JP2012201858A - Aqueous curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous curable resin composition which enables a coating film to be formed, the coating film holding a high rate of elongation in addition to high durability, high weatherability and high substrate followup ability.SOLUTION: The aqueous curable resin composition includes: a composite resin (A) in which a hydrophilic group-containing polyurethane (a1) and a vinyl polymer (a2) are bound via a polysiloxane (a3); a resin (D) having preferable elongation; and an aqueous medium, wherein the bond between the hydrophilic group-containing polyurethane (a1) and a polysiloxane (a3) is formed by a reaction between a hydrolyzable silyl group and/or silanol group of the hydrophilic group-containing polyurethane (a1) and a hydrolyzable silyl group and/or silanol group of the polysiloxane (a3), and a mass proportion of the structure originated from the polysiloxane (a3) with respect to the whole of the composite resin (A) falls into the range of 15 to 55 wt.%.

Description

  The present invention relates to an aqueous curable resin composition suitable for coating agents, paints and the like.

  The coating agent is required not only to impart design properties to various substrates, but also to form a coating film with excellent durability capable of preventing deterioration of the substrate. Particularly in recent years, even when organic solvent or acid rain adheres to the coating film surface, the durability and weather resistance at a level that does not cause dissolution or peeling of the coating film, loss of gloss, occurrence of cracks, etc. The coating agent which can form the coating film with the property is calculated | required from the industry.

  As a coating agent that can form a coating film having excellent durability and weather resistance as described above, for example, a composite resin in which a hydrophilic group-containing polyurethane and a vinyl polymer are bonded via a polysiloxane is used. It has been proposed (see, for example, Patent Document 1).

  However, with the above composition, although a coating film with excellent substrate followability can be obtained, the elongation of the coating film tends to decrease as the coating film changes with time, and as a result, high elongation is maintained over the long term. It was insufficient to obtain a coating film.

JP 2010-1457 A

  The problem to be solved by the present invention is to provide an aqueous curable resin composition capable of forming a coating film having high elongation in addition to high durability, high weather resistance, and high substrate followability.

  As a result of intensive studies to solve the above problems, the present inventor impairs high durability, high weather resistance, and high substrate followability by using a resin component with good elongation in the aqueous composite resin composition. The present invention was completed by finding that a coating film with no decrease in elongation was obtained over time.

That is, the present invention relates to a composite resin (A) in which a hydrophilic group-containing polyurethane (a1) and a vinyl polymer (a2) are bonded via a polysiloxane (a3), a resin (D) with good elongation, and an aqueous medium. The hydrolyzable silyl group of the hydrophilic group-containing polyurethane (a1) is a bond between the hydrophilic group-containing polyurethane (a1) and the polysiloxane (a3). And / or formed by a reaction between a hydrolyzable silyl group and / or a silanol group of the polysiloxane (a3), and the vinyl polymer (a2) and the polysiloxane (a3). The hydrolyzable silyl group and / or silanol group of the vinyl polymer (a2) and the polysiloxane (a3). The mass ratio of the structure derived from the polysiloxane (a3) to the entire composite resin (A) is in the range of 15 to 55% by weight, which is formed by a reaction with a ryl group and / or a silanol group. An aqueous curable resin composition is provided.

The aqueous curable resin composition of the present invention has good adhesion to various substrates such as metal substrates, plastic substrates, inorganic substrates, fibrous substrates, cloth materials, paper, and wooden substrates. Since it has, it can be used for a coating agent or an adhesive. In particular, since the aqueous composite resin composition of the present invention can form a coating film excellent in durability, weather resistance, and substrate followability, a primer layer forming coating agent and a top coat layer forming coating agent for various substrates. Etc. can be used suitably.

  In addition, the water-based curable resin composition of the present invention can form a coating film having excellent rust resistance as well as excellent durability and weather resistance, so that, for example, building members such as outer walls and roofs, guardrails, soundproof walls, Galvanized steel sheets used for civil engineering members such as drainage grooves, household appliances, industrial machinery, and automobile parts, plated steel sheets such as aluminum-zinc alloy steel sheets, aluminum plates, aluminum alloy plates, electromagnetic steel plates, copper plates, stainless steel plates It can be suitably used as a coating agent for surface coating of a metal substrate such as the above, and a primer coating layer forming coating agent between the above-described various steel plates and the topcoat layer.

  In addition, the aqueous curable resin composition of the present invention has excellent adhesion to various plastic substrates such as polycarbonate substrates and acrylonitrile-butadiene-styrene substrates. It can be suitably used as a coating agent for surface coating of plastic products such as products, OA equipment and automobile interior materials.

  Moreover, since the aqueous curable resin composition of the present invention can form a coating film that retains high elongation over time for a long time, it can be used, for example, as an adhesive for various functional films constituting a polarizing plate. it can.

  The aqueous curable resin composition used in the present invention is, for example, a composite resin (A) in which a hydrophilic group-containing polyurethane (a1) and a vinyl polymer (a2) are bonded via a polysiloxane (a3), and good elongation. Resin (D), an aqueous medium, and other additives as necessary, wherein the weight ratio of the structure derived from the polysiloxane (a3) to the entire composite resin (A) is 15 to 55% by weight is preferred.

  In addition, the weight ratio of the structure derived from the polysiloxane (a3) in the aqueous curable resin composition is 5 to 50% by weight of the total of the composite resin (A) and the resin with good elongation (D). Preferably, 10 to 40 weight% is more preferable.

  Further, the resin (D) having good elongation is preferably contained in an amount of 10 to 1000 parts by weight, more preferably 35 to 450 parts by weight, based on 100 parts by weight of the composite (A).

  The composite resin (A) is dispersed in an aqueous medium, but a part of the composite resin (A) may be dissolved in the aqueous medium. The composite resin (A) dispersed in the aqueous medium has an average particle diameter of 10 to 500 nm, and forms a coating film with excellent substrate followability and excellent durability such as crack resistance and weather resistance. This is preferable. Here, the average particle diameter refers to a value measured by a method for obtaining a particle size distribution by a measurement principle for detecting dynamic scattered light of particles.

  The composite resin (A) has a structure derived from 15 to 55% by weight of the polysiloxane (a3) based on the entire composite resin (A) in forming a coating film excellent in durability and weather resistance. It is important to have. For example, in the composite resin in which the weight ratio of the polysiloxane (a3) is 10% by weight, a coating film having a relatively good substrate followability can be formed, but such a coating film is in terms of durability and weather resistance. It is not sufficient, and peeling from the substrate may occur over time.

  On the other hand, the composite resin-containing composition in which the weight ratio of the structure derived from the polysiloxane (a3) is 65% by weight is the weight of the structure derived from the hydrophilic group-containing polyurethane (a1) or the vinyl polymer (a2). As the ratio decreases, the film-forming property decreases, and as a result, cracks may occur on the coating film surface.

  The weight ratio of the structure derived from the polysiloxane (a3) to the entire composite resin (A) is in the range of 20% by weight to 35% by weight, and has excellent durability, weather resistance, and substrate followability. It is preferable for forming a coated film.

  The structure derived from the polysiloxane (a3) means that the main chain constituting the connecting portion between the hydrophilic group-containing polyurethane (a1) and the vinyl polymer (a2) constituting the composite resin (A) is an oxygen atom. And a silicon atom. Further, the weight ratio of the structure derived from the polysiloxane (a3) is methanol that can be generated by a hydrolysis condensation reaction of the polysiloxane (a3) or the like based on the charging ratio of the raw material used for the production of the composite resin (A). It is a value calculated in consideration of the generation of by-products such as ethanol and ethanol.

  The composite resin (A) must have a hydrophilic group content in order to stably disperse it in an aqueous medium.

  The hydrophilic group is preferably present mainly in the polyurethane (a1) constituting the outer layer of the composite resin (A), but if necessary, it may be present in the vinyl polymer (a2). good.

  As the hydrophilic group, an anionic group, a cationic group, and a nonionic group may be contained.

  Examples of the hydrophilic group of the anionic group include those in which a part or all of acid groups such as carboxyl group, carboxylate group, sulfonic acid group, and sulfonate group are neutralized with a basic compound or the like.

  Examples of basic compounds that can be used for neutralizing the anionic group include organic amines such as ammonia, triethylamine, pyridine, and morpholine, alkanolamines such as monoethanolamine, Na, K, Li, and Ca. A metal base compound etc. are mentioned.

  The hydrophilic group is preferably present in the range of 50 to 1000 mmol / kg with respect to the entire composite resin (A) in order to maintain good water dispersion stability of the particles containing the composite resin (A).

Moreover, as said cationic group, a tertiary amino group etc. can be used, for example.
Examples of the acid that can be used when neutralizing part or all of the tertiary amino group include organic acids such as acetic acid, propionic acid, lactic acid, and maleic acid, sulfonic acid, methanesulfonic acid, and the like. Organic sulfonic acids and inorganic acids such as hydrochloric acid, sulfuric acid, orthophosphoric acid and orthophosphorous acid may be used alone or in combination of two or more.

  Examples of the quaternizing agent that can be used for quaternizing a part or all of the tertiary amino group include dialkyl sulfates such as dimethyl sulfate and diethyl sulfate, methyl chloride, and ethyl chloride. Alkyl halides such as benzyl chloride, alkyls such as methyl methanesulfonate and methyl paratoluenesulfonate, and epoxies such as ethylene oxide, propylene oxide, and epichlorohydrin may be used alone or in combination of two or more.

  Examples of the nonionic group include polyoxyalkylene groups such as a polyoxyethylene group, a polyoxypropylene group, a polyoxybutylene group, a poly (oxyethylene-oxypropylene) group, and a polyoxyethylene-polyoxypropylene group. Can be used. Among these, it is preferable to use a polyoxyalkylene group having an oxyethylene unit in order to further improve the hydrophilicity.

  Moreover, as said composite resin (A), the weight ratio [(a2) / (a1)] of the said hydrophilic group containing polyurethane (a1) and the said vinyl polymer (a2) is 20/1-1/20. In order to form a coating film having excellent substrate followability and excellent durability and weather resistance, it is more preferable that the range is 1/1 to 1/12. preferable.

  The bond between the hydrophilic group-containing polyurethane (a1) and the polysiloxane (a3) is, for example, the hydrolyzable silyl group and / or silanol group and the polysiloxane (the hydrophilic group-containing polyurethane (a1)). It is preferably formed by a reaction with a hydrolyzable silyl group and / or silanol group possessed by a3). Further, the bond between the vinyl polymer (a2) and the polysiloxane (a3) is a hydrolyzable silyl group and / or silanol group possessed by the vinyl polymer (a2) and a hydrolyzate possessed by the polysiloxane (a3). It is preferably formed by a reaction with a decomposable silyl group and / or silanol group.

  Next, the hydrophilic group-containing polyurethane (a1) constituting the composite resin (A) will be described.

  The hydrophilic group-containing polyurethane (a1) is an essential component for imparting excellent substrate followability to the aqueous curable resin composition of the present invention.

  As the hydrophilic group-containing polyurethane (a1), various types can be used. For example, those having a number average molecular weight of 3000 to 100,000 are preferably used, and have a number average molecular weight of 5000 to 10,000. It is preferable to use a material for forming a coating film excellent in substrate followability and excellent in durability and weather resistance.

  The hydrophilic group-containing polyurethane (a1) must have a hydrophilic group in order to impart water dispersion stability to the composite resin (A). The hydrophilic group is preferably present in the range of 50 to 1000 mmol / kg with respect to the entire hydrophilic group-containing polyurethane (a1) in order to impart better water dispersibility to the composite resin.

  As said hydrophilic group containing polyurethane (a1), the polyurethane obtained by making a polyol and polyisocyanate react can be used, for example. The hydrophilic group which the said polyurethane (a1) has can be introduce | transduced in the said polyurethane (a1), for example by using a hydrophilic group containing polyol as one component which comprises the said polyol.

  As a polyol that can be used for the production of the hydrophilic group-containing polyurethane (a1), for example, the hydrophilic group-containing polyol and other polyols can be used in combination.

  Examples of the hydrophilic group-containing polyol include carboxyl groups such as 2,2′-dimethylolpropionic acid, 2,2′-dimethylolbutanoic acid, 2,2′-dimethylolbutyric acid, and 2,2′-dimethylolvaleric acid. Containing polyols and sulfonic acid group-containing polyols such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, and 5 [4-sulfophenoxy] isophthalic acid can be used. Further, as the hydrophilic group-containing polyol, a hydrophilic group-containing polyester polyol obtained by reacting the above-described low molecular weight hydrophilic group-containing polyol with various polycarboxylic acids such as adipic acid is used. You can also.

  Other polyols that can be used in combination with the hydrophilic group-containing polyol are appropriately used according to the characteristics required for the aqueous curable resin composition of the present invention, the application to which the aqueous curable resin composition is applied, and the like. For example, polyether polyol, polyester polyol, polycarbonate polyol, and the like can be used.

  Since the polyether polyol can impart particularly excellent substrate followability to the aqueous curable resin composition of the present invention, it is preferably used in combination with the hydrophilic group-containing polyol.

  As the polyether polyol, for example, one obtained by addition polymerization of alkylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator can be used.

  Examples of the initiator include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, Trimethylolethane, trimethylolpropane and the like can be used.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran.

  Since the polyester polyol can impart particularly excellent durability to the aqueous curable resin composition of the present invention, it is preferably used in combination with the hydrophilic group-containing polyol.

  Examples of the polyester polyol include a ring-opening polymerization reaction of a cyclic ester compound such as an aliphatic polyester polyol, an aromatic polyester polyol, or ε-caprolactone obtained by esterifying a low molecular weight polyol and a polycarboxylic acid. Polyesters obtained by the above, copolymerized polyesters thereof, and the like can be used.

  Examples of the low molecular weight polyol include ethylene glycol and propylene glycol.

  Examples of the polycarboxylic acid that can be used include succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, and anhydrides or ester-forming derivatives thereof.

  Moreover, the polycarbonate polyol which can be used for manufacture of the said hydrophilic group containing polyurethane (a1) is preferable when improving the adhesiveness with respect to the plastic base material of the water-based curable resin composition of this invention markedly.

  As said polycarbonate polyol, what is obtained by making carbonate ester and a polyol react, for example, and what is obtained by making phosgene, bisphenol A, etc. react can be used.

  As the carbonate ester, methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like can be used.

  Examples of the polyol capable of reacting with the carbonate ester include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3- Butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptane Diol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 3-methyl-1,5-pentanediol, 2- Ethyl-1,3-hexanediol, 2-methyl-1,3-propa Diol, 2-methyl-1,8-octanediol, 2-butyl-2-ethylpropanediol, 2-methyl-1,8-octanediol, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexane Relatively low molecular weight dihydroxy compounds such as dimethanol, hydroquinone, resorcin, bisphenol-A, bisphenol-F, 4,4′-biphenol, polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, Polyester polyols such as hexamethylene adipate, polyhexamethylene succinate, and polycaprolactone can be used.

  As the polycarbonate polyol, use of a product obtained by reacting the dimethyl carbonate and the 1,6-hexanediol achieves both excellent adhesion to a plastic substrate and excellent substrate followability. It is more preferable because it is possible and inexpensive.

  Moreover, as said polycarbonate polyol, it is preferable to use what has the number average molecular weight of the range of 500-6000.

  The polycarbonate polyol may be used in an amount of 30 to 95% by weight based on the total amount of polyol and polyisocyanate used in the production of the polyurethane (a1), so that adhesion to a plastic substrate, weather resistance, and durability are achieved. It is preferable to achieve both.

  Moreover, as polyisocyanate used when manufacturing the said hydrophilic group containing polyurethane (a1), aromatic diisocyanates, such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, Aliphatic or aliphatic cyclic structure-containing diisocyanates such as cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate can be used alone or in combination of two or more. . Among them, it is preferable to use an aliphatic cyclic structure-containing diisocyanate because a coating film having excellent long-term weather resistance can be formed.

  The hydrophilic group-containing polyurethane resin (a1) may have other functional groups as needed in addition to the hydrophilic groups as described above. Examples of such functional groups include polysiloxane (described later) Examples of the hydrolyzable silyl group, silanol group, amino group, imino group, and hydroxyl group that can react with a3) include hydrolyzable silyl group. Among them, a hydrolyzable silyl group can form a coating film having excellent long-term weather resistance. Therefore, it is preferable.

  The hydrolyzable silyl group that the hydrophilic group-containing polyurethane (a1) may have is a functional group in which the hydrolyzable group is directly bonded to a silicon atom, and is represented by the following general formula, for example. A functional group is mentioned.

Wherein R ¹ is a monovalent organic group such as an alkyl group, aryl group or aralkyl group, R ² is a halogen atom, alkoxy group, acyloxy group, phenoxy group, aryloxy group, mercapto group, amino group, amide A group, an aminooxy group, an iminooxy group or an alkenyloxy group, and x is an integer of 0 to 2.)

Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, neopentyl, 1-methylbutyl, 2-methylbutyl, hexyl, and isohexyl groups. It is done.

  Examples of the aryl group include a phenyl group, a naphthyl group, and a 2-methylphenyl group. Examples of the aralkyl group include a benzyl group, a diphenylmethyl group, and a naphthylmethyl group.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group.

  Examples of the acyloxy group include acetoxy, propanoyloxy, butanoyloxy, phenylacetoxy, acetoacetoxy, and the like. Examples of the aryloxy group include phenyloxy, naphthyloxy, and the like. Examples of the group include an allyloxy group, a 1-propenyloxy group, and an isopropenyloxy group.

R ² is preferably independently an alkoxy group, since it is easy to remove a leaving component such as the general formula R ² OH that can be generated by hydrolysis.

  Further, the silanol group that the hydrophilic group-containing polyurethane (a1) may have is a functional group in which a hydroxyl group is directly bonded to a silicon atom, and the hydrolyzable silyl group described above is mainly hydrolyzed. The resulting functional group.

  The hydrolyzable silyl group and silanol group are preferably present in an amount of 10 to 400 mmol / kg with respect to the entire hydrophilic group-containing polyurethane (a1) in order to ensure good water dispersion stability of the composite resin.

Next, the vinyl polymer (a2) constituting the composite resin (A) will be described.
The vinyl polymer (a2) can be bonded to the hydrophilic group-containing polyurethane (a1) via a polysiloxane (a3) described later.

  As the vinyl polymer (a1), those having a number average molecular weight of 3000 to 100,000 are preferably used, and those having a number average molecular weight of 5000 to 25000 are excellent in substrate followability, And it is more preferable when forming the coating film excellent in durability, such as crack resistance, and a weather resistance.

  As the vinyl polymer (a1), for example, those produced by polymerizing various vinyl monomers in the presence of a polymerization initiator can be used.

  The vinyl monomer is a hydrolyzable silyl group-containing vinyl from the viewpoint of introducing a functional group capable of reacting with the hydrolyzable silyl group or the like of the polysiloxane (a3) into the vinyl polymer (a1). It is preferable to use a monomer or a hydroxyl group-containing vinyl monomer.

  Examples of the hydrolyzable silyl group-containing vinyl monomer include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinyltri (2-methoxyethoxy) silane, vinyltriacetoxysilane, vinyltrichlorosilane, 2- Trimethoxysilylethyl vinyl ether, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyl Trichlorosilane and the like can be mentioned. Among them, the hydrolysis reaction can easily proceed, and the by-product after the reaction can be easily removed. Therefore, vinyltrimethoxysilane, 3- (meth) acryloyl Trimethoxysilane is preferred.

  In addition, as the hydroxyl group-containing vinyl monomer, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, or the like is used. Can do.

  As the vinyl monomer, in addition to the hydrolyzable silyl group-containing vinyl monomer and the hydroxyl group-containing vinyl monomer, other vinyl monomers may be used in combination as necessary.

  Examples of the other vinyl monomers include (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, and n-butyl (meth) acrylate; N, N-dimethylaminoethyl (meth) Tertiary amino group-containing vinyl monomers such as acrylates; Secondary amino group-containing vinyl monomers such as N-methylaminoethyl (meth) acrylate; Bases such as primary amino group-containing vinyl monomers such as aminomethyl acrylate Nitrogen-containing group-containing vinyl monomers; fluorine-containing vinyl monomers such as 2,2,2-trifluoroethyl (meth) acrylate; vinyl esters such as vinyl acetate; vinyl ethers such as methyl vinyl ether; ) Nitriles of unsaturated carboxylic acids such as acrylonitrile; vinyl compounds having an aromatic ring such as styrene Α-olefins such as isoprene; epoxy group-containing vinyl monomers such as glycidyl (meth) acrylate; amide group-containing vinyl monomers such as (meth) acrylamide; methylolamide groups such as N-methylol (meth) acrylamide; An alkoxy compound-containing vinyl monomer; 2-aziridinylethyl (meth) acrylate-containing vinyl monomer; an isocyanate group such as (meth) acryloyl isocyanate and / or a blocked isocyanate group-containing vinyl Monomer; Oxazoline group-containing vinyl monomer such as 2-isopropenyl-2-oxazoline; Cyclopentenyl group-containing vinyl monomer such as dicyclopentenyl (meth) acrylate; Carbonyl group-containing vinyl monomer such as acrolein Acetoacetoxyethyl (meth) acryle Use acetoacetyl group-containing vinyl monomers such as carbonate; carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, or half esters or salts thereof, or the like Can do.

  Examples of the polymerization initiator that can be used in producing the vinyl polymer (a2) include radical polymerization initiators such as persulfates, organic peroxides, and hydrogen peroxide, and 4,4′-azobis ( An azo initiator such as 4-cyanovaleric acid) or 2,2′-azobis (2-amidinopropane) dihydrochloride can be used. The radical polymerization initiator may be used as a redox polymerization initiator in combination with a reducing agent such as ascorbic acid.

  Examples of the persulfates that are representative of the polymerization initiator include potassium persulfate, sodium persulfate, and ammonium persulfate. Specific examples of organic peroxides include, for example, peroxidation. Diacyl peroxides such as benzoyl, lauroyl peroxide, decanoyl peroxide, dialkyl peroxides such as t-butylcumyl peroxide, dicumyl peroxide, t-butylperoxylaurate, t-butylperoxybenzoate, etc. Peroxyesters, cumene hydroperoxide, paramentane hydroperoxide, hydroperoxides such as t-butyl hydroperoxide, and the like can be used.

  The polymerization initiator may be used in an amount that allows the polymerization to proceed smoothly, but should be 10% by weight or less based on the total amount of vinyl monomers used in the production of the vinyl polymer (a2). Is preferred.

Next, the polysiloxane (a3) constituting the composite resin (A) will be described.
The polysiloxane (a3) constitutes a connecting portion between the hydrophilic group-containing polyurethane (a1) and the vinyl polymer (a2).

  The polysiloxane (a3) has a chain structure consisting of a silicon atom and an oxygen atom, a branched structure, a cyclic structure, or a cage structure, and if necessary, a hydrolyzable silyl group, a silanol group, etc. It is what has.

  The hydrolyzable silyl group is an atomic group in which the hydrolyzable group is directly bonded to the silicon atom. For example, the hydrolyzable silyl group is represented by the general formula (I) exemplified in the description of the hydrophilic group-containing polyurethane (a1). Can be used.

  The hydrolyzable group is capable of forming a hydroxyl group under the influence of water, for example, a halogen atom, an alkoxy group, a substituted alkoxy group, an acyloxy group, a phenoxy group, a mercapto group, an amino group, an amide group, an aminooxy group , An iminooxy group, an alkenyloxy group, and the like. Among them, an alkoxy group and a substituted alkoxy group are preferable.

  The silanol group indicates an atomic group in which a hydroxyl group is directly bonded to the silicon atom, and is formed when the hydrolyzable silyl group is hydrolyzed.

  Moreover, as said polysiloxane (a3), what has alkyl groups, such as a methyl group, a phenyl group, etc. other than what was mentioned above as needed can be used, for example, polysiloxane (a3) 1 or more selected from the group consisting of an aromatic cyclic structure such as a phenyl group, an alkyl group having 1 to 3 carbon atoms, and an alkoxy group having 1 to 3 carbon atoms. It is more preferable to use those in which are directly bonded in order to maintain good aqueous dispersion stability of the aqueous composite resin.

  As said polysiloxane (a3), what is obtained, for example by hydrolyzing and condensing the silane compound mentioned later completely or partially can be used.

  Examples of the silane compound include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, iso-butyltrimethoxysilane, cyclohexyltrimethoxysilane, and phenyltrimethoxysilane. Organotrialkoxysilanes such as methoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane or 3- (meth) acryloyloxypropyltrimethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-butoxysilane, diethyldimethoxysilane , Diorganodialkoxysilanes such as diphenyldimethoxysilane, methylcyclohexyldimethoxysilane or methylphenyldimethoxysilane Various chlorosilanes such as methyltrichlorosilane, ethyltrichlorosilane, phenyltrichlorosilane, vinyltrichlorosilane, 3- (meth) acryloyloxypropyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane or diphenyldichlorosilane, and their partial hydrolysis A decomposition condensate or the like can be used, and among them, organotrialkoxysilane and diorganodialkoxysilane are preferably used. These silane compounds may be used alone or in combination of two or more.

  Moreover, it is preferable to form the said polysiloxane (a3) by passing through a two-step reaction process in the process of manufacturing composite resin (A). Specifically, a polysiloxane structure is formed by reacting a hydrolyzable group or the like of the vinyl polymer (a2) with a relatively low molecular weight silane compound such as phenyltrimethoxysilane, and then the reaction. A structure composed of polysiloxane (a3) can be formed by reacting a product with a condensate such as methyltrimethoxysilane or ethyltrimethoxysilane. Thereby, the aqueous | water-based composite resin composition which can form the coating film which was further excellent in base material followability | trackability and excellent in durability and stain resistance can be obtained.

  Further, as other silane compounds, for example, tetrafunctional alkoxysilane compounds such as tetramethoxysilane, tetraethoxysilane or tetra n-propoxysilane; hydrolysis condensates of the tetrafunctional alkoxysilane compounds, etc. They can be used in combination as long as they are not impaired.

  When the tetrafunctional alkoxysilane compound or its hydrolysis condensate is used in combination, the tetrafunctional alkoxysilane compound or its hydrolysis condensate is used with respect to 100 mol% of all silicon atoms constituting the polysiloxane (a3). It is preferable to use together in the range which the silicon atom which has does not exceed 20 mol%.

  Next, the resin (D) with good elongation used in the present invention will be described.

The resin (D) with good elongation of the present invention is a resin having an elongation at 25 ° C. of 100% or more. For example, acrylic resin, urethane resin, acrylic modified urethane resin, urethane modified acrylic resin, silicone resin, modified resin Silicone resin, phenol resin, polyester resin, urea resin, melamine resin, alkyd resin, epoxy resin, polyamide resin, polycarbonate resin, petroleum resin, fluorine resin, etc. can be mentioned, and these can be used alone or in combination of two or more Can be used as a mixture.

  Among these, acrylic resin, urethane resin, acrylic modified urethane resin, urethane modified acrylic resin, silicone resin, modified silicone resin, and the like are preferable from the viewpoint of excellent coating film elongation.

In addition, the resin (D) having good elongation of the present invention is preferably an aqueous solution previously dissolved or dispersed in an aqueous medium. As an aqueous medium used at that time, only water may be used, A mixed solution of water-soluble solvents may be used. Examples of the water-soluble solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethyl carbitol, ethyl cellosolve, and butyl cellosolve, and polar solvents such as N-methylpyrrolidone, one or more of these. Can be used.

  The water-based product of the resin (D) having good elongation suppresses a rapid increase in viscosity during mixing with the composite resin (A), and is easy to apply and dryability of the aqueous curable resin composition. From the viewpoint of improving the above, it is preferable to have a nonvolatile content of 20 to 70% by mass, and more preferably in the range of 30 to 60% by mass.

  Further, the water-based product of the aqueous resin (D) with good elongation according to the present invention may contain an emulsifier and a dispersion stabilizer as necessary, but from the viewpoint of suppressing a decrease in water resistance of the coating film, It is preferable that it is 5 mass% or less with respect to solid content of aqueous resin (D).

The aqueous resin having an acrylic structure used in the present invention can be used without particular limitation as long as it is a resin that exhibits high elongation as a coating film. For example, as an acrylic resin, an emulsion type acrylic copolymer, a disperser can be used. A John type acrylic copolymer is mentioned.

As the monomer constituting the acrylic copolymer, a (meth) acrylic acid alkyl ester, and a functional monomer or other monomer, if desired, can be used. The (meth) acrylic acid ester is preferably a (meth) acrylic acid ester having 1 to 20 carbon atoms in the alkyl group. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, (meth) Cyclohexyl acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, (meta ) Stearyl acrylate and the like. These may be used alone or in combination of two or more.

  Moreover, as a functional monomer, (meth) acrylic acid 2-hydroxylethyl, (meth) acrylic acid 2-hydroxylpropyl, (meth) acrylic acid 2-hydroxylbutyl, (meth) 3-hydroxylbutyl, (meth) (Meth) acrylic acid hydroxyalkyl esters such as 4-hydroxylbutyl acrylate, (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, diacetone Acrylamides such as acrylamide, (meth) acrylic acid mono or dimethylaminoethyl, (meth) acrylic acid mono or diethylaminoethyl, (meth) acrylic acid mono or dimethylaminopropyl, (meth) acrylic acid mono or diethylaminopropyl ( Me ) Acrylic acid mono- or dialkylaminoalkyl, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, maleic anhydride, phthalic acid, phthalic anhydride, ethylene unsaturated carboxylic acids such as citraconic acid. These monomers may be used alone or in combination of two or more.

  Further, other monomers include vinyl esters such as vinyl acetate and vinyl propionate, olefins such as ethylene, propylene, and isobutylene, halogenated olefins such as vinyl chloride and vinylidene chloride, styrene, and α-methylstyrene. And nitrile monomers such as acrylonitrile and methacrylonitrile. These may be used alone or in combination of two or more.

  An emulsion-type acrylic copolymer can be obtained by copolymerizing the above-mentioned acrylic monomer in an aqueous medium by an ordinary known emulsion polymerization method.

In addition, the above-mentioned acrylic monomer is copolymerized by, for example, an ordinary known solution polymerization method in the presence of an organic solvent, and is mixed with an aqueous medium to make it aqueous, whereby a dispersion-type acrylic copolymer. Can get

The aqueous resin having a urethane structure used in the present invention can be used without particular limitation as long as it is a resin that exhibits high elongation as a coating film, and examples thereof include a dispersion type urethane resin.

  The dispersion type urethane resin, for example, produces a carboxyl group-containing urethane prepolymer by reacting a polyol containing a carboxyl group-containing polyol with a polyisocyanate in the absence of a solvent or in the presence of an organic solvent, It can be produced by mixing a neutralized carboxyl group with an aqueous medium to make it aqueous, and if necessary, reacting with a chain extender such as polyamine to adjust to a desired molecular weight.

  The reaction between the polyol and the polyisocyanate is preferably carried out, for example, in an equivalent ratio of the isocyanate group of the polyisocyanate to the hydroxyl group of the polyol in the range of 1.05 to 3, It is more preferable to carry out within a range.

  Further, when the urethane resin is dispersed in the aqueous medium, a machine such as a homogenizer may be used as necessary.

  Here, as polyols that can be used for the production of the urethane resin, for example, polyester polyols, polyether polyols, polycarbonate polyols, polyacetal polyols, polyacrylate polyols, polyester amide polyols, polythioether polyols, polyolefin polyols such as polybutadiene, etc. Or can be used in combination of two or more.

  Examples of the polyester polyol include those obtained by an esterification reaction of a low molecular weight polyol and a polycarboxylic acid, polyesters obtained by a ring-opening polymerization reaction of a cyclic ester compound such as ε-caprolactone, and copolymers of these. Polymerized polyester or the like can be used.

  Examples of the low molecular weight polyol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, Neopentyl glycol, 1,8-octanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (molecular weight 300-6000), dipropylene glycol, tripropylene glycol Bis-hydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, hydroquinone and their alkylene oxide adducts can do.

  Examples of the polycarboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid. Acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p , P′-dicarboxylic acid, and anhydrides or ester-forming derivatives thereof can be used.

  As the polyester polyol, in addition to the polyol and polycarboxylic acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, ester-forming derivatives of these hydroxybenzoic acids, and the like are reacted. The one obtained can be used.

  In addition, as the polyether polyol, for example, one obtained by addition polymerization of alkylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator can be used.

  Examples of the initiator include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, Trimethylolethane, trimethylolpropane, sorbitol, sucrose, aconite sugar, trimellitic acid, hemimellitic acid, phosphoric acid, ethylenediamine, diethylenetriamine, triisopropanolamine, pyrogallol, dihydroxybenzoic acid, hydroxyphthalic acid, 1,2,3- Propane trithiol or the like can be used.

  As the alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, cyclohexylene and the like can be used.

  Examples of the polycarbonate polyol include 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, cyclohexanedimethanol and other glycols and caprolactone, diphenyl carbonate, dimethyl carbonate, phosgene and the like. What was obtained by reacting can be used.

  As the above-mentioned polyol, it is preferable to use the polyether polyol from the viewpoint of further improving the elongation of the crosslinked coating film formed by the aqueous resin composition of the present invention. Moreover, as said polyol, it is preferable to use a thing with a weight average molecular weight of 300-10000, Preferably it is 500-5000.

  Moreover, when manufacturing a urethane resin, it is preferable to use together a carboxyl group-containing polyol for the purpose of introducing a carboxyl group into the urethane resin.

  Examples of the carboxyl group-containing polyol include 2,2′-dimethylolpropionic acid, 2,2′-dimethylolbutanoic acid, 2,2′-dimethylolbutyric acid, 2,2′-dimethylolvaleric acid, and the like. Can do. Moreover, the carboxyl group-containing polyester polyol obtained by making the said carboxyl group-containing polyol and various polycarboxylic acids react can also be used.

  In addition, as the polyisocyanate used in producing the urethane resin, for example, aromatic diisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, Aliphatic or alicyclic diisocyanates such as dicyclohexylmethane diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate can be used alone or in combination of two or more.

  As the polyisocyanate, an aliphatic diisocyanate or an alicyclic diisocyanate is preferably used from the viewpoint of further improving the solvent resistance of the crosslinked coating film formed by the aqueous resin composition of the present invention. Preference is given to using methylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate.

  Examples of basic compounds that can be used for neutralizing the carboxyl group in the urethane resin include organic amines such as ammonia, triethylamine, and morpholine, alkanolamines such as monoethanolamine and diethylethanolamine, Na, and K. , Metals including Li and the like can be used. The amount of the basic compound used is [basic compound / carboxyl group] = 0.5 to 3.0 (moles) with respect to the carboxyl group from the viewpoint of improving the water dispersion stability of the resulting aqueous resin composition. The ratio is preferably in the range of 0.9 to 2.0 (molar ratio).

  When producing the urethane resin, for the purpose of designing a polyurethane resin having physical properties such as various mechanical properties and thermal properties, a chain extender such as a polyamine or other active hydrogen atom-containing compound is used as necessary. May be used.

Examples of such polyamines include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4′-dicyclohexylmethanediamine, and 3,3′-. Diamines such as dimethyl-4,4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, Diamines containing one primary amino group and one secondary amino group such as N-methylaminopropylamine; polyamines such as diethylenetriamine, dipropylenetriamine, triethylenetetramine; hydrazine, N, Hydrazines such as' -dimethylhydrazine and 1,6-hexamethylenebishydrazine; Dihydrazides such as succinic acid dihydrazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide; β-semicarbazide propionic acid hydrazide, 3 -Semicarbazides such as semicarbazide-propyl-carbazic acid ester, semicarbazide-3-semicarbazide methyl-3,5,5-trimethylcyclohexane can be used.

  When polyamine is used as the chain extender, it is preferably used in the range where the equivalent ratio of the amino group and excess isocyanate group of the polyamine is 1.9 or less (equivalent ratio). More preferably, it is used in the range of 0.0 (equivalent ratio). By using the chain extender in the above-described range, the solvent resistance and mechanical strength of the coating film formed by the obtained aqueous resin composition can be improved.

  Examples of the other active hydrogen-containing compound include ethylene glycol, diethylene recall, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, and sucrose. , Glycols such as methylene glycol, glycerin, sorbitol; phenols such as bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, hydroquinone , And water can be used singly or in combination of two or more in a range where the storage stability of the aqueous paint of the present invention does not deteriorate.

  When the urethane resin is produced in the presence of an organic solvent, for example, ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; acetate esters such as ethyl acetate and butyl acetate; Nitriles: Amides such as dimethylformamide and N-methylpyrrolidone can be used alone or in combination of two or more. In particular, it is preferable to use methyl ethyl ketone or N-methylpyrrolidone because the urethane resin (a1) is easily dissolved.

Next, a method for producing the aqueous composite resin composition used in the present invention will be described.
The method for producing an aqueous composite resin composition of the present invention mainly comprises (i) a step of producing a composite resin (A), (ii) a step of dispersing the composite resin (A) in an aqueous medium, and (iii) stretching. The resin (D) having a good degree of temperature is added after the step (i) or (ii).

  First, the process for producing the composite resin (A) will be described.

  The composite resin (A) can be produced, for example, by the following steps (I) to (III).

  The step (I) is a step of obtaining an organic solvent solution of the vinyl polymer (a2) by polymerizing the above vinyl monomer in the presence of the polymerization initiator in an organic solvent.

  Such a reaction may be performed, for example, by sequentially or collectively supplying the vinyl monomer in an organic solvent containing a polymerization initiator, and then, for about 0.5 to 24 hours in the range of 20 to 120 ° C. with stirring. preferable.

  In the step (II), a reactive functional group such as a hydrolyzable silyl group possessed by the vinyl polymer (a2) under the organic solvent solution of the vinyl polymer (a2) and a hydrolyzate possessed by the silane compound. The organic of the resin (C) in which the vinyl polymer (a2) and the polysiloxane (a3) are bonded by a reaction with a decomposable silyl group or silanol group and a hydrolysis condensation reaction between the silane compounds. This is a step of obtaining a solvent solution.

  For example, following the step (I), the reaction may be performed by sequentially or collectively supplying the silane compound capable of forming the polysiloxane (a3) into the organic solvent solution of the vinyl polymer (a2). Under stirring, it is preferably carried out in the range of 20 to 120 ° C. for about 0.5 to 24 hours.

  The step (II) preferably further undergoes a two-step reaction step. Specifically, a step of reacting the hydrolyzable silyl group or silanol group of the vinyl polymer (a2) with a relatively low molecular weight silane compound such as phenyltrimethoxysilane, and then the reaction product And a step of reacting a methyltrialkoxysilane such as methyltrimethoxysilane or ethyltrimethoxysilane and a condensate obtained by condensing ethyltrialkoxysilane in advance. By carrying out the structure formation of polysiloxane (a3) in the above two steps, it is possible to obtain an aqueous composite resin composition capable of forming a coating film having excellent substrate followability and durability. it can.

  In the step (III), the resin (C) and the hydrophilic group-containing polyurethane (a1) are mixed and hydrolytically condensed, whereby the vinyl polymer (a2) and the hydrophilic group-containing polyurethane ( a1) is a step of obtaining an organic solvent solution of the composite resin (A) bonded with the polysiloxane (a3).

  The reaction is, for example, following the step (II), containing a hydrophilic group obtained by reacting a polyol containing the hydrophilic group-containing polyol with the polyisocyanate in an organic solvent solution of the resin (C). It is preferable that the polyurethane (a1) is sequentially or collectively supplied, and then is stirred for about 0.5 to 24 hours in the range of 20 to 120 ° C.

  The organic solvent solution of the composite resin (A) obtained by the steps (I) to (III) is preferably made aqueous by the following step (IV).

  Step (IV) is a step of neutralizing the hydrophilic group of the composite resin (A) and dispersing the neutralized product in an aqueous medium following the step (III), for example.

  Neutralization of the hydrophilic group is not necessarily performed, but is preferably performed from the viewpoint of improving the water dispersion stability of the composite resin (A). In particular, when the hydrophilic group is an anionic group such as a carboxyl group or a sulfonic acid group, all or a part thereof is neutralized with a basic compound to form a carboxylate group or a sulfonate group. Is preferable for further improving the water dispersion stability.

  The neutralization can be performed, for example, by sequentially or collectively supplying a basic compound or the like into the organic solvent solution of the composite resin (A) and stirring.

  After the neutralization, an aqueous medium is supplied into the organic solvent solution of the composite resin (A) neutralized product, and then the organic solvent is removed to produce an aqueous product of the composite resin (A) of the present invention. .

  The removal of the organic solvent can be performed, for example, by distillation.

  By adding the resin (D) having good elongation after the step of producing the composite resin (A) or the step of dispersing the composite resin (A) in an aqueous medium, the aqueous curability of the present invention. A resin composition can be obtained.

Examples of the aqueous medium include water, organic solvents miscible with water, and mixtures thereof. Examples of the organic solvent miscible with water include alcohols such as methanol, ethanol, n- and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; Alkyl ethers; lactams such as N-methyl-2-pyrrolidone, and the like. In the present invention, only water may be used, a mixture of water and an organic solvent miscible with water may be used, or only an organic solvent miscible with water may be used.
From the viewpoint of safety and load on the environment, water alone or a mixture of water and an organic solvent miscible with water is preferable, and only water is particularly preferable.

  The aqueous curable resin composition of the present invention suppresses a rapid increase in viscosity during production, and improves the productivity of the aqueous curable resin composition, ease of coating, drying properties, and the like. From the above, it is preferable to have a non-volatile content of 20 to 70% by weight, and more preferably in the range of 30 to 60% by weight.

  The aqueous curable resin composition of the present invention can be used as a paint or various coating agents as it is, or by adding a curing agent or an additive described later.

  The aqueous curable resin composition of the present invention may be used in combination with a curing agent as necessary.

  As said hardening | curing agent, the compound which has the functional group which reacts with the hydrophilic group and silanol group which an aqueous curable resin composition has can be used.

  Specific examples of the curing agent include a compound having a silanol group and / or a hydrolyzable silyl group, a polyepoxy compound, a polyoxazoline compound, and a polyisocyanate. In particular, when the composite resin having a carboxyl group or a carboxylate group is used, a combination using an epoxy group, a silanol group and / or a hydrolyzable silyl group, a polyepoxy compound, a polyoxazoline compound It is preferable that

  Examples of the compound having a silanol group and / or a hydrolyzable silyl group include those similar to the silane compounds exemplified as usable in the production of the composite resin, and other 3-glycidoxypropyltrimethoxy. Silane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. These hydrolysis-condensation products are exemplified.

  Examples of the polyepoxy compound include polyglycidyl ethers having a structure derived from an aliphatic or alicyclic polyol such as ethylene glycol, hexanediol, neopentyl glycol, trimethylolpropane, pentaerythritol, sorbitol, hydrogenated bisphenol A and the like. Polyglycidyl ethers of aromatic diols such as bisphenol A, bisphenol S and bisphenol F; polyglycidyl ethers of polyether polyols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol; tris (2-hydroxyethyl) Polyglycidyl ethers of isocyanurates; polyglycidies of aliphatic or aromatic polycarboxylic acids such as adipic acid, butanetetracarboxylic acid, phthalic acid, terephthalic acid Bisepoxides of hydrocarbon dienes such as cyclooctadiene and vinylcyclohexene; bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, etc. And alicyclic polyepoxy compounds.

  Examples of the polyoxazoline compound include 2,2′-p-phenylene-bis (1,3-oxazoline), 2,2′-tetramethylene-bis (1,3-oxazoline), and 2,2′-octa. Methylene-bis (2-oxazoline), 2-isopropenyl-1,3-oxazoline, or a polymer thereof can be used.

  Examples of the polyisocyanate include aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane-4,4′-diisocyanate; meta-xylylene diisocyanate, α, α, α ′, α′-tetramethyl-meta-xylylene diisocyanate Aralkyl diisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, 1,3-bisisocyanate methylcyclohexane, 2-methyl-1,3-diisocyanate cyclohexane, 2-methyl-1,5-diisocyanate cyclohexane, isophorone Diisocyanate and the like can be used.

  As the polyisocyanate, various prepolymers having an isocyanate group, prepolymers having an isocyanurate ring, polyisocyanate having a biuret structure, and isocyanate group-containing vinyl monomers can also be used.

  The isocyanate group of the polyisocyanate as a curing agent may be blocked with a conventionally known blocking agent such as methanol as necessary.

  The curing agent is preferably used in the range of 0.1 to 50 parts by weight of solid content, for example, in the range of 0.5 to 30 parts by weight with respect to 100 parts by weight of the aqueous curable resin composition. It is more preferable to use within the range of 1 to 20 parts by weight.

  In addition, when the aqueous curable resin composition has a carboxyl group as a hydrophilic group, the curing agent is an epoxy group, cyclohexane, or the like included in the curing agent with respect to 1 equivalent of the carboxyl group of the aqueous curable resin composition. The equivalent of the reactive functional group such as carbonate group, hydroxyl group, oxazoline group, carbodiimide group, hydrazino group is preferably in the range of 0.2 to 5.0 equivalent, and in the range of 0.5 to 3.0 equivalent. It is more preferable that it is in the range of 0.7 to 2.0 equivalents.

  Moreover, the aqueous curable resin composition of the present invention can contain a curing catalyst as necessary.

  Examples of the curing catalyst include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methylate, tetraisopropyl titanate, tetra-n-butyl titanate, tin octylate, lead octylate, cobalt octylate, and zinc octylate. Calcium octylate, zinc naphthenate, cobalt naphthenate, di-n-butyltin diacetate, di-n-butyltin dioctoate, di-n-butyltin dilaurate, di-n-butyltin maleate, p-toluenesulfone Acid, trichloroacetic acid, phosphoric acid, monoalkyl phosphoric acid, dialkyl phosphoric acid, monoalkyl phosphorous acid, dialkyl phosphorous acid and the like can be used.

  The aqueous curable resin composition of the present invention can contain a thermosetting resin as necessary. Examples of such thermosetting resins include vinyl resins, polyester resins, epoxy resins, epoxy ester resins, acrylic resins, phenol resins, petroleum resins, ketone resins, silicone resins, and modified resins thereof.

  In the aqueous curable resin composition of the present invention, various inorganic particles such as clay mineral, metal, metal oxide, and glass can be used as necessary. Examples of the metal include gold, silver, copper, platinum, titanium, zinc, nickel, aluminum, iron, silicon, germanium, antimony, and metal oxides thereof.

  The aqueous curable resin composition of the present invention includes an inorganic pigment, an organic pigment, an extender pigment, a wax, a surfactant, a stabilizer, a flow regulator, a dye, a leveling agent, a rheology control agent, and an ultraviolet absorber as necessary. Various additives such as antioxidants and plasticizers can be used.

  Since the aqueous curable resin composition can form a coating film excellent in substrate followability, it can be used for various applications such as a coating agent and an adhesive. Among them, the aqueous curable resin composition of the present invention is preferably used as a coating agent because it can form a coating film excellent in durability and weather resistance as well as the substrate followability. And more preferably used as a primer layer-forming coating agent.

  There are various types of base materials that can be coated with the coating agent to form a coating film. Typical examples of such base materials include various metal base materials, plastic base materials, inorganic base materials, and fiber base materials. , Cloth, paper, woody base material and the like.

  The base materials may be plate-shaped, spherical, film-shaped, and sheet-shaped, respectively. In addition, since the coating agent is particularly excellent in substrate followability, a film-like or sheet-like substrate that easily causes deformation or expansion due to the influence of external force or temperature, a substrate having fine irregularities on the surface, It can also be suitably used for large structures, complex shaped assemblies and molded articles.

  In addition to the durability, weather resistance, and substrate followability, the coating agent has a level of corrosion resistance that can prevent the occurrence of rust on the surface of the substrate and prevent peeling and swelling of the coating film due to the rust. For example, building materials such as outer walls and roofs, guard rails, sound barriers, civil engineering members such as drainage grooves, home appliances, industrial machinery, and parts for various metal substrates that make up automobile parts, etc. Can do. In particular, the coating agent obtained by reacting the polyol and polyisocyanate containing the polyether polyol and the hydrophilic group-containing polyol with the hydrophilic group-containing polyurethane (a1) constituting the composite resin (A), Because it is excellent in adhesion to metal substrates and substrate followability, it can be used exclusively for coating agents for metal substrates, and in particular, it can be preferably used for steel sheet surface treatment agents that can replace conventional chromate treatment. it can.

  Specific examples of the metal substrate include simple metals such as iron, nickel, chromium, aluminum, magnesium, copper, and lead; alloys obtained from the above-described simple metals such as stainless steel and brass; zinc, nickel, Metals subjected to plating treatment such as iron plated with a metal such as chrome; The above-mentioned metal simple substances, alloys or metal subjected to plating treatment were subjected to chemical conversion treatment such as chromate treatment or phosphate treatment. Metals are mentioned.

  Of the coating agents, the hydrophilic group-containing polyurethane (a1) constituting the composite resin (A) contained in the coating agent is reacted with a polyol and a polyisocyanate containing a polycarbonate polyol and a hydrophilic group-containing polyol. The coating agent obtained by the above has excellent adhesion to various types of plastic substrates without impairing the durability, weather resistance, and substrate followability. It can be suitably used as a coating agent for coating.

  Moreover, since the said coating agent can form a comparatively transparent coating film, it can be used for the surface coating of a transparent plastic base material, for example. Here, as the transparent plastic substrate, a substrate made of polymethyl methacrylate resin (PMMA resin), polycarbonate resin, or the like can be used. These transparent plastic substrates are commonly referred to as organic glass, and have characteristics such as being lighter and harder to break than general inorganic glass. In recent years, they have been used as substitutes for inorganic glass in window glass for houses and automobiles. The application of is being considered. According to the coating agent of the present invention, it is possible to impart excellent weather resistance, durability, contamination resistance, and the like to the organic glass without impairing the transparency of the organic glass used for window glass in houses and the like. it can.

  Specific examples of plastic substrates include molded products of thermoplastic resins such as polystyrene, polycarbonate, polymethyl methacrylate, ABS resin, polyphenylene oxide, polyurethane, polyethylene, polyvinyl chloride, polypropylene, polybutylene terephthalate, and polyethylene terephthalate; unsaturated Examples thereof include molded products of thermosetting resins such as polyester resins, phenol resins, cross-linked polyurethane, cross-linked acrylic resins, cross-linked saturated polyester resins, and the like. The plastic substrate may have a single layer or a laminated structure of two or more layers. Moreover, these plastic base materials may be unstretched, uniaxially stretched, or biaxially stretched.

  In order to further improve the adhesiveness with the coating agent, the plastic substrate may be subjected to various surface treatments on the surface of the substrate. Examples of such surface treatment include corona discharge treatment and plasma treatment. , Flame plasma treatment, electron beam irradiation treatment, ultraviolet irradiation treatment, and the like, and a treatment combining one or more of these may be performed.

  In addition, the plastic substrate has an antistatic agent, an antifogging agent, an antiblocking agent, an antioxidant, a light stabilizer, a crystal nucleating agent, a lubricant, etc. The additive may be contained.

  In addition, examples of the inorganic base material include those mainly composed of inorganic materials typified by cement-based, silicate-based, such as calcium silicate, gypsum-based, and ceramic-based materials. Wet) base materials include exposed concrete, cement mortar, gypsum plaster, dolomite plaster, plaster, etc. Also, factory-produced (dry) base materials include lightweight cellular concrete (ALC), glass fiber reinforced calcium silicate , Various types of fired products of clay such as gypsum board and tile, or glass.

  Examples of the fiber substrate include organic fibers made of organic materials such as cotton, silk, hair, acrylic, polyester, polyethylene terephthalate, and cellulose, and metal fibers made of metals such as iron, aluminum, gold, silver, and copper. And inorganic fibers made of inorganic materials such as ceramic fibers and glass fibers.

The fiber base material may be a processed fiber product such as a nonwoven fabric, and various surface treatments may be applied to the base material surface in order to further improve the adhesion to the coating agent. . Examples of such surface treatment include corona discharge treatment, plasma treatment, flame plasma treatment, electron beam irradiation treatment, ultraviolet ray irradiation treatment, and the like, and a treatment combining one or more of these may be performed.

  A coated product can be obtained by applying and curing the coating agent on various substrates as described above. At that time, (1) the paint is directly applied to the base material, (2) the base coat is applied on the base in advance, and then the coating agent is applied as the top coat. (3) the base is applied to the base. A coated product can be obtained by a coating method such as coating the coating agent as a coating material, and then applying another top coating material to form a coating film.

  In order to obtain a coated product by the direct coating method described in (1) above, the coating agent is applied to the substrate by brush coating, roller coating, spray coating, dip coating, flow coater coating, roll coater coating, electric coating. What is necessary is just to make it harden | cure after painting by the painting methods, such as wearing painting.

Moreover, when obtaining the coating material which has the coating film which consists of the said coating agent by the coating method of said (2) or (3), conventionally known acrylic resin-type coating material and polyester as undercoat paint and topcoat paint Resin-based paints, alkyd resin-based paints, epoxy resin-based paints, fatty acid-modified epoxy resin-based paints, silicone resin-based paints, polyurethane resin-based paints, and the like can be used.

  The method of drying the coating agent and proceeding with curing may be a method of curing for about 1 to 10 days at room temperature, but from the viewpoint of rapidly curing, at a temperature of 50 to 250 ° C., 1 A method of heating for about ~ 600 seconds is preferred. Moreover, when using the plastic base material which deform | transforms and discolors easily at comparatively high temperature, it is preferable to perform curing at comparatively low temperature of about 30-100 degreeC.

Although the film thickness of the coating film formed using the said coating agent can be suitably adjusted according to the use etc. which a base material is used for, it is preferable that it is normally about 0.5 micrometer-100 micrometers.

Examples of the painted materials include automobiles, motorcycles, trains, bicycles, ships, airplanes, and other transport-related equipment and various parts used for them; TVs, radios, refrigerators, washing machines, coolers, cooler outdoor units, Home appliances such as computers and air purifiers and various parts used in them; inorganic tiles, metal roofing materials, inorganic outer wall materials, metal wall materials, metal window frames, metal Building materials such as made or wooden doors, inner wall materials; outdoor structures such as roads, road signs, guardrails, bridges, tanks, chimneys, buildings; painted on films made of polyester resin film, acrylic resin film, fluororesin film, etc. Packaging materials such as various coating films; Containers such as plastic bottles and metal cans; Clothes such as tents and lab coats, masks, sheets, curtains, wallpaper, etc. Textile products like; other, musical instruments made from the base class, office supplies, sports outfit, there is such as toys.

Next, the present invention will be specifically described with reference to examples and comparative examples. In the examples, all parts and% are based on weight except for the specular reflectance (gloss value) and gloss retention.

Synthesis example 1 [Preparation example of condensate of methyltrimethoxysilane (a3′-1)]
Into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser tube and a nitrogen gas inlet, 1421 parts of methyltrimethoxysilane (MTMS) was charged and heated to 60 ° C.

  Next, a mixture of 0.17 part of “A-3” (iso-propyl acid phosphate manufactured by Sakai Chemical Co., Ltd.) and 207 parts of deionized water was dropped into the reaction vessel over 5 minutes, and then at 80 ° C. The mixture was stirred at temperature for 4 hours to cause hydrolysis and condensation reaction.

  The condensate obtained by the hydrolysis-condensation reaction has a temperature of 40 to 60 ° C. and a reduced pressure of 300 to 10 mmHg. (Hereinafter the same shall apply)) to remove the methanol and water produced in the reaction process, thereby removing a mixed liquid (active ingredient) of methyltrimethoxysilane condensate (a3′-1) having a number average molecular weight of 1000 70%) 1000 parts were obtained.

  The active ingredient is a value obtained by dividing the theoretical yield (parts) when all methoxy groups of silane monomers such as methyltrimethoxysilane (MTMS) undergo a condensation reaction by the actual yield (parts) after the condensation reaction [ The theoretical yield (parts) when all the methoxy groups of the silane monomer undergo a condensation reaction / the actual yield after the condensation reaction (parts)].

“MTMS” described below for abbreviations in Table 1: methyltrimethoxysilane

Synthesis Example 2 [Preparation of Composite Resin Intermediate Containing Liquid (C-1)]
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel, condenser and nitrogen gas inlet, 125 parts of propylene glycol monopropyl ether (PnP), 168 parts of phenyltrimethoxysilane (PTMS) and dimethyldimethoxysilane (DMDMS) 102 The temperature was raised to 80 ° C.

  Next, at the same temperature, methyl methacrylate (MMA) 38 parts, butyl methacrylate (BMA) 24 parts, butyl acrylate (BA) 36 parts, acrylic acid (AA) 24 parts, 3-methacryloxypropyltrimethoxysilane (MPTS) 4 A mixture containing 5 parts of PnP, 54 parts of PnP and 6 parts of tert-butylperoxy-2-ethylhexanoate (TBPEH) is dropped into the reaction vessel over 4 hours, and further reacted at the same temperature for 2 hours. As a result, an acrylic polymer organic solvent solution (c1) having a number average molecular weight of 10200 having a carboxyl group and a hydrolyzable silyl group was obtained.

  Next, a mixture of 2.7 parts of “A-3” (iso-propyl acid phosphate manufactured by Sakai Chemical Co., Ltd.) and 76 parts of deionized water was added dropwise over 5 minutes, and the mixture was further stirred at the same temperature for 1 hour. By hydrolytic condensation reaction, the hydrolyzable silyl group of the acrylic polymer in the organic solvent solution (c1) and the hydrolyzable silyl group and silanol group of the polysiloxane derived from PTMS and DMDMS are combined. A composite resin intermediate-containing liquid (C′-1) was obtained.

  Next, the composite resin intermediate-containing liquid (C′-1) and 291 parts of the methyltrimethoxysilane condensate (a3′-1) are mixed, and 49 parts of deionized water is added to the same temperature. The composite resin in which the condensate of methyltrimethoxysilane (a3′-1) is further bonded to the composite resin intermediate in the liquid containing (C′-1) by stirring for 16 hours at Obtained 1000 parts of intermediate-containing liquid (C-1).

Synthesis Example 3 [Preparation of aqueous composite resin composition (I)]
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe and a nitrogen gas inlet, 158 parts of polytetramethylene glycol (PTMG-2000 manufactured by Mitsubishi Chemical Corporation), isophorone diisocyanate (IPDI) 66 parts were charged, the temperature was raised to 100 ° C., and the mixture was reacted at the same temperature for 1 hour.

  Next, the temperature was lowered to 80 ° C., 13 parts of dimethylolpropionic acid (DMPA), 5 parts of neopentyl glycol (NPG), and 121 parts of methyl ethyl ketone (MEK) were charged into the reaction vessel, and further at 80 ° C. The reaction was allowed for 5 hours.

  Next, the temperature is lowered to 50 ° C., and 30 parts of 3-aminopropyltriethoxysilane (APTES) and 285 parts of isopropyl alcohol (IPA) are put into the reaction vessel and reacted, whereby a carboxyl group and a hydrolyzable silyl group are reacted. An organic solvent solution (i) of polyurethane having a number average molecular weight of 7400 having a group was produced.

  Next, the total amount of the polyurethane organic solvent solution (i) and 158 parts of the composite resin intermediate-containing solution (C-1) are mixed, and subjected to a hydrolysis condensation reaction at 80 ° C. for 1 hour with stirring, Liquid containing composite resin in which hydrolyzable silyl group of polyurethane in organic solvent solution (i) and hydrolyzable silyl group of composite resin intermediate in said containing liquid (C-1) are combined (I ') Got.

Next, the composite resin-containing liquid (I ′) and 10 parts of triethylamine (TEA) are mixed to obtain a neutralized product in which carboxyl groups in the composite resin are neutralized. A mixture of 610 parts of ionic water was distilled under reduced pressure of 300 to 10 mmHg for 4 hours under the condition of 40 to 60 ° C., and the produced methanol, organic solvent and water were removed, so that the nonvolatile content was 35. 1000 parts of 0% aqueous composite resin composition (I) was obtained.
Table 2 shows the weight ratios of [polysiloxane structure / composite resin] and [vinyl polymer structure / hydrophilic group-containing polyurethane structure] of the composite resin in the aqueous composite resin composition obtained.

Synthesis Example 4 [Preparation of aqueous composite resin composition (II)]
A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser tube and a nitrogen gas inlet is charged with 122 parts of polytetramethylene glycol having a number average molecular weight of 2000 (PTMG-2000 manufactured by Mitsubishi Chemical Corporation) and 51 parts of IPDI. The mixture was heated to 100 ° C. and reacted at the same temperature for 1 hour.

  Next, the temperature was lowered to 80 ° C., 10 parts of DMPA, 4 parts of NPG, and 94 parts of MEK were put into the reaction vessel, and further reacted at 80 ° C. for 5 hours.

  Next, the temperature is lowered to 50 ° C., and 23 parts of APTES and 221 parts of IPA are put into the reaction vessel and reacted, whereby an organic polyurethane having a number average molecular weight of 7500 having a carboxyl group and a hydrolyzable silyl group is obtained. A solvent solution (ii) was obtained.

  Next, the whole amount of the organic solvent solution (ii) of polyurethane and 279 parts of the composite resin intermediate-containing liquid (C-1) are mixed and subjected to a hydrolytic condensation reaction at 80 ° C. for 1 hour with stirring, whereby the organic Liquid containing composite resin (II ′) in which the hydrolyzable silyl group possessed by polyurethane in solvent solution (ii) and the hydrolyzable silyl group possessed by the composite resin intermediate in said containing liquid (C-1) are combined. Got.

  Next, the composite resin-containing liquid (II ′) and 14 parts of TEA were mixed to obtain a neutralized product obtained by neutralizing the carboxyl group in the composite resin, and then the neutralized product and 610 parts of deionized water. Was mixed under the same conditions as in Example 1 to obtain 1000 parts of an aqueous composite resin composition (II) having a non-volatile content of 35.0%.

Synthesis Example 5 [Preparation of aqueous composite resin composition (III)]
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel, condenser and nitrogen gas inlet, 61 parts of polytetramethylene glycol having a number average molecular weight of 2000 (PTMG-2000 manufactured by Mitsubishi Chemical Corporation) and 26 parts of IPDI were charged. The mixture was heated to 100 ° C. and reacted at the same temperature for 1 hour.

  Next, the temperature was lowered to 80 ° C., 5 parts of DMPA, 2 parts of NPG, and 47 parts of MEK were put into the reaction vessel, and further reacted at 80 ° C. for 5 hours.

  Next, the temperature is lowered to 50 ° C., and 12 parts of APTES and 110 parts of IPA are put into the reaction vessel and reacted to form an organic polyurethane having a number average molecular weight of 7500 having a carboxyl group and a hydrolyzable silyl group. A solvent solution (iii) was obtained.

  Next, the total amount of the organic solvent solution (iii) of polyurethane and 489 parts of the composite resin intermediate-containing solution (C-1) are mixed and subjected to a hydrolytic condensation reaction at 80 ° C. for 1 hour with stirring, whereby the organic Liquid containing composite resin (III ′) in which hydrolyzable silyl group of polyurethane in solvent solution (iii) and hydrolyzable silyl group of composite resin intermediate in said liquid containing (C-1) are combined Got.

  Next, by mixing the composite resin-containing liquid (III ′) and 16 parts of TEA, a neutralized product obtained by neutralizing the carboxyl group in the composite resin (III ′) was obtained, and then the neutralized product and A mixture of 560 parts of deionized water was distilled under the same conditions as in Example 1 to obtain 1000 parts of an aqueous composite resin composition (III) having a non-volatile content of 35.0%.

Synthesis Example 6 [Preparation of aqueous composite resin composition (IV)]
A polycarbonate polyol having a number average molecular weight of 2000 having a 1,6-hexanediol skeleton (UH-200, Ube Industries, Ltd.) having a 1,6-hexanediol skeleton in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser, and a nitrogen gas inlet 123 And 50 parts of IPDI were heated to 100 ° C. and reacted at the same temperature for 1 hour.

  Next, the temperature was lowered to 80 ° C., 10 parts of DMPA, 4 parts of NPG, and 94 parts of MEK were put into the reaction vessel, and further reacted at 80 ° C. for 5 hours.

  Next, the temperature is lowered to 50 ° C., and 23 parts of APTES and 221 parts of IPA are put into the reaction vessel and reacted, whereby a polyurethane organic solvent having a number average molecular weight of 7300 having a carboxyl group and a hydrolyzable silyl group is obtained. Solution (iv) was obtained.

  Next, the total amount of the polyurethane organic solvent solution (iv) and 279 parts of the composite resin intermediate-containing liquid (C-1) are mixed, and the mixture is subjected to a hydrolytic condensation reaction at 80 ° C. for 1 hour with stirring. A composite resin containing liquid (IV ′) in which the hydrolyzable silyl group of the polyurethane in the solution (iv) and the hydrolyzable silyl group of the composite resin intermediate in the containing liquid (C-1) are bonded to each other. Obtained.

Next, the composite resin-containing liquid (IV ′) and 14 parts of TEA were mixed to obtain a neutralized product in which the carboxyl group in the composite resin was neutralized, and then the neutralized product and the deionized product. A mixture of 610 parts of water was distilled under the same conditions as in Example 1 to obtain 1000 parts of an aqueous composite resin composition (IV) having a nonvolatile content of 35.0%.

Comparative synthesis example 1 [Preparation of comparative aqueous composite resin composition (V)]
A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe and a nitrogen gas inlet is charged with 171 parts of polytetramethylene glycol (PTMG-2000 manufactured by Mitsubishi Chemical Corporation) and 72 parts of IPDI. The mixture was heated to 100 ° C. and reacted at the same temperature for 1 hour.

  Next, the temperature was lowered to 80 ° C., 14 parts of DMPA, 5 parts of NPG, and 132 parts of MEK were put into the reaction vessel, and further reacted at 80 ° C. for 5 hours.

Subsequently, the temperature is lowered to 50 ° C., and 33 parts of APTES and 309 parts of IPA are put into the reaction vessel and reacted, thereby polyurethane having a number average molecular weight of 7,500 having a carboxyl group and a hydrolyzable silyl group. Next, the total amount of the organic solvent solution (v) of polyurethane and 112 parts of the composite resin intermediate-containing liquid (C-1) were mixed and stirred at 80 ° C. for 1 hour. By carrying out the hydrolysis-condensation reaction, a comparative composite resin containing liquid (V ′) in which the polyurethane in the organic solvent solution (v) and the composite resin intermediate in the containing liquid (C-1) are combined is obtained. It was.

  Next, a neutralized product obtained by neutralizing the carboxyl group in the comparative composite resin (V ′) by mixing the comparative composite resin-containing liquid (V ′) and 12 parts of TEA was obtained, A mixture of the neutralized product and 610 parts of deionized water was distilled under the same conditions as in Example 1 to obtain 1000 parts of an aqueous composite resin composition (V) having a nonvolatile content of 35.0%. .

Comparative Synthesis Example 2 [Preparation Example of Comparative Aqueous Composite Resin Composition (VI)]
A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser tube and a nitrogen gas inlet is charged with 27 parts of polytetramethylene glycol having a number average molecular weight of 2000 (PTMG-2000 manufactured by Mitsubishi Chemical Corporation) and 11 parts of IPDI. The mixture was heated to 100 ° C. and reacted at the same temperature for 1 hour.

  Subsequently, the temperature was lowered to 80 ° C., and 2 parts of DMPA, 1 part of NPG, and 144 parts of MEK were put into the reaction vessel, and further reacted at 80 ° C. for 5 hours.

Next, the temperature is lowered to 50 ° C., 5 parts of APTES and 49 parts of IPA are put into the reaction vessel and reacted, whereby an organic solvent of polyurethane having a number average molecular weight of 7400 having a carboxyl group and a hydrolyzable silyl group A solution (vi) was obtained.
Next, the whole amount of the organic solvent solution (vi) of polyurethane and 676 parts of the composite resin intermediate-containing solution (C-1) are mixed and subjected to a hydrolytic condensation reaction at 80 ° C. for 1 hour with stirring. A comparative composite resin containing liquid (VI ′) in which the polyurethane in the solution (vi) and the composite resin intermediate in the containing liquid (C-1) were bonded together was obtained.

  Next, the composite resin-containing liquid (VI ′) and 12 parts of TEA were mixed to obtain a neutralized product in which the carboxyl group in the comparative composite resin was neutralized. A mixture of 610 parts of ionic water was distilled under the same conditions as in Example 1 to obtain 1000 parts of an aqueous composite resin composition (VI) having a non-volatile content of 35.0%.

Comparative synthesis example 3 [Preparation of comparative aqueous composite resin composition (VII)]
PnP 36 parts, IPA 80 parts, PTMS 32 parts and DMDMS 19 parts were charged in a reaction vessel equipped with a stirrer, thermometer, dropping funnel, condenser and nitrogen gas inlet, and the temperature was raised to 80 ° C.

  Next, after the mixture containing 9 parts of MMA, 86 parts of BMA, 67 parts of BA, 14 parts of MPTS, 16 parts of AA, 14 parts of PnP and 14 parts of TBPEH at the same temperature was dropped into the reaction vessel in 4 hours. Further, by reacting at the same temperature for 2 hours, an organic solvent solution (vii) of an acrylic polymer having a carboxyl group and a hydrolyzable silyl group and having a number average molecular weight of 13100 was obtained.

  Next, in a reaction vessel containing the organic solvent solution (vii) of the acrylic polymer, 0.9 part of “A-3” (iso-propyl acid phosphate manufactured by Sakai Chemical Co., Ltd.), 24 parts of deionized water, Is added dropwise over 5 minutes, and further stirred at 80 ° C. for 10 hours to cause hydrolysis and condensation reaction, whereby the hydrolyzable silyl group of the acrylic polymer in the organic solvent solution (vii) is added to PTMS and A liquid (VII ′) containing a composite resin for comparison to which polysiloxane derived from DMDMS was bonded was obtained.

  Next, a neutralized product obtained by neutralizing the carboxyl group in the comparative composite resin was obtained by mixing the comparative composite resin-containing liquid (VII ′) and 18 parts of TEA, and then the neutralized product and After reacting with 124 parts of methyltrimethoxysilane condensate (a3′-1), it was mixed with 550 parts of deionized water and distilled under the same conditions as in Example 1 to obtain a non-volatile content of 40.0. % Of aqueous composite resin composition (VII) for comparison was obtained.

  The storage stability described in Tables 2 to 3 shows the viscosity (initial viscosity) of the aqueous composite resin composition and the viscosity after standing the aqueous composite resin composition in a 50 ° C. environment for 30 days (viscosity with time). ) And the value obtained by dividing the viscosity with time by the initial viscosity [viscosity with time / initial viscosity]. If the value is about 0.5 to 3.0, it can be used as a paint.

  The [polysiloxane structure / composite resin] and [vinyl polymer (a2) structure / hydrophilic group-containing polyurethane (a1) structure] are based on the ratio of raw materials used in the production of the composite resin (A). Asked. The weight ratio of the [polysiloxane structure / composite resin] was calculated in consideration of the formation of by-products such as methanol and ethanol that can be generated when the polysiloxane structure is formed.

  It is obtained by mixing the aqueous composite resin compositions (I) to (IV) and the aqueous composite resin compositions (V) to (VII) for comparison according to the blending compositions shown in Tables 4 to 10. An aqueous curable resin composition comprising the obtained aqueous composite resin compositions (I) to (IV) and comparative aqueous composite resin compositions (V) to (VII) was obtained. A coating film was formed using the obtained aqueous curable resin composition, and various physical properties of the coating film were evaluated according to the following evaluation methods.

The following resins were used as resins having good elongation.
“HW-311”; “Hydran HW-311” manufactured by DIC Corporation; aqueous polyurethane resin, non-volatile content 45%, elongation 900% (25 ° C./film thickness 200 μm)
“HY-364”; “Hydran HY-364” manufactured by DIC Corporation; urethane-modified acrylic emulsion, non-volatile content 45%, elongation 500% (25 ° C./film thickness 200 μm)
“WLS-201”; “Hydran WLS-201” manufactured by DIC Corporation; water-based polyurethane resin, non-volatile content 35%, elongation 700% (25 ° C./film thickness 200 μm)
“SA-6360”; “Boncoat SA-6360” manufactured by DIC Corporation; acrylic silicon emulsion, non-volatile content 50%, elongation 300% (25 ° C./film thickness 200 μm)

The following curing agents were used.
“GPTMS”; 3-glycidoxypropyltrimethoxysilane “GPTES”; 3-glycidoxypropyltriethoxysilane “EX-614B”; “Denacol EX-614B” manufactured by Nagase ChemteX Corporation (epoxy equivalent is 173 g) / Eq epoxy compound)
“WS-500”; “Epocross WS-500” manufactured by Nippon Shokubai Co., Ltd. (aqueous solution of 1,3-oxazoline group-containing water-soluble resin having an equivalent of 220 g / eq of oxazoline group, nonvolatile content 40%)

[Method for evaluating adhesion, durability (solvent resistance, acid resistance), weather resistance of coating film]
[Test plate preparation method]
The aqueous curable resin composition is applied to a chromate-treated aluminum plate manufactured by Engineering Test Service Co., Ltd. so as to have a film thickness of 30 μm and dried for 7 days in an environment of 23 ° C. and 50% RH. This was used as a test plate.

Adhesion: Measured based on JIS K-5600 cross cut test method. A 1 mm wide cut is made on the cured coating film with a cutter, the number of grids is 100, cellophane tape is applied so as to cover all grids, and they are peeled off quickly to adhere and remain. Judgment was made by counting the number of. The evaluation criteria are as follows.
○: No peeling.
Δ: The area of peeling is 1 to 64% of the total grid area.
X: The area of peeling is 65% or more of the total grid area.

Solvent resistance: The cured coating film was rubbed 20 times back and forth with a felt soaked with methyl ethyl ketone and ethanol. The state of the coating film before rubbing and after rubbing was judged by finger touch and visual observation. The evaluation criteria are as follows.
○: Softening and gloss reduction are not recognized.
(Triangle | delta): Some softening or gloss reduction is recognized.
X: Significant softening or gloss reduction is observed.

Acid resistance: Pour 2.0 ml each of 5% aqueous sulfuric acid solution into a glass cup, place it on the surface of the coating film at 25 ° C. and expose it for 24 hours, then wash and dry the coating film surface, then visually check its surface condition. The evaluation was determined. The evaluation criteria are as follows.
○: Etching is not recognized.
(Triangle | delta): Some etching or gloss reduction is recognized.
X: Significant etching or gloss reduction is observed.

  Weather resistance: Dew panel light weather meter [manufactured by Suga Test Instruments Co., Ltd., light irradiation: 30 W / m 2, 70 ° C., wetting: humidity 90% or more, 50 ° C., light irradiation / wetting cycle = 8 After an exposure test of 1000 hours using [Time / 4 hours], the appearance of the coating film on the surface of the test plate was visually evaluated according to the following evaluation criteria.

○: No cracks are observed on the coating surface.
Δ: Some cracks are observed on a very small part of the coating film surface.
X: Generation | occurrence | production of a crack is seen in the whole coating-film surface.

  Here, the specular gloss reflectance of the surface coating film of the test plate before and after the exposure test was measured using HG-268 manufactured by Suga Test Instruments Co., Ltd., and the gloss retention was determined based on the following formula. .

  [100 × (specular reflectance of coating film after exposure test) / specular reflectance of coating film before exposure test]] The larger the gloss retention value, the better the weather resistance, approximately 80% The above is preferable.

  Contamination resistance: The cured coating film was exposed for 3 months in a DIC Corporation Sakai Factory in Takaishi City, Osaka Prefecture. The color difference (ΔE) between the unwashed coating film after the exposure test and the coating film before the exposure test was evaluated using CM-3500d manufactured by Konica Minolta Sensing Co., Ltd. The smaller the color difference (ΔE), the better the stain resistance.

Evaluation Method of Substrate Followability The substrate followability of the coating film was evaluated based on the elongation of the coating film.
First, the aqueous composite resin composition is coated on a base material made of a polypropylene film so as to have a film thickness of 200 μm, dried in an environment of 140 ° C. for 5 minutes, and then further subjected to 24 in an environment of 25 ° C. What was dried for a time and peeled from this base material was made into the test coating film (10 mm x 70 mm).

  For the measurement of the elongation of the test coating film, Autograph AGS-1kNG manufactured by Shimadzu Corporation (distance between chucks: 20 mm, pulling speed: 300 mm / min., Measurement atmosphere: 22 ° C., 60% RH) was used. And evaluated based on the elongation percentage with respect to the coating film before the tensile test. It is practically preferable that the elongation is approximately 100% or more.

Elongation retention rate (%): The test coating film was cured for 7 days in an environment of temperature: 40 ° C. and humidity: 60%, and the elongation was measured. The elongation retention rate of the test coating film before and after curing. Was determined based on the following equation.

  [100 × (elongation of the coating film after curing for 7 days) / elongation of the coating film before curing]] The larger the elongation retention, the smaller the change with time of the coating film, which is better. In general, it is preferably 80% or more.

Claims (5)

Aqueous curing containing a composite resin (A) in which a hydrophilic group-containing polyurethane (a1) and a vinyl polymer (a2) are bonded via a polysiloxane (a3), a resin (D) with good elongation, and an aqueous medium The hydrolyzable silyl group and / or silanol group of the hydrophilic group-containing polyurethane (a1) is a bond between the hydrophilic group-containing polyurethane (a1) and the polysiloxane (a3). And the hydrolyzable silyl group and / or silanol group of the polysiloxane (a3), and the bond between the vinyl polymer (a2) and the polysiloxane (a3) is Hydrolyzable silyl group and / or silanol group possessed by the vinyl polymer (a2) and hydrolyzable silyl group possessed by the polysiloxane (a3) and / or Or formed by a reaction with a silanol group, and the mass ratio of the structure derived from the polysiloxane (a3) to the entire composite resin (A) is in the range of 15 to 55% by weight. An aqueous curable resin composition.   The aqueous curable resin composition according to claim 1, wherein the content of the polysiloxane segment in the aqueous curable resin composition is 5 to 50% by weight of the total of the composite resin (A) and the resin (D) having good elongation. .   The aqueous curable resin composition according to claim 1, wherein the resin (D) having a good elongation is a resin having an elongation at 25 ° C of 100% or more. The aqueous curable resin composition according to claim 3, wherein the resin (D) having a good elongation is at least one resin selected from the group consisting of a resin having an acrylic structure and a resin having a urethane structure.   The aqueous curable resin composition according to claim 3, wherein the resin (D) having good elongation is at least one resin selected from the group consisting of urethane-modified acrylic resins and acrylic-modified urethane resins.