WO2021045136A1 - Water-soluble (meth)acrylic resin and use thereof - Google Patents

Water-soluble (meth)acrylic resin and use thereof Download PDF

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Publication number
WO2021045136A1
WO2021045136A1 PCT/JP2020/033363 JP2020033363W WO2021045136A1 WO 2021045136 A1 WO2021045136 A1 WO 2021045136A1 JP 2020033363 W JP2020033363 W JP 2020033363W WO 2021045136 A1 WO2021045136 A1 WO 2021045136A1
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meth
acrylic resin
group
weight
water
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PCT/JP2020/033363
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French (fr)
Japanese (ja)
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宙是 横井
松尾　陽一
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株式会社カネカ
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Priority to JP2021544017A priority Critical patent/JPWO2021045136A1/ja
Publication of WO2021045136A1 publication Critical patent/WO2021045136A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • 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
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
    • C08L43/04—Homopolymers or copolymers of monomers containing silicon
    • 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
    • C09D143/00—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 containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon

Definitions

  • the present invention relates to a water-soluble (meth) acrylic resin and its use.
  • Patent Document 1 describes a polymerizable monomer, a specific silicon compound and / or a partially hydrolyzed condensate thereof, an emulsifying agent and / or a water-soluble polymer in the presence of seed particles dispersed in an aqueous medium.
  • a method for producing a resin emulsion composed of polymer particles containing a silicon compound and / or a partially hydrolyzed condensate thereof, which polymerizes while being absorbed, and an aqueous coating material containing the resin emulsion are disclosed.
  • the present invention has been made in view of the above problems, and an object of the present invention is that when used as a water-based paint, the coating film is excellent in transparency (glossiness), impregnation property (reinforcing property) and film forming property. It is an object of the present invention to provide a water-soluble (meth) acrylic resin having good storage stability and a technique for utilizing the same.
  • one aspect of the present invention is a (meth) acrylic resin having a hydrolyzable silyl group, further having a salt structure composed of a strong acid and a strong base, and being water-soluble.
  • resin having a hydrolyzable silyl group, further having a salt structure composed of a strong acid and a strong base, and being water-soluble.
  • the coating film when used as a water-based paint, is excellent in transparency (glossiness), impregnation property (reinforcing property) and film-forming property, and has good storage stability, and is water-soluble.
  • (Meta) acrylic resin and its utilization technology can be provided.
  • the (meth) acrylic resin (hereinafter, referred to as “the present acrylic resin”) according to one embodiment of the present invention is a (meth) acrylic resin having a hydrolyzable silyl group, and further comprises a strong acid. It has a salt structure composed of a strong base and is characterized by being water-soluble.
  • the conventional acrylic silicone resin is insoluble in water, it was necessary to disperse it as an emulsion using an emulsifier in order to obtain a composition for water-based paints.
  • the water-based paint containing the emulsion type acrylic silicone resin there is room for improvement in terms of the transparency (glossiness), impregnation property (reinforcing property) and film forming property of the coating film. It was presumed that this is because the particle size of the emulsion is relatively large, so that the acrylic silicone resin is not uniform on the coating film when the paint is applied, and does not sufficiently penetrate into the base material.
  • the present inventor conducted a study to improve the solubility of acrylic silicon resin in water in order to develop a water-based paint other than an emulsion-type water-based paint using an emulsifier.
  • increasing the water solubility of the acrylic silicone resin caused a new problem that the storage stability was lowered. It is considered that this is because the hydrolyzable silyl group in the acrylic silicone resin is hydrolyzed over time in the aqueous solvent.
  • the present acrylic resin may be a (meth) acrylic resin having a hydrolyzable silyl group, further having a salt structure composed of a strong acid and a strong base, and being water-soluble.
  • this acrylic resin Since this acrylic resin has the above-mentioned characteristic structure, it is excellent in storage stability, and when the (meth) acrylic resin is used as a water-based paint, the coating film obtained is transparent. Excellent in (glossiness), impregnation (reinforcing property) and film forming property.
  • strong acid means an electrolyte having an acid dissociation constant pKa of less than 0.
  • the strong acid is not particularly limited as long as it satisfies the above definition, and examples thereof include hydrochloric acid, sulfuric acid, nitric acid and the like.
  • the strong acid is preferably sulfuric acid.
  • strong base means an electrolyte having a base dissociation constant pKb of less than 0.
  • the strong base is not particularly limited as long as it satisfies the above definition, and examples thereof include sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide and the like.
  • the strong base is preferably sodium hydroxide, potassium hydroxide, calcium hydroxide.
  • the “salt structure” means the structure of a neutral salt obtained by neutralizing a strong acid and a strong base.
  • the salt structure is not particularly limited as long as it satisfies the above definition, and examples thereof include sodium sulfonate, potassium sulfonate, calcium sulfonate, and the like.
  • the salt structure is preferably sodium sulfonate.
  • water-soluble means that the haze value at 1 atm and 25 ° C. when the resin is dissolved or dispersed in water so that the solid content concentration is 20% is 20.0 or less. Means. The haze value is measured by the method described in Examples described later.
  • the "(meth) acrylic resin” means a resin containing acrylic as a main component, and 70% by weight or more of all the constituent units is a constituent unit derived from the (meth) acrylic monomer. preferable.
  • the (meth) acrylic resin is not particularly limited as long as it satisfies the above definition, and examples thereof include acrylic silicone resins and acrylic polyols.
  • the (meth) acrylic resin is preferably an acrylic silicone resin from the viewpoint of weather resistance.
  • the "hydrolyzable silyl group” means a hydrolyzable silyl group.
  • the hydrolyzable silyl group is not particularly limited as long as it satisfies the above definition, but for example, an alkoxysilyl group can be preferably exemplified, and examples of the alkoxy group contained in the alkoxysilyl group include a methoxysilyl (-SiOMe) group and an ethoxysilyl group. Examples thereof include a (-SiOEt) group, a propoxysilyl group, and a butoxysilyl group.
  • the hydrolyzable silyl group is preferably a dialkoxysilyl group or a trialkoxysilyl group.
  • the dialkoxysilyl group include a methyldiethoxysilyl group, an ethyldiethoxysilyl group, a methyldipropoxysilyl group, an ethyldipropoxysilyl group, a methyldibutoxysilyl group, an ethyldibutoxysilyl group and the like.
  • the trialkoxysilyl group include a trimethoxysilyl group, a triethoxysilyl group, a tripropoxysilyl group, and a tributoxysilyl group. From the viewpoints of storage stability, hydrolysis rate, availability and the like, an ethoxysilyl group is preferable, and a triethoxysilyl group is particularly preferable.
  • the acrylic resin has a salt structure consisting of a strong acid and a strong base as a constituent unit, and radical polymerization of at least one of a (meth) acryloyl group and a (meth) acrylamide group. It preferably contains a structural unit (a) derived from a monomer having a sex unsaturated group. From another point of view, it can be said that the present acrylic resin contains either a (meth) acryloyloxy unit or a (meth) acrylamide unit.
  • the acrylic resin has a salt structure composed of a strong acid and a strong base as a constituent unit, and at least one of a (meth) acryloyl group and a (meth) acrylamide group. It contains a structural unit (a) derived from a monomer having a radically polymerizable unsaturated group, and further comprises a structural unit (b) derived from a monomer having a hydrolyzable silyl group and a radically polymerizable unsaturated group. It is preferable to include a structural unit (c) derived from a monomer having a radically polymerizable unsaturated group other than the above (a) and (b).
  • constituent unit (b) derived from a monomer having a hydrolyzable silyl group and a radically polymerizable unsaturated group
  • constituent unit (b) the "constituent unit (b) derived from a monomer having a hydrolyzable silyl group and a radically polymerizable unsaturated group”
  • the (a) above the "constituent unit (c)" derived from a monomer having a radically polymerizable unsaturated group other than and (b) is simply referred to as a “constituent unit (c)".
  • the structural unit (a) is derived from a monomer having a salt structure consisting of a strong acid and a strong base and having a radically polymerizable unsaturated group of at least one of a (meth) acryloyl group and a (meth) acrylamide group. It consists of structural units.
  • the monomer from which the structural unit (a) is derived is bound to the structural unit (c) by a radical polymerization reaction.
  • the monomer from which the structural unit (a) is derived has a salt structure consisting of a strong acid and a strong base, this acrylic resin is excellent in storage stability even though it is water-soluble.
  • the monomer from which the structural unit (a) is derived has a radically polymerizable unsaturated group of at least one of a (meth) acryloyl group and a (meth) acrylamide group, whereby the acrylic resin is copolymerized.
  • the polymerization stability becomes good and water solubility is developed.
  • the radical polymerization reaction rate is significantly slower than that of the structural unit (b) and the structural unit (c), so that water solubility is exhibited. do not do.
  • the monomer from which the structural unit (a) is derived has a salt structure consisting of a strong acid and a strong base, and is a radically polymerizable unsaturated group of at least one of a (meth) acryloyl group and a (meth) acrylamide group.
  • the monomer is not particularly limited as long as it has, but for example, 2- (methacryloyloxy) sodium ethanesulfonate, 2- (methacryloyloxy) polyalkylene oxide sulfonate sodium, acrylamide-t butyl sulfonate sodium, 2-( Potassium methacryloxy) ethanesulfonate, potassium 2- (methacryloyloxy) polyalkylene oxide sulfonate, potassium acrylamide-t butylsulfonate, calcium 2- (methacryloyloxy) ethanesulfonate, 2- (methacryloyloxy) polyalkylene oxide sulfone
  • Examples thereof include calcium acid, acrylamide-t butyl sulfonate, calcium and the like.
  • the monomer from which the structural unit (a) is derived can be obtained as a commercially available product.
  • commercially available products include "Antox MS-2N-D” manufactured by Nippon Emulsion Co., Ltd., “ATBS-Na” manufactured by Toagosei Co., Ltd., and "Ereminol RS-3000” manufactured by Sanyo Chemical Industries, Ltd. , Etc. can be mentioned.
  • the content of the structural unit (a) is, for example, 6% by weight or more, preferably 7% by weight or more, based on the total amount of the above (a) to (c). , More preferably 8% by weight or more, particularly preferably 9% by weight or more, and particularly preferably 10% by weight or more.
  • the upper limit of the content of the structural unit (a) is not particularly limited as long as the effect of the present invention is exhibited, but is, for example, 50% by weight or less, preferably 30% by weight or less, and more preferably 20% by weight. It is 5% by weight or less, and particularly preferably 15% by weight or less.
  • the structural unit (b) is composed of a structural unit derived from a monomer having a hydrolyzable silyl group and a radically polymerizable unsaturated group.
  • the compound from which the structural unit (b) is derived is bound to the structural unit (c) by a radical polymerization reaction.
  • the compound from which the structural unit (b) is derived is not particularly limited as long as it is a monomer having a hydrolyzable silyl group and a radically polymerizable unsaturated group. Radical compounds can be mentioned.
  • R 1 is a monovalent organic group having 5 to 10 carbon atoms having a polymerizable double bond
  • R 2 is an alkyl group having 1 to 4 carbon atoms
  • X is an alkyl group having 1 to 4 carbon atoms. It is an alkoxyl group of ⁇ 4, and n is 1, 2 or 3). That is, the organic silicon compound is a compound having 1 to 3 alkoxyl groups and having a reactive double bond.
  • ⁇ - (meth) acryloxypropyltrimethoxysilane ⁇ - (meth) acryloxypropyltriethoxysilane, ⁇ - (meth) acryloxypropyltripropoxysilane, and ⁇ - (meth) acry.
  • examples thereof include loxypropylmethyldibutoxysilane. These compounds may be used alone or in combination of two or more.
  • the carbon number of X is preferably 2 to 4 from the viewpoint of storage stability, and the carbon number of X is preferably 2 from the viewpoint of storage stability and hydrolysis rate.
  • the compound from which the structural unit (b) is derived can be obtained as a commercially available product.
  • Examples of such commercial products include "A-174" manufactured by Momentive Performance Materials Japan LLC, "Z-6033” manufactured by Dow Toray Co., Ltd., and Momentive Performance Materials Japan.
  • Examples include "Y-9936” manufactured by a limited liability company.
  • the content of the structural unit (b) is, for example, 1% by weight or more, preferably 3% by weight or more, based on the total amount of the above (a) to (c). , More preferably 5% by weight or more.
  • the upper limit of the content of the structural unit (b) is not particularly limited as long as the effect of the present invention is exhibited, but is, for example, 30% by weight or less, preferably 20% by weight or less, and more preferably 15. It is 10% by weight or less, particularly preferably 10% by weight or less.
  • the structural unit (c) is composed of a structural unit derived from a monomer having a radically polymerizable unsaturated group other than the above (a) and (b).
  • the monomer from which the structural unit (c) is derived is bonded to the structural unit (a) and the structural unit (b) by a radical polymerization reaction.
  • the monomer from which the structural unit (c) is derived is not particularly limited as long as it is a monomer having a radically polymerizable unsaturated group other than the above (a) and (b), and is shown below, for example.
  • Examples thereof include monomers other than the (meth) acrylic acid alkyl ester and the (meth) acrylic acid alkyl ester.
  • the (meth) acrylic acid alkyl ester is a (meth) acrylic acid ester having an alkyl group having 1 to 18 carbon atoms and does not contain a functional group such as a hydroxyl group or an epoxy group (meth). ) It can be an alkyl monomer.
  • the alkyl group in the (meth) acrylic acid alkyl ester may be linear or branched, or may be a cyclic cycloalkyl group.
  • Cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) methacrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, isobonyl (meth) acrylate and the like can be mentioned.
  • the monomer other than the (meth) acrylic acid alkyl ester include a nitrile group-containing radical polymerizable monomer such as (meth) acrylonitrile; an epoxy group-containing radical polymerizable monomer such as glycidyl (meth) acrylate; 2-Hydroxypropyl (meth) acrylate; 2-hydroxypropyl (meth) acrylate; radically polymerizable monomer having hydrophilicity such as 2-sulfoethyl methacrylateammonium, radically polymerizable monomer having a polyoxyalkylene chain; Monomer having two or more polymerizable unsaturated bonds such as polyethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, and allyl (meth) acrylate; trifluoro (meth) acrylate, pentafluoro (meth) Examples thereof include flu
  • the radically polymerizable monomer having the polyoxyalkylene chain is not particularly limited, but an acrylic acid ester or a methacrylic acid ester having a polyoxyalkylene chain is preferable. Specific examples thereof include Bremmer PE-90, PE-200, PE-350, AE-90, AE-200, AE-350, PP-500, PP-800, PP-1000 manufactured by Nippon Oil & Fats Co., Ltd.
  • MPG-130MA RMA-150M, RMA-300M, RMA-450M, RA-1020, RA-1120, RA-1820, NK-ESTER M-20G, M-40G, M-90G manufactured by Shin Nakamura Chemical Industry Co., Ltd. , M-230G, AMP-10G, AMP-20G, AMP-60G, AM-90G, LA and the like.
  • the content of the structural unit (c) is, for example, 30% by weight or more, preferably 50% by weight or more, based on the total amount of the above (a) to (c). , More preferably 60% by weight or more.
  • the upper limit of the content of the structural unit (c) is not particularly limited as long as the effect of the present invention is exhibited, but is, for example, 93% by weight or less, preferably 90% by weight or less, and more preferably 85% by weight. It is 0% by weight or less, and particularly preferably 80% by weight or less.
  • the average molecular weight of the structural unit (c) is, for example, in the range of 1,000 to 1,000,000 in terms of number average molecular weight (Mn), more preferably 10,000 to 200,000.
  • Mn number average molecular weight
  • the haze value of the acrylic resin may be 20.0 or less, which is the standard of water solubility in the present specification, when measured by the method described in Examples described later. It is preferably 15.0 or less, and more preferably 13.0 or less.
  • the storage stability of the acrylic resin is, for example, 2 weeks or more when measured by the method described in Examples described later. When the storage stability is within the above range, the storage stability is excellent.
  • the minimum film formation temperature of the acrylic resin is, for example, less than 15 ° C., preferably 10 ° C. or lower, when measured by the method described in Examples described later. More preferably, it is 5 ° C. or lower, and particularly preferably 0 ° C. or lower. When the minimum film forming temperature is within the above range, it can be used as a coating material having high film forming property.
  • the water-based paint according to the embodiment of the present invention (hereinafter, referred to as “the water-based paint”) is described in the above [2.
  • (Meta) Acrylic Resin] is a water-based paint containing the (meth) acrylic resin. This water-based paint has excellent storage stability, and when used as a water-based paint, the resulting coating film is a (meth) acrylic type with excellent transparency (glossiness), impregnation (reinforcing property), and film-forming property. Since it contains a resin, it is useful in paint applications.
  • This water-based paint is [2.
  • a curing catalyst may be contained.
  • the cross-linking reaction is promoted by adding a curing catalyst that promotes the hydrolysis-condensation reaction of the alkoxysilyl group.
  • the curing catalyst is not particularly limited, and examples thereof include organometallic compounds, acidic catalysts, and basic catalysts. Among them, from the viewpoint of activity, an organotin compound, an acidic phosphoric acid ester, and a reaction product of an acidic phosphoric acid ester and an amine compound are preferable.
  • organic tin compound examples include dibutyltin dilaurate, dibutyltin dimarate, dibutyltin dioleylmalate, dioctyltin dilaurate, dibutyltin diacetate, dibutyltin dimethoxide, dibutyltin thioglycolate, and dibutyltin bisisononyl 3-mercaptopropio.
  • dibutyl tin thioglycolate dibutyl tin bisisononyl 3-mercaptopropionate
  • dibutyl tin bisisooctyl thioglycolate dibutyl tin bis 2-ethylhexyl thioglycolate
  • dimethyl tin bis dodecyl mercaptide, dibutyl tin bisdodecyl mercaptide, dimethyl tin bis (octylthioglucolate) salt and other mercaptides are preferred.
  • Examples of the acidic phosphoric acid ester compound include propyl acid phosphate, dibutyl phosphate, 2-ethylhexyl acid phosphate, di-2-ethylhexyl phosphate, monoisodecyl acid phosphate, diisodecyl phosphate, lauryl acid phosphate, stearyl acid phosphate and the like. ..
  • Examples of the amine compound that can react with the above acidic phosphate compound include triethylamine, n-butylamine, hexylamine, triethanolamine, diazabicycloundecene, and ammonia.
  • the amount of the curing catalyst added is preferably 0.1 to 10 parts by weight, particularly 0.5 to 5 parts by weight, based on 100 parts by weight of the solid content of the (meth) acrylic resin. Parts by weight are preferred. If it is less than 0.1 parts by weight, the curing activity is low, and if it exceeds 10 parts by weight, the pot life of the paint is shortened, and there is a concern that the water resistance and weather resistance of the coating film are lowered.
  • the present water-based paint may contain additives usually used in the technical field (particularly, the field of paint) as long as the effects of the present invention are exhibited.
  • additives include, for example, agents, fillers, plasticizers, film forming aids, wetting / dispersing agents, thickeners, antifoaming agents, preservatives, antioxidants, antioxidants, leveling agents, etc.
  • examples thereof include ultraviolet absorbers, antistatic agents, antifreeze agents, antibacterial agents, antifungal agents, tackifiers, rust preventives and the like.
  • As the additive only one kind may be contained, or two or more kinds may be contained. The amount of these additives can be appropriately set by those skilled in the art according to the purpose of use.
  • the above [2] An aqueous solution containing the (meth) acrylic resin described in [(Meta) Acrylic Resin] (hereinafter, referred to as “the present aqueous solution”) can be provided.
  • the "aqueous solution” means a solution containing a resin satisfying the above definition of "water-soluble” and in which water accounts for 40% by weight or more of the total medium. Therefore, the aqueous solution may contain a medium other than water (eg, solvent) in an amount of less than 10%.
  • a medium other than water eg, solvent
  • This aqueous solution has excellent storage stability, and when used as a water-based paint, the obtained coating film has an effect of excellent transparency (glossiness), impregnation property (reinforcing property), and film-forming property ( Since it contains a meta) acrylic resin, it is particularly useful in water-based paint applications.
  • the water content of the aqueous solution is, for example, 40% by weight or more, preferably 50% by weight or more, when measured by the method described in Examples described later. Preferably, it is 60% by weight or more. When the water content is within the above range, it can be used as a water-based paint.
  • the alcohol content of the aqueous solution is, for example, 10% by weight or less, preferably 8% by weight or less, as measured by the method described in Examples described later. Preferably, it is 5% by weight or less.
  • the alcohol content is within the above range, it can be used as a water-based paint.
  • the gloss value of the coating film when the aqueous solution is used is, for example, 65 or more, preferably 70 or more, when measured by the method described in Examples described later. , More preferably 75 or more.
  • the gloss value is within the above range, the appearance (gloss and transparency) of the coating film is excellent.
  • the above [2] A coating film obtained by curing the (meth) acrylic resin described in [(Meta) Acrylic Resin] can be provided.
  • the present coating film includes a coating film obtained by curing the above-mentioned water-based paint and a coating film obtained from the above-mentioned aqueous solution.
  • the method for producing a water-soluble (meth) acrylic resin according to an embodiment of the present invention has (A) a salt structure composed of a strong acid and a strong base, and has a salt structure.
  • a monomer having at least one of a (meth) acrylic group and a (meth) acrylamide group having a radically polymerizable unsaturated group and (B) a monomer having a hydrolyzable silyl group and a radically polymerizable unsaturated group.
  • the conventional acrylic silicone resin is insoluble in water, it was necessary to disperse it as an emulsion using an emulsifier in order to obtain a composition for water-based paints.
  • a mixed solvent of water and an organic solvent is used. Copolymerization inside is possible.
  • Copolymerization in a mixed solvent of water and an organic solvent in this production method can be carried out by a method known in the art.
  • a polymerization initiator is added to a mixture containing the monomer (A), the compound (B), and the monomer (C), and the mixture is in a mixed solvent of water and an organic solvent. Obtained by copolymerization.
  • the polymerization initiator is not particularly limited, but is, for example, 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2). -Methylbutyronitrile), tert-butylperoxypivalate, tert-butylperoxybenzoate, tert-butylperoxy-2-ethylhexanoate, di-tert-butylperoxide, cumenehydroperoxide, diisopropylper Oxycarbonate and the like can be mentioned.
  • the amount of the polymerization initiator used is, for example, 0.01 to 10 parts, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the total amount of the monomers. If the amount of the polymerization initiator used is less than 0.01 parts by weight, the polymerization may be difficult to proceed, and if it exceeds 10 parts by weight, the molecular weight of the produced polymer tends to decrease. is there.
  • the amount of the monomer of (A) is, for example, 6% by weight or more, preferably 7% by weight or more, based on the total amount of (A) to (C). Yes, more preferably 8% by weight or more, particularly preferably 9% by weight or more, and particularly preferably 10% by weight or more.
  • the upper limit of the amount of the monomer (A) is not particularly limited as long as the effect of the present invention is exhibited, but is, for example, 50% by weight or less, preferably 30% by weight or less, and more preferably. It is 20% by weight or less, and particularly preferably 15% by weight or less.
  • organic solvent used in the copolymerization examples include alcohol solvents such as methanol, ethanol, 2-propanol, 1-propanol, butanol and pentanol, water-soluble solvents such as acetone and tetrahydrofuran, and among them. , 2-Propanol is preferred.
  • water: organic solvent is preferably 1:10 to 8:10 by weight, and more preferably 2:10 to 5:10.
  • the polymerization temperature is, for example, 40 to 100 ° C., preferably 60 to 80 ° C., from the viewpoint of maintaining the stability of the mixed solution during polymerization and stably performing the polymerization. ..
  • the polymerization time is, for example, 3 hours or more, preferably 4 to 8 hours, from the viewpoint of maintaining the stability of the mixed solution during polymerization and stably performing the polymerization. is there.
  • the acrylic resin, the aqueous solution, and the water-based paint are used, for example, for interior and exterior of buildings, for automobiles such as clear on metallic base or metallic base, for direct coating of metals such as aluminum, stainless steel, and silver, slate, concrete, and roof tiles. Paints or top treatment agents for ceramics such as mortar, gypsum board, asbestos slate, asbestos board, precast concrete, lightweight aerated concrete, calcium silicate board, tile, brick, etc., for glass, natural marble, stone materials such as mikage stone, etc. It is preferably used as.
  • one aspect of the present invention includes the following inventions.
  • ⁇ 2> Derived from a monomer having a salt structure consisting of a strong acid and a strong base and having a radically polymerizable unsaturated group of at least one of a (meth) acryloyl group and a (meth) acrylamide group as a constituent unit.
  • the (meth) acrylic resin according to ⁇ 1> which comprises the structural unit (a) to be formed.
  • a structural unit (b) derived from a monomer having a hydrolyzable silyl group and a radically polymerizable unsaturated group and
  • the (meth) acrylic resin according to ⁇ 2> which comprises a structural unit (c) derived from a monomer having a radically polymerizable unsaturated group other than the above (a) and (b).
  • ⁇ 4> The (meth) acrylic according to ⁇ 2> or ⁇ 3>, wherein the structural unit (a) is 6% by weight or more and 50% by weight or less with respect to the total amount of the above (a) to (c). System resin.
  • the structural unit (b) is 1% by weight or more and 30% by weight or less with respect to the total amount of the (a) to (c), and the structural unit (c) is the above (a) to (c).
  • ⁇ 6> The (meth) acrylic system according to any one of ⁇ 1> to ⁇ 5>, wherein the salt structure is any one selected from the group consisting of sodium sulfonate, potassium sulfonate, and calcium sulfonate. resin.
  • ⁇ 7> The (meth) acrylic resin according to any one of ⁇ 1> to ⁇ 6>, wherein the hydrolyzable silyl group is an ethoxysilyl (-SiOEt) group.
  • ⁇ 8> The (meth) acrylic resin according to any one of ⁇ 1> to ⁇ 7>, wherein the hydrolyzable silyl group is a triethoxysilyl group.
  • ⁇ 9> When the (meth) acrylic resin is dissolved or dispersed in water so that the solid content concentration is 20%, the haze value at 1 atm and 25 ° C. is 20.0 or less.
  • ⁇ 10> An aqueous solution containing the (meth) acrylic resin according to any one of ⁇ 1> to ⁇ 9>.
  • ⁇ 12> A water-based paint containing the (meth) acrylic resin according to any one of ⁇ 1> to ⁇ 9>.
  • ⁇ 13> A coating film obtained by curing the (meth) acrylic resin according to any one of ⁇ 1> to ⁇ 9>.
  • a monomer having a salt structure consisting of (A) a strong acid and a strong base and having a radically polymerizable unsaturated group of at least one of a (meth) acryloyl group and a (meth) acrylamide group.
  • (B) Monomers having hydrolyzable silyl groups and radically polymerizable unsaturated groups
  • (C) A step of copolymerizing a monomer having a radically polymerizable unsaturated group other than the above (A) and (B) in a mixed solvent of water and an organic solvent, ⁇ 3> to ⁇ .
  • 9> The method for producing a water-soluble (meth) acrylic resin according to any one of 9.
  • MMA Methyl methacrylate
  • BA Butyl acrylate
  • TESMA Compound ⁇ -methacryloxypropyltriethoxysilane
  • AANa Compound ⁇ -methacryloxypropyltriethoxysilane
  • the polymerization stability (gelation during polymerization) was evaluated based on whether or not the thickening during polymerization caused the fluidity to be lost and stirring was impossible. The case where the polymerization was carried out without any problem was regarded as "possible”, and the case where the fluidity was lost due to the thickening during the polymerization and stirring became impossible was regarded as "impossible”.
  • the water content in the aqueous solution was measured by measuring the solid content concentration after distilling under reduced pressure and diluting with water.
  • Alcohol content The alcohol content in the aqueous solution was measured by measuring the solid content concentration before distilling under reduced pressure and diluting with water.
  • the water solubility of the (meth) acrylic resin was evaluated with reference to Japanese Patent No. 52527558. Briefly, the (meth) acrylic resin (copolymer) obtained in the synthetic example was diluted with pure water to bring the resin solid content concentration to 20%. The haze value of the (meth) acrylic resin was measured using pure water as a standard solution using COH400 manufactured by Nippon Denshoku Kogyo Co., Ltd. at 1 atm and 25 ° C. When the haze value was 20.0 or less, it was judged to be water-soluble (“ ⁇ ” in the table).
  • Storage stability A resin-containing aqueous solution adjusted to a solid content concentration of 40% was sealed in a glass bottle and allowed to stand in a hot air dryer heated to 25 ° C., and when the glass bottle was tilted 45 degrees, the fluidity of the internal solution was confirmed. Storage stability (room temperature gelation date) was evaluated with the time when it became impossible as the gelation point.
  • the minimum film formation temperature was measured using the minimum film formation temperature measuring device MFT-1 manufactured by Yoshimitsu Seiki. The lower the MFT, the higher the film forming property.
  • Adhesion test An adhesion test (a grid adhesion test) was performed with reference to Japanese Patent Application Laid-Open No. 2014-118557. Briefly, a calcium silicate board is coated with a resin having a solid content concentration of 30% in an amount of 100 g per square meter, and then cured at 23 ° C. and 50% RH for 1 week, in accordance with JIS K5600. Then, an adhesion test of a grid consisting of 25 squares at 1 mm intervals was performed. The evaluation was performed as follows based on the number of cells in which the resin remained on the calcium silicate plate after the test. The evaluation is good in the order of A, B, and C. That is, A is the best, B is good, and C is not.
  • a reactor equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas introduction tube and a dropping funnel is charged with the type and amount of component b shown in Table 1, and the temperature is 75 ° C. while introducing nitrogen gas.
  • a mixed solution of the type and amount of component a shown in Table 1 was added dropwise from the dropping funnel at a constant rate over 5 hours.
  • a mixed solution of the c component of the type and amount shown in Table 1 was added dropwise at a constant velocity over 1 hour. Then, after stirring continuously at 75 ° C.
  • a reactor equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas introduction tube and a dropping funnel is charged with the type and amount of component b shown in Table 1, and the temperature is 75 ° C. while introducing nitrogen gas.
  • a mixed solution of the type and amount of component a shown in Table 1 was added dropwise from the dropping funnel at a constant rate over 5 hours.
  • a mixed solution of the c component of the type and amount shown in Table 1 was added dropwise at a constant velocity over 1 hour. Then, the mixture was subsequently stirred at 75 ° C. for 2 hours and then cooled to room temperature to obtain a copolymer (A-9).
  • Examples 1 to 6 and Comparative Examples 1 to 3 Using each of the copolymers (A-1 to A-9) obtained in Synthesis Examples 1 to 9, various parameters were measured and / or evaluated by the method described above. The results are shown in Table 2. In addition, each copolymer (A-1 to A-9) corresponds to Examples 1 to 6 and Comparative Examples 1 to 3, respectively.
  • Comparative Example 1 since the amount of ATBS-Na was small (5% by weight), the gloss value was low, and the impregnation property (reinforcing property) was low, so that the adhesiveness was also poor. In addition, the minimum film forming temperature was high and the film forming property was inferior.
  • this acrylic resin When used as a water-based paint, this acrylic resin is excellent in transparency (glossiness), impregnation (reinforcing property) and film-forming property of the coating film, and also has good storage stability. Therefore, the present invention can be suitably used in various coating agent fields.

Abstract

The purpose of the present invention is to provide: a water-soluble (meth)acrylic resin which, when used as an aqueous coating material, exhibits excellent coating film transparency (glossiness), impregnability (reinforcability), film formability, and good shelf life; and a technique for use thereof. The problem is solved by providing a (meth)acrylic resin which has hydrolyzable silyl groups, which has a salt structure comprising strong acid and strong base groups, and which is water-soluble.

Description

水溶性（メタ）アクリル系樹脂およびその利用Water-soluble (meth) acrylic resin and its use
　本発明は、水溶性の（メタ）アクリル系樹脂およびその利用に関する。 The present invention relates to a water-soluble (meth) acrylic resin and its use.
　近年、塗料の分野においても、公害対策および省資源の観点より、有機溶剤を使用するものから、水溶性あるいは水分散性樹脂への転換が試みられている。しかし、水性塗料により形成された塗膜は、溶剤系塗料を用いて形成した塗膜に比べ、一般的に性能が劣るという欠点を有していた。 In recent years, in the field of paints as well, from the viewpoint of pollution control and resource saving, conversion from those using organic solvents to water-soluble or water-dispersible resins has been attempted. However, the coating film formed by the water-based paint has a drawback that the performance is generally inferior to that of the coating film formed by using the solvent-based paint.
　このような課題を解決するために、種々の技術が開発されている。例えば、特許文献１には、水性媒体中に分散された種粒子の存在下に、重合性単量体、特定のシリコン化合物および／またはその部分加水分解縮合物、乳化剤および／または水溶性高分子化合物、および水からなる混合物に機械的剪断を加えることによって形成した乳化液を添加し、種粒子に重合性単量体並びにシリコン化合物および／またはその部分加水分解縮合物を吸収させた後、または吸収させながら重合を行うシリコン化合物および／またはその部分加水分解縮合物が包含された重合体粒子よりなる樹脂エマルションの製造方法、並びに当該樹脂エマルションを含む水性塗料が開示されている。 Various technologies have been developed to solve such problems. For example, Patent Document 1 describes a polymerizable monomer, a specific silicon compound and / or a partially hydrolyzed condensate thereof, an emulsifying agent and / or a water-soluble polymer in the presence of seed particles dispersed in an aqueous medium. After adding an emulsion formed by mechanical shearing to a mixture of compound and water to allow the seed particles to absorb the polymerizable monomer and the silicon compound and / or its partially hydrolyzed condensate, or A method for producing a resin emulsion composed of polymer particles containing a silicon compound and / or a partially hydrolyzed condensate thereof, which polymerizes while being absorbed, and an aqueous coating material containing the resin emulsion are disclosed.
特開２００２－１３８１２３号公報JP-A-2002-138123
　しかしながら、上述した特許文献１のような樹脂エマルションを用いたアクリルシリコン樹脂を含む水性塗料では、塗膜の透明性（光沢性）、含浸性（補強性）および製膜性において、さらなる改善の余地があった。また、水性塗料として流通するため、貯蔵安定性も良好であることが求められる。 However, in the water-based paint containing the acrylic silicon resin using the resin emulsion as described in Patent Document 1, there is room for further improvement in the transparency (glossiness), impregnation property (reinforcing property) and film forming property of the coating film. was there. Further, since it is distributed as a water-based paint, it is required to have good storage stability.
　本発明は、上記問題点に鑑みなされたものであり、その目的は、水性塗料として使用した場合に、塗膜の透明性（光沢性）、含浸性（補強性）および製膜性に優れ、かつ貯蔵安定性も良好な、水溶性の（メタ）アクリル系樹脂およびその利用技術を提供することにある。 The present invention has been made in view of the above problems, and an object of the present invention is that when used as a water-based paint, the coating film is excellent in transparency (glossiness), impregnation property (reinforcing property) and film forming property. It is an object of the present invention to provide a water-soluble (meth) acrylic resin having good storage stability and a technique for utilizing the same.
　本発明者らは、上記課題を解決すべく鋭意検討した結果、加水分解性シリル基を有する（メタ）アクリル系樹脂において、さらに、強酸と強塩基からなる塩構造を付加することにより、水溶性の（メタ）アクリル系樹脂が得られるとの新規知見を見出し、本発明を完成するに至った。 As a result of diligent studies to solve the above problems, the present inventors have made water-soluble by further adding a salt structure composed of a strong acid and a strong base to the (meth) acrylic resin having a hydrolyzable silyl group. We have found a new finding that the (meth) acrylic resin can be obtained, and have completed the present invention.
　すなわち、本発明の一態様は、加水分解性シリル基を有する（メタ）アクリル系樹脂であって、さらに、強酸と強塩基からなる塩構造を有し、水溶性である、（メタ）アクリル系樹脂に関する。 That is, one aspect of the present invention is a (meth) acrylic resin having a hydrolyzable silyl group, further having a salt structure composed of a strong acid and a strong base, and being water-soluble. Regarding resin.
　本発明の一態様によれば、水性塗料として使用した場合に、塗膜の透明性（光沢性）、含浸性（補強性）および製膜性に優れ、かつ貯蔵安定性も良好な、水溶性の（メタ）アクリル系樹脂およびその利用技術を提供することができる。 According to one aspect of the present invention, when used as a water-based paint, the coating film is excellent in transparency (glossiness), impregnation property (reinforcing property) and film-forming property, and has good storage stability, and is water-soluble. (Meta) acrylic resin and its utilization technology can be provided.
　本発明の実施の一形態について、以下に詳細に説明する。なお、本明細書において特記しない限り、数値範囲を表す「Ａ～Ｂ」は、「Ａ以上、Ｂ以下」を意味する。また、本明細書中に記載された文献の全てが、本明細書中において参考文献として援用される。 An embodiment of the present invention will be described in detail below. Unless otherwise specified in the present specification, "A to B" representing a numerical range means "A or more and B or less". In addition, all of the documents described herein are incorporated herein by reference.
　〔１．本発明の概要〕
　本発明の一実施形態に係る（メタ）アクリル系樹脂（以下、「本アクリル系樹脂」と称する。）は、加水分解性シリル基を有する（メタ）アクリル系樹脂であって、さらに、強酸と強塩基からなる塩構造を有し、水溶性であることを特徴とする。 [1. Outline of the present invention]
The (meth) acrylic resin (hereinafter, referred to as “the present acrylic resin”) according to one embodiment of the present invention is a (meth) acrylic resin having a hydrolyzable silyl group, and further comprises a strong acid. It has a salt structure composed of a strong base and is characterized by being water-soluble.
　従来のアクリルシリコン樹脂は水に不溶性のため、水性塗料用組成物とするためには、乳化剤を用いて、エマルションとして分散させる必要があった。しかし、エマルション型のアクリルシリコン樹脂を含む水性塗料では、塗膜の透明性（光沢性）、含浸性（補強性）および製膜性の面で改善の余地があった。これは、エマルションの粒径が比較的大きいため、塗料を塗布した際にアクリルシリコン樹脂が塗膜上で均一とならず、また基材に十分に浸透しないためと推測された。 Since the conventional acrylic silicone resin is insoluble in water, it was necessary to disperse it as an emulsion using an emulsifier in order to obtain a composition for water-based paints. However, in the water-based paint containing the emulsion type acrylic silicone resin, there is room for improvement in terms of the transparency (glossiness), impregnation property (reinforcing property) and film forming property of the coating film. It was presumed that this is because the particle size of the emulsion is relatively large, so that the acrylic silicone resin is not uniform on the coating film when the paint is applied, and does not sufficiently penetrate into the base material.
　かかる課題を解決するために、本発明者は、乳化剤を用いたエマルション型の水性塗料以外の水性塗料を開発すべく、アクリルシリコン樹脂の水への溶解性を高める検討を行った。この検討過程において、アクリルシリコン樹脂の水溶性を高めると、今度は貯蔵安定性が低下するという新たな問題点が発生した。これは、水系溶媒中において、アクリルシリコン樹脂中の加水分解性シリル基が経時的に加水分解してしまうためと考えられた。 In order to solve this problem, the present inventor conducted a study to improve the solubility of acrylic silicon resin in water in order to develop a water-based paint other than an emulsion-type water-based paint using an emulsifier. In this study process, increasing the water solubility of the acrylic silicone resin caused a new problem that the storage stability was lowered. It is considered that this is because the hydrolyzable silyl group in the acrylic silicone resin is hydrolyzed over time in the aqueous solvent.
　そこで、水溶性と貯蔵安定性とを両立させるために、本発明者が鋭意検討を行ったところ、加水分解性シリル基を有する（メタ）アクリル系樹脂において、さらに、強酸と強塩基からなる塩構造を含む構成とすることにより、水溶性であるにも関わらず、貯蔵安定性にも優れる（メタ）アクリル系樹脂が得られることを見出した。また、かかる（メタ）アクリル系樹脂を水性塗料として用いた場合、得られる塗膜は、透明性（光沢性）、含浸性（補強性）および製膜性に優れることがわかった。 Therefore, in order to achieve both water solubility and storage stability, the present inventor has conducted diligent studies. As a result, in a (meth) acrylic resin having a hydrolyzable silyl group, a salt composed of a strong acid and a strong base is further obtained. It has been found that a (meth) acrylic resin having excellent storage stability can be obtained by adopting a structure including a structure, although it is water-soluble. Further, it was found that when such (meth) acrylic resin was used as a water-based paint, the obtained coating film was excellent in transparency (glossiness), impregnation property (reinforcing property) and film forming property.
　〔２．（メタ）アクリル系樹脂〕
　本アクリル系樹脂は、加水分解性シリル基を有する（メタ）アクリル系樹脂であって、さらに、強酸と強塩基からなる塩構造を有し、水溶性であればよい。 [2. (Meta) acrylic resin]
The present acrylic resin may be a (meth) acrylic resin having a hydrolyzable silyl group, further having a salt structure composed of a strong acid and a strong base, and being water-soluble.
　本アクリル系樹脂は、上記のような特徴的な構成を有することにより、貯蔵安定性に優れ、かつかかる（メタ）アクリル系樹脂を水性塗料として用いた場合に、得られる塗膜が、透明性（光沢性）、含浸性（補強性）および製膜性に優れる。 Since this acrylic resin has the above-mentioned characteristic structure, it is excellent in storage stability, and when the (meth) acrylic resin is used as a water-based paint, the coating film obtained is transparent. Excellent in (glossiness), impregnation (reinforcing property) and film forming property.
　本明細書において「強酸」とは、酸解離定数ｐＫａが０未満である電解質を意味する。強酸としては、上記定義を満たすものであれば特に限定されないが、例えば、塩酸、硫酸、硝酸等が挙げられる。本発明の一実施形態において、強酸は、好ましくは、硫酸である。 As used herein, the term "strong acid" means an electrolyte having an acid dissociation constant pKa of less than 0. The strong acid is not particularly limited as long as it satisfies the above definition, and examples thereof include hydrochloric acid, sulfuric acid, nitric acid and the like. In one embodiment of the invention, the strong acid is preferably sulfuric acid.
　本明細書において「強塩基」とは、塩基解離定数ｐＫｂが０未満である電解質を意味する。強塩基としては、上記定義を満たすものであれば特に限定されないが、例えば、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム、水酸化バリウム等が挙げられる。本発明の一実施形態において、強塩基は、好ましくは、水酸化ナトリウム、水酸化カリウム、水酸化カルシウムである。 As used herein, the term "strong base" means an electrolyte having a base dissociation constant pKb of less than 0. The strong base is not particularly limited as long as it satisfies the above definition, and examples thereof include sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide and the like. In one embodiment of the invention, the strong base is preferably sodium hydroxide, potassium hydroxide, calcium hydroxide.
　本明細書において「塩構造」とは、強酸と強塩基とを中和することにより得られる中性塩の構造を意味する。塩構造としては、上記定義を満たすものであれば特に限定されないが、例えば、スルホン酸ナトリウム、スルホン酸カリウム、スルホン酸カルシウム等が挙げられる。本発明の一実施形態において、塩構造は、好ましくは、スルホン酸ナトリウムである。 In the present specification, the "salt structure" means the structure of a neutral salt obtained by neutralizing a strong acid and a strong base. The salt structure is not particularly limited as long as it satisfies the above definition, and examples thereof include sodium sulfonate, potassium sulfonate, calcium sulfonate, and the like. In one embodiment of the invention, the salt structure is preferably sodium sulfonate.
　本明細書において「水溶性」とは、樹脂を、固形分濃度が２０％となるように水に溶解または分散させた場合の、１気圧、２５℃におけるヘイズ値が２０．０以下であることを意味する。なお、ヘイズ値は、後述する実施例に記載の方法により測定される。 As used herein, the term "water-soluble" means that the haze value at 1 atm and 25 ° C. when the resin is dissolved or dispersed in water so that the solid content concentration is 20% is 20.0 or less. Means. The haze value is measured by the method described in Examples described later.
　本明細書において「（メタ）アクリル系樹脂」とは、主成分としてアクリルを含む樹脂を意味し、全構成単位の７０重量％以上が（メタ）アクリル単量体由来の構成単位であることが好ましい。（メタ）アクリル系樹脂としては、上記定義を満たすものであれば特に限定されないが、例えば、アクリルシリコン樹脂、アクリルポリオール等が挙げられる。本発明の一実施形態において、（メタ）アクリル系樹脂は、耐候性の観点から、好ましくは、アクリルシリコン樹脂である。 In the present specification, the "(meth) acrylic resin" means a resin containing acrylic as a main component, and 70% by weight or more of all the constituent units is a constituent unit derived from the (meth) acrylic monomer. preferable. The (meth) acrylic resin is not particularly limited as long as it satisfies the above definition, and examples thereof include acrylic silicone resins and acrylic polyols. In one embodiment of the present invention, the (meth) acrylic resin is preferably an acrylic silicone resin from the viewpoint of weather resistance.
　本明細書において「加水分解性シリル基」とは、加水分解可能なシリル基を意味する。加水分解性シリル基としては、上記定義を満たすものであれば特に限定されないが、例えば、アルコキシシリル基が好ましく例示でき、アルコキシシリル基が有するアルコキシ基として、メトキシシリル（－ＳｉＯＭｅ）基、エトキシシリル（－ＳｉＯＥｔ）基、プロポキシシリル基、ブトキシシリル基等が挙げられる。本発明の一実施形態において、加水分解性シリル基は、ジアルコキシシリル基またはトリアルコキシシリル基であることが好ましい。ジアルコキシシリル基としては、例えば、メチルジエトキシシリル基、エチルジエトキシシリル基、メチルジプロポキシシリル基、エチルジプロポキシシリル基、メチルジブトキシシリル基、エチルジブトキシシリル基等が挙げられる。また、トリアルコキシシリル基としては、例えば、トリメトキシシリル基、トリエトキシシリル基、トリプロポキシシリル基、トリブトキシシリル基等が挙げられる。貯蔵安定性、加水分解速度、入手容易性等の観点から、エトキシシリル基が好ましく、トリエトキシシリル基がとりわけ好ましい。 In the present specification, the "hydrolyzable silyl group" means a hydrolyzable silyl group. The hydrolyzable silyl group is not particularly limited as long as it satisfies the above definition, but for example, an alkoxysilyl group can be preferably exemplified, and examples of the alkoxy group contained in the alkoxysilyl group include a methoxysilyl (-SiOMe) group and an ethoxysilyl group. Examples thereof include a (-SiOEt) group, a propoxysilyl group, and a butoxysilyl group. In one embodiment of the present invention, the hydrolyzable silyl group is preferably a dialkoxysilyl group or a trialkoxysilyl group. Examples of the dialkoxysilyl group include a methyldiethoxysilyl group, an ethyldiethoxysilyl group, a methyldipropoxysilyl group, an ethyldipropoxysilyl group, a methyldibutoxysilyl group, an ethyldibutoxysilyl group and the like. Examples of the trialkoxysilyl group include a trimethoxysilyl group, a triethoxysilyl group, a tripropoxysilyl group, and a tributoxysilyl group. From the viewpoints of storage stability, hydrolysis rate, availability and the like, an ethoxysilyl group is preferable, and a triethoxysilyl group is particularly preferable.
　本発明の一実施形態において、本アクリル系樹脂は、構成単位として、強酸と強塩基からなる塩構造を有し、かつ（メタ）アクリロイル基および（メタ）アクリルアミド基の少なくともいずれか一方のラジカル重合性不飽和基を有する単量体に由来する構成単位（ａ）を含むことが好ましい。また、別の観点から、本アクリル系樹脂は、（メタ）アクリロイルオキシ単位または（メタ）アクリルアミド単位のいずれか一方の単位を含むとも言える。なお、以下において、「強酸と強塩基からなる塩構造を有し、かつ（メタ）アクリロイル基および（メタ）アクリルアミド基の少なくともいずれか一方のラジカル重合性不飽和基を有する単量体に由来する構成単位（ａ）」を、単に「構成単位（ａ）」と称する。 In one embodiment of the present invention, the acrylic resin has a salt structure consisting of a strong acid and a strong base as a constituent unit, and radical polymerization of at least one of a (meth) acryloyl group and a (meth) acrylamide group. It preferably contains a structural unit (a) derived from a monomer having a sex unsaturated group. From another point of view, it can be said that the present acrylic resin contains either a (meth) acryloyloxy unit or a (meth) acrylamide unit. In the following, it is derived from a monomer having a salt structure consisting of a strong acid and a strong base and having a radically polymerizable unsaturated group of at least one of a (meth) acryloyl group and a (meth) acrylamide group. The "constituent unit (a)" is simply referred to as the "constituent unit (a)".
　また、本発明の一実施形態において、本アクリル系樹脂は、構成単位として、強酸と強塩基からなる塩構造を有し、かつ（メタ）アクリロイル基および（メタ）アクリルアミド基の少なくともいずれか一方のラジカル重合性不飽和基を有する単量体に由来する構成単位（ａ）を含み、さらに、加水分解性シリル基およびラジカル重合性不飽和基を有する単量体に由来する構成単位（ｂ）と、前記（ａ）および（ｂ）以外の、ラジカル重合性不飽和基を有する単量体に由来する構成単位（ｃ）とを含むことが好ましい。なお、以下において、「加水分解性シリル基およびラジカル重合性不飽和基を有する単量体に由来する構成単位（ｂ）」を、単に「構成単位（ｂ）」と称し、「前記（ａ）および（ｂ）以外の、ラジカル重合性不飽和基を有する単量体に由来する構成単位（ｃ）」を、単に「構成単位（ｃ）」と称する。 Further, in one embodiment of the present invention, the acrylic resin has a salt structure composed of a strong acid and a strong base as a constituent unit, and at least one of a (meth) acryloyl group and a (meth) acrylamide group. It contains a structural unit (a) derived from a monomer having a radically polymerizable unsaturated group, and further comprises a structural unit (b) derived from a monomer having a hydrolyzable silyl group and a radically polymerizable unsaturated group. It is preferable to include a structural unit (c) derived from a monomer having a radically polymerizable unsaturated group other than the above (a) and (b). In the following, the "constituent unit (b) derived from a monomer having a hydrolyzable silyl group and a radically polymerizable unsaturated group" is simply referred to as "constituent unit (b)", and "the (a) above. A "constituent unit (c)" derived from a monomer having a radically polymerizable unsaturated group other than and (b) is simply referred to as a "constituent unit (c)".
　（構成単位（ａ））
　構成単位（ａ）は、強酸と強塩基からなる塩構造を有し、かつ（メタ）アクリロイル基および（メタ）アクリルアミド基の少なくともいずれか一方のラジカル重合性不飽和基を有する単量体に由来する構成単位からなる。構成単位（ａ）が由来する単量体は、ラジカル重合反応により、構成単位（ｃ）に結合する。 (Structural unit (a))
The structural unit (a) is derived from a monomer having a salt structure consisting of a strong acid and a strong base and having a radically polymerizable unsaturated group of at least one of a (meth) acryloyl group and a (meth) acrylamide group. It consists of structural units. The monomer from which the structural unit (a) is derived is bound to the structural unit (c) by a radical polymerization reaction.
　構成単位（ａ）が由来する単量体が、強酸と強塩基からなる塩構造を有することにより、本アクリル系樹脂は、水溶性であるにも関わらず、貯蔵安定性にも優れる。 Since the monomer from which the structural unit (a) is derived has a salt structure consisting of a strong acid and a strong base, this acrylic resin is excellent in storage stability even though it is water-soluble.
　また、構成単位（ａ）が由来する単量体が、（メタ）アクリロイル基および（メタ）アクリルアミド基の少なくともいずれか一方のラジカル重合性不飽和基を有することにより、本アクリル系樹脂の共重合の際の重合安定性が良好となり、水溶性が発現する。なお、ビニル基等のラジカル重合性不飽和基を有する単量体を用いた場合は、ラジカル重合反応速度が、構成単位（ｂ）および構成単位（ｃ）よりも著しく遅いため、水溶性は発現しない。 Further, the monomer from which the structural unit (a) is derived has a radically polymerizable unsaturated group of at least one of a (meth) acryloyl group and a (meth) acrylamide group, whereby the acrylic resin is copolymerized. In this case, the polymerization stability becomes good and water solubility is developed. When a monomer having a radically polymerizable unsaturated group such as a vinyl group is used, the radical polymerization reaction rate is significantly slower than that of the structural unit (b) and the structural unit (c), so that water solubility is exhibited. do not do.
　構成単位（ａ）が由来する単量体としては、強酸と強塩基からなる塩構造を有し、かつ（メタ）アクリロイル基および（メタ）アクリルアミド基の少なくともいずれか一方のラジカル重合性不飽和基を有する単量体であれば特に限定されないが、例えば、２－（メタクリロイルオキシ）エタンスルホン酸ナトリウム、２－（メタクリロイルオキシ）ポリアルキレンオキシドスルホン酸ナトリウム、アクリルアミド－ｔブチルスルホン酸ナトリウム、２－（メタクリロイルオキシ）エタンスルホン酸カリウム、２－（メタクリロイルオキシ）ポリアルキレンオキシドスルホン酸カリウム、アクリルアミド－ｔブチルスルホン酸カリウム、２－（メタクリロイルオキシ）エタンスルホン酸カルシウム、２－（メタクリロイルオキシ）ポリアルキレンオキシドスルホン酸カルシウム、アクリルアミド－ｔブチルスルホン酸カルシウム等が挙げられる。 The monomer from which the structural unit (a) is derived has a salt structure consisting of a strong acid and a strong base, and is a radically polymerizable unsaturated group of at least one of a (meth) acryloyl group and a (meth) acrylamide group. The monomer is not particularly limited as long as it has, but for example, 2- (methacryloyloxy) sodium ethanesulfonate, 2- (methacryloyloxy) polyalkylene oxide sulfonate sodium, acrylamide-t butyl sulfonate sodium, 2-( Potassium methacryloxy) ethanesulfonate, potassium 2- (methacryloyloxy) polyalkylene oxide sulfonate, potassium acrylamide-t butylsulfonate, calcium 2- (methacryloyloxy) ethanesulfonate, 2- (methacryloyloxy) polyalkylene oxide sulfone Examples thereof include calcium acid, acrylamide-t butyl sulfonate, calcium and the like.
　また、構成単位（ａ）が由来する単量体は、市販品として入手することができる。そのような市販品としては、例えば、日本乳化剤（株）製の「アントックスＭＳ－２Ｎ－Ｄ」、東亞合成（株）製の「ＡＴＢＳ－Ｎａ」、三洋化成工業製の「エレミノールＲＳ－３０００」等が挙げられる。 Further, the monomer from which the structural unit (a) is derived can be obtained as a commercially available product. Examples of such commercially available products include "Antox MS-2N-D" manufactured by Nippon Emulsion Co., Ltd., "ATBS-Na" manufactured by Toagosei Co., Ltd., and "Ereminol RS-3000" manufactured by Sanyo Chemical Industries, Ltd. , Etc. can be mentioned.
　本発明の一実施形態において、構成単位（ａ）の含有量は、例えば、上記（ａ）～（ｃ）の全量に対して、６重量％以上であり、好ましくは、７重量％以上であり、より好ましくは、８重量％以上であり、特に好ましくは、９重量％以上であり、とりわけ好ましくは、１０重量％以上である。構成単位（ａ）の含有量が上記範囲内であると、水溶性の効果を奏する。また、構成単位（ａ）の含有量の上限は、本発明の効果を奏する限り特に限定されないが、例えば、５０重量％以下であり、好ましくは、３０重量％以下であり、より好ましくは、２０重量％以下であり、特に好ましくは、１５重量％以下である。 In one embodiment of the present invention, the content of the structural unit (a) is, for example, 6% by weight or more, preferably 7% by weight or more, based on the total amount of the above (a) to (c). , More preferably 8% by weight or more, particularly preferably 9% by weight or more, and particularly preferably 10% by weight or more. When the content of the structural unit (a) is within the above range, a water-soluble effect is exhibited. The upper limit of the content of the structural unit (a) is not particularly limited as long as the effect of the present invention is exhibited, but is, for example, 50% by weight or less, preferably 30% by weight or less, and more preferably 20% by weight. It is 5% by weight or less, and particularly preferably 15% by weight or less.
　（構成単位（ｂ））
　構成単位（ｂ）は、加水分解性シリル基およびラジカル重合性不飽和基を有する単量体に由来する構成単位からなる。構成単位（ｂ）が由来する化合物は、ラジカル重合反応により、構成単位（ｃ）に結合する。 (Constituent unit (b))
The structural unit (b) is composed of a structural unit derived from a monomer having a hydrolyzable silyl group and a radically polymerizable unsaturated group. The compound from which the structural unit (b) is derived is bound to the structural unit (c) by a radical polymerization reaction.
　構成単位（ｂ）が由来する化合物としては、加水分解性シリル基およびラジカル重合性不飽和基を有する単量体であれば特に限定されないが、例えば、以下の式（１）で示される有機けい素化合物が挙げられる。 The compound from which the structural unit (b) is derived is not particularly limited as long as it is a monomer having a hydrolyzable silyl group and a radically polymerizable unsaturated group. Radical compounds can be mentioned.
　Ｒ１Ｒ２ （３－ｎ）ＳｉＸｎ　・・・（１）
　（式中、Ｒ１は、重合性二重結合を有する炭素数５～１０の１価の有機基であり、Ｒ２は、炭素数１～４のアルキル基であり、Ｘは、炭素数１～４のアルコキシル基であり、ｎは、１か２か３である。）
　すなわち、上記有機けい素化合物は、１～３個のアルコキシル基を有し、かつ反応性二重結合を有する化合物である。その具体例としては、例えば、γ－（メタ）アクリロキシプロピルトリメトキシシラン、γ－（メタ）アクリロキシプロピルトリエトキシシラン、γ－（メタ）アクリロキシプロピルトリプロポキシシラン、γ－（メタ）アクリロキシプロピルトリブトキシシラン、γ－（メタ）アクリロキシプロピルメチルジメトキシシラン、γ－（メタ）アクリロキシプロピルメチルジエトキシシラン、γ－（メタ）アクリロキシプロピルメチルジプロポキシシラン、γ－（メタ）アクリロキシプロピルメチルジブトキシシラン等が挙げられる。これらの化合物は、１種で用いてもよいし、２種以上を併用してもよい。なかでも、貯蔵安定性の観点から、Ｘの炭素数は２～４であることが好ましく、貯蔵安定性および加水分解速度の観点から、Ｘの炭素数は２であることが好ましい。 R 1 R 2 (3-n) SiX n ... (1)
(In the formula, R 1 is a monovalent organic group having 5 to 10 carbon atoms having a polymerizable double bond, R 2 is an alkyl group having 1 to 4 carbon atoms, and X is an alkyl group having 1 to 4 carbon atoms. It is an alkoxyl group of ~ 4, and n is 1, 2 or 3).
That is, the organic silicon compound is a compound having 1 to 3 alkoxyl groups and having a reactive double bond. Specific examples thereof include γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltripropoxysilane, and γ- (meth) acry. Loxypropyltributoxysilane, γ- (meth) acryloxipropylmethyldimethoxysilane, γ- (meth) acryloxipropylmethyldiethoxysilane, γ- (meth) acryloxipropylmethyldipropoxysilane, γ- (meth) acry Examples thereof include loxypropylmethyldibutoxysilane. These compounds may be used alone or in combination of two or more. Among them, the carbon number of X is preferably 2 to 4 from the viewpoint of storage stability, and the carbon number of X is preferably 2 from the viewpoint of storage stability and hydrolysis rate.
　また、構成単位（ｂ）が由来する化合物は、市販品として入手することができる。そのような市販品としては、例えば、モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製の「Ａ－１７４」、ダウ・東レ（株）製の「Ｚ－６０３３」、モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製の「Ｙ－９９３６」等が挙げられる。 Further, the compound from which the structural unit (b) is derived can be obtained as a commercially available product. Examples of such commercial products include "A-174" manufactured by Momentive Performance Materials Japan LLC, "Z-6033" manufactured by Dow Toray Co., Ltd., and Momentive Performance Materials Japan. Examples include "Y-9936" manufactured by a limited liability company.
　本発明の一実施形態において、構成単位（ｂ）の含有量は、例えば、上記（ａ）～（ｃ）の全量に対して、１重量％以上であり、好ましくは、３重量％以上であり、より好ましくは、５重量％以上である。構成単位（ｂ）の含有量が上記範囲内であると、高耐候性の効果を奏する。また、構成単位（ｂ）の含有量の上限は、本発明の効果を奏する限り特に限定されないが、例えば、３０重量％以下であり、好ましくは、２０重量％以下であり、より好ましくは、１５重量％以下であり、特に好ましくは、１０重量％以下である。 In one embodiment of the present invention, the content of the structural unit (b) is, for example, 1% by weight or more, preferably 3% by weight or more, based on the total amount of the above (a) to (c). , More preferably 5% by weight or more. When the content of the structural unit (b) is within the above range, the effect of high weather resistance is exhibited. The upper limit of the content of the structural unit (b) is not particularly limited as long as the effect of the present invention is exhibited, but is, for example, 30% by weight or less, preferably 20% by weight or less, and more preferably 15. It is 10% by weight or less, particularly preferably 10% by weight or less.
　（構成単位（ｃ））
　構成単位（ｃ）は、上記（ａ）および（ｂ）以外の、ラジカル重合性不飽和基を有する単量体に由来する構成単位からなる。構成単位（ｃ）が由来する単量体は、ラジカル重合反応により、構成単位（ａ）および構成単位（ｂ）に結合する。 (Constituent unit (c))
The structural unit (c) is composed of a structural unit derived from a monomer having a radically polymerizable unsaturated group other than the above (a) and (b). The monomer from which the structural unit (c) is derived is bonded to the structural unit (a) and the structural unit (b) by a radical polymerization reaction.
　構成単位（ｃ）が由来する単量体としては、上記（ａ）および（ｂ）以外の、ラジカル重合性不飽和基を有する単量体であれば特に限定されないが、例えば、以下で示すような（メタ）アクリル酸アルキルエステル、および（メタ）アクリル酸アルキルエステル以外の単量体が挙げられる。 The monomer from which the structural unit (c) is derived is not particularly limited as long as it is a monomer having a radically polymerizable unsaturated group other than the above (a) and (b), and is shown below, for example. Examples thereof include monomers other than the (meth) acrylic acid alkyl ester and the (meth) acrylic acid alkyl ester.
　＜（メタ）アクリル酸アルキルエステル＞
　本発明の一実施形態において、（メタ）アクリル酸アルキルエステルは、炭素数１～１８個のアルキル基を有する（メタ）アクリル酸エステルであり、水酸基、エポキシ基等の官能基を含まない（メタ）アルキル単量体であり得る。本発明の一実施形態において、（メタ）アクリル酸アルキルエステル中のアルキル基は、直鎖状であっても分岐状であってもよく、また、環状であるシクロアルキル基であってもよい。その具体例としては、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－ブチル（メタ）アクリレート、ｉｓｏ－ブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、ベンジル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、イソデシル（メタ）メタクリレート、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、イソボニル（メタ）アクリレート等が挙げられる。 <(Meta) acrylic acid alkyl ester>
In one embodiment of the present invention, the (meth) acrylic acid alkyl ester is a (meth) acrylic acid ester having an alkyl group having 1 to 18 carbon atoms and does not contain a functional group such as a hydroxyl group or an epoxy group (meth). ) It can be an alkyl monomer. In one embodiment of the present invention, the alkyl group in the (meth) acrylic acid alkyl ester may be linear or branched, or may be a cyclic cycloalkyl group. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, and benzyl (meth) acrylate. Cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) methacrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, isobonyl (meth) acrylate and the like can be mentioned.
　＜（メタ）アクリル酸アルキルエステル以外の単量体＞
　（メタ）アクリル酸アルキルエステル以外の単量体としては、例えば、（メタ）アクリロニトリル等のニトリル基含有ラジカル重合性単量体；グリシジル（メタ）アクリレート等のエポキシ基含有ラジカル重合性単量体；２－ヒドロキシプロピル（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；２－スルホエチルメタクリレートアンモニウム、ポリオキシアルキレン鎖を有するラジカル重合性単量体等の親水性を有するラジカル重合性単量体；ポリエチレングリコールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、アリル（メタ）アクリレート等の重合性の不飽和結合を２つ以上有する単量体；トリフルオロ（メタ）アクリレート、ペンタフルオロ（メタ）アクリレート、パーフルオロシクロヘキシル（メタ）アクリレート、２，２，３，３－テトラフルオロプロピルメタクリレート、β－（パーフルオロオクチル）エチル（メタ）アクリレート等のふっ素含有ラジカル重合性単量体；等が挙げられる。 <Monomers other than (meth) acrylic acid alkyl esters>
Examples of the monomer other than the (meth) acrylic acid alkyl ester include a nitrile group-containing radical polymerizable monomer such as (meth) acrylonitrile; an epoxy group-containing radical polymerizable monomer such as glycidyl (meth) acrylate; 2-Hydroxypropyl (meth) acrylate; 2-hydroxypropyl (meth) acrylate; radically polymerizable monomer having hydrophilicity such as 2-sulfoethyl methacrylateammonium, radically polymerizable monomer having a polyoxyalkylene chain; Monomer having two or more polymerizable unsaturated bonds such as polyethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, and allyl (meth) acrylate; trifluoro (meth) acrylate, pentafluoro (meth) Examples thereof include fluorine-containing radically polymerizable monomers such as acrylate, perfluorocyclohexyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl methacrylate and β- (perfluorooctyl) ethyl (meth) acrylate. ..
　また、上記ポリオキシアルキレン鎖を有するラジカル重合性単量体としては、特に限定されないが、ポリオキアルキレン鎖を有するアクリル酸エステルまたはメタクリル酸エステルが好ましい。その具体例としては、例えば、日本油脂（株）製ブレンマーＰＥ－９０、ＰＥ－２００、ＰＥ－３５０、ＡＥ－９０、ＡＥ－２００、ＡＥ－３５０、ＰＰ－５００、ＰＰ－８００、ＰＰ－１０００、ＡＰ－４００、ＡＰ－５５０、ＡＰ－８００、７００ＰＥＰ－３５０Ｂ、１０ＰＥＰ－５５０Ｂ、５５ＰＥＴ－４００、３０ＰＥＴ－８００、５５ＰＥＴ－８００、３０ＰＰＴ－８００、５０ＰＰＴ－８００、７０ＰＰＴ－８００、ＰＭＥ－１００、ＰＭＥ－２００、ＰＭＥ－４００、ＰＭＥ－１０００、ＰＭＥ－４０００、ＡＭＥ－４００、５０ＰＯＥＰ－８００Ｂ、５０ＡＯＥＰ－８００Ｂ、ＡＥＰ、ＡＥＴ、ＡＰＴ、ＰＬＥ、ＡＬＥ、ＰＳＥ、ＡＳＥ、ＰＫＥ、ＡＫＥ、ＰＮＥ、ＡＮＥ、ＰＮＰ、ＡＮＰ、ＰＮＥＰ－６００、共栄社化学（株）製ライトエステル１３０ＭＡ、０４１ＭＡ、ＭＴＧ、ライトアクリレートＥＣ－Ａ、ＭＴＧ－Ａ、１３０Ａ、ＤＰＭ－Ａ、Ｐ－２００Ａ、ＮＰ－４ＥＡ、ＮＰ－８ＥＡ、ＥＨＤＧ－Ａ、日本乳化剤（株）製ＭＡ－３０、ＭＡ－５０、ＭＡ－１００、ＭＡ－１５０、ＲＭＡ－１１２０、ＲＭＡ－５６４、ＲＭＡ－５６８、ＲＭＡ－５０６、ＭＰＧ１３０－ＭＡ、Ａｎｔｏｘ　ＭＳ－６０、ＭＰＧ－１３０ＭＡ、ＲＭＡ－１５０Ｍ、ＲＭＡ－３００Ｍ、ＲＭＡ－４５０Ｍ、ＲＡ－１０２０、ＲＡ－１１２０、ＲＡ－１８２０、新中村化学工業（株）製ＮＫ－ＥＳＴＥＲ　Ｍ－２０Ｇ、Ｍ－４０Ｇ、Ｍ－９０Ｇ、Ｍ－２３０Ｇ、ＡＭＰ－１０Ｇ、ＡＭＰ－２０Ｇ、ＡＭＰ－６０Ｇ、ＡＭ－９０Ｇ、ＬＡ等があげられる。 The radically polymerizable monomer having the polyoxyalkylene chain is not particularly limited, but an acrylic acid ester or a methacrylic acid ester having a polyoxyalkylene chain is preferable. Specific examples thereof include Bremmer PE-90, PE-200, PE-350, AE-90, AE-200, AE-350, PP-500, PP-800, PP-1000 manufactured by Nippon Oil & Fats Co., Ltd. , AP-400, AP-550, AP-800, 700PEP-350B, 10PEP-550B, 55PET-400, 30PET-800, 55PET-800, 30PPT-800, 50PPT-800, 70PPT-800, PME-100, PME -200, PME-400, PME-1000, PME-4000, AME-400, 50POEP-800B, 50AOEP-800B, AEP, AET, APT, PLE, ALE, PSE, ASE, PKE, AKE, PNE, ANE, PNP , ANP, PNEP-600, Light Ester 130MA, 041MA, MTG, Light Acrylate EC-A, MTG-A, 130A, DPM-A, P-200A, NP-4EA, NP-8EA, EHDG manufactured by Kyoeisha Chemical Co., Ltd. -A, MA-30, MA-50, MA-100, MA-150, RMA-1120, RMA-564, RMA-568, RMA-506, MPG130-MA, Antox MS-60, manufactured by Nippon Ester Co., Ltd. MPG-130MA, RMA-150M, RMA-300M, RMA-450M, RA-1020, RA-1120, RA-1820, NK-ESTER M-20G, M-40G, M-90G manufactured by Shin Nakamura Chemical Industry Co., Ltd. , M-230G, AMP-10G, AMP-20G, AMP-60G, AM-90G, LA and the like.
　本発明の一実施形態において、構成単位（ｃ）の含有量は、例えば、上記（ａ）～（ｃ）の全量に対して、３０重量％以上であり、好ましくは、５０重量％以上であり、より好ましくは、６０重量％以上である。構成単位（ｃ）の含有量が上記範囲内であると、柔軟性等の効果を奏する。また、構成単位（ｃ）の含有量の上限は、本発明の効果を奏する限り特に限定されないが、例えば、９３重量％以下であり、好ましくは、９０重量％以下であり、より好ましくは、８５重量％以下であり、特に好ましくは、８０重量％以下である。 In one embodiment of the present invention, the content of the structural unit (c) is, for example, 30% by weight or more, preferably 50% by weight or more, based on the total amount of the above (a) to (c). , More preferably 60% by weight or more. When the content of the structural unit (c) is within the above range, effects such as flexibility are exhibited. The upper limit of the content of the structural unit (c) is not particularly limited as long as the effect of the present invention is exhibited, but is, for example, 93% by weight or less, preferably 90% by weight or less, and more preferably 85% by weight. It is 0% by weight or less, and particularly preferably 80% by weight or less.
　構成単位（ｃ）の平均分子量は、数平均分子量（Ｍｎ）換算で、例えば、１，０００～１，０００，０００の範囲内であり、１０，０００～２００，０００がより好ましい。構成単位（ｃ）の数平均分子量が上記範囲内であれば、耐候性等の利点を有する。 The average molecular weight of the structural unit (c) is, for example, in the range of 1,000 to 1,000,000 in terms of number average molecular weight (Mn), more preferably 10,000 to 200,000. When the number average molecular weight of the structural unit (c) is within the above range, it has advantages such as weather resistance.
　（物性）
　本発明の一実施形態において、本アクリル系樹脂のヘイズ値は、後述する実施例に記載の方法で測定した場合に、本明細書における水溶性の基準である２０．０以下であればよく、好ましくは、１５．０以下であり、より好ましくは、１３．０以下である。 (Physical characteristics)
In one embodiment of the present invention, the haze value of the acrylic resin may be 20.0 or less, which is the standard of water solubility in the present specification, when measured by the method described in Examples described later. It is preferably 15.0 or less, and more preferably 13.0 or less.
　本発明の一実施形態において、本アクリル系樹脂の貯蔵安定性は、後述する実施例に記載の方法で測定した場合に、例えば、２週間以上である。貯蔵安定性が上記範囲内であると、貯蔵安定性に優れる。 In one embodiment of the present invention, the storage stability of the acrylic resin is, for example, 2 weeks or more when measured by the method described in Examples described later. When the storage stability is within the above range, the storage stability is excellent.
　本発明の一実施形態において、本アクリル系樹脂の最低成膜温度は、後述する実施例に記載の方法で測定した場合に、例えば、１５℃未満であり、好ましくは、１０℃以下であり、より好ましくは、５℃以下であり、特に好ましくは、０℃以下である。最低成膜温度が上記範囲内であると、高い成膜性を有する塗料として利用することが可能である。 In one embodiment of the present invention, the minimum film formation temperature of the acrylic resin is, for example, less than 15 ° C., preferably 10 ° C. or lower, when measured by the method described in Examples described later. More preferably, it is 5 ° C. or lower, and particularly preferably 0 ° C. or lower. When the minimum film forming temperature is within the above range, it can be used as a coating material having high film forming property.
　〔３．水性塗料、塗膜、水溶液〕
　本発明の一実施形態に係る水性塗料（以下、「本水性塗料」と称する。）は、上記〔２．（メタ）アクリル系樹脂〕に記載の（メタ）アクリル系樹脂を含む水性塗料である。本水性塗料は、貯蔵安定性に優れ、かつ水性塗料として用いた場合に、得られる塗膜が、透明性（光沢性）、含浸性（補強性）および製膜性に優れる（メタ）アクリル系樹脂を含むため、塗料用途において有用である。 [3. Water-based paint, coating film, aqueous solution]
The water-based paint according to the embodiment of the present invention (hereinafter, referred to as “the water-based paint”) is described in the above [2. (Meta) Acrylic Resin] is a water-based paint containing the (meth) acrylic resin. This water-based paint has excellent storage stability, and when used as a water-based paint, the resulting coating film is a (meth) acrylic type with excellent transparency (glossiness), impregnation (reinforcing property), and film-forming property. Since it contains a resin, it is useful in paint applications.
　本水性塗料は、〔２．（メタ）アクリル系樹脂〕に記載の（メタ）アクリル系樹脂の他に、硬化触媒を含んでいてもよい。本水性塗料を塗装する際に、アルコキシシリル基の加水分解縮合反応を促進させる硬化触媒を添加することにより、架橋反応が促進される。 This water-based paint is [2. In addition to the (meth) acrylic resin described in [(Meta) Acrylic Resin], a curing catalyst may be contained. When the present water-based paint is applied, the cross-linking reaction is promoted by adding a curing catalyst that promotes the hydrolysis-condensation reaction of the alkoxysilyl group.
　硬化触媒としては、特に限定されないが、例えば、有機金属化合物、酸性触媒、塩基性触媒等が挙げられる。なかでも、活性の観点から、有機錫化合物、酸性リン酸エステル、酸性リン酸エステルとアミン化合物との反応物が好ましい。 The curing catalyst is not particularly limited, and examples thereof include organometallic compounds, acidic catalysts, and basic catalysts. Among them, from the viewpoint of activity, an organotin compound, an acidic phosphoric acid ester, and a reaction product of an acidic phosphoric acid ester and an amine compound are preferable.
　有機錫化合物としては、例えば、ジブチル錫ジラウレート、ジブチル錫ジマレート、ジブチル錫ジオレイルマレート、ジオクチル錫ジラウレート、ジブチル錫ジアセテート、ジブチル錫ジメトキサイド、ジブチル錫チオグリコレート、ジブチル錫ビスイソノニル３－メルカプトプロピオネート、ジブチル錫ビスイソオクチルチオグリコレート、ジブチル錫ビス２－エチルヘキシルチオグリコレート、ジメチル錫ビスドデシルメルカプチド、ジメチル錫ビス（オクチルチオグルコール酸エステル）塩、オクチル酸錫等が挙げられる。 Examples of the organic tin compound include dibutyltin dilaurate, dibutyltin dimarate, dibutyltin dioleylmalate, dioctyltin dilaurate, dibutyltin diacetate, dibutyltin dimethoxide, dibutyltin thioglycolate, and dibutyltin bisisononyl 3-mercaptopropio. Nate, dibutyltin bisisooctylthioglycolate, dibutyltin bis2-ethylhexylthioglycolate, dimethyltin bisdodecyl mercaptide, dimethyltin bis (octylthioglucolate) salt, tin octylate and the like can be mentioned.
　なかでも、水中での安定性の観点から、ジブチル錫チオグリコレート、ジブチル錫ビスイソノニル３－メルカプトプロピオネート、ジブチル錫ビスイソオクチルチオグリコレート、ジブチル錫ビス２－エチルヘキシルチオグリコレート、ジメチル錫ビスドデシルメルカプチド、ジブチル錫ビスドデシルメルカプチド、ジメチル錫ビス（オクチルチオグルコール酸エステル）塩等のメルカプチド系のものが好ましい。 Among them, from the viewpoint of stability in water, dibutyl tin thioglycolate, dibutyl tin bisisononyl 3-mercaptopropionate, dibutyl tin bisisooctyl thioglycolate, dibutyl tin bis 2-ethylhexyl thioglycolate, dimethyl tin bis Dodecyl mercaptide, dibutyl tin bisdodecyl mercaptide, dimethyl tin bis (octylthioglucolate) salt and other mercaptides are preferred.
　酸性リン酸エステル化合物としては、例えば、プロピルアシッドホスフェート、ジブチルホスフェート、２－エチルヘキシルアシッドホスフェート、ジ－２－エチルヘキシルホスフェート、モノイソデシルアシッドホスフェート、ジイソデシルホスフェート、ラウリルアシッドホスフェート、ステアリルアシッドホスフェート等が挙げられる。 Examples of the acidic phosphoric acid ester compound include propyl acid phosphate, dibutyl phosphate, 2-ethylhexyl acid phosphate, di-2-ethylhexyl phosphate, monoisodecyl acid phosphate, diisodecyl phosphate, lauryl acid phosphate, stearyl acid phosphate and the like. ..
　また、上記の酸性リン酸エステル化合物と反応させ得るアミン化合物としては、例えば、トリエチルアミン、ｎ－ブチルアミン、ヘキシルアミン、トリエタノールアミン、ジアザビシクロウンデセン、アンモニア等が挙げられる。 Examples of the amine compound that can react with the above acidic phosphate compound include triethylamine, n-butylamine, hexylamine, triethanolamine, diazabicycloundecene, and ammonia.
　本発明の一実施形態において、硬化触媒の添加量は、（メタ）アクリル系樹脂の固形分１００重量部に対し、０．１～１０重量部配合することが好ましく、特に、０．５～５重量部が好ましい。０．１重量部未満では、硬化活性が低く、１０重量部を超えると塗料の可使時間が短くなり、また、塗膜の耐水性、耐候性が低下する等の懸念がある。 In one embodiment of the present invention, the amount of the curing catalyst added is preferably 0.1 to 10 parts by weight, particularly 0.5 to 5 parts by weight, based on 100 parts by weight of the solid content of the (meth) acrylic resin. Parts by weight are preferred. If it is less than 0.1 parts by weight, the curing activity is low, and if it exceeds 10 parts by weight, the pot life of the paint is shortened, and there is a concern that the water resistance and weather resistance of the coating film are lowered.
　本水性塗料は、本発明の効果を奏する範囲で、当該技術分野（とりわけ、塗料の分野）において通常用いられる添加剤を含んでいてもよい。そのような添加剤としては、例えば、料、充填剤、可塑剤、成膜助剤、湿潤・分散剤、増粘剤、消泡剤、防腐剤、酸化防止剤、沈降防止剤、レベリング剤、紫外線吸収剤、帯電防止剤、凍結防止剤、抗菌剤、抗かび剤、粘着付与剤、防錆剤等が挙げられる。添加剤としては、１種のみが含まれていてもよいし、２種以上が含まれていてもよい。これら添加剤の量は、その使用目的に応じて当業者が適宜設定可能である。 The present water-based paint may contain additives usually used in the technical field (particularly, the field of paint) as long as the effects of the present invention are exhibited. Such additives include, for example, agents, fillers, plasticizers, film forming aids, wetting / dispersing agents, thickeners, antifoaming agents, preservatives, antioxidants, antioxidants, leveling agents, etc. Examples thereof include ultraviolet absorbers, antistatic agents, antifreeze agents, antibacterial agents, antifungal agents, tackifiers, rust preventives and the like. As the additive, only one kind may be contained, or two or more kinds may be contained. The amount of these additives can be appropriately set by those skilled in the art according to the purpose of use.
　また、本発明の一実施形態において、上記〔２．（メタ）アクリル系樹脂〕に記載の（メタ）アクリル系樹脂を含む水溶液（以下、「本水溶液」と称する。）を提供し得る。 Further, in one embodiment of the present invention, the above [2. An aqueous solution containing the (meth) acrylic resin described in [(Meta) Acrylic Resin] (hereinafter, referred to as “the present aqueous solution”) can be provided.
　本明細書において「水溶液」とは、上記「水溶性」の定義を満たす樹脂を含み、かつ、水が全媒体の４０重量％以上を占める溶液を意味する。したがって、本水溶液は、水以外の媒体（例えば、溶剤）を１０％未満の量で含み得る。 In the present specification, the "aqueous solution" means a solution containing a resin satisfying the above definition of "water-soluble" and in which water accounts for 40% by weight or more of the total medium. Therefore, the aqueous solution may contain a medium other than water (eg, solvent) in an amount of less than 10%.
　本水溶液は、貯蔵安定性に優れ、かつ水性塗料として用いた場合に、得られる塗膜が、透明性（光沢性）、含浸性（補強性）および製膜性に優れるとの効果を奏する（メタ）アクリル系樹脂を含むため、とりわけ水性塗料用途において有用である。 This aqueous solution has excellent storage stability, and when used as a water-based paint, the obtained coating film has an effect of excellent transparency (glossiness), impregnation property (reinforcing property), and film-forming property ( Since it contains a meta) acrylic resin, it is particularly useful in water-based paint applications.
　本発明の一実施形態において、本水溶液の水含有率は、後述する実施例に記載の方法で測定した場合に、例えば、４０重量％以上であり、好ましくは、５０重量％以上であり、より好ましくは、６０重量％以上である。水含有率が上記範囲内であると、水性の塗料として利用が可能である。 In one embodiment of the present invention, the water content of the aqueous solution is, for example, 40% by weight or more, preferably 50% by weight or more, when measured by the method described in Examples described later. Preferably, it is 60% by weight or more. When the water content is within the above range, it can be used as a water-based paint.
　本発明の一実施形態において、本水溶液のアルコール含有率は、後述する実施例に記載の方法で測定した場合に、例えば、１０重量％以下であり、好ましくは、８重量％以下であり、より好ましくは、５重量％以下である。アルコール含有率が上記範囲内であると、水性の塗料として利用が可能である。 In one embodiment of the present invention, the alcohol content of the aqueous solution is, for example, 10% by weight or less, preferably 8% by weight or less, as measured by the method described in Examples described later. Preferably, it is 5% by weight or less. When the alcohol content is within the above range, it can be used as a water-based paint.
　本発明の一実施形態において、本水溶液を使用した場合の塗膜の光沢値は、後述する実施例に記載の方法で測定した場合に、例えば、６５以上であり、好ましくは、７０以上であり、より好ましくは、７５以上である。光沢値が上記範囲内であると、塗膜の外観（光沢性や透明性）に優れる。 In one embodiment of the present invention, the gloss value of the coating film when the aqueous solution is used is, for example, 65 or more, preferably 70 or more, when measured by the method described in Examples described later. , More preferably 75 or more. When the gloss value is within the above range, the appearance (gloss and transparency) of the coating film is excellent.
　また、本発明の一実施形態において、上記〔２．（メタ）アクリル系樹脂〕に記載の（メタ）アクリル系樹脂を硬化した塗膜を提供し得る。本塗膜は、上述した水性塗料を硬化して得られた塗膜、また上述した水溶液から得られた塗膜を含む。 Further, in one embodiment of the present invention, the above [2. A coating film obtained by curing the (meth) acrylic resin described in [(Meta) Acrylic Resin] can be provided. The present coating film includes a coating film obtained by curing the above-mentioned water-based paint and a coating film obtained from the above-mentioned aqueous solution.
　〔４．製造方法〕
　本発明の一実施形態に係る水溶性の（メタ）アクリル系樹脂の製造方法（以下、「本製造方法」と称する。）は、（Ａ）強酸と強塩基からなる塩構造を有し、かつ（メタ）アクリロイル基および（メタ）アクリルアミド基の少なくともいずれか一方のラジカル重合性不飽和基を有する単量体と、（Ｂ）加水分解性シリル基およびラジカル重合性不飽和を有する単量体と、（Ｃ）前記（Ａ）および（Ｂ）以外のラジカル重合性不飽和基を有する単量体と、を水と有機溶媒との混合溶媒中にて共重合する工程を有することを特徴とする。 [4. Production method〕
The method for producing a water-soluble (meth) acrylic resin according to an embodiment of the present invention (hereinafter referred to as "the present production method") has (A) a salt structure composed of a strong acid and a strong base, and has a salt structure. A monomer having at least one of a (meth) acrylic group and a (meth) acrylamide group having a radically polymerizable unsaturated group, and (B) a monomer having a hydrolyzable silyl group and a radically polymerizable unsaturated group. , (C) It is characterized by having a step of copolymerizing a monomer having a radically polymerizable unsaturated group other than the above (A) and (B) in a mixed solvent of water and an organic solvent. ..
　上述の通り、従来のアクリルシリコン樹脂は水に不溶性のため、水性塗料用組成物とするためには、乳化剤を用いて、エマルションとして分散させる必要があった。しかし、本製造方法では、特定の構造を有する、上記（Ａ）の単量体、上記（Ｂ）の化合物および上記（Ｃ）の単量体を用いることにより、水と有機溶媒との混合溶媒中での共重合が可能となる。 As described above, since the conventional acrylic silicone resin is insoluble in water, it was necessary to disperse it as an emulsion using an emulsifier in order to obtain a composition for water-based paints. However, in the present production method, by using the above-mentioned monomer (A), the above-mentioned compound (B), and the above-mentioned monomer (C) having a specific structure, a mixed solvent of water and an organic solvent is used. Copolymerization inside is possible.
　なお、「上記（Ａ）の単量体」、「上記（Ｂ）の化合物」および「上記（Ｃ）の単量体」は、それぞれ、〔２．（メタ）アクリル系樹脂〕に記載の「構成単位（ａ）が由来する単量体」、「構成単位（ｂ）が由来する化合物」および「構成単位（ｃ）が由来する単量体」に対応する。 The "monomer of (A) above", "compound of (B) above" and "monomer of (C) above" are [2. (Meta) acrylic resin] described in "monomer from which structural unit (a) is derived", "compound from which structural unit (b) is derived", and "monomer from which structural unit (c) is derived". Correspond.
　本製造方法における水と有機溶媒との混合溶媒中での共重合は、当該技術分野で公知の方法により行うことができる。例えば、本アクリル系樹脂は、（Ａ）の単量体、（Ｂ）の化合物および（Ｃ）の単量体を含む混合物に重合開始剤を添加し、水と有機溶媒との混合溶媒中で共重合することにより得られる。 Copolymerization in a mixed solvent of water and an organic solvent in this production method can be carried out by a method known in the art. For example, in this acrylic resin, a polymerization initiator is added to a mixture containing the monomer (A), the compound (B), and the monomer (C), and the mixture is in a mixed solvent of water and an organic solvent. Obtained by copolymerization.
　重合開始剤としては、特に限定されないが、例えば、２，２’－アゾビス（イソブチロニトリル）、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－メチルブチロニトリル）、tert－ブチルパーオキシピバレート、tert－ブチルパーオキシベンゾエート、tert－ブチルパーオキシ－２－エチルヘキサノエート、ジ－tert－ブチルパーオキサイド、クメンハイドロパーオキサイド、ジイソプロピルパーオキシカーボネート等が挙げられる。 The polymerization initiator is not particularly limited, but is, for example, 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2). -Methylbutyronitrile), tert-butylperoxypivalate, tert-butylperoxybenzoate, tert-butylperoxy-2-ethylhexanoate, di-tert-butylperoxide, cumenehydroperoxide, diisopropylper Oxycarbonate and the like can be mentioned.
　上記重合開始剤の使用量は、例えば、単量体全量１００重量部に対して０．０１～１０部であり、好ましくは０．０５～５重量部である。かかる重合開始剤の使用量が０．０１重量部未満である場合には、重合が進行しにくくなることがあり、１０重量部を超える場合には、生成する重合体の分子量が低下する傾向がある。 The amount of the polymerization initiator used is, for example, 0.01 to 10 parts, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the total amount of the monomers. If the amount of the polymerization initiator used is less than 0.01 parts by weight, the polymerization may be difficult to proceed, and if it exceeds 10 parts by weight, the molecular weight of the produced polymer tends to decrease. is there.
　本発明の一実施形態において、（Ａ）の単量体の量は、例えば、前記（Ａ）～（Ｃ）の全量に対して、６重量％以上であり、好ましくは、７重量％以上であり、より好ましくは、８重量％以上であり、特に好ましくは、９重量％以上であり、とりわけ好ましくは、１０重量％以上である。（Ａ）の単量体の量が上記範囲内であると、水溶性の効果を奏する。また、（Ａ）の単量体の量の上限は、本発明の効果を奏する限り特に限定されないが、例えば、５０重量％以下であり、好ましくは、３０重量％以下であり、より好ましくは、２０重量％以下であり、特に好ましくは、１５重量％以下である。 In one embodiment of the present invention, the amount of the monomer of (A) is, for example, 6% by weight or more, preferably 7% by weight or more, based on the total amount of (A) to (C). Yes, more preferably 8% by weight or more, particularly preferably 9% by weight or more, and particularly preferably 10% by weight or more. When the amount of the monomer of (A) is within the above range, a water-soluble effect is exhibited. The upper limit of the amount of the monomer (A) is not particularly limited as long as the effect of the present invention is exhibited, but is, for example, 50% by weight or less, preferably 30% by weight or less, and more preferably. It is 20% by weight or less, and particularly preferably 15% by weight or less.
　共重合の際に用いる有機溶媒としては、メタノール、エタノール、２－プロパノール、１－プロパノール、ブタノール、ペンタノール等のアルコール系溶媒、アセトン、テトラヒドロフラン等の水溶性溶媒等を挙げることができ、なかでも、２－プロパノールが好ましい。 Examples of the organic solvent used in the copolymerization include alcohol solvents such as methanol, ethanol, 2-propanol, 1-propanol, butanol and pentanol, water-soluble solvents such as acetone and tetrahydrofuran, and among them. , 2-Propanol is preferred.
　水と有機溶媒の混合比率としては、水：有機溶媒が、重量比率で１：１０～８：１０が好ましく、２：１０～５：１０がより好ましい。 As the mixing ratio of water and the organic solvent, water: organic solvent is preferably 1:10 to 8:10 by weight, and more preferably 2:10 to 5:10.
　本発明の一実施形態において、重合温度は、重合中の混合液の安定性を保持し、重合を安定に行なう観点から、例えば、４０～１００℃であり、好ましくは、６０～８０℃である。また、本発明の一実施形態において、重合時間は、重合中の混合液の安定性を保持し、重合を安定に行なう観点から、例えば、３時間以上であり、好ましくは、４～８時間である。 In one embodiment of the present invention, the polymerization temperature is, for example, 40 to 100 ° C., preferably 60 to 80 ° C., from the viewpoint of maintaining the stability of the mixed solution during polymerization and stably performing the polymerization. .. Further, in one embodiment of the present invention, the polymerization time is, for example, 3 hours or more, preferably 4 to 8 hours, from the viewpoint of maintaining the stability of the mixed solution during polymerization and stably performing the polymerization. is there.
　〔５．用途〕
　本アクリル系樹脂、本水溶液および本水性塗料は、例えば、建築内外装用、メタリックベースあるいはメタリックベース上のクリアー等の自動車用、アルミニウム、ステンレス、銀等の金属直塗用、スレート、コンクリート、瓦、モルタル、石膏ボード、石綿スレート、アスベストボード、プレキャストコンクリート、軽量気泡コンクリート、珪酸カルシウム板、タイル、レンガ等の窯業系直塗用、ガラス用、天然大理石、御影石等の石材用の塗料あるいは上面処理剤として好適に用いられる。 [5. Use]
The acrylic resin, the aqueous solution, and the water-based paint are used, for example, for interior and exterior of buildings, for automobiles such as clear on metallic base or metallic base, for direct coating of metals such as aluminum, stainless steel, and silver, slate, concrete, and roof tiles. Paints or top treatment agents for ceramics such as mortar, gypsum board, asbestos slate, asbestos board, precast concrete, lightweight aerated concrete, calcium silicate board, tile, brick, etc., for glass, natural marble, stone materials such as mikage stone, etc. It is preferably used as.
　すなわち、本発明の一態様は、以下の発明を包含する。
＜１＞加水分解性シリル基を有する（メタ）アクリル系樹脂であって、
　さらに、強酸と強塩基からなる塩構造を有し、
　水溶性である、（メタ）アクリル系樹脂。
＜２＞構成単位として、強酸と強塩基からなる塩構造を有し、かつ（メタ）アクリロイル基および（メタ）アクリルアミド基の少なくともいずれか一方のラジカル重合性不飽和基を有する単量体に由来する構成単位（ａ）を含む、＜１＞に記載の（メタ）アクリル系樹脂。
＜３＞構成単位として、さらに、加水分解性シリル基およびラジカル重合性不飽和基を有する単量体に由来する構成単位（ｂ）と、
　前記（ａ）および（ｂ）以外の、ラジカル重合性不飽和基を有する単量体に由来する構成単位（ｃ）と、を含む、＜２＞に記載の（メタ）アクリル系樹脂。
＜４＞前記構成単位（ａ）は、前記（ａ）～（ｃ）の全量に対して、６重量％以上５０重量％以下である、＜２＞または＜３＞に記載の（メタ）アクリル系樹脂。
＜５＞前記構成単位（ｂ）は、前記（ａ）～（ｃ）の全量に対して、１重量％以上３０重量％以下であり、前記構成単位（ｃ）は、前記（ａ）～（ｃ）の全量に対して、３０重量％以上９３重量％以下である、＜３＞または＜４＞に記載の（メタ）アクリル系樹脂。
＜６＞前記塩構造は、スルホン酸ナトリウム、スルホン酸カリウム、およびスルホン酸カルシウムからなる群より選択されるいずれかである、＜１＞～＜５＞のいずれかに記載の（メタ）アクリル系樹脂。
＜７＞前記加水分解性シリル基は、エトキシシリル（－ＳｉＯＥｔ）基である、＜１＞～＜６＞のいずれかに記載の（メタ）アクリル系樹脂。
＜８＞前記加水分解性シリル基は、トリエトキシシリル基である、＜１＞～＜７＞のいずれか１項に記載の（メタ）アクリル系樹脂。
＜９＞前記（メタ）アクリル系樹脂を、固形分濃度が２０％となるように水に溶解または分散させた場合の、１気圧、２５℃におけるヘイズ値が２０．０以下である、＜１＞～＜８＞のいずれかに記載の（メタ）アクリル系樹脂。
＜１０＞＜１＞～＜９＞のいずれかに記載の（メタ）アクリル系樹脂を含む、水溶液。
＜１１＞前記水溶液の水含有率が４０重量％以上であり、アルコール含有率が１０重量％以下である、＜１０＞に記載の水溶液。
＜１２＞＜１＞～＜９＞のいずれかに記載の（メタ）アクリル系樹脂を含む水性塗料。
＜１３＞＜１＞～＜９＞のいずれかに記載の（メタ）アクリル系樹脂を硬化した塗膜。
＜１４＞（Ａ）強酸と強塩基からなる塩構造を有し、かつ（メタ）アクリロイル基および（メタ）アクリルアミド基の少なくともいずれか一方のラジカル重合性不飽和基を有する単量体と、
　（Ｂ）加水分解性シリル基およびラジカル重合性不飽和を有する単量体と、
　（Ｃ）前記（Ａ）および（Ｂ）以外のラジカル重合性不飽和基を有する単量体と、を水と有機溶媒との混合溶媒中にて共重合する工程を有する、＜３＞～＜９＞のいずれかに記載の水溶性の（メタ）アクリル系樹脂の製造方法。
＜１５＞前記（Ａ）の単量体は、前記（Ａ）～（Ｃ）の全量に対して、６重量％以上５０重量％以下である、＜１４＞に記載の（メタ）アクリル系樹脂の製造方法。 That is, one aspect of the present invention includes the following inventions.
<1> A (meth) acrylic resin having a hydrolyzable silyl group.
Furthermore, it has a salt structure consisting of a strong acid and a strong base.
A water-soluble (meth) acrylic resin.
<2> Derived from a monomer having a salt structure consisting of a strong acid and a strong base and having a radically polymerizable unsaturated group of at least one of a (meth) acryloyl group and a (meth) acrylamide group as a constituent unit. The (meth) acrylic resin according to <1>, which comprises the structural unit (a) to be formed.
<3> As the structural unit, further, a structural unit (b) derived from a monomer having a hydrolyzable silyl group and a radically polymerizable unsaturated group, and
The (meth) acrylic resin according to <2>, which comprises a structural unit (c) derived from a monomer having a radically polymerizable unsaturated group other than the above (a) and (b).
<4> The (meth) acrylic according to <2> or <3>, wherein the structural unit (a) is 6% by weight or more and 50% by weight or less with respect to the total amount of the above (a) to (c). System resin.
<5> The structural unit (b) is 1% by weight or more and 30% by weight or less with respect to the total amount of the (a) to (c), and the structural unit (c) is the above (a) to (c). The (meth) acrylic resin according to <3> or <4>, which is 30% by weight or more and 93% by weight or less based on the total amount of c).
<6> The (meth) acrylic system according to any one of <1> to <5>, wherein the salt structure is any one selected from the group consisting of sodium sulfonate, potassium sulfonate, and calcium sulfonate. resin.
<7> The (meth) acrylic resin according to any one of <1> to <6>, wherein the hydrolyzable silyl group is an ethoxysilyl (-SiOEt) group.
<8> The (meth) acrylic resin according to any one of <1> to <7>, wherein the hydrolyzable silyl group is a triethoxysilyl group.
<9> When the (meth) acrylic resin is dissolved or dispersed in water so that the solid content concentration is 20%, the haze value at 1 atm and 25 ° C. is 20.0 or less. <1 > To the (meth) acrylic resin according to any one of <8>.
<10> An aqueous solution containing the (meth) acrylic resin according to any one of <1> to <9>.
<11> The aqueous solution according to <10>, wherein the aqueous solution has a water content of 40% by weight or more and an alcohol content of 10% by weight or less.
<12> A water-based paint containing the (meth) acrylic resin according to any one of <1> to <9>.
<13> A coating film obtained by curing the (meth) acrylic resin according to any one of <1> to <9>.
<14> A monomer having a salt structure consisting of (A) a strong acid and a strong base and having a radically polymerizable unsaturated group of at least one of a (meth) acryloyl group and a (meth) acrylamide group.
(B) Monomers having hydrolyzable silyl groups and radically polymerizable unsaturated groups,
(C) A step of copolymerizing a monomer having a radically polymerizable unsaturated group other than the above (A) and (B) in a mixed solvent of water and an organic solvent, <3> to <. 9> The method for producing a water-soluble (meth) acrylic resin according to any one of 9.
<15> The (meth) acrylic resin according to <14>, wherein the monomer of (A) is 6% by weight or more and 50% by weight or less with respect to the total amount of (A) to (C). Manufacturing method.
　本発明は上述した各実施形態に限定されるものではなく、請求項に示した範囲で種々の変更が可能であり、異なる実施形態にそれぞれ開示された技術的手段を適宜組み合わせて得られる実施形態についても本発明の技術的範囲に含まれる。 The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope of the claims, and the embodiments obtained by appropriately combining the technical means disclosed in the different embodiments. Is also included in the technical scope of the present invention.
　以下、本発明を実施例に基づいてより詳細に説明するが、本発明はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.
　〔材料〕
　実施例および比較例において、以下の材料を使用した。 〔material〕
The following materials were used in Examples and Comparative Examples.
　（ａ成分）
・構成単位（ｃ）が由来する単量体
　メチルメタクリレート（略称「ＭＭＡ」）：三菱ガス化学株式会社製
　ブチルアクリレート（略称「ＢＡ」）：株式会社日本触媒製
・構成単位（ｂ）が由来する化合物
　γ－メタアクリロキシプロピルトリエトキシシラン（略称「ＴＥＳＭＡ」）：モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製の「Ｙ－９９３６」
・構成単位（ａ）が由来する単量体
　アクリルアミド－ｔブチルスルホン酸ナトリウム：東亞合成（株）製の「ＡＴＢＳ－Ｎａ」、市販分類「モノマー」
　スルホエチルメタクリル酸ナトリウム：日本乳化剤（株）製の「アントックスＭＳ－２Ｎ－Ｄ」、市販分類「乳化剤」
　エレミノールＲＳ－３０００：三洋化成工業製、スルホン酸（強酸）および水酸化ナトリウム（強塩基）からなる塩構造を有する化合物、市販分類「乳化剤」
　アクリル酸ナトリウム（略称「ＡＡＮａ」）：浅田化学工業（株）製、弱酸と強塩基からなる塩構造を有する（強酸と強塩基からなる塩構造を有さない）化合物、市販分類「モノマー」
　アデカリアソープＳＲ－１０：（株）アデカ製、（メタ）アクリロイル基および（メタ）アクリルアミド基のいずれも含まない化合物、市販分類「乳化剤」
・重合開始剤
　２，２’－アゾビス（２，４－ジメチルバレロニトリル）：東京化成工業（株）
・その他
　２－プロパノール：ナカライテスク（株）製
　（ｂ成分）
・その他
　純水
　２－プロパノール：ナカライテスク（株）製
　過硫酸カリウム：三菱ガス化学（株）製
　（ｃ成分）
・重合開始剤
　２，２’－アゾビス（２，４－ジメチルバレロニトリル）：東京化成工業（株）
・その他
　２－プロパノール：ナカライテスク（株）製
　過硫酸カリウム：三菱ガス化学（株）製。 (Component a)
-Monomer from which the structural unit (c) is derived Methyl methacrylate (abbreviated as "MMA"): Butyl acrylate (abbreviated as "BA") manufactured by Mitsubishi Gas Chemical Company, Inc. Compound γ-methacryloxypropyltriethoxysilane (abbreviation "TESMA"): "Y-9936" manufactured by Momentive Performance Materials Japan LLC
-Monomer from which the structural unit (a) is derived: Sodium acrylamide-t butyl sulfonate: "ATBS-Na" manufactured by Toa Synthetic Co., Ltd., commercially available classification "monomer"
Sodium sulfoethyl methacrylate: "Antox MS-2ND" manufactured by Nippon Emulsifier Co., Ltd., commercially available classification "emulsifier"
Eleminor RS-3000: Sanyo Kasei Kogyo, a compound having a salt structure consisting of sulfonic acid (strong acid) and sodium hydroxide (strong base), commercially available classification "emulsifier"
Sodium acrylate (abbreviation "AANa"): Made by Asada Chemical Industry Co., Ltd., a compound having a salt structure consisting of a weak acid and a strong base (not having a salt structure consisting of a strong acid and a strong base), commercially available classification "monomer"
Adecaria Soap SR-10: Made by ADEKA CORPORATION, a compound containing neither (meth) acryloyl group nor (meth) acrylamide group, commercially available classification "emulsifier"
-Polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile): Tokyo Chemical Industry Co., Ltd.
・ Other 2-propanol: manufactured by Nacalai Tesque Co., Ltd. (component b)
・ Other pure water 2-propanol: manufactured by Nacalai Tesque Co., Ltd. Potassium persulfate: manufactured by Mitsubishi Gas Chemical Company, Inc. (component c)
-Polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile): Tokyo Chemical Industry Co., Ltd.
-Other 2-propanol: manufactured by Nacalai Tesque Co., Ltd. Potassium persulfate: manufactured by Mitsubishi Gas Chemical Company, Inc.
　〔測定および評価方法〕
　実施例および比較例における測定および評価を、以下の方法で行った。 [Measurement and evaluation method]
Measurements and evaluations in Examples and Comparative Examples were performed by the following methods.
　（重合安定性）
　重合中の増粘により流動性がなくなり攪拌が不可能になるか否かにより、重合安定性（重合中のゲル化）を評価した。問題なく重合が行われた場合を「可」とし、重合中の増粘により流動性がなくなり攪拌が不可能になった場合を「不可」とした。 (Polymerization stability)
The polymerization stability (gelation during polymerization) was evaluated based on whether or not the thickening during polymerization caused the fluidity to be lost and stirring was impossible. The case where the polymerization was carried out without any problem was regarded as "possible", and the case where the fluidity was lost due to the thickening during the polymerization and stirring became impossible was regarded as "impossible".
　（水含有率）
　減圧蒸留し、水希釈を行った後の固形分濃度の測定により、水溶液中の水含有率を測定した。 (Water content)
The water content in the aqueous solution was measured by measuring the solid content concentration after distilling under reduced pressure and diluting with water.
　（アルコール含有率）
　減圧蒸留し、水希釈を行う前の固形分濃度の測定により、水溶液中のアルコール含有率を測定した。 (Alcohol content)
The alcohol content in the aqueous solution was measured by measuring the solid content concentration before distilling under reduced pressure and diluting with water.
　（水溶性評価）
　特許第５２５２７５８号公報を参照して、（メタ）アクリル系樹脂の水溶性を評価した。簡潔には、合成例で得られた（メタ）アクリル系樹脂（共重合体）を純水で希釈し、樹脂固形分濃度を２０％とした。１気圧、２５℃下において、日本電色工業（株）製ＣＯＨ４００を用いて、純水を標準液にして、（メタ）アクリル系樹脂のヘイズ値を測定した。上記ヘイズ値が２０．０以下である場合を水溶性（表中では「○」）と判断した。 (Water solubility evaluation)
The water solubility of the (meth) acrylic resin was evaluated with reference to Japanese Patent No. 52527558. Briefly, the (meth) acrylic resin (copolymer) obtained in the synthetic example was diluted with pure water to bring the resin solid content concentration to 20%. The haze value of the (meth) acrylic resin was measured using pure water as a standard solution using COH400 manufactured by Nippon Denshoku Kogyo Co., Ltd. at 1 atm and 25 ° C. When the haze value was 20.0 or less, it was judged to be water-soluble (“◯” in the table).
　（貯蔵安定性）
　固形分濃度４０％に調整した樹脂含有水溶液をガラス瓶内に密閉した状態で、２５℃に昇温した熱風乾燥機内に静置し、前記ガラス瓶を４５度傾けた際に内溶液に流動性が確認できなくなった時点をゲル化点として、貯蔵安定性（室温ゲル化日）を評価した。 (Storage stability)
A resin-containing aqueous solution adjusted to a solid content concentration of 40% was sealed in a glass bottle and allowed to stand in a hot air dryer heated to 25 ° C., and when the glass bottle was tilted 45 degrees, the fluidity of the internal solution was confirmed. Storage stability (room temperature gelation date) was evaluated with the time when it became impossible as the gelation point.
　（最低成膜温度）
　最低成膜温度（ＭＦＴ）を、ヨシミツ精機製最低造膜温度測定装置　ＭＦＴ－１を用いて測定した。ＭＦＴが低いほど成膜性が高いことを示す。 (Minimum film formation temperature)
The minimum film formation temperature (MFT) was measured using the minimum film formation temperature measuring device MFT-1 manufactured by Yoshimitsu Seiki. The lower the MFT, the higher the film forming property.
　（光沢値）
　特許第５６９５９５０号公報を参照して、（メタ）アクリル系樹脂の水溶液を使用した場合の塗膜の光沢値を測定した。簡潔には、合成例で得られた固形分濃度が４０％の（メタ）アクリル系樹脂（共重合体）の水溶液を１５ｃｍ×７ｃｍのガラス基板上に６ｍｉｌのアプリケーターで塗工し、２３℃、５０％ＲＨにて１週間養生後、ミノルタ（株）製光沢計Ｍｕｌｔｉ－Ｇｌｏｓｓ２６８を用いて、入射角６０°の光沢値を測定した。光沢値が高いほど外観に優れることを示す。 (Gloss value)
With reference to Japanese Patent No. 5695950, the gloss value of the coating film when an aqueous solution of a (meth) acrylic resin was used was measured. Briefly, an aqueous solution of a (meth) acrylic resin (copolymer) having a solid content concentration of 40% obtained in the synthetic example was applied onto a glass substrate of 15 cm × 7 cm with a 6 mil applicator, and the temperature was 23 ° C. After curing at 50% RH for 1 week, the gloss value at an incident angle of 60 ° was measured using a gloss meter Multi-Gloss 268 manufactured by Minolta Co., Ltd. The higher the gloss value, the better the appearance.
　（付着性試験）
　特開２０１４－１１８５５７号公報を参照して、付着性試験（碁盤目密着性試験）を行った。簡潔には、ケイ酸カルシウム板に、固形分濃度が３０％の樹脂を１平方メートあたり１００ｇの量で塗装し、その後、２３℃、５０％ＲＨにて１週間養生し、ＪＩＳ　Ｋ５６００に準拠して、１ｍｍ間隔の２５マスからなる碁盤目の密着性試験を行った。試験後にケイ酸カルシウム板上に樹脂が残存するマスの数を基準として、以下のとおり評価した。尚、評価は、Ａ、Ｂ、Ｃの順に良好である。すなわち、Ａが最良であり、Ｂが良であり、Ｃは不可である。 (Adhesion test)
An adhesion test (a grid adhesion test) was performed with reference to Japanese Patent Application Laid-Open No. 2014-118557. Briefly, a calcium silicate board is coated with a resin having a solid content concentration of 30% in an amount of 100 g per square meter, and then cured at 23 ° C. and 50% RH for 1 week, in accordance with JIS K5600. Then, an adhesion test of a grid consisting of 25 squares at 1 mm intervals was performed. The evaluation was performed as follows based on the number of cells in which the resin remained on the calcium silicate plate after the test. The evaluation is good in the order of A, B, and C. That is, A is the best, B is good, and C is not.
　Ａ：２０マス以上
　Ｂ：１０マスから１９マス
　Ｃ：９マス以下。 A: 20 squares or more B: 10 squares to 19 squares C: 9 squares or less.
　〔合成例１～８〕
　（水溶性共重合体：Ａ－１～Ａ－８）
　表１に記載の各種成分を表１に記載の量で用いて、各共重合体（Ａ－１～Ａ－８）を合成した。 [Synthesis Examples 1 to 8]
(Water-soluble copolymer: A-1 to A-8)
Each copolymer (A-1 to A-8) was synthesized by using various components shown in Table 1 in the amounts shown in Table 1.
　具体的には、攪拌機、温度計、還流冷却器、窒素ガス導入管および滴下ロートを備えた反応器に、表１に記載の種類および量のｂ成分を仕込み、窒素ガスを導入しつつ７５℃に昇温した後、表１に記載の種類および量のａ成分の混合溶液を滴下ロートから５時間かけて等速滴下した。次に、表１に記載の種類および量のｃ成分の混合溶液を１時間かけて等速滴下した。その後、引き続き、７５℃で２時間攪拌した後、ロータリーエバポレーターにより不揮発成分が９０％以上になるまで脱気を行い、続いて、不揮発成分が４０％になるように水で希釈を行った。室温まで冷却し、各共重合体（Ａ－１～Ａ－８）を得た。 Specifically, a reactor equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas introduction tube and a dropping funnel is charged with the type and amount of component b shown in Table 1, and the temperature is 75 ° C. while introducing nitrogen gas. After the temperature was raised to the above, a mixed solution of the type and amount of component a shown in Table 1 was added dropwise from the dropping funnel at a constant rate over 5 hours. Next, a mixed solution of the c component of the type and amount shown in Table 1 was added dropwise at a constant velocity over 1 hour. Then, after stirring continuously at 75 ° C. for 2 hours, degassing was performed by a rotary evaporator until the non-volatile component became 90% or more, and then diluted with water so that the non-volatile component became 40%. The mixture was cooled to room temperature to obtain each copolymer (A-1 to A-8).
　〔合成例９〕
　（水性エマルション共重合体：Ａ－９）
　表１に記載の各種成分を表１に記載の量で用いて、共重合体（Ａ－９）を合成した。 [Synthesis Example 9]
(Aqueous emulsion copolymer: A-9)
A copolymer (A-9) was synthesized by using various components shown in Table 1 in the amounts shown in Table 1.
　具体的には、攪拌機、温度計、還流冷却器、窒素ガス導入管および滴下ロートを備えた反応器に、表１に記載の種類および量のｂ成分を仕込み、窒素ガスを導入しつつ７５℃に昇温した後、表１に記載の種類および量のａ成分の混合溶液を滴下ロートから５時間かけて等速滴下した。次に、表１に記載の種類および量のｃ成分の混合溶液を１時間かけて等速滴下した。その後、引き続き、７５℃で２時間攪拌した後、室温まで冷却し、共重合体（Ａ－９）を得た。 Specifically, a reactor equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas introduction tube and a dropping funnel is charged with the type and amount of component b shown in Table 1, and the temperature is 75 ° C. while introducing nitrogen gas. After the temperature was raised to the above, a mixed solution of the type and amount of component a shown in Table 1 was added dropwise from the dropping funnel at a constant rate over 5 hours. Next, a mixed solution of the c component of the type and amount shown in Table 1 was added dropwise at a constant velocity over 1 hour. Then, the mixture was subsequently stirred at 75 ° C. for 2 hours and then cooled to room temperature to obtain a copolymer (A-9).
Figure JPOXMLDOC01-appb-T000001
 　〔実施例１～６および比較例１～３〕
　上記合成例１～９で得られた各共重合体（Ａ－１～Ａ－９）を用いて、上記に記載の方法により、各種パラメータの測定および／または評価を行った。結果を表２に示す。なお、各共重合体（Ａ－１～Ａ－９）は、それぞれ実施例１～６および比較例１～３に対応する。
Figure JPOXMLDOC01-appb-T000001
 [Examples 1 to 6 and Comparative Examples 1 to 3]
Using each of the copolymers (A-1 to A-9) obtained in Synthesis Examples 1 to 9, various parameters were measured and / or evaluated by the method described above. The results are shown in Table 2. In addition, each copolymer (A-1 to A-9) corresponds to Examples 1 to 6 and Comparative Examples 1 to 3, respectively.
Figure JPOXMLDOC01-appb-T000002
 　〔結果〕
　表２より、実施例１～６では、光沢値（塗膜の透明性）、付着性（含浸性、補強性）および最低成膜温度（成膜性に関連し、低い方が好ましい。）に優れ、かつ貯蔵安定性も良好であった。
Figure JPOXMLDOC01-appb-T000002
 〔result〕
From Table 2, in Examples 1 to 6, the gloss value (transparency of the coating film), the adhesiveness (impregnation property, the reinforcing property) and the minimum film forming temperature (the lower one is preferable in relation to the film forming property). It was excellent and had good storage stability.
　一方、比較例１では、ＡＴＢＳ－Ｎａの量が少ないため（５重量％）光沢値が低く、含浸性（補強性）が低いことにより付着性も不良であった。また、最低成膜温度が高く成膜性も劣る結果となった。 On the other hand, in Comparative Example 1, since the amount of ATBS-Na was small (5% by weight), the gloss value was low, and the impregnation property (reinforcing property) was low, so that the adhesiveness was also poor. In addition, the minimum film forming temperature was high and the film forming property was inferior.
　比較例２では、弱酸と強塩基からなる塩構造を有するアクリル酸ナトリウムを用いたため、重合安定性が悪くなり、目的の樹脂を得ることができなかった。 In Comparative Example 2, since sodium acrylate having a salt structure consisting of a weak acid and a strong base was used, the polymerization stability was deteriorated and the target resin could not be obtained.
　比較例３では、（メタ）アクリロイル基および（メタ）アクリルアミド基のいずれも含まないアデカリアソープＳＲ－１０を用いたため、光沢値が低く、付着性も不良であった。また、最低成膜温度が高く成膜性が劣る結果となった。 In Comparative Example 3, since Adecaria Soap SR-10 containing neither (meth) acryloyl group nor (meth) acrylamide group was used, the gloss value was low and the adhesiveness was also poor. In addition, the minimum film forming temperature was high and the film forming property was inferior.
　本アクリル系樹脂は、水性塗料として使用した場合に、塗膜の透明性（光沢性）、含浸性（補強性）および製膜性に優れ、かつ貯蔵安定性も良好である。したがって、本発明は、様々なコーティング剤の分野に好適に利用することができる。 When used as a water-based paint, this acrylic resin is excellent in transparency (glossiness), impregnation (reinforcing property) and film-forming property of the coating film, and also has good storage stability. Therefore, the present invention can be suitably used in various coating agent fields.

Claims (15)

  1. 　加水分解性シリル基を有する（メタ）アクリル系樹脂であって、
    　さらに、強酸と強塩基からなる塩構造を有し、
    　水溶性である、（メタ）アクリル系樹脂。     A (meth) acrylic resin having a hydrolyzable silyl group.
    Furthermore, it has a salt structure consisting of a strong acid and a strong base.
    A water-soluble (meth) acrylic resin.
  2. 　構成単位として、強酸と強塩基からなる塩構造を有し、かつ（メタ）アクリロイル基および（メタ）アクリルアミド基の少なくともいずれか一方のラジカル重合性不飽和基を有する単量体に由来する構成単位（ａ）を含む、請求項１に記載の（メタ）アクリル系樹脂。 As a structural unit, a structural unit derived from a monomer having a salt structure consisting of a strong acid and a strong base and having a radically polymerizable unsaturated group of at least one of a (meth) acryloyl group and a (meth) acrylamide group. The (meth) acrylic resin according to claim 1, which comprises (a).
  3. 　構成単位として、さらに、加水分解性シリル基およびラジカル重合性不飽和基を有する単量体に由来する構成単位（ｂ）と、
    　前記（ａ）および（ｂ）以外の、ラジカル重合性不飽和基を有する単量体に由来する構成単位（ｃ）と、を含む、請求項２に記載の（メタ）アクリル系樹脂。     As the structural unit, a structural unit (b) derived from a monomer having a hydrolyzable silyl group and a radically polymerizable unsaturated group, and
    The (meth) acrylic resin according to claim 2, which comprises a structural unit (c) derived from a monomer having a radically polymerizable unsaturated group other than the above (a) and (b).
  4. 　前記構成単位（ａ）は、前記（ａ）～（ｃ）の全量に対して、６重量％以上５０重量％以下である、請求項２または３に記載の（メタ）アクリル系樹脂。 The (meth) acrylic resin according to claim 2 or 3, wherein the structural unit (a) is 6% by weight or more and 50% by weight or less with respect to the total amount of the above (a) to (c).
  5. 　前記構成単位（ｂ）は、前記（ａ）～（ｃ）の全量に対して、１重量％以上３０重量％以下であり、前記構成単位（ｃ）は、前記（ａ）～（ｃ）の全量に対して、３０重量％以上９３重量％以下である、請求項３または４に記載の（メタ）アクリル系樹脂。 The structural unit (b) is 1% by weight or more and 30% by weight or less with respect to the total amount of the (a) to (c), and the structural unit (c) is the same as the above (a) to (c). The (meth) acrylic resin according to claim 3 or 4, which is 30% by weight or more and 93% by weight or less based on the total amount.
  6. 　前記塩構造は、スルホン酸ナトリウム、スルホン酸カリウム、およびスルホン酸カルシウムからなる群より選択されるいずれかである、請求項１～５のいずれか１項に記載の（メタ）アクリル系樹脂。 The (meth) acrylic resin according to any one of claims 1 to 5, wherein the salt structure is any one selected from the group consisting of sodium sulfonate, potassium sulfonate, and calcium sulfonate.
  7. 　前記加水分解性シリル基は、エトキシシリル基である、請求項１～６のいずれか１項に記載の（メタ）アクリル系樹脂。 The (meth) acrylic resin according to any one of claims 1 to 6, wherein the hydrolyzable silyl group is an ethoxysilyl group.
  8. 　前記加水分解性シリル基は、トリエトキシシリル基である、請求項１～７のいずれか１項に記載の（メタ）アクリル系樹脂。 The (meth) acrylic resin according to any one of claims 1 to 7, wherein the hydrolyzable silyl group is a triethoxysilyl group.
  9. 　前記（メタ）アクリル系樹脂を、固形分濃度が２０％となるように水に溶解または分散させた場合の、１気圧、２５℃におけるヘイズ値が２０．０以下である、請求項１～８のいずれか１項に記載の（メタ）アクリル系樹脂。 Claims 1 to 8 in which the haze value at 1 atm and 25 ° C. when the (meth) acrylic resin is dissolved or dispersed in water so that the solid content concentration is 20% is 20.0 or less. The (meth) acrylic resin according to any one of the above.
  10. 　請求項１～９のいずれか１項に記載の（メタ）アクリル系樹脂を含む、水溶液。 An aqueous solution containing the (meth) acrylic resin according to any one of claims 1 to 9.
  11. 　前記水溶液の水含有率が４０重量％以上であり、アルコール含有率が１０重量％以下である、請求項１０に記載の水溶液。 The aqueous solution according to claim 10, wherein the aqueous solution has a water content of 40% by weight or more and an alcohol content of 10% by weight or less.
  12. 　請求項１～９のいずれか１項に記載の（メタ）アクリル系樹脂を含む水性塗料。 A water-based paint containing the (meth) acrylic resin according to any one of claims 1 to 9.
  13. 　請求項１～９のいずれか１項に記載の（メタ）アクリル系樹脂を硬化した塗膜。 A coating film obtained by curing the (meth) acrylic resin according to any one of claims 1 to 9.
  14. 　（Ａ）強酸と強塩基からなる塩構造を有し、かつ（メタ）アクリロイル基および（メタ）アクリルアミド基の少なくともいずれか一方のラジカル重合性不飽和基を有する単量体と、
    　（Ｂ）加水分解性シリル基およびラジカル重合性不飽和を有する単量体と、
    　（Ｃ）前記（Ａ）および（Ｂ）以外のラジカル重合性不飽和基を有する単量体と、を水と有機溶媒との混合溶媒中にて共重合する工程を有する、請求項３～９のいずれか１項に記載の水溶性の（メタ）アクリル系樹脂の製造方法。     (A) A monomer having a salt structure consisting of a strong acid and a strong base and having a radically polymerizable unsaturated group of at least one of a (meth) acryloyl group and a (meth) acrylamide group.
    (B) Monomers having hydrolyzable silyl groups and radically polymerizable unsaturated groups,
    (C) Claims 3 to 9 comprising a step of copolymerizing a monomer having a radically polymerizable unsaturated group other than the above (A) and (B) in a mixed solvent of water and an organic solvent. The method for producing a water-soluble (meth) acrylic resin according to any one of the above items.
  15. 　前記（Ａ）の単量体は、前記（Ａ）～（Ｃ）の全量に対して、６重量％以上５０重量％以下である、請求項１４に記載の（メタ）アクリル系樹脂の製造方法。

          The method for producing a (meth) acrylic resin according to claim 14, wherein the monomer of (A) is 6% by weight or more and 50% by weight or less with respect to the total amount of (A) to (C). ..
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