80 ° C. for 60 minutes, and 5 parts of 25% aqueous ammonia was added.
引き続いて、脱イオン水163部、アニオン性乳化剤〔(株)ADEKA製、商品名:アデカリアソープSR-10、反応性のアニオン性乳化剤〕の25%水溶液80部、2-エチルヘキシルアクリレート225部、ブチルアクリレート150部、シクロヘキシルメタクリレート105部、ヒドロキシエチルメタクリレート10部、2,2,6,6-テトラメチルピペリジルメタクリレート10部、およびダイアセトンアクリルアミド10部からなる2段目滴下用プレエマルションと過硫酸カリウムの5%水溶液10部と2.5%亜硫酸水素ナトリウム水溶液10部を120分間にわたってフラスコ内に均一に滴下した。滴下終了後、80℃で60分間フラスコの内容物を維持し、25%アンモニア水を添加し、pHを9に調整することにより、重合反応を終了した。
Subsequently, 163 parts of deionized water, 80 parts of a 25% aqueous solution of an anionic emulsifier (manufactured by ADEKA, trade name: ADEKA rear soap SR-10, a reactive anionic emulsifier), 225 parts of 2-ethylhexyl acrylate, Pre-emulsion for second-stage dropping and potassium persulfate comprising 150 parts of butyl acrylate, 105 parts of cyclohexyl methacrylate, 10 parts of hydroxyethyl methacrylate, 10 parts of 2,2,6,6-tetramethylpiperidyl methacrylate, and 10 parts of diacetone acrylamide 10 parts of a 5% aqueous solution and 10 parts of a 2.5% aqueous sodium hydrogen sulfite solution were added dropwise uniformly over 120 minutes. After completion of the dropping, the content of the flask was maintained at 80 ° C. for 60 minutes, 25% aqueous ammonia was added, and the pH was adjusted to 9, thereby terminating the polymerization reaction.
得られた反応液を室温まで冷却した後、300メッシュの金網で濾過することにより、不揮発分含量が49質量%である水性樹脂分散体を得た。得られた水性樹脂分散体に含まれるエマルション粒子は、平均粒子径が150nmの2層構造を有し、内層のガラス転移温度は85.3℃、外層のガラス転移温度は-38.6℃であり、エマルション粒子全体のガラス転移温度は9.1℃であった。
The obtained reaction liquid was cooled to room temperature and then filtered through a 300 mesh wire netting to obtain an aqueous resin dispersion having a nonvolatile content of 49% by mass. The emulsion particles contained in the obtained aqueous resin dispersion have a two-layer structure with an average particle diameter of 150 nm, the glass transition temperature of the inner layer is 85.3 ° C., and the glass transition temperature of the outer layer is −38.6 ° C. Yes, the glass transition temperature of the entire emulsion particles was 9.1 ° C.
(製造例A4)
滴下ロート、撹拌機、窒素導入管、温度計および還流冷却管を備えたフラスコ内に脱イオン水507部を仕込んだ。 (Production Example A4)
507 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer, and a reflux condenser.
滴下ロート、撹拌機、窒素導入管、温度計および還流冷却管を備えたフラスコ内に脱イオン水507部を仕込んだ。 (Production Example A4)
507 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer, and a reflux condenser.
滴下ロ-トに脱イオン水163部、アニオン性乳化剤〔(株)ADEKA製、商品名:アデカリアソープSR-10、反応性のアニオン性乳化剤〕の25%水溶液80部、2-エチルヘキシルアクリレート330部、シクロヘキシルメタクリレート50部、スチレン40部、メチルメタクリレート20部、tert-ブチルメタクリレート15部、ブチルアクリレート30部、アクリル酸5部、メタクリル酸5部およびヒドロキシエチルメタクリレート5部からなる1段目滴下用プレエマルションを調製し、そのうちの74部をフラスコ内に添加し、ゆるやかに窒素ガスを吹き込みながら80℃まで昇温し、過硫酸カリウムの5%水溶液20部をフラスコ内に添加することにより、重合反応を開始した。
In a dropping funnel, 163 parts of deionized water, 80 parts of 25% aqueous solution of an anionic emulsifier (manufactured by ADEKA, trade name: ADEKA rear soap SR-10, a reactive anionic emulsifier), 2-ethylhexyl acrylate 330 For first-stage dripping comprising 50 parts of cyclohexyl methacrylate, 40 parts of styrene, 20 parts of methyl methacrylate, 15 parts of tert-butyl methacrylate, 30 parts of butyl acrylate, 5 parts of acrylic acid, 5 parts of methacrylic acid and 5 parts of hydroxyethyl methacrylate. A pre-emulsion was prepared, 74 parts thereof were added into the flask, the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and 20 parts of a 5% aqueous solution of potassium persulfate was added into the flask to polymerize. The reaction was started.
次に、滴下用プレエマルションの残部と過硫酸カリウムの5%水溶液10部と2.5%亜硫酸水素ナトリウム水溶液10部を120分間にわたり均一にフラスコ内に滴下した。滴下終了後、80℃で60分間フラスコの内容物を維持し、25%アンモニア水5部を添加した。
Next, the remainder of the pre-emulsion for dripping, 10 parts of a 5% aqueous solution of potassium persulfate and 10 parts of a 2.5% aqueous solution of sodium hydrogen sulfite were uniformly dropped into the flask over 120 minutes. After completion of the dropping, the contents of the flask were maintained at 80 ° C. for 60 minutes, and 5 parts of 25% aqueous ammonia was added.
引き続いて、脱イオン水163部、アニオン性乳化剤〔(株)ADEKA製、商品名:アデカリアソープSR-10、反応性のアニオン性乳化剤〕の25%水溶液80部、2-エチルヘキシルアクリレート50部、ブチルアクリレート15部、メチルメタクリレート120部、tert-ブチルメタクリレート120部、シクロヘキシルメタクリレート120部、スチレン40部、γ-メタクリロイルオキシプロピルトリメトキシシラン5部、ヒドロキエチルメタクリレート10部、2,2,6,6-テトラメチルピペリジルメタクリレート10部、およびダイアセトンアクリルアミド10部からなる2段目滴下用プレエマルションと過硫酸カリウムの5%水溶液10部と2.5%亜硫酸水素ナトリウム水溶液10部を120分間にわたってフラスコ内に均一に滴下した。滴下終了後、80℃で60分間フラスコの内容物を維持し、25%アンモニア水を添加し、pHを9に調整することにより、重合反応を終了した。
Subsequently, 163 parts of deionized water, 80 parts of a 25% aqueous solution of an anionic emulsifier (manufactured by ADEKA, trade name: ADEKA rear soap SR-10, a reactive anionic emulsifier), 50 parts of 2-ethylhexyl acrylate, 15 parts butyl acrylate, 120 parts methyl methacrylate, 120 parts tert-butyl methacrylate, 120 parts cyclohexyl methacrylate, 40 parts styrene, 5 parts γ-methacryloyloxypropyltrimethoxysilane, 10 parts hydroxyethyl methacrylate, 2, 2, 6, 6 -A second stage pre-emulsion consisting of 10 parts of tetramethylpiperidyl methacrylate and 10 parts of diacetone acrylamide, 10 parts of a 5% aqueous solution of potassium persulfate and 10 parts of a 2.5% aqueous sodium hydrogen sulfite solution over 120 minutes. It was uniformly added dropwise into the flask. After completion of the dropping, the content of the flask was maintained at 80 ° C. for 60 minutes, 25% aqueous ammonia was added, and the pH was adjusted to 9, thereby terminating the polymerization reaction.
得られた反応液を室温まで冷却した後、300メッシュの金網で濾過することにより、不揮発分含量が49質量%である水性樹脂分散体を得た。得られた水性樹脂分散体に含まれるエマルション粒子は、平均粒子径が150nmの2層構造を有し、内層のガラス転移温度は-39.9℃、外層のガラス転移温度は62.0℃であり、エマルション粒子全体のガラス転移温度は1.9℃であった。
The obtained reaction liquid was cooled to room temperature and then filtered through a 300 mesh wire netting to obtain an aqueous resin dispersion having a nonvolatile content of 49% by mass. The emulsion particles contained in the obtained aqueous resin dispersion have a two-layer structure with an average particle diameter of 150 nm, the inner layer has a glass transition temperature of −39.9 ° C., and the outer layer has a glass transition temperature of 62.0 ° C. Yes, the glass transition temperature of the entire emulsion particles was 1.9 ° C.
(製造例A5)
滴下ロート、撹拌機、窒素導入管、温度計および還流冷却管を備えたフラスコ内に脱イオン水750部を仕込んだ。滴下ロートに脱イオン水163部、アニオン性乳化剤〔(株)ADEKA製、商品名:アデカリアソープSR-10、反応性のアニオン性乳化剤〕の25%水溶液80部、2-エチルヘキシルアクリレート250部、2,2,6,6-テトラメチルピペリジルメタクリレート(4-メタクリロイルオキシ-2,2,6,6-テトラメチルピペリジン)60部、ブチルアクリレート30部、スチレン50部、ヒドロキシエチルメタクリレート10部、ブチルメタクリレート350部、アクリル酸10部およびメチルメタクリレート240部からなる滴下用プレエマルションを調製し、そのうちの74部をフラスコ内に添加し、ゆるやかに窒素ガスを吹き込みながら80℃まで昇温し、過硫酸カリウムの5%水溶液10部をフラスコ内に添加することにより、重合を開始した。 (Production Example A5)
750 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer, and a reflux condenser. In a dropping funnel, 163 parts of deionized water, 80 parts of a 25% aqueous solution of an anionic emulsifier (manufactured by ADEKA, trade name: ADEKA rear soap SR-10, a reactive anionic emulsifier), 250 parts of 2-ethylhexyl acrylate, 2,2,6,6-tetramethylpiperidyl methacrylate (4-methacryloyloxy-2,2,6,6-tetramethylpiperidine) 60 parts, butyl acrylate 30 parts, styrene 50 parts, hydroxyethyl methacrylate 10 parts, butyl methacrylate Prepare a pre-emulsion for dropping consisting of 350 parts, 10 parts of acrylic acid and 240 parts of methyl methacrylate, add 74 parts of the emulsion into the flask, raise the temperature to 80 ° C. while gently blowing nitrogen gas, and potassium persulfate Add 10 parts of 5% aqueous solution to the flask. By and, to initiate the polymerization.
滴下ロート、撹拌機、窒素導入管、温度計および還流冷却管を備えたフラスコ内に脱イオン水750部を仕込んだ。滴下ロートに脱イオン水163部、アニオン性乳化剤〔(株)ADEKA製、商品名:アデカリアソープSR-10、反応性のアニオン性乳化剤〕の25%水溶液80部、2-エチルヘキシルアクリレート250部、2,2,6,6-テトラメチルピペリジルメタクリレート(4-メタクリロイルオキシ-2,2,6,6-テトラメチルピペリジン)60部、ブチルアクリレート30部、スチレン50部、ヒドロキシエチルメタクリレート10部、ブチルメタクリレート350部、アクリル酸10部およびメチルメタクリレート240部からなる滴下用プレエマルションを調製し、そのうちの74部をフラスコ内に添加し、ゆるやかに窒素ガスを吹き込みながら80℃まで昇温し、過硫酸カリウムの5%水溶液10部をフラスコ内に添加することにより、重合を開始した。 (Production Example A5)
750 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer, and a reflux condenser. In a dropping funnel, 163 parts of deionized water, 80 parts of a 25% aqueous solution of an anionic emulsifier (manufactured by ADEKA, trade name: ADEKA rear soap SR-10, a reactive anionic emulsifier), 250 parts of 2-ethylhexyl acrylate, 2,2,6,6-tetramethylpiperidyl methacrylate (4-methacryloyloxy-2,2,6,6-tetramethylpiperidine) 60 parts, butyl acrylate 30 parts, styrene 50 parts, hydroxyethyl methacrylate 10 parts, butyl methacrylate Prepare a pre-emulsion for dropping consisting of 350 parts, 10 parts of acrylic acid and 240 parts of methyl methacrylate, add 74 parts of the emulsion into the flask, raise the temperature to 80 ° C. while gently blowing nitrogen gas, and potassium persulfate Add 10 parts of 5% aqueous solution to the flask. By and, to initiate the polymerization.
次に、滴下用プレエマルションの残部と過硫酸カリウムの5%水溶液10部と2.5%亜硫酸水素ナトリウム水溶液20部を120分間にわたり均一にフラスコ内に滴下した。滴下終了後、フラスコの内容物を80℃で60分間維持し、25%アンモニア水をフラスコ内に添加し、pHを9に調整し、重合反応を終了した。
Next, the remaining part of the pre-emulsion for dripping, 10 parts of a 5% aqueous solution of potassium persulfate and 20 parts of a 2.5% aqueous sodium hydrogen sulfite solution were uniformly dropped into the flask over 120 minutes. After completion of the dropping, the contents of the flask were maintained at 80 ° C. for 60 minutes, 25% aqueous ammonia was added into the flask, the pH was adjusted to 9, and the polymerization reaction was terminated.
得られた反応液を室温まで冷却した後、300メッシュ(JISメッシュ、以下同じ)の金網で濾過することにより、不揮発分含量が49質量%である水性樹脂分散体を得た。得られた水性樹脂分散体に含まれるエマルション粒子は、平均粒子径が150nmの1層構造を有し、エマルション粒子全体のガラス転移温度は9.5℃であった。
The obtained reaction liquid was cooled to room temperature, and then filtered through a 300 mesh (JIS mesh, hereinafter the same) wire mesh to obtain an aqueous resin dispersion having a nonvolatile content of 49% by mass. The emulsion particles contained in the obtained aqueous resin dispersion had a one-layer structure with an average particle diameter of 150 nm, and the glass transition temperature of the whole emulsion particles was 9.5 ° C.
(実施例B1)
冷却管、窒素導入ラインおよび温度計を設置した重合容器内に脱イオン水594部を仕込んだ。フラスコ内に窒素ガスを導入し、フラスコ内を窒素ガス雰囲気にした。 (Example B1)
594 parts of deionized water was charged into a polymerization vessel equipped with a cooling pipe, a nitrogen introduction line and a thermometer. Nitrogen gas was introduced into the flask, and the atmosphere in the flask was changed to a nitrogen gas atmosphere.
冷却管、窒素導入ラインおよび温度計を設置した重合容器内に脱イオン水594部を仕込んだ。フラスコ内に窒素ガスを導入し、フラスコ内を窒素ガス雰囲気にした。 (Example B1)
594 parts of deionized water was charged into a polymerization vessel equipped with a cooling pipe, a nitrogen introduction line and a thermometer. Nitrogen gas was introduced into the flask, and the atmosphere in the flask was changed to a nitrogen gas atmosphere.
滴下ロートA内にN-ビニルピロリドン255部、ダイアセトンアクリルアミド2.6部および2,2,6,6-テトラメチルピペリジルメタクリレート2.6部を添加し、プレミックスを調製した。滴下ロートB内に脱イオン水129部および2,2’-アゾビス(2-メチルプロピオンアミジン)二塩酸塩6.5部を添加した。
In the dropping funnel A, 255 parts of N-vinylpyrrolidone, 2.6 parts of diacetone acrylamide, and 2.6 parts of 2,2,6,6-tetramethylpiperidyl methacrylate were added to prepare a premix. In the dropping funnel B, 129 parts of deionized water and 6.5 parts of 2,2'-azobis (2-methylpropionamidine) dihydrochloride were added.
滴下ロートAおよび滴下ロートBの各内容物をそれぞれ2時間かけて均一に重合容器内に滴下し、重合反応を開始した。重合容器内の温度が重合熱によって上昇した後、80℃の温度で2時間撹拌した。
The contents of the dropping funnel A and the dropping funnel B were dropped uniformly into the polymerization vessel over 2 hours to initiate the polymerization reaction. After the temperature in the polymerization vessel rose due to the heat of polymerization, the mixture was stirred for 2 hours at a temperature of 80 ° C.
次に、滴下ロートAおよび滴下ロートBをそれぞれ脱イオン水51部で洗浄し、得られた洗浄液を重合容器内に添加し、80℃の温度で1時間撹拌した。1時間後、脱イオン水に溶かした2,2’-アゾビス(2-メチルプロピオンアミジン)二塩酸塩10%水溶液2.6部を重合容器内に添加し、さらに80℃の温度で1時間撹拌することにより、水溶性ポリマー溶液を得た。得られた水溶性ポリマー溶液の不揮発分含量は25.0質量%であり、得られたポリマーの重量平均分子量は20000であった。
Next, the dropping funnel A and the dropping funnel B were each washed with 51 parts of deionized water, and the obtained washing solution was added to the polymerization vessel and stirred at a temperature of 80 ° C. for 1 hour. After 1 hour, 2.6 parts of a 10% aqueous solution of 2,2′-azobis (2-methylpropionamidine) dihydrochloride dissolved in deionized water was added to the polymerization vessel, and further stirred at a temperature of 80 ° C. for 1 hour. As a result, a water-soluble polymer solution was obtained. The obtained water-soluble polymer solution had a nonvolatile content of 25.0% by mass, and the polymer obtained had a weight average molecular weight of 20000.
(実施例B2)
冷却管、窒素導入ラインおよび温度計を設置した重合容器内に脱イオン水594部を仕込んだ。フラスコ内に窒素ガスを導入し、フラスコ内を窒素ガス雰囲気にした。 (Example B2)
594 parts of deionized water was charged into a polymerization vessel equipped with a cooling pipe, a nitrogen introduction line and a thermometer. Nitrogen gas was introduced into the flask, and the atmosphere in the flask was changed to a nitrogen gas atmosphere.
冷却管、窒素導入ラインおよび温度計を設置した重合容器内に脱イオン水594部を仕込んだ。フラスコ内に窒素ガスを導入し、フラスコ内を窒素ガス雰囲気にした。 (Example B2)
594 parts of deionized water was charged into a polymerization vessel equipped with a cooling pipe, a nitrogen introduction line and a thermometer. Nitrogen gas was introduced into the flask, and the atmosphere in the flask was changed to a nitrogen gas atmosphere.
滴下ロートA内にN-ビニルピロリドン234部、ダイアセトンアクリルアミド13部および2,2,6,6-テトラメチルピペリジルメタクリレート13部を添加し、プレミックスを調製した。滴下ロートB内に脱イオン水129部および2,2’-アゾビス(2-メチルプロピオンアミジン)二塩酸塩6.5部を添加した。
In the dropping funnel A, 234 parts of N-vinylpyrrolidone, 13 parts of diacetone acrylamide and 13 parts of 2,2,6,6-tetramethylpiperidyl methacrylate were added to prepare a premix. In the dropping funnel B, 129 parts of deionized water and 6.5 parts of 2,2'-azobis (2-methylpropionamidine) dihydrochloride were added.
滴下ロートAおよび滴下ロートBの各内容物をそれぞれ2時間かけて均一に重合容器内に滴下し、重合反応を開始した。重合容器内の温度が重合熱によって上昇した後、80℃の温度で2時間撹拌した。
The contents of the dropping funnel A and the dropping funnel B were dropped uniformly into the polymerization vessel over 2 hours to initiate the polymerization reaction. After the temperature in the polymerization vessel rose due to the heat of polymerization, the mixture was stirred for 2 hours at a temperature of 80 ° C.
次に、滴下ロートAおよび滴下ロートBをそれぞれ脱イオン水51部で洗浄し、得られた洗浄液を重合容器内に添加し、80℃の温度で1時間撹拌した。1時間後、脱イオン水に溶かした2,2’-アゾビス(2-メチルプロピオンアミジン)二塩酸塩10%水溶液2.6部を重合容器内に添加し、さらに80℃の温度で1時間撹拌することにより、水溶性ポリマー溶液を得た。得られた水溶性ポリマー溶液の不揮発分含量は25.0質量%であり、得られたポリマーの重量平均分子量は20000であった。
Next, the dropping funnel A and the dropping funnel B were each washed with 51 parts of deionized water, and the obtained washing solution was added to the polymerization vessel and stirred at a temperature of 80 ° C. for 1 hour. After 1 hour, 2.6 parts of a 10% aqueous solution of 2,2′-azobis (2-methylpropionamidine) dihydrochloride dissolved in deionized water was added to the polymerization vessel, and further stirred at a temperature of 80 ° C. for 1 hour. As a result, a water-soluble polymer solution was obtained. The obtained water-soluble polymer solution had a nonvolatile content of 25.0% by mass, and the polymer obtained had a weight average molecular weight of 20000.
(実施例B3)
冷却管、窒素導入ラインおよび温度計を設置した重合容器内に脱イオン水594部を仕込んだ。フラスコ内に窒素ガスを導入し、フラスコ内を窒素ガス雰囲気にした。 (Example B3)
594 parts of deionized water was charged into a polymerization vessel equipped with a cooling pipe, a nitrogen introduction line and a thermometer. Nitrogen gas was introduced into the flask, and the atmosphere in the flask was changed to a nitrogen gas atmosphere.
冷却管、窒素導入ラインおよび温度計を設置した重合容器内に脱イオン水594部を仕込んだ。フラスコ内に窒素ガスを導入し、フラスコ内を窒素ガス雰囲気にした。 (Example B3)
594 parts of deionized water was charged into a polymerization vessel equipped with a cooling pipe, a nitrogen introduction line and a thermometer. Nitrogen gas was introduced into the flask, and the atmosphere in the flask was changed to a nitrogen gas atmosphere.
滴下ロートA内にN-ビニルピロリドン255部、ダイアセトンアクリルアミド2.6部および1,2,2,6,6-ペンタメチルピペリジルメタクリレート2.6部を添加し、プレミックスを調製した。滴下ロートB内に脱イオン水129部および2,2’-アゾビス(2-メチルプロピオンアミジン)二塩酸塩6.5部を添加した。
In the dropping funnel A, 255 parts of N-vinylpyrrolidone, 2.6 parts of diacetone acrylamide, and 2.6 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate were added to prepare a premix. In the dropping funnel B, 129 parts of deionized water and 6.5 parts of 2,2'-azobis (2-methylpropionamidine) dihydrochloride were added.
滴下ロートAおよび滴下ロートBの各内容物をそれぞれ2時間かけて均一に重合容器内に滴下し、重合反応を開始した。重合容器内の温度が重合熱によって上昇した後、80℃の温度で2時間撹拌した。
The contents of the dropping funnel A and the dropping funnel B were dropped uniformly into the polymerization vessel over 2 hours to initiate the polymerization reaction. After the temperature in the polymerization vessel rose due to the heat of polymerization, the mixture was stirred for 2 hours at a temperature of 80 ° C.
次に、滴下ロートAおよび滴下ロートBをそれぞれ脱イオン水51部で洗浄し、得られた洗浄液を重合容器内に添加し、80℃の温度で1時間撹拌した。1時間後、脱イオン水に溶かした2,2’-アゾビス(2-メチルプロピオンアミジン)二塩酸塩10%水溶液2.6部を重合容器内に添加し、さらに80℃の温度で1時間撹拌することにより、水溶性ポリマー溶液を得た。得られた水溶性ポリマー溶液の不揮発分含量は25.0質量%であり、得られたポリマーの重量平均分子量は20000であった。
Next, the dropping funnel A and the dropping funnel B were each washed with 51 parts of deionized water, and the obtained washing solution was added to the polymerization vessel and stirred at a temperature of 80 ° C. for 1 hour. After 1 hour, 2.6 parts of a 10% aqueous solution of 2,2′-azobis (2-methylpropionamidine) dihydrochloride dissolved in deionized water was added to the polymerization vessel, and further stirred at a temperature of 80 ° C. for 1 hour. As a result, a water-soluble polymer solution was obtained. The obtained water-soluble polymer solution had a nonvolatile content of 25.0% by mass, and the polymer obtained had a weight average molecular weight of 20000.
(実施例B4)
冷却管、窒素導入ラインおよび温度計を設置した重合容器内に脱イオン水300部を仕込んだ。フラスコ内に窒素ガスを導入し、フラスコ内を窒素ガス雰囲気にした。 (Example B4)
300 parts of deionized water was charged into a polymerization vessel equipped with a cooling pipe, a nitrogen introduction line and a thermometer. Nitrogen gas was introduced into the flask, and the atmosphere in the flask was changed to a nitrogen gas atmosphere.
冷却管、窒素導入ラインおよび温度計を設置した重合容器内に脱イオン水300部を仕込んだ。フラスコ内に窒素ガスを導入し、フラスコ内を窒素ガス雰囲気にした。 (Example B4)
300 parts of deionized water was charged into a polymerization vessel equipped with a cooling pipe, a nitrogen introduction line and a thermometer. Nitrogen gas was introduced into the flask, and the atmosphere in the flask was changed to a nitrogen gas atmosphere.
滴下ロートA内にN-ビニルピロリドン252部、ダイアセトンアクリルアミド2.6部、25%アンモニア水2.0部、アクリル酸2.1部および2,2,6,6-テトラメチルピペリジルメタクリレート2.6部を添加し、プレミックスを調製した。滴下ロートB内に脱イオン水129部および2,2’-アゾビス(2-メチルプロピオンアミジン)二塩酸塩6.5部を添加した。
In the dropping funnel A, 252 parts of N-vinylpyrrolidone, 2.6 parts of diacetone acrylamide, 2.0 parts of 25% aqueous ammonia, 2.1 parts of acrylic acid and 2,2,6,6-tetramethylpiperidyl methacrylate 6 parts were added to prepare a premix. In the dropping funnel B, 129 parts of deionized water and 6.5 parts of 2,2'-azobis (2-methylpropionamidine) dihydrochloride were added.
滴下ロートAおよび滴下ロートBの各内容物をそれぞれ2時間かけて均一に重合容器内に滴下し、重合反応を開始した。重合容器内の温度が重合熱によって上昇した後、80℃の温度で2時間撹拌した。
The contents of the dropping funnel A and the dropping funnel B were dropped uniformly into the polymerization vessel over 2 hours to initiate the polymerization reaction. After the temperature in the polymerization vessel rose due to the heat of polymerization, the mixture was stirred for 2 hours at a temperature of 80 ° C.
次に、滴下ロートAおよび滴下ロートBをそれぞれ脱イオン水345部で洗浄し、得られた洗浄液を重合容器内に添加し、80℃の温度で1時間撹拌した。1時間後、脱イオン水に溶かした2,2’-アゾビス(2-メチルプロピオンアミジン)二塩酸塩10%水溶液2.6部を重合容器内に添加し、さらに80℃の温度で1時間撹拌することにより、水溶性ポリマー溶液を得た。得られた水溶性ポリマー溶液の不揮発分含量は25.0質量%であり、得られたポリマーの重量平均分子量は40000であった。
Next, the dropping funnel A and the dropping funnel B were each washed with 345 parts of deionized water, and the obtained washing solution was added to the polymerization vessel and stirred at a temperature of 80 ° C. for 1 hour. After 1 hour, 2.6 parts of a 10% aqueous solution of 2,2′-azobis (2-methylpropionamidine) dihydrochloride dissolved in deionized water was added to the polymerization vessel, and further stirred at a temperature of 80 ° C. for 1 hour. As a result, a water-soluble polymer solution was obtained. The obtained water-soluble polymer solution had a nonvolatile content of 25.0% by mass, and the obtained polymer had a weight average molecular weight of 40000.
(実施例B5)
冷却管、窒素導入ラインおよび温度計を設置した重合容器内に脱イオン水198部を仕込んだ。フラスコ内に窒素ガスを導入し、フラスコ内を窒素ガス雰囲気にした。 (Example B5)
198 parts of deionized water was charged into a polymerization vessel equipped with a cooling pipe, a nitrogen introduction line and a thermometer. Nitrogen gas was introduced into the flask, and the atmosphere in the flask was changed to a nitrogen gas atmosphere.
冷却管、窒素導入ラインおよび温度計を設置した重合容器内に脱イオン水198部を仕込んだ。フラスコ内に窒素ガスを導入し、フラスコ内を窒素ガス雰囲気にした。 (Example B5)
198 parts of deionized water was charged into a polymerization vessel equipped with a cooling pipe, a nitrogen introduction line and a thermometer. Nitrogen gas was introduced into the flask, and the atmosphere in the flask was changed to a nitrogen gas atmosphere.
滴下ロートA内にN-ビニルピロリドン252部、ダイアセトンアクリルアミド2.6部、ヒドロキシエチルメタクリレート2.6部、2,2,6,6-テトラメチルピペリジルメタクリレート1.3部および1,2,2,6,6-ペンタメチルピペリジルメタクリレート1.3部を添加し、プレミックスを調製した。滴下ロートB内に脱イオン水129部および2,2’-アゾビス(2-メチルプロピオンアミジン)二塩酸塩6.5部を添加した。
In dropping funnel A, 252 parts of N-vinylpyrrolidone, 2.6 parts of diacetone acrylamide, 2.6 parts of hydroxyethyl methacrylate, 1.3 parts of 2,2,6,6-tetramethylpiperidyl methacrylate and 1,2,2 , 6,6-Pentamethylpiperidylmethacrylate 1.3 parts was added to prepare a premix. In the dropping funnel B, 129 parts of deionized water and 6.5 parts of 2,2'-azobis (2-methylpropionamidine) dihydrochloride were added.
滴下ロートAおよび滴下ロートBの各内容物をそれぞれ2時間かけて均一に重合容器内に滴下し、重合反応を開始した。重合容器内の温度が重合熱によって上昇した後、80℃の温度で2時間撹拌した。
The contents of the dropping funnel A and the dropping funnel B were dropped uniformly into the polymerization vessel over 2 hours to initiate the polymerization reaction. After the temperature in the polymerization vessel rose due to the heat of polymerization, the mixture was stirred for 2 hours at a temperature of 80 ° C.
次に、滴下ロートAおよび滴下ロートBをそれぞれ脱イオン水447部で洗浄し、得られた洗浄液を重合容器内に添加し、80℃の温度で1時間撹拌した。1時間後、脱イオン水に溶かした2,2’-アゾビス(2-メチルプロピオンアミジン)二塩酸塩10%水溶液2.6部を重合容器内に添加し、さらに80℃の温度で1時間撹拌することにより、水溶性ポリマー溶液を得た。得られた水溶性ポリマー溶液の不揮発分含量は25.0質量%であり、得られたポリマーの重量平均分子量は200000であった。
Next, the dropping funnel A and the dropping funnel B were each washed with 447 parts of deionized water, and the obtained washing solution was added to the polymerization vessel and stirred at a temperature of 80 ° C. for 1 hour. After 1 hour, 2.6 parts of a 10% aqueous solution of 2,2′-azobis (2-methylpropionamidine) dihydrochloride dissolved in deionized water was added to the polymerization vessel, and further stirred at a temperature of 80 ° C. for 1 hour. As a result, a water-soluble polymer solution was obtained. The obtained water-soluble polymer solution had a nonvolatile content of 25.0% by mass, and the obtained polymer had a weight average molecular weight of 200,000.
(製造例B6)
冷却管、窒素導入ラインおよび温度計を設置した重合容器内に脱イオン水594部を仕込んだ。フラスコ内に窒素ガスを導入し、フラスコ内を窒素ガス雰囲気にした。 (Production Example B6)
594 parts of deionized water was charged into a polymerization vessel equipped with a cooling pipe, a nitrogen introduction line and a thermometer. Nitrogen gas was introduced into the flask, and the atmosphere in the flask was changed to a nitrogen gas atmosphere.
冷却管、窒素導入ラインおよび温度計を設置した重合容器内に脱イオン水594部を仕込んだ。フラスコ内に窒素ガスを導入し、フラスコ内を窒素ガス雰囲気にした。 (Production Example B6)
594 parts of deionized water was charged into a polymerization vessel equipped with a cooling pipe, a nitrogen introduction line and a thermometer. Nitrogen gas was introduced into the flask, and the atmosphere in the flask was changed to a nitrogen gas atmosphere.
滴下ロートA内にN-ビニルピロリドン255部およびダイアセトンアクリルアミド2.6部を添加し、プレミックスを調製した。滴下ロートB内に脱イオン水129部および2,2’-アゾビス(2-メチルプロピオンアミジン)二塩酸塩6.5部を添加した。
In the dropping funnel A, 255 parts of N-vinylpyrrolidone and 2.6 parts of diacetone acrylamide were added to prepare a premix. In the dropping funnel B, 129 parts of deionized water and 6.5 parts of 2,2'-azobis (2-methylpropionamidine) dihydrochloride were added.
滴下ロートAおよび滴下ロートBの各内容物をそれぞれ2時間かけて均一に重合容器内に滴下し、重合反応を開始した。重合容器内の温度が重合熱によって上昇した後、80℃の温度で2時間撹拌した。
The contents of the dropping funnel A and the dropping funnel B were dropped uniformly into the polymerization vessel over 2 hours to initiate the polymerization reaction. After the temperature in the polymerization vessel rose due to the heat of polymerization, the mixture was stirred for 2 hours at a temperature of 80 ° C.
次に、滴下ロートAおよび滴下ロートBをそれぞれ脱イオン水48部で洗浄し、得られた洗浄液を重合容器内に添加し、80℃の温度で1時間撹拌した。1時間後、脱イオン水に溶かした2,2’-アゾビス(2-メチルプロピオンアミジン)二塩酸塩10%水溶液2.6部を重合容器内に添加し、さらに80℃の温度で1時間撹拌することにより、水溶性ポリマー溶液を得た。得られた水溶性ポリマー溶液の不揮発分含量は25.0質量%であり、得られたポリマーの重量平均分子量は20000であった。
Next, the dropping funnel A and the dropping funnel B were each washed with 48 parts of deionized water, and the obtained washing solution was added to the polymerization vessel and stirred at a temperature of 80 ° C. for 1 hour. After 1 hour, 2.6 parts of a 10% aqueous solution of 2,2′-azobis (2-methylpropionamidine) dihydrochloride dissolved in deionized water was added to the polymerization vessel, and further stirred at a temperature of 80 ° C. for 1 hour. As a result, a water-soluble polymer solution was obtained. The obtained water-soluble polymer solution had a nonvolatile content of 25.0% by mass, and the polymer obtained had a weight average molecular weight of 20000.
(製造例B7)
冷却管、窒素導入ラインおよび温度計を設置した重合容器内に脱イオン水198部を仕込んだ。フラスコ内に窒素ガスを導入し、フラスコ内を窒素ガス雰囲気にした。 (Production Example B7)
198 parts of deionized water was charged into a polymerization vessel equipped with a cooling pipe, a nitrogen introduction line and a thermometer. Nitrogen gas was introduced into the flask, and the atmosphere in the flask was changed to a nitrogen gas atmosphere.
冷却管、窒素導入ラインおよび温度計を設置した重合容器内に脱イオン水198部を仕込んだ。フラスコ内に窒素ガスを導入し、フラスコ内を窒素ガス雰囲気にした。 (Production Example B7)
198 parts of deionized water was charged into a polymerization vessel equipped with a cooling pipe, a nitrogen introduction line and a thermometer. Nitrogen gas was introduced into the flask, and the atmosphere in the flask was changed to a nitrogen gas atmosphere.
滴下ロートA内にN-ビニルピロリドン252部およびダイアセトンアクリルアミド2.6部を添加し、プレミックスを調製した。滴下ロートB内に脱イオン水129部および2,2’-アゾビス(2-メチルプロピオンアミジン)二塩酸塩6.5部を添加した。
In the dropping funnel A, 252 parts of N-vinylpyrrolidone and 2.6 parts of diacetone acrylamide were added to prepare a premix. In the dropping funnel B, 129 parts of deionized water and 6.5 parts of 2,2'-azobis (2-methylpropionamidine) dihydrochloride were added.
滴下ロートAおよび滴下ロートBの各内容物をそれぞれ2時間かけて均一に重合容器内に滴下し、重合反応を開始した。重合容器内の温度が重合熱によって上昇した後、80℃の温度で2時間撹拌した。
The contents of the dropping funnel A and the dropping funnel B were dropped uniformly into the polymerization vessel over 2 hours to initiate the polymerization reaction. After the temperature in the polymerization vessel rose due to the heat of polymerization, the mixture was stirred for 2 hours at a temperature of 80 ° C.
次に、滴下ロートAおよび滴下ロートBをそれぞれ脱イオン水430部で洗浄し、得られた洗浄液を重合容器内に添加し、80℃の温度で1時間撹拌した。1時間後、脱イオン水に溶かした2,2’-アゾビス(2-メチルプロピオンアミジン)二塩酸塩10%水溶液2.6部を重合容器内に添加し、さらに80℃の温度で1時間撹拌することにより、水溶性ポリマー溶液を得た。得られた水溶性ポリマー溶液の不揮発分含量は25.0質量%であり、得られたポリマーの重量平均分子量は200000であった。
Next, the dropping funnel A and the dropping funnel B were each washed with 430 parts of deionized water, and the obtained washing solution was added to the polymerization vessel and stirred at a temperature of 80 ° C. for 1 hour. After 1 hour, 2.6 parts of a 10% aqueous solution of 2,2′-azobis (2-methylpropionamidine) dihydrochloride dissolved in deionized water was added to the polymerization vessel, and further stirred at a temperature of 80 ° C. for 1 hour. As a result, a water-soluble polymer solution was obtained. The obtained water-soluble polymer solution had a nonvolatile content of 25.0% by mass, and the obtained polymer had a weight average molecular weight of 200,000.
(実施例B8)
冷却管、窒素導入ラインおよび温度計を設置した重合容器内に脱イオン水300部を仕込んだ。フラスコ内に窒素ガスを導入し、フラスコ内を窒素ガス雰囲気にした。滴下ロートA内にN-ビニルピロリドン226部、ヒドロキシエチルメタクリレート26部、25%アンモニア水4.0部、アクリル酸4.2部および2,2,6,6-テトラメチルピペリジルメタクリレート2.6部を添加し、プレミックスを調製した。滴下ロートB内に脱イオン水129部および2,2’-アゾビス(2-メチルプロピオンアミジン)二塩酸塩6.5部を添加した。 (Example B8)
300 parts of deionized water was charged into a polymerization vessel equipped with a cooling pipe, a nitrogen introduction line and a thermometer. Nitrogen gas was introduced into the flask, and the atmosphere in the flask was changed to a nitrogen gas atmosphere. In dropping funnel A, 226 parts of N-vinylpyrrolidone, 26 parts of hydroxyethyl methacrylate, 4.0 parts of 25% aqueous ammonia, 4.2 parts of acrylic acid and 2.6 parts of 2,2,6,6-tetramethylpiperidyl methacrylate Was added to prepare a premix. In the dropping funnel B, 129 parts of deionized water and 6.5 parts of 2,2′-azobis (2-methylpropionamidine) dihydrochloride were added.
冷却管、窒素導入ラインおよび温度計を設置した重合容器内に脱イオン水300部を仕込んだ。フラスコ内に窒素ガスを導入し、フラスコ内を窒素ガス雰囲気にした。滴下ロートA内にN-ビニルピロリドン226部、ヒドロキシエチルメタクリレート26部、25%アンモニア水4.0部、アクリル酸4.2部および2,2,6,6-テトラメチルピペリジルメタクリレート2.6部を添加し、プレミックスを調製した。滴下ロートB内に脱イオン水129部および2,2’-アゾビス(2-メチルプロピオンアミジン)二塩酸塩6.5部を添加した。 (Example B8)
300 parts of deionized water was charged into a polymerization vessel equipped with a cooling pipe, a nitrogen introduction line and a thermometer. Nitrogen gas was introduced into the flask, and the atmosphere in the flask was changed to a nitrogen gas atmosphere. In dropping funnel A, 226 parts of N-vinylpyrrolidone, 26 parts of hydroxyethyl methacrylate, 4.0 parts of 25% aqueous ammonia, 4.2 parts of acrylic acid and 2.6 parts of 2,2,6,6-tetramethylpiperidyl methacrylate Was added to prepare a premix. In the dropping funnel B, 129 parts of deionized water and 6.5 parts of 2,2′-azobis (2-methylpropionamidine) dihydrochloride were added.
滴下ロートAおよび滴下ロートBの各内容物をそれぞれ2時間かけて均一に重合容器内に滴下し、重合反応を開始した。重合容器内の温度が重合熱によって上昇した後、80℃の温度で2時間撹拌した。
The contents of the dropping funnel A and the dropping funnel B were dropped uniformly into the polymerization vessel over 2 hours to initiate the polymerization reaction. After the temperature in the polymerization vessel rose due to the heat of polymerization, the mixture was stirred for 2 hours at a temperature of 80 ° C.
次に、滴下ロートAおよび滴下ロートBをそれぞれ脱イオン水345部で洗浄し、得られた洗浄液を重合容器内に添加し、80℃の温度で1時間撹拌した。1時間後、脱イオン水に溶かした2,2’-アゾビス(2-メチルプロピオンアミジン)二塩酸塩10%水溶液2.6部を重合容器内に添加し、さらに80℃の温度で1時間撹拌することにより、水溶性ポリマー溶液を得た。得られた水溶性ポリマー溶液の不揮発分含量は25.0質量%であり、得られたポリマーの重量平均分子量は40000であった。
Next, the dropping funnel A and the dropping funnel B were each washed with 345 parts of deionized water, and the obtained washing solution was added to the polymerization vessel and stirred at a temperature of 80 ° C. for 1 hour. After 1 hour, 2.6 parts of a 10% aqueous solution of 2,2′-azobis (2-methylpropionamidine) dihydrochloride dissolved in deionized water was added to the polymerization vessel, and further stirred at a temperature of 80 ° C. for 1 hour. As a result, a water-soluble polymer solution was obtained. The obtained water-soluble polymer solution had a nonvolatile content of 25.0% by mass, and the obtained polymer had a weight average molecular weight of 40000.
(実施例1)
製造例A1で得られた水性樹脂分散体(エマルション粒子)A1に実施例B1で得られた水溶性ポリマーB1を両者の固形分の質量比(A1/B1)が97/3となるように添加し、水性樹脂組成物を得た。 Example 1
The water-soluble polymer B1 obtained in Example B1 was added to the aqueous resin dispersion (emulsion particles) A1 obtained in Production Example A1 so that the mass ratio (A1 / B1) of both solids was 97/3 As a result, an aqueous resin composition was obtained.
製造例A1で得られた水性樹脂分散体(エマルション粒子)A1に実施例B1で得られた水溶性ポリマーB1を両者の固形分の質量比(A1/B1)が97/3となるように添加し、水性樹脂組成物を得た。 Example 1
The water-soluble polymer B1 obtained in Example B1 was added to the aqueous resin dispersion (emulsion particles) A1 obtained in Production Example A1 so that the mass ratio (A1 / B1) of both solids was 97/3 As a result, an aqueous resin composition was obtained.
(実施例2)
製造例A1で得られた水性樹脂分散体A1に実施例B1で得られた水溶性ポリマーB1を両者の固形分の質量比(A1/B1)が93/7となるように添加し、得られた混合物100部に架橋剤として5%のヒドラジン系架橋剤(アジピン酸ジヒドラジド)水溶液10部を添加することにより、水性樹脂組成物を得た。 (Example 2)
The water-soluble polymer B1 obtained in Example B1 was added to the aqueous resin dispersion A1 obtained in Production Example A1 so that the mass ratio (A1 / B1) of both solids was 93/7. An aqueous resin composition was obtained by adding 10 parts of a 5% hydrazine-based crosslinking agent (adipic acid dihydrazide) aqueous solution as a crosslinking agent to 100 parts of the obtained mixture.
製造例A1で得られた水性樹脂分散体A1に実施例B1で得られた水溶性ポリマーB1を両者の固形分の質量比(A1/B1)が93/7となるように添加し、得られた混合物100部に架橋剤として5%のヒドラジン系架橋剤(アジピン酸ジヒドラジド)水溶液10部を添加することにより、水性樹脂組成物を得た。 (Example 2)
The water-soluble polymer B1 obtained in Example B1 was added to the aqueous resin dispersion A1 obtained in Production Example A1 so that the mass ratio (A1 / B1) of both solids was 93/7. An aqueous resin composition was obtained by adding 10 parts of a 5% hydrazine-based crosslinking agent (adipic acid dihydrazide) aqueous solution as a crosslinking agent to 100 parts of the obtained mixture.
(実施例3)
製造例A1で得られた水性樹脂分散体(エマルション粒子)A1に実施例B3で得られた水溶性ポリマーB3を両者の固形分の質量比(A1/B3)が97/3となるように添加し、水性樹脂組成物を得た。 (Example 3)
The water-soluble polymer B3 obtained in Example B3 was added to the aqueous resin dispersion (emulsion particles) A1 obtained in Production Example A1 so that the mass ratio (A1 / B3) of both solids was 97/3 As a result, an aqueous resin composition was obtained.
製造例A1で得られた水性樹脂分散体(エマルション粒子)A1に実施例B3で得られた水溶性ポリマーB3を両者の固形分の質量比(A1/B3)が97/3となるように添加し、水性樹脂組成物を得た。 (Example 3)
The water-soluble polymer B3 obtained in Example B3 was added to the aqueous resin dispersion (emulsion particles) A1 obtained in Production Example A1 so that the mass ratio (A1 / B3) of both solids was 97/3 As a result, an aqueous resin composition was obtained.
(実施例4)
製造例A1で得られた水性樹脂分散体A1に実施例B2で得られた水溶性ポリマーB2を両者の固形分の質量比(A1/B2)が90/10となるように添加し、得られた混合物100部に架橋剤として5%のヒドラジン系架橋剤(アジピン酸ジヒドラジド)水溶液10部を添加することにより、水性樹脂組成物を得た。 Example 4
The water-soluble polymer B2 obtained in Example B2 was added to the aqueous resin dispersion A1 obtained in Production Example A1 so that the mass ratio (A1 / B2) of both solids was 90/10. An aqueous resin composition was obtained by adding 10 parts of a 5% hydrazine-based crosslinking agent (adipic acid dihydrazide) aqueous solution as a crosslinking agent to 100 parts of the obtained mixture.
製造例A1で得られた水性樹脂分散体A1に実施例B2で得られた水溶性ポリマーB2を両者の固形分の質量比(A1/B2)が90/10となるように添加し、得られた混合物100部に架橋剤として5%のヒドラジン系架橋剤(アジピン酸ジヒドラジド)水溶液10部を添加することにより、水性樹脂組成物を得た。 Example 4
The water-soluble polymer B2 obtained in Example B2 was added to the aqueous resin dispersion A1 obtained in Production Example A1 so that the mass ratio (A1 / B2) of both solids was 90/10. An aqueous resin composition was obtained by adding 10 parts of a 5% hydrazine-based crosslinking agent (adipic acid dihydrazide) aqueous solution as a crosslinking agent to 100 parts of the obtained mixture.
(実施例5)
製造例A2で得られた水性樹脂分散体A2に実施例B1で得られた水溶性ポリマーB1を両者の固形分の質量比(A2/B1)が97/3となるように添加し、水性樹脂組成物を得た。 (Example 5)
The water-soluble polymer B1 obtained in Example B1 was added to the aqueous resin dispersion A2 obtained in Production Example A2 so that the mass ratio (A2 / B1) of both solids was 97/3. A composition was obtained.
製造例A2で得られた水性樹脂分散体A2に実施例B1で得られた水溶性ポリマーB1を両者の固形分の質量比(A2/B1)が97/3となるように添加し、水性樹脂組成物を得た。 (Example 5)
The water-soluble polymer B1 obtained in Example B1 was added to the aqueous resin dispersion A2 obtained in Production Example A2 so that the mass ratio (A2 / B1) of both solids was 97/3. A composition was obtained.
(実施例6)
製造例A2で得られた水性樹脂分散体A2に実施例B4で得られた水溶性ポリマーB4を両者の固形分の質量比(A2/B4)が95/5となるように添加し、得られた混合物100部に架橋剤としてオキサゾリン系架橋剤(エポクロスWS-500〔(株)日本触媒製〕)4部添加することにより、水性樹脂組成物を得た。 (Example 6)
The water-soluble polymer B4 obtained in Example B4 was added to the aqueous resin dispersion A2 obtained in Production Example A2 so that the mass ratio (A2 / B4) of both solids was 95/5. An aqueous resin composition was obtained by adding 4 parts of an oxazoline-based crosslinking agent (Epocross WS-500 [manufactured by Nippon Shokubai Co., Ltd.]) as a crosslinking agent to 100 parts of the mixture.
製造例A2で得られた水性樹脂分散体A2に実施例B4で得られた水溶性ポリマーB4を両者の固形分の質量比(A2/B4)が95/5となるように添加し、得られた混合物100部に架橋剤としてオキサゾリン系架橋剤(エポクロスWS-500〔(株)日本触媒製〕)4部添加することにより、水性樹脂組成物を得た。 (Example 6)
The water-soluble polymer B4 obtained in Example B4 was added to the aqueous resin dispersion A2 obtained in Production Example A2 so that the mass ratio (A2 / B4) of both solids was 95/5. An aqueous resin composition was obtained by adding 4 parts of an oxazoline-based crosslinking agent (Epocross WS-500 [manufactured by Nippon Shokubai Co., Ltd.]) as a crosslinking agent to 100 parts of the mixture.
(実施例7)
製造例A1で得られた水性樹脂分散体A1に実施例B5で得られた水溶性ポリマーB5を両者の固形分の質量比(A1/B5)が90/10となるように添加し、得られた混合物100部に架橋剤として5%のヒドラジン系架橋剤(アジピン酸ジヒドラジド)水溶液10部を添加することにより、水性樹脂組成物を得た。 (Example 7)
The water-soluble polymer B5 obtained in Example B5 was added to the aqueous resin dispersion A1 obtained in Production Example A1 so that the mass ratio (A1 / B5) of both solids was 90/10. An aqueous resin composition was obtained by adding 10 parts of a 5% hydrazine-based crosslinking agent (adipic acid dihydrazide) aqueous solution as a crosslinking agent to 100 parts of the obtained mixture.
製造例A1で得られた水性樹脂分散体A1に実施例B5で得られた水溶性ポリマーB5を両者の固形分の質量比(A1/B5)が90/10となるように添加し、得られた混合物100部に架橋剤として5%のヒドラジン系架橋剤(アジピン酸ジヒドラジド)水溶液10部を添加することにより、水性樹脂組成物を得た。 (Example 7)
The water-soluble polymer B5 obtained in Example B5 was added to the aqueous resin dispersion A1 obtained in Production Example A1 so that the mass ratio (A1 / B5) of both solids was 90/10. An aqueous resin composition was obtained by adding 10 parts of a 5% hydrazine-based crosslinking agent (adipic acid dihydrazide) aqueous solution as a crosslinking agent to 100 parts of the obtained mixture.
(実施例8)
製造例A3で得られた水性樹脂分散体A3に実施例B4で得られた水溶性ポリマーB4を両者の固形分の質量比(A3/B4)が95/5となるように添加し、得られた混合物100部に架橋剤としてオキサゾリン系架橋剤(エポクロスWS-500〔(株)日本触媒製〕)4部、5%のヒドラジン系架橋剤(アジピン酸ジヒドラジド)水溶液10部を添加することにより、水性樹脂組成物を得た。 (Example 8)
The water-soluble polymer B4 obtained in Example B4 was added to the aqueous resin dispersion A3 obtained in Production Example A3 so that the mass ratio (A3 / B4) of both solids was 95/5. By adding 4 parts of an oxazoline-based crosslinking agent (Epocross WS-500 [manufactured by Nippon Shokubai Co., Ltd.]) as a crosslinking agent and 10 parts of a 5% aqueous solution of a hydrazine-based crosslinking agent (adipic acid dihydrazide) An aqueous resin composition was obtained.
製造例A3で得られた水性樹脂分散体A3に実施例B4で得られた水溶性ポリマーB4を両者の固形分の質量比(A3/B4)が95/5となるように添加し、得られた混合物100部に架橋剤としてオキサゾリン系架橋剤(エポクロスWS-500〔(株)日本触媒製〕)4部、5%のヒドラジン系架橋剤(アジピン酸ジヒドラジド)水溶液10部を添加することにより、水性樹脂組成物を得た。 (Example 8)
The water-soluble polymer B4 obtained in Example B4 was added to the aqueous resin dispersion A3 obtained in Production Example A3 so that the mass ratio (A3 / B4) of both solids was 95/5. By adding 4 parts of an oxazoline-based crosslinking agent (Epocross WS-500 [manufactured by Nippon Shokubai Co., Ltd.]) as a crosslinking agent and 10 parts of a 5% aqueous solution of a hydrazine-based crosslinking agent (adipic acid dihydrazide) An aqueous resin composition was obtained.
(実施例9)
製造例A4で得られた水性樹脂分散体A4に実施例B1で得られた水溶性ポリマーB1を両者の固形分の質量比(A4/B1)が95/5となるように添加し、得られた混合物100部に架橋剤として5%のヒドラジン系架橋剤(アジピン酸ジヒドラジド)水溶液10部を添加することにより、水性樹脂組成物を得た。 Example 9
The water-soluble polymer B1 obtained in Example B1 was added to the aqueous resin dispersion A4 obtained in Production Example A4 so that the mass ratio (A4 / B1) of both solids was 95/5. An aqueous resin composition was obtained by adding 10 parts of a 5% hydrazine-based crosslinking agent (adipic acid dihydrazide) aqueous solution as a crosslinking agent to 100 parts of the obtained mixture.
製造例A4で得られた水性樹脂分散体A4に実施例B1で得られた水溶性ポリマーB1を両者の固形分の質量比(A4/B1)が95/5となるように添加し、得られた混合物100部に架橋剤として5%のヒドラジン系架橋剤(アジピン酸ジヒドラジド)水溶液10部を添加することにより、水性樹脂組成物を得た。 Example 9
The water-soluble polymer B1 obtained in Example B1 was added to the aqueous resin dispersion A4 obtained in Production Example A4 so that the mass ratio (A4 / B1) of both solids was 95/5. An aqueous resin composition was obtained by adding 10 parts of a 5% hydrazine-based crosslinking agent (adipic acid dihydrazide) aqueous solution as a crosslinking agent to 100 parts of the obtained mixture.
(実施例10)
製造例A5で得られた水性樹脂分散体A5に実施例B8で得られた水溶性ポリマーB8を両者の固形分の質量比(A5/B8)が97/3となるように添加し、得られた混合物100部に架橋剤としてオキサゾリン系架橋剤(エポクロスWS-500〔(株)日本触媒製〕)4部を添加することにより、水性樹脂組成物を得た。 (Example 10)
The water-soluble polymer B8 obtained in Example B8 was added to the aqueous resin dispersion A5 obtained in Production Example A5 so that the mass ratio (A5 / B8) of both solids was 97/3. By adding 4 parts of an oxazoline-based crosslinking agent (Epocross WS-500 [manufactured by Nippon Shokubai Co., Ltd.]) as a crosslinking agent to 100 parts of the mixture, an aqueous resin composition was obtained.
製造例A5で得られた水性樹脂分散体A5に実施例B8で得られた水溶性ポリマーB8を両者の固形分の質量比(A5/B8)が97/3となるように添加し、得られた混合物100部に架橋剤としてオキサゾリン系架橋剤(エポクロスWS-500〔(株)日本触媒製〕)4部を添加することにより、水性樹脂組成物を得た。 (Example 10)
The water-soluble polymer B8 obtained in Example B8 was added to the aqueous resin dispersion A5 obtained in Production Example A5 so that the mass ratio (A5 / B8) of both solids was 97/3. By adding 4 parts of an oxazoline-based crosslinking agent (Epocross WS-500 [manufactured by Nippon Shokubai Co., Ltd.]) as a crosslinking agent to 100 parts of the mixture, an aqueous resin composition was obtained.
(実施例11)
製造例A3で得られた水性樹脂分散体A3に実施例B4で得られた水溶性ポリマーB4を両者の固形分の質量比(A3/B4)が80/20となるように添加し、得られた混合物100部に架橋剤としてオキサゾリン系架橋剤(エポクロスWS-500〔(株)日本触媒製〕)4部、5%のヒドラジン系架橋剤(アジピン酸ジヒドラジド)水溶液10部を添加することにより、水性樹脂組成物を得た。 (Example 11)
The water-soluble polymer B4 obtained in Example B4 was added to the aqueous resin dispersion A3 obtained in Production Example A3 so that the mass ratio of both solids (A3 / B4) was 80/20. By adding 4 parts of an oxazoline-based crosslinking agent (Epocross WS-500 [manufactured by Nippon Shokubai Co., Ltd.]) as a crosslinking agent and 10 parts of a 5% aqueous solution of a hydrazine-based crosslinking agent (adipic acid dihydrazide) to 100 parts of the resulting mixture, An aqueous resin composition was obtained.
製造例A3で得られた水性樹脂分散体A3に実施例B4で得られた水溶性ポリマーB4を両者の固形分の質量比(A3/B4)が80/20となるように添加し、得られた混合物100部に架橋剤としてオキサゾリン系架橋剤(エポクロスWS-500〔(株)日本触媒製〕)4部、5%のヒドラジン系架橋剤(アジピン酸ジヒドラジド)水溶液10部を添加することにより、水性樹脂組成物を得た。 (Example 11)
The water-soluble polymer B4 obtained in Example B4 was added to the aqueous resin dispersion A3 obtained in Production Example A3 so that the mass ratio of both solids (A3 / B4) was 80/20. By adding 4 parts of an oxazoline-based crosslinking agent (Epocross WS-500 [manufactured by Nippon Shokubai Co., Ltd.]) as a crosslinking agent and 10 parts of a 5% aqueous solution of a hydrazine-based crosslinking agent (adipic acid dihydrazide) to 100 parts of the resulting mixture, An aqueous resin composition was obtained.
(比較例1)
製造例A1で得られた水性樹脂分散体A1に製造例B6で得られた水溶性ポリマーB6を両者の固形分の質量比(A1/B6)が97/3となるように添加し、得られた混合物100部に架橋剤として5%のヒドラジン系架橋剤(アジピン酸ジヒドラジド)水溶液10部を添加することにより、水性樹脂組成物を得た。 (Comparative Example 1)
The water-soluble polymer B6 obtained in Production Example B6 was added to the aqueous resin dispersion A1 obtained in Production Example A1 so that the mass ratio (A1 / B6) of both solids was 97/3. An aqueous resin composition was obtained by adding 10 parts of a 5% hydrazine-based crosslinking agent (adipic acid dihydrazide) aqueous solution as a crosslinking agent to 100 parts of the obtained mixture.
製造例A1で得られた水性樹脂分散体A1に製造例B6で得られた水溶性ポリマーB6を両者の固形分の質量比(A1/B6)が97/3となるように添加し、得られた混合物100部に架橋剤として5%のヒドラジン系架橋剤(アジピン酸ジヒドラジド)水溶液10部を添加することにより、水性樹脂組成物を得た。 (Comparative Example 1)
The water-soluble polymer B6 obtained in Production Example B6 was added to the aqueous resin dispersion A1 obtained in Production Example A1 so that the mass ratio (A1 / B6) of both solids was 97/3. An aqueous resin composition was obtained by adding 10 parts of a 5% hydrazine-based crosslinking agent (adipic acid dihydrazide) aqueous solution as a crosslinking agent to 100 parts of the obtained mixture.
(比較例2)
製造例A1で得られた水性樹脂分散体A1に製造例B7で得られた水溶性ポリマーB6を両者の固形分の質量比(A1/B7)が90/10となるように添加し、得られた混合物100部に架橋剤として5%のヒドラジン系架橋剤(アジピン酸ジヒドラジド)水溶液10部を添加することにより、水性樹脂組成物を得た。 (Comparative Example 2)
The water-soluble polymer B6 obtained in Production Example B7 was added to the aqueous resin dispersion A1 obtained in Production Example A1 so that the mass ratio (A1 / B7) of both solids was 90/10. An aqueous resin composition was obtained by adding 10 parts of a 5% hydrazine-based crosslinking agent (adipic acid dihydrazide) aqueous solution as a crosslinking agent to 100 parts of the obtained mixture.
製造例A1で得られた水性樹脂分散体A1に製造例B7で得られた水溶性ポリマーB6を両者の固形分の質量比(A1/B7)が90/10となるように添加し、得られた混合物100部に架橋剤として5%のヒドラジン系架橋剤(アジピン酸ジヒドラジド)水溶液10部を添加することにより、水性樹脂組成物を得た。 (Comparative Example 2)
The water-soluble polymer B6 obtained in Production Example B7 was added to the aqueous resin dispersion A1 obtained in Production Example A1 so that the mass ratio (A1 / B7) of both solids was 90/10. An aqueous resin composition was obtained by adding 10 parts of a 5% hydrazine-based crosslinking agent (adipic acid dihydrazide) aqueous solution as a crosslinking agent to 100 parts of the obtained mixture.
次に、水性樹脂組成物の物性を以下の方法に基づいて調べた。
Next, the physical properties of the aqueous resin composition were examined based on the following method.
〔耐候性〕
(1)評価用試料の調製
水性樹脂組成物100部に成膜助剤として2,2,4-トリメチル-1,3-ペンタンジオールイソブチレート〔JNC(株)製、品番:CS-12〕とブチルセロソルブを等量で混合することによって得られた混合溶液10部を添加し、ホモディスパーで回転速度1500回/分にて10分間撹拌した後、白色ペースト30部および消泡剤〔サンノプコ(株)製、商品名:ノプコ8034L〕0.5部を添加し、クレーブス単位粘度計(ブルックフィールド社製、品番:KU-1)を用いて25℃で測定したときの粘度が80KUとなるように増粘剤〔(株)日本触媒製、商品名:アクリセットWR-503A〕を添加し、その状態で30分間撹拌することにより、試料を調製した。 〔Weatherability〕
(1) Preparation of evaluation sample 2,2,4-trimethyl-1,3-pentanediol isobutyrate (product number: CS-12, manufactured by JNC Corporation) as a film-forming auxiliary agent in 100 parts of an aqueous resin composition 10 parts of a mixed solution obtained by mixing butyl cellosolve in equal amounts and stirring with a homodisper at a rotation speed of 1500 times / minute for 10 minutes, followed by 30 parts of white paste and an antifoaming agent [Sannopco Corp. Product name: NOPCO 8034L] 0.5 part is added so that the viscosity is 80 KU when measured at 25 ° C. using a Craves unit viscometer (Brookfield, product number: KU-1). A sample was prepared by adding a thickener [manufactured by Nippon Shokubai Co., Ltd., trade name: ACRRESET WR-503A] and stirring in that state for 30 minutes.
(1)評価用試料の調製
水性樹脂組成物100部に成膜助剤として2,2,4-トリメチル-1,3-ペンタンジオールイソブチレート〔JNC(株)製、品番:CS-12〕とブチルセロソルブを等量で混合することによって得られた混合溶液10部を添加し、ホモディスパーで回転速度1500回/分にて10分間撹拌した後、白色ペースト30部および消泡剤〔サンノプコ(株)製、商品名:ノプコ8034L〕0.5部を添加し、クレーブス単位粘度計(ブルックフィールド社製、品番:KU-1)を用いて25℃で測定したときの粘度が80KUとなるように増粘剤〔(株)日本触媒製、商品名:アクリセットWR-503A〕を添加し、その状態で30分間撹拌することにより、試料を調製した。 〔Weatherability〕
(1) Preparation of evaluation sample 2,2,4-trimethyl-1,3-pentanediol isobutyrate (product number: CS-12, manufactured by JNC Corporation) as a film-forming auxiliary agent in 100 parts of an aqueous resin composition 10 parts of a mixed solution obtained by mixing butyl cellosolve in equal amounts and stirring with a homodisper at a rotation speed of 1500 times / minute for 10 minutes, followed by 30 parts of white paste and an antifoaming agent [Sannopco Corp. Product name: NOPCO 8034L] 0.5 part is added so that the viscosity is 80 KU when measured at 25 ° C. using a Craves unit viscometer (Brookfield, product number: KU-1). A sample was prepared by adding a thickener [manufactured by Nippon Shokubai Co., Ltd., trade name: ACRRESET WR-503A] and stirring in that state for 30 minutes.
なお、白色ペーストは、脱イオン水210部、分散剤〔花王(株)製、商品名:デモールEP〕60部、分散剤〔第一工業製薬(株)製、商品名:ディスコートN-14〕50部、湿潤剤〔花王(株)製、商品名:エマルゲンLS-106〕10部、プロピレングリコール60部、酸化チタン〔石原産業(株)製、品番:CR-95〕1000部およびガラスビーズ(直径:1mm)200部をホモディスパーで回転速度3000回/分にて60分間分散させることによって調製した。
The white paste consists of 210 parts of deionized water, 60 parts of a dispersant (trade name: Demol EP, manufactured by Kao Corporation), and a dispersant (trade name: DISCOAT N-14, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). ] 50 parts, 10 parts of wetting agent [trade name: Emulgen LS-106], propylene glycol 60 parts, titanium oxide [product of Ishihara Sangyo Co., Ltd., product number: CR-95] 1000 parts and glass beads It was prepared by dispersing 200 parts (diameter: 1 mm) with a homodisper at a rotational speed of 3000 times / minute for 60 minutes.
(2)評価用被膜の作製および試験
スレート板〔日本テストパネル(株)製、縦:70mm、横:150mm、厚さ:6mm〕にシーラー〔エスケー化研(株)製、商品名:EXシーラー〕をエアスプレーで150g/m2の塗布量で均一に塗布し、23℃で1週間乾燥させた。 (2) Preparation and Test of Evaluation Coating Film A slate plate (manufactured by Nippon Test Panel Co., Ltd., length: 70 mm, width: 150 mm, thickness: 6 mm) and sealer [manufactured by SK Kaken Co., Ltd., trade name: EX sealer ] Was uniformly applied by air spray at an application amount of 150 g / m 2 and dried at 23 ° C. for 1 week.
スレート板〔日本テストパネル(株)製、縦:70mm、横:150mm、厚さ:6mm〕にシーラー〔エスケー化研(株)製、商品名:EXシーラー〕をエアスプレーで150g/m2の塗布量で均一に塗布し、23℃で1週間乾燥させた。 (2) Preparation and Test of Evaluation Coating Film A slate plate (manufactured by Nippon Test Panel Co., Ltd., length: 70 mm, width: 150 mm, thickness: 6 mm) and sealer [manufactured by SK Kaken Co., Ltd., trade name: EX sealer ] Was uniformly applied by air spray at an application amount of 150 g / m 2 and dried at 23 ° C. for 1 week.
次に、試料を10milアプリケーターでスレートの被膜上に塗布し、23℃にて1週間乾燥させた後、当該試料が塗布されたスレート板の側面および背面をアルミニウムテープでシールし、試料が塗布された面の60°鏡面光沢を光沢計〔日本電色工業(株)製、品番:VG-7000〕で測定し、さらに以下の条件を1サイクルとして連続で1000時間繰り返す耐候性試験を行ない、前記光沢計で当該スレート板の塗装面の光沢を測定し、式:
[光沢保持率(%)]=
〔[耐候性試験後の光沢]÷[耐候性試験前の光沢]〕×100
に基づいて光沢保持率を求め、以下の評価基準に基づいて耐候性を評価した。 Next, the sample was applied on the slate film with a 10 mil applicator and dried at 23 ° C. for 1 week, and then the side and back of the slate plate on which the sample was applied were sealed with aluminum tape, and the sample was applied. The 60 ° specular gloss of the surface was measured with a gloss meter (manufactured by Nippon Denshoku Industries Co., Ltd., product number: VG-7000), and the weather resistance test was repeated continuously for 1000 hours under the following conditions as one cycle. Measure the gloss of the painted surface of the slate plate with a gloss meter, formula:
[Gloss retention (%)] =
[[Gloss after weather resistance test] ÷ [Gloss before weather resistance test]] × 100
The gloss retention was determined based on the above, and the weather resistance was evaluated based on the following evaluation criteria.
[光沢保持率(%)]=
〔[耐候性試験後の光沢]÷[耐候性試験前の光沢]〕×100
に基づいて光沢保持率を求め、以下の評価基準に基づいて耐候性を評価した。 Next, the sample was applied on the slate film with a 10 mil applicator and dried at 23 ° C. for 1 week, and then the side and back of the slate plate on which the sample was applied were sealed with aluminum tape, and the sample was applied. The 60 ° specular gloss of the surface was measured with a gloss meter (manufactured by Nippon Denshoku Industries Co., Ltd., product number: VG-7000), and the weather resistance test was repeated continuously for 1000 hours under the following conditions as one cycle. Measure the gloss of the painted surface of the slate plate with a gloss meter, formula:
[Gloss retention (%)] =
[[Gloss after weather resistance test] ÷ [Gloss before weather resistance test]] × 100
The gloss retention was determined based on the above, and the weather resistance was evaluated based on the following evaluation criteria.
(耐候性試験の試験条件)
・試験機:メタルウェザー〔ダイプラ・ウィンテス(株)製、品番:KU-R4〕
・照射:気温65℃で相対湿度50%の雰囲気中で4時間照射(照射強度:80mW/cm2)
・湿潤:気温35℃で相対湿度98%の雰囲気中で4時間暴露
・シャワー:湿潤前後に各30秒間シャワー (Test conditions for weather resistance test)
・ Testing machine: Metal weather [Daipura Wintes Co., Ltd., product number: KU-R4]
・ Irradiation: Irradiation for 4 hours in an atmosphere with a temperature of 65 ° C. and a relative humidity of 50% (irradiation intensity: 80 mW / cm 2 )
-Wet: exposed for 4 hours in an atmosphere with a relative humidity of 98% at a temperature of 35 ° C-Shower: Shower for 30 seconds before and after wetting
・試験機:メタルウェザー〔ダイプラ・ウィンテス(株)製、品番:KU-R4〕
・照射:気温65℃で相対湿度50%の雰囲気中で4時間照射(照射強度:80mW/cm2)
・湿潤:気温35℃で相対湿度98%の雰囲気中で4時間暴露
・シャワー:湿潤前後に各30秒間シャワー (Test conditions for weather resistance test)
・ Testing machine: Metal weather [Daipura Wintes Co., Ltd., product number: KU-R4]
・ Irradiation: Irradiation for 4 hours in an atmosphere with a temperature of 65 ° C. and a relative humidity of 50% (irradiation intensity: 80 mW / cm 2 )
-Wet: exposed for 4 hours in an atmosphere with a relative humidity of 98% at a temperature of 35 ° C-Shower: Shower for 30 seconds before and after wetting
(評価基準)
○:光沢保持率が80%以上
△:光沢保持率が60%以上80%未満
×:光沢保持率が60%未満または測定不可能
〔耐水白化性〕
(1)評価用試料の調製
水性樹脂組成物100部に成膜助剤として2,2,4-トリメチル-1,3-ペンタンジオールイソブチレート〔JNC(株)製、品番:CS-12〕とブチルセロソルブを等質量で混合することによって得られた混合溶液10部を添加し、ホモディスパーで回転速度1500回/分にて10分間攪拌した後、消泡剤〔サンノプコ(株)製、商品名:ノプコ8034L〕0.5部を添加し、クレーブス単位粘度計(ブルックフィールド社製、品番:KU-1)を用いて25℃で測定したときの粘度が60KUになるように増粘剤〔(株)日本触媒製、商品名:アクリセットWR-503A〕を添加し、その状態で30分間攪拌することにより、試料を調製した。 (Evaluation criteria)
○: Gloss retention is 80% or more Δ: Gloss retention is 60% or more and less than 80% ×: Gloss retention is less than 60% or cannot be measured [water whitening resistance]
(1) Preparation of evaluation sample 2,2,4-trimethyl-1,3-pentanediol isobutyrate (product number: CS-12, manufactured by JNC Corporation) as a film-forming auxiliary agent in 100 parts of an aqueous resin composition 10 parts of a mixed solution obtained by mixing butyl cellosolve with equal mass and stirring with a homodisper at a rotation speed of 1500 times / minute for 10 minutes, followed by defoaming agent (trade name, manufactured by San Nopco Co., Ltd.) : Nopco 8034L] 0.5 part was added, and a thickener [((No .: KU-1 manufactured by Brookfield Co., Ltd.) was used to increase the viscosity to 60 KU when measured at 25 ° C. A product was manufactured by Nippon Shokubai Co., Ltd., trade name: Acryset WR-503A], and stirred in that state for 30 minutes to prepare a sample.
○:光沢保持率が80%以上
△:光沢保持率が60%以上80%未満
×:光沢保持率が60%未満または測定不可能
〔耐水白化性〕
(1)評価用試料の調製
水性樹脂組成物100部に成膜助剤として2,2,4-トリメチル-1,3-ペンタンジオールイソブチレート〔JNC(株)製、品番:CS-12〕とブチルセロソルブを等質量で混合することによって得られた混合溶液10部を添加し、ホモディスパーで回転速度1500回/分にて10分間攪拌した後、消泡剤〔サンノプコ(株)製、商品名:ノプコ8034L〕0.5部を添加し、クレーブス単位粘度計(ブルックフィールド社製、品番:KU-1)を用いて25℃で測定したときの粘度が60KUになるように増粘剤〔(株)日本触媒製、商品名:アクリセットWR-503A〕を添加し、その状態で30分間攪拌することにより、試料を調製した。 (Evaluation criteria)
○: Gloss retention is 80% or more Δ: Gloss retention is 60% or more and less than 80% ×: Gloss retention is less than 60% or cannot be measured [water whitening resistance]
(1) Preparation of evaluation sample 2,2,4-trimethyl-1,3-pentanediol isobutyrate (product number: CS-12, manufactured by JNC Corporation) as a film-forming auxiliary agent in 100 parts of an aqueous resin composition 10 parts of a mixed solution obtained by mixing butyl cellosolve with equal mass and stirring with a homodisper at a rotation speed of 1500 times / minute for 10 minutes, followed by defoaming agent (trade name, manufactured by San Nopco Co., Ltd.) : Nopco 8034L] 0.5 part was added, and a thickener [((No .: KU-1 manufactured by Brookfield Co., Ltd.) was used to increase the viscosity to 60 KU when measured at 25 ° C. A product was manufactured by Nippon Shokubai Co., Ltd., trade name: Acryset WR-503A], and stirred in that state for 30 minutes to prepare a sample.
(2)評価用被膜の作製および試験
スレート板〔日本テストパネル(株)製、縦:70mm、横:150mm、厚さ:6mm〕にシーラー〔エスケー化研(株)製、商品名:EXシーラー]をエアスプレーで150g/m2の塗布量で均一に塗布し、23℃で1週間乾燥させた。 (2) Preparation and Test of Evaluation Coating Film A slate plate [manufactured by Nippon Test Panel Co., Ltd., length: 70 mm, width: 150 mm, thickness: 6 mm] on a sealer [manufactured by SK Kaken Co., Ltd., trade name: EX sealer ] By air spray at a coating amount of 150 g / m 2 and dried at 23 ° C. for 1 week.
スレート板〔日本テストパネル(株)製、縦:70mm、横:150mm、厚さ:6mm〕にシーラー〔エスケー化研(株)製、商品名:EXシーラー]をエアスプレーで150g/m2の塗布量で均一に塗布し、23℃で1週間乾燥させた。 (2) Preparation and Test of Evaluation Coating Film A slate plate [manufactured by Nippon Test Panel Co., Ltd., length: 70 mm, width: 150 mm, thickness: 6 mm] on a sealer [manufactured by SK Kaken Co., Ltd., trade name: EX sealer ] By air spray at a coating amount of 150 g / m 2 and dried at 23 ° C. for 1 week.
次に、前記で得られた試料を6milアプリケーターでスレート板の被膜上に塗布し、23℃にて1週間乾燥させた。
Next, the sample obtained above was applied onto a slate plate coating with a 6 mil applicator and dried at 23 ° C. for 1 week.
試験板のL値(L0)を色差計〔日本電色工業(株)製、品番:ZE-6000〕で測定し、さらにこの試験板を23℃の水に24時間浸漬させた後、水から引き上げ、キムタオル〔日本製紙クレシア(株)製〕で水分を拭き取り、1分間以内に前記色差計でL値(L1)を測定した。
The L value (L 0 ) of the test plate was measured with a color difference meter [manufactured by Nippon Denshoku Industries Co., Ltd., product number: ZE-6000], and this test plate was immersed in water at 23 ° C. for 24 hours, The water content was wiped off with Kim Towel (manufactured by Nippon Paper Crecia Co., Ltd.), and the L value (L 1 ) was measured with the color difference meter within 1 minute.
次に、L値の変化値を式:
ΔL=(L1)-(L0)
に基づいて求め、以下の評価基準に基づいて評価した。 Next, the change value of the L value is expressed by the formula:
ΔL = (L 1 ) − (L 0 )
And evaluated based on the following evaluation criteria.
ΔL=(L1)-(L0)
に基づいて求め、以下の評価基準に基づいて評価した。 Next, the change value of the L value is expressed by the formula:
ΔL = (L 1 ) − (L 0 )
And evaluated based on the following evaluation criteria.
[評価基準]
○:ΔLが5未満
△:ΔLが5以上10未満
×:ΔLが10以上 [Evaluation criteria]
○: ΔL is less than 5 Δ: ΔL is 5 or more and less than 10 x: ΔL is 10 or more
○:ΔLが5未満
△:ΔLが5以上10未満
×:ΔLが10以上 [Evaluation criteria]
○: ΔL is less than 5 Δ: ΔL is 5 or more and less than 10 x: ΔL is 10 or more
〔耐汚染性(1)、(2)〕
(1)評価用試料の調製
水性樹脂組成物100部に成膜助剤として2,2,4-トリメチル-1,3-ペンタンジオールイソブチレート〔JNC(株)製、品番:CS-12〕とブチルセロソルブを等質量で混合することによって得られた混合溶液10部を添加し、ホモディスパーで回転速度1500回/分にて10分間撹拌した後、白色ペースト30部および消泡剤〔サンノプコ(株)製、商品名:ノプコ8034L〕0.5部を添加し、クレーブス単位粘度計(ブルックフィールド社製、品番:KU-1)を用いて25℃で測定したときの粘度が80KUとなるように増粘剤〔(株)日本触媒製、商品名:アクリセットWR-503A〕を添加し、その状態で30分間撹拌することにより、試料を調製した。 [Contamination resistance (1), (2)]
(1) Preparation of evaluation sample 2,2,4-trimethyl-1,3-pentanediol isobutyrate (product number: CS-12, manufactured by JNC Corporation) as a film-forming auxiliary agent in 100 parts of an aqueous resin composition 10 parts of a mixed solution obtained by mixing butyl cellosolve with equal mass and stirring with a homodisper at a rotation speed of 1500 times / minute for 10 minutes, followed by 30 parts of white paste and an antifoaming agent [Sannopco Corp. Product name: NOPCO 8034L] 0.5 part is added so that the viscosity is 80 KU when measured at 25 ° C. using a Craves unit viscometer (Brookfield, product number: KU-1). A sample was prepared by adding a thickener [manufactured by Nippon Shokubai Co., Ltd., trade name: ACRRESET WR-503A] and stirring in that state for 30 minutes.
(1)評価用試料の調製
水性樹脂組成物100部に成膜助剤として2,2,4-トリメチル-1,3-ペンタンジオールイソブチレート〔JNC(株)製、品番:CS-12〕とブチルセロソルブを等質量で混合することによって得られた混合溶液10部を添加し、ホモディスパーで回転速度1500回/分にて10分間撹拌した後、白色ペースト30部および消泡剤〔サンノプコ(株)製、商品名:ノプコ8034L〕0.5部を添加し、クレーブス単位粘度計(ブルックフィールド社製、品番:KU-1)を用いて25℃で測定したときの粘度が80KUとなるように増粘剤〔(株)日本触媒製、商品名:アクリセットWR-503A〕を添加し、その状態で30分間撹拌することにより、試料を調製した。 [Contamination resistance (1), (2)]
(1) Preparation of evaluation sample 2,2,4-trimethyl-1,3-pentanediol isobutyrate (product number: CS-12, manufactured by JNC Corporation) as a film-forming auxiliary agent in 100 parts of an aqueous resin composition 10 parts of a mixed solution obtained by mixing butyl cellosolve with equal mass and stirring with a homodisper at a rotation speed of 1500 times / minute for 10 minutes, followed by 30 parts of white paste and an antifoaming agent [Sannopco Corp. Product name: NOPCO 8034L] 0.5 part is added so that the viscosity is 80 KU when measured at 25 ° C. using a Craves unit viscometer (Brookfield, product number: KU-1). A sample was prepared by adding a thickener [manufactured by Nippon Shokubai Co., Ltd., trade name: ACRRESET WR-503A] and stirring in that state for 30 minutes.
なお、白色ペーストは、脱イオン水210部、分散剤〔花王(株)製、商品名:デモールEP〕60部、分散剤〔第一工業製薬(株)製、商品名:ディスコートN-14〕50部、湿潤剤〔花王(株)製、商品名:エマルゲンLS-106〕10部、プロピレングリコール60部、酸化チタン〔石原産業(株)製、品番:CR-95〕1000部およびガラスビーズ(直径:1mm)200部をホモディスパーで回転速度3000回/分にて60分間分散させることによって調製した。
The white paste consists of 210 parts of deionized water, 60 parts of a dispersant (trade name: Demol EP, manufactured by Kao Corporation), and a dispersant (trade name: DISCOAT N-14, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). ] 50 parts, 10 parts of wetting agent [trade name: Emulgen LS-106], propylene glycol 60 parts, titanium oxide [product of Ishihara Sangyo Co., Ltd., product number: CR-95] 1000 parts and glass beads It was prepared by dispersing 200 parts (diameter: 1 mm) with a homodisper at a rotational speed of 3000 times / minute for 60 minutes.
(2)評価用被膜の作製および試験
アルミ板〔日本テストパネル(株)製、縦:400mm、横:100mm、厚さ:1mm〕に上記白色塗料を6milアプリケーターで2回塗布し、23℃で1週間乾燥させた。 (2) Preparation and test of coating for evaluation The above white paint was applied to an aluminum plate [manufactured by Nippon Test Panel Co., Ltd., length: 400 mm, width: 100 mm, thickness: 1 mm] with a 6 mil applicator at 23 ° C. Dry for 1 week.
アルミ板〔日本テストパネル(株)製、縦:400mm、横:100mm、厚さ:1mm〕に上記白色塗料を6milアプリケーターで2回塗布し、23℃で1週間乾燥させた。 (2) Preparation and test of coating for evaluation The above white paint was applied to an aluminum plate [manufactured by Nippon Test Panel Co., Ltd., length: 400 mm, width: 100 mm, thickness: 1 mm] with a 6 mil applicator at 23 ° C. Dry for 1 week.
試験板を縦方向に半分のところ(200mm)で南面30度の傾斜がつくように折り曲げた。試験板の斜面の部位に関して初期L値(L0)を色差計〔日本電色工業(株)製、品番:ZE-6000〕で測定し、JIS Z2381(大気暴露試験方法通則)に準じ、以下の条件にて屋外暴露試験を行った。3ヵ月後、6ヵ月後に試験板を引き上げ、上記色差計で試験板の斜面の部位に関してL値(L1)を測定した。
-試験条件-
(南面30度、直接暴露(暴露地:大阪府吹田市/(株)日本触媒敷地内))。 The test plate was bent so as to have an inclination of 30 degrees on the south surface at half (200 mm) in the vertical direction. The initial L value (L 0 ) of the sloped part of the test plate was measured with a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., product number: ZE-6000), and in accordance with JIS Z2381 (general rules for atmospheric exposure test methods) An outdoor exposure test was conducted under the following conditions. After 3 months and 6 months, the test plate was pulled up, and the L value (L 1 ) was measured with respect to the slope portion of the test plate with the color difference meter.
-Test conditions-
(South surface 30 degrees, direct exposure (exposure location: Suita City, Osaka / Nippon Catalyst Co., Ltd.)).
-試験条件-
(南面30度、直接暴露(暴露地:大阪府吹田市/(株)日本触媒敷地内))。 The test plate was bent so as to have an inclination of 30 degrees on the south surface at half (200 mm) in the vertical direction. The initial L value (L 0 ) of the sloped part of the test plate was measured with a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., product number: ZE-6000), and in accordance with JIS Z2381 (general rules for atmospheric exposure test methods) An outdoor exposure test was conducted under the following conditions. After 3 months and 6 months, the test plate was pulled up, and the L value (L 1 ) was measured with respect to the slope portion of the test plate with the color difference meter.
-Test conditions-
(South surface 30 degrees, direct exposure (exposure location: Suita City, Osaka / Nippon Catalyst Co., Ltd.)).
次に、L値の変化値を式:
ΔL=(L1)-(L0)
に基づいて求め、以下の評価基準に基づいて斜面部の耐汚染性を評価した。 Next, the change value of the L value is expressed by the formula:
ΔL = (L 1 ) − (L 0 )
The contamination resistance of the slope was evaluated based on the following evaluation criteria.
ΔL=(L1)-(L0)
に基づいて求め、以下の評価基準に基づいて斜面部の耐汚染性を評価した。 Next, the change value of the L value is expressed by the formula:
ΔL = (L 1 ) − (L 0 )
The contamination resistance of the slope was evaluated based on the following evaluation criteria.
[耐汚染性(1)(斜面の耐汚染性)評価基準]
○:ΔLが5未満
△:ΔLが5以上10未満
×:ΔLが10以上 [Contamination Resistance (1) (Slope Contamination Resistance) Evaluation Criteria]
○: ΔL is less than 5 Δ: ΔL is 5 or more and less than 10 x: ΔL is 10 or more
○:ΔLが5未満
△:ΔLが5以上10未満
×:ΔLが10以上 [Contamination Resistance (1) (Slope Contamination Resistance) Evaluation Criteria]
○: ΔL is less than 5 Δ: ΔL is 5 or more and less than 10 x: ΔL is 10 or more
次に、試験板の垂直部位に関して雨筋汚染性を目視により以下の評価基準で評価した。
Next, rain stripe contamination was visually evaluated on the vertical part of the test plate according to the following evaluation criteria.
[耐汚染性(2)(垂直面の耐汚染性(雨筋汚染性))評価基準]
○:雨筋が見られない
△:薄い雨筋が見られる
×:濃い雨筋が見られる [Contamination Resistance (2) (Vertical Surface Pollution Resistance (Rainline Contamination) Evaluation Criteria)]
○: No rain stripes are seen △: Light rain stripes are seen ×: Dark rain stripes are seen
○:雨筋が見られない
△:薄い雨筋が見られる
×:濃い雨筋が見られる [Contamination Resistance (2) (Vertical Surface Pollution Resistance (Rainline Contamination) Evaluation Criteria)]
○: No rain stripes are seen △: Light rain stripes are seen ×: Dark rain stripes are seen
〔総合評価〕
前記各物性の評価において、○の評価を5点、△の評価を3点、×の評価を0点とし、各得点を合計することにより、総合得点を求めた。 〔Comprehensive evaluation〕
In the evaluation of each physical property, an evaluation of “◯” was 5 points, an evaluation of “Δ” was 3 points, an evaluation of “x” was 0 points, and the total score was obtained by summing up each score.
前記各物性の評価において、○の評価を5点、△の評価を3点、×の評価を0点とし、各得点を合計することにより、総合得点を求めた。 〔Comprehensive evaluation〕
In the evaluation of each physical property, an evaluation of “◯” was 5 points, an evaluation of “Δ” was 3 points, an evaluation of “x” was 0 points, and the total score was obtained by summing up each score.
結果を表1及び表2に示す。なお、表において、「OX」とはエポクロスWS-500(オキサゾリン系架橋剤)、「ADH」とはアジピン酸ジヒドラジド(ヒドラジン系架橋剤)を、それぞれ示す。
Results are shown in Tables 1 and 2. In the table, “OX” represents Epocros WS-500 (oxazoline-based crosslinking agent), and “ADH” represents adipic acid dihydrazide (hydrazine-based crosslinking agent).
上記表の結果から明らかなように、実施例のポリマー及び組成物によれば、長期親水性をはじめとして、優れた塗膜性能を実現できた。
As is clear from the results in the above table, according to the polymers and compositions of the examples, excellent coating performance including long-term hydrophilicity could be realized.
(実施例12)
製造例A1で得られた水性樹脂分散体(エマルション粒子)A1に実施例B1で得られた水溶性ポリマーB1を両者の固形分の質量比(A1/B1)が50/50となるように添加し、水性樹脂組成物を得た。
得られた水性樹脂組成物の「耐汚染性(1)」及び「耐汚染性(2)」を、前記と同じ方法にて調べたところ、いずれの評価も「△」であった。 (Example 12)
The water-soluble polymer B1 obtained in Example B1 is added to the aqueous resin dispersion (emulsion particles) A1 obtained in Production Example A1 so that the mass ratio (A1 / B1) of both solids is 50/50. As a result, an aqueous resin composition was obtained.
When the “stain resistance (1)” and “stain resistance (2)” of the obtained aqueous resin composition were examined by the same method as described above, both evaluations were “Δ”.
製造例A1で得られた水性樹脂分散体(エマルション粒子)A1に実施例B1で得られた水溶性ポリマーB1を両者の固形分の質量比(A1/B1)が50/50となるように添加し、水性樹脂組成物を得た。
得られた水性樹脂組成物の「耐汚染性(1)」及び「耐汚染性(2)」を、前記と同じ方法にて調べたところ、いずれの評価も「△」であった。 (Example 12)
The water-soluble polymer B1 obtained in Example B1 is added to the aqueous resin dispersion (emulsion particles) A1 obtained in Production Example A1 so that the mass ratio (A1 / B1) of both solids is 50/50. As a result, an aqueous resin composition was obtained.
When the “stain resistance (1)” and “stain resistance (2)” of the obtained aqueous resin composition were examined by the same method as described above, both evaluations were “Δ”.
本発明は、塗料用などとして有用なポリマー及びこのポリマーを含む組成物を提供できる。
The present invention can provide a polymer useful for coatings and the like and a composition containing this polymer.
Claims (15)
- ビニルラクタム系モノマー及びヒンダードアミン系モノマーを少なくとも重合成分とするポリマー。 Polymers containing at least a vinyl lactam monomer and a hindered amine monomer as polymerization components.
- ヒンダードアミン系モノマーの割合が、ビニルラクタム系モノマー100モルに対して、0.01~15モルである請求項1記載のポリマー。 2. The polymer according to claim 1, wherein the ratio of the hindered amine monomer is 0.01 to 15 mol with respect to 100 mol of the vinyl lactam monomer.
- ビニルラクタム系モノマーの割合が重合成分全体の80モル%以上であり、ヒンダードアミン系モノマーの割合がビニルラクタム系モノマー100モルに対して0.05~10モルである請求項1又は2記載のポリマー。 The polymer according to claim 1 or 2, wherein the ratio of the vinyl lactam monomer is 80 mol% or more of the entire polymerization component, and the ratio of the hindered amine monomer is 0.05 to 10 mol with respect to 100 mol of the vinyl lactam monomer.
- 重合成分が、さらに、カルボニル基、酸基、カーボネート基、イソシアネート基、オキサゾリン基、オキサゾリジン基、ヒドラジノ基、エポキシ基、アミノ基、ヒドロキシル基、及びメルカプト基から選択された少なくとも1種の官能基を有する単量体を含む請求項1~3のいずれかに記載のポリマー。 The polymerization component further comprises at least one functional group selected from a carbonyl group, an acid group, a carbonate group, an isocyanate group, an oxazoline group, an oxazolidine group, a hydrazino group, an epoxy group, an amino group, a hydroxyl group, and a mercapto group. The polymer according to any one of claims 1 to 3, comprising a monomer having
- 重合成分が、さらに、カルボニル基含有単量体を含有する官能基を有する単量体を含む請求項1~3のいずれかに記載のポリマー。 The polymer according to any one of claims 1 to 3, wherein the polymerization component further comprises a monomer having a functional group containing a carbonyl group-containing monomer.
- 重合成分が、さらに、ダイアセトン(メタ)アクリルアミドを含有する官能基を含有する単量体を含む請求項1~3のいずれかに記載のポリマー。 The polymer according to any one of claims 1 to 3, wherein the polymerization component further contains a monomer containing a functional group containing diacetone (meth) acrylamide.
- エマルション(A)と、請求項1~6のいずれかに記載のポリマー(B)とを含む組成物。 A composition comprising an emulsion (A) and the polymer (B) according to any one of claims 1 to 6.
- エマルション(A)がアクリル系エマルションである請求項7記載の組成物。 The composition according to claim 7, wherein the emulsion (A) is an acrylic emulsion.
- エマルション(A)が、アニオン性である請求項7又は8記載の組成物。 The composition according to claim 7 or 8, wherein the emulsion (A) is anionic.
- エマルション(A)が、官能基αを有する単量体を含む単量体成分(a)を重合成分とする樹脂で構成され、ポリマー(B)の重合成分が、官能基αと架橋構造を形成しうる官能基βを有する単量体を含む請求項7~9のいずれかに記載の組成物。 The emulsion (A) is composed of a resin having a monomer component (a) containing a monomer having a functional group α as a polymerization component, and the polymerization component of the polymer (B) forms a crosslinked structure with the functional group α. The composition according to any one of claims 7 to 9, comprising a monomer having a functional group β that can be treated.
- エマルション(A)とポリマー(B)との割合が、前者/後者(質量比)=99/1~60/40である請求項7~10のいずれかに記載の組成物。 11. The composition according to claim 7, wherein the ratio of the emulsion (A) to the polymer (B) is the former / the latter (mass ratio) = 99/1 to 60/40.
- エマルション(A)及びポリマー(B)を含む塗料用水性組成物である請求項7~11のいずれかに記載の組成物。 The composition according to any one of claims 7 to 11, which is an aqueous composition for coatings comprising an emulsion (A) and a polymer (B).
- 請求項7~12のいずれかに記載の組成物で形成された塗膜。 A coating film formed from the composition according to any one of claims 7 to 12.
- 基材とこの基材上に形成された請求項13に記載の塗膜とで構成されたコート基材。 A coated substrate composed of a substrate and the coating film according to claim 13 formed on the substrate.
- エマルション(A)を含む組成物で形成された塗膜に対する耐汚染化剤であって、請求項1~6のいずれかに記載のポリマー(B)を含有する耐汚染化剤。 An antifouling agent for a coating film formed from a composition containing the emulsion (A), the antifouling agent containing the polymer (B) according to any one of claims 1 to 6.
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