Classifications

• • 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.

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