JP5928155B2 - Aqueous composite resin composition, coating agent using the same, and article having a coating film of the coating agent - Google Patents

Description

  The present invention relates to an aqueous composite resin composition that can be used for various applications including coating agents and adhesives.

  In recent years, highly functional materials that combine the characteristics of inorganic and organic materials have been widely developed in various industrial fields. Inorganic materials have excellent durability such as weather resistance, heat resistance, and scratch resistance. It is generally known that is rich in flexibility and workability. Among these, an aqueous resin in which an inorganic material and an organic material are combined has been proposed (for example, see Patent Document 1). Since the coating film of this water-based resin is relatively hard, the coating film cannot follow the deformation of the base material when used for the surface coating of the base material that is likely to cause deformation or expansion due to the influence of external force or temperature change, In some cases, peeling of the coating film, generation of cracks due to bending, and the like occurred.

As a material that can suppress the above-described peeling of the coating film, generation of cracks, and the like, a material in which polyurethane having excellent flexibility is combined has been proposed (for example, see Patent Document 2). The coating film of this polyurethane composite material has excellent weather resistance, excellent crack resistance, high elongation and substrate followability, but when high durability is required. It was essential to use a curing agent, and it was pointed out that the workability was poor. Further, in the two-part curing specification using a curing agent, the coating film elongation decreased with time, and the substrate followability was sometimes impaired.

  Therefore, there has been a demand for a material capable of forming a coating film having excellent weatherability, crack resistance, and substrate followability with a one-component curing specification excellent in workability.

JP-A-11-279408 JP 2010-1457 A

  The problem to be solved by the present invention is a one-component curing specification with excellent workability, coating film appearance, substrate adhesion, surface hardness, solvent resistance, crack resistance, weather resistance, contamination resistance, and substrate following. It is to provide an aqueous composite resin composition capable of forming a coating film having excellent properties, a coating agent using the composition, and an article having a coating film of the coating agent.

  As a result of intensive studies to solve the above problems, the present inventors have obtained a composite resin in which a polyurethane having a hydrophilic group and a vinyl polymer are bonded via a polysiloxane, and a specific proportion of the polysiloxane. Among those having an origin component, an aqueous composite resin composition containing a polysiloxane having an epoxy group and an aqueous medium has a coating film appearance, substrate adhesion, surface hardness, solvent resistance, crack resistance, It was found that a coating film excellent in weather resistance, stain resistance and substrate followability could be formed, and the present invention was completed.

  That is, an aqueous composite resin composition comprising a composite resin (A) in which a polyurethane (a1) having a hydrophilic group and a vinyl polymer (a2) are bonded via a polysiloxane (a3) and an aqueous medium, The bond between the polyurethane (a1) having the hydrophilic group and the polysiloxane (a3) is the hydrolysis of the hydrolyzable silyl group and / or silanol group and the polysiloxane (a3) of the polyurethane (a1). Formed by a reaction with a reactive silyl group and / or a silanol group, and the bond between the vinyl polymer (a2) and the polysiloxane (a3) is hydrolyzable possessed by the vinyl polymer (a2). Reaction between silyl group and / or silanol group and hydrolyzable silyl group and / or silanol group of polysiloxane (a3) The mass ratio of the structure derived from the polysiloxane (a3) in the composite resin (A) is in the range of 15 to 55% by mass, and the polysiloxane (a3) has an epoxy group. It has an aqueous composite resin composition characterized by having. The present invention also relates to a coating agent comprising the aqueous composite resin composition.

  The aqueous composite resin composition of the present invention has good adhesion to various base materials such as metal base materials, plastic base materials, inorganic base materials, fibrous base materials, cloth materials, paper, and wood base materials. Therefore, it can be used for coating agents and adhesives. In particular, since the aqueous composite resin composition of the present invention can form a coating film excellent in durability and weather resistance, it is suitably used as a primer layer forming coating agent or a top coating layer forming coating agent for various substrates. can do.

  Moreover, since the aqueous composite resin composition of the present invention can form a coating film having excellent rust resistance as well as excellent durability and weather resistance, for example, an outer wall, a building member such as a roof, a guardrail, a soundproof wall, 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.

  Further, the aqueous composite resin composition of the present invention has excellent adhesion to various plastic substrates including 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 | water-based composite resin composition of this invention can form the coating film which is excellent in base material followability, it can be used for the adhesive agent of the various functional films which comprise a polarizing plate, for example.

  The aqueous composite resin composition of the present invention includes an aqueous medium containing a composite resin (A) in which a polyurethane (a1) having a hydrophilic group and a vinyl polymer (a2) are bonded via a polysiloxane (a3) and an aqueous medium. In the composite resin composition, a bond between the polyurethane (a1) having the hydrophilic group and the polysiloxane (a3) is a hydrolyzable silyl group and / or silanol group and the polysiloxane (a1). It is formed by a reaction with a hydrolyzable silyl group and / or silanol group of siloxane (a3), and the bond between the vinyl polymer (a2) and the polysiloxane (a3) is the vinyl polymer. (A2) hydrolyzable silyl group and / or silanol group and polysiloxane (a3) hydrolyzable silyl group and / or It is formed by reaction with a silanol group, and the mass ratio of the structure derived from the polysiloxane (a3) in the composite resin (A) is in the range of 15 to 55 mass%, and the polysiloxane (a3) Have an epoxy group.

  First, the composite resin (A) will be described. The composite resin (A) is obtained by bonding a polyurethane (a1) having a hydrophilic group and a vinyl polymer (a2) through a polysiloxane (a3).

  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. It is preferable because it is possible. Here, the average particle diameter means a value measured by a method for obtaining a particle size distribution by a measurement principle for detecting dynamic scattered light of particles.

  Moreover, since the said composite resin (A) can form the coating film excellent in durability and a weather resistance, it has a structure derived from 15-55 mass% polysiloxane (a3) with respect to the whole composite resin (A). This is very important. For example, in the composite resin in which the mass ratio of the polysiloxane (a3) is 10% by mass, 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 mass ratio of the structure derived from the polysiloxane (a3) is 65% by mass has a structure derived from the polyurethane (a1) having the hydrophilic group and the vinyl polymer (a2). As the mass ratio decreases, the film-forming property decreases, and as a result, cracks may occur on the surface of the coating film.

  The mass ratio of the structure derived from the polysiloxane (a3) in the composite resin (A) is in the range of 20 to 35 mass%, which has excellent durability, weather resistance, and substrate followability. It is preferable because a coating film can be formed.

  The structure derived from the polysiloxane (a3) means that the main chain constituting the connecting part between the polyurethane (a1) having a hydrophilic group constituting the composite resin (A) and the vinyl polymer (a2) is oxygen. A structure consisting of atoms and silicon atoms. Further, the mass 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 preparation 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 for stable dispersion in an aqueous medium.

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

  As the hydrophilic group, an anionic group, a cationic group, and a nonionic group can be used, and among these, it is more preferable to use an anionic group.

  As the anionic group, for example, a carboxyl group, a carboxylate group, a sulfonic acid group, a sulfonate group and the like can be used. Among these, a part or all of the carboxyl group is neutralized with a basic compound or the like. Use of a rate group or a sulfonate group is preferable in preparing a composite resin having good water dispersibility.

  Examples of basic compounds that can be used for neutralizing the anionic group include ammonia; organic amines such as triethylamine, pyridine, and morpholine; alkanolamines such as monoethanolamine; metal bases such as sodium, potassium, lithium, and calcium. Compound etc. are mentioned.

  When a carboxylate group or a sulfonate group is used as the anionic group, it is preferable that the aqueous composite resin (A) particles are present in the range of 50 to 1000 mmol / kg with respect to the entire composite resin (A). It is preferable because water dispersion stability can be maintained.

  Moreover, as said cationic group, a tertiary amino group etc. are mentioned, for example. Examples of the acid that can be used for 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 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 polyoxyethylene group, polyoxypropylene group, polyoxybutylene group, poly (oxyethylene-oxypropylene) group, and polyoxyethylene-polyoxypropylene group. Groups. 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), mass ratio [(a2) / (a1)] of the polyurethane (a1) which has the said hydrophilic group, and the said vinyl polymer (a2) is 20/1-1 / It is preferable to use a material in the range of 20 because a coating film excellent in substrate followability and excellent in durability and weather resistance can be formed, and more preferably in the range of 10/1 to 1/10. The range of 5/1 to 1/5 is particularly preferable.

  In addition, the bond between the hydrophilic group-containing polyurethane (a1) and the polysiloxane (a3) is, for example, the hydrolyzable silyl group and / or silanol group included in the hydrophilic group-containing polyurethane (a1) and the above-mentioned The polysiloxane (a3) is formed by a reaction with a hydrolyzable silyl group and / or a silanol group. 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 formed by reaction with a decomposable silyl group and / or silanol group.

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

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

  As the polyurethane (a1) having a hydrophilic group, various types can be used. For example, a polyurethane having a number average molecular weight of 3,000 to 100,000 is preferably used. It is preferable to use those having a number average molecular weight of 10,000 to 10,000 because a coating film excellent in substrate followability and excellent in durability and weather resistance can be formed.

  The polyurethane (a1) having the hydrophilic group 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 1,000 mmol / kg with respect to the entire polyurethane (a1) having the hydrophilic group in order to impart better water dispersibility to the composite resin. .

  As the polyurethane (a1) having a hydrophilic group, for example, a polyurethane obtained by reacting a polyol and a polyisocyanate can be used. The hydrophilic group possessed by the polyurethane (a1) having the hydrophilic group is, for example, a polyurethane having the hydrophilic group (a1) by using a polyol having a hydrophilic group as one component constituting the polyol. Can be introduced inside.

  As a polyol which can be used for manufacture of the polyurethane (a1) having the hydrophilic group, for example, a polyol having the hydrophilic group and another polyol can be used in combination.

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

  Other polyols that can be used in combination with the polyol having the hydrophilic group may be appropriately used depending on the characteristics required for the aqueous composite resin composition of the present invention, the application to which the aqueous composite resin composition is applied, and the like. Examples thereof include polyether polyol, polyester polyol, and polycarbonate polyol.

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

  Examples of the polyether polyol include those obtained by addition polymerization of alkylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator.

  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, and glycerin. , Trimethylolethane, trimethylolpropane and the like.

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

  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.

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

  Examples of the polycarboxylic acid 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 polyurethane (a1) having the hydrophilic group is preferable because the adhesion of the aqueous composite resin composition of the present invention to the plastic substrate can be remarkably improved. Examples of the polycarbonate polyol include those obtained by reacting a carbonate with a polyol, and those obtained by reacting phosgene with bisphenol A and the like.

  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 that can react 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- Heptanediol, 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-pro 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, Examples include polyester polyols such as hexamethylene adipate, polyhexamethylene succinate, and polycaprolactone.

  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 500-6,000.

  The polycarbonate polyol is used in the range of 30 to 95% by mass with respect to the total amount of polyol and polyisocyanate used in the production of the polyurethane (a1), and thus the adhesion, weather resistance and durability to the plastic substrate are used. It is preferable to achieve both.

  The aqueous composite resin composition of the present invention obtained using the polycarbonate polyol includes, among others, a polycarbonate substrate, a polyester substrate, an acrylonitrile-butadiene-styrene substrate, a polyacryl substrate, a polystyrene substrate, a polyurethane substrate, Because it has excellent adhesion to various plastic substrates that are generally known as hard-to-adhere substrates, such as epoxy resin substrates, polyvinyl chloride substrates, and polyamide substrates, it is exclusively for plastic substrates. Can be used in coating agents.

  Examples of the polyisocyanate used in producing the polyurethane (a1) having the hydrophilic group include aromatic diisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate, hexamethylene diisocyanate, and lysine. Diisocyanates having an aliphatic or aliphatic cyclic structure such as diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, etc. are used alone or in combination of two or more. be able to. Among these, it is preferable to use a diisocyanate having an aliphatic cyclic structure because a coating film having excellent long-term weather resistance can be formed.

  The polyurethane resin (a1) having a hydrophilic group may have other functional groups as necessary in addition to the hydrophilic group 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 a hydrolyzable silyl group, and among these, a coating film having excellent long-term weather resistance. Is preferable.

  The hydrolyzable silyl group that the polyurethane (a1) having a hydrophilic group may have is a functional group in which the hydrolyzable group is directly bonded to a silicon atom. For example, in the following general formula (III) The functional group represented is mentioned.

（式中、Ｒ^１はアルキル基、アリール基またはアラルキル基等の１価の有機基であり、Ｒ^２はハロゲン原子、アルコキシ基、アシロキシ基、フェノキシ基、アリールオキシ基、メルカプト基、アミノ基、アミド基、アミノオキシ基、イミノオキシ基またはアルケニルオキシ基である。また、ｘは０〜２の整数である。）

(Wherein R ¹ is a monovalent organic group such as an alkyl group, an aryl group or an aralkyl group, and R ² is a halogen atom, an alkoxy group, an acyloxy group, a phenoxy group, an aryloxy group, a mercapto group, an amino group, An amide 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 polyurethane (a1) having the hydrophilic group may have is a functional group in which a hydroxyl group is directly bonded to a silicon atom, and mainly the hydrolyzable silyl group described above is hydrolyzed. It is a functional group that occurs.

  The hydrolyzable silyl group and silanol group are preferably present in an amount of 10 to 400 mmol / kg with respect to the entire polyurethane (a1) having the hydrophilic group, since good water dispersion stability of the composite resin can be ensured.

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

  As the vinyl polymer (a2), those having a number average molecular weight of 3,000 to 100,000 are preferably used, and those having a number average molecular weight of 5,000 to 25,000 are used. Further, it is more preferable because a coating film having excellent substrate followability and excellent durability such as crack resistance and weather resistance can be formed.

  Examples of the vinyl polymer (a2) include those produced by polymerizing various vinyl monomers in the presence of a polymerization initiator.

  The vinyl monomer has a hydrolyzable silyl group 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 (a2). It is preferable to use a vinyl monomer or a vinyl monomer having a hydroxyl group.

  Examples of the vinyl monomer having a hydrolyzable silyl group include 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, and 3- (meth) acryloyloxypropylmethyl. Dimethoxysilane or the like can be used, and among these, 3- (meth) acryloyloxypropyltrimethoxysilane is preferably used.

  In the present invention, “(meth) acrylate” refers to one or both of methacrylate and acrylate.

  Examples of the vinyl monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, and the like. It is done.

  As the vinyl monomer, in addition to the vinyl monomer having a hydrolyzable silyl group or the vinyl monomer having a hydroxyl group, other vinyl monomers may be used in combination as required.

  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) ) Vinyl monomer having tertiary amino group such as acrylate; Vinyl monomer having secondary amino group such as N-methylaminoethyl (meth) acrylate; Vinyl monomer having primary amino group such as aminomethyl acrylate Vinyl monomers having basic nitrogen atoms such as vinyl; vinyl monomers having fluorine 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 (meth) acrylonitrile; aromatic rings such as styrene Vinyl compounds; α-olefins such as isoprene; vinyl monomers having an epoxy group such as glycidyl (meth) acrylate; vinyl monomers having an amide group such as (meth) acrylamide; N-methylol (meth) acrylamide A vinyl monomer having a methylolamide group and an alkoxy product thereof; a vinyl monomer having an aziridinyl group such as 2-aziridinylethyl (meth) acrylate; an isocyanate group such as (meth) acryloyl isocyanate and / or Or vinyl monomer having a blocked isocyanate group; vinyl monomer having an oxazoline group such as 2-isopropenyl-2-oxazoline; vinyl monomer having a cyclopentenyl group such as dicyclopentenyl (meth) acrylate A vinyline having a carbonyl group such as acrolein Monomer having a carboxyl group such as (meth) acrylic acid, maleic acid, or a half ester thereof, or a salt thereof; vinyl monomer having an acetoacetyl group such as acetoacetoxyethyl (meth) acrylate; A body etc. can be used 1 type, or 2 or more types.

  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. Examples include azo initiators such as (4-cyanovaleric acid) and 2,2′-azobis (2-amidinopropane) dihydrochloride. 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.

  The polymerization initiator may be used in an amount that allows the polymerization to proceed smoothly, but should be 10% by mass 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 polyurethane (a1) having the hydrophilic group and the vinyl polymer (a2).

  In addition, it is important that the polysiloxane (a3) has an epoxy group in order to form a coating film having excellent weather resistance and stain resistance.

  The epoxy group is excellent in weather resistance, stain resistance, and can form a coating film excellent in substrate followability, and is 0.1 mol% to 50 mol% with respect to the whole polysiloxane (a3). It is preferable that it exists in the range.

  The polysiloxane (a3) has a chain structure composed of silicon atoms and oxygen atoms, and has a hydrolyzable silyl group, a silanol group, or the like as necessary. As said polysiloxane (a3), what has 1 or more types of structures chosen from the group which consists of the following general formula (I) and (II) is preferable.

（一般式（Ｉ）中のＲ^１は、エポキシ基を有する有機基、及び／または、炭素原子数が４〜１２の有機基であり、一般式（ＩＩ）中のＲ^２及びＲ^３は、それぞれ独立にメチル基またはエチル基である。）

(R ¹ in the general formula (I) is an organic group having an epoxy group and / or an organic group having 4 to 12 carbon atoms, and R ² and R ³ in the general formula (II) are Each independently a methyl or ethyl group.)

Specific examples of the case where R ¹ in the general formula (I) is an organic group having an epoxy group include a glycidoxyalkyl group and an epoxycyclohexylalkyl group.

Specific examples in the case where R ¹ in the general formula (I) is an organic group having 4 to 12 carbon atoms include butyl group, isobutyl group, pentyl group, neopentyl group, 1-methylbutyl group, 2- Examples include a methylbutyl group, a hexyl group, an isohexyl group, a cyclohexyl group, a phenyl group, a naphthyl group, a 2-methylphenyl group, a benzyl group, and a naphthylmethyl group.

  Moreover, as said polysiloxane (a3), what was formed using the condensate of the alkyl trialkoxysilane whose carbon atom number of an alkyl group is 1-3 is preferable.

  The hydrolyzable silyl group is an atomic group in which the hydrolyzable group is directly bonded to the silicon atom, for example, the general formula (III) exemplified in the description of the polyurethane (a1) having the hydrophilic group. Those having a structure as shown in FIG.

  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 Group, iminooxy group, alkenyloxy group and the like. Among these, an alkoxy group and a substituted alkoxy group are preferable.

  The silanol group represents 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.

  As the polysiloxane (a3), one obtained by completely or partially hydrolyzing and condensing a compound having an epoxy group and a hydrolyzable silyl group and / or silanol group and another silane compound is used. can do.

  Examples of the compound having an epoxy group and a hydrolyzable silyl group and / or silanol group include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane. Epoxy groups such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and alkoxysilyl groups A partially hydrolyzed condensate of a compound having an epoxy group and an alkoxysilyl group; a reaction product of an aminosilane compound and an epoxy compound, and among these, a coating having excellent durability and weather resistance Since a film can be formed, an epoxy group and an alkoxy It is preferred to use a compound having a group. These compounds may be used alone or in combination of two or more.

  Examples of the aminosilane compound include 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldiethoxysilane, and 3- (2-aminoethyl) aminopropyltrimethoxysilane. , 3- (2-aminoethyl) aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and the like.

  Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, hydroquinone diglycidyl ether, adipic acid diglycidyl ether, and phthalic acid diglycidyl ether. And sorbitol polyglycidyl ether.

  Examples of the silane compound other than the compound having an epoxy group and a hydrolyzable silyl group and / or silanol group include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, n -Organotrialkoxysilanes such as propyltrimethoxysilane, iso-butyltrimethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane or 3- (meth) acryloyloxypropyltrimethoxysilane Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-butoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane, methylcyclohexyldimethoxy Diorganodialkoxysilanes such as lan or methylphenyldimethoxysilane; methyltrichlorosilane, ethyltrichlorosilane, phenyltrichlorosilane, vinyltrichlorosilane, 3- (meth) acryloyloxypropyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane or Various chlorosilanes such as diphenyldichlorosilane, partially hydrolyzed condensates thereof, and the like can be used, and among these, organotrialkoxysilane and diorganodialkoxysilane are preferably used. These silane compounds may be used alone or in combination of two or more.

  Next, the manufacturing method of the composite resin (A) used by this invention is demonstrated.

  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 is performed, for example, by sequentially or collectively supplying the vinyl monomer in an organic solvent containing a polymerization initiator, and then performing stirring at a temperature of 20 to 120 ° C. for about 0.5 to 24 hours. Is preferred.

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

  In the reaction, for example, following the step (I), the silane compound capable of forming the polysiloxane (a3) is sequentially supplied or collectively supplied into the organic solvent solution of the vinyl polymer (a2), and then 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 the polysiloxane (a3) in the above-described steps, an aqueous composite resin composition capable of forming a coating film having excellent substrate followability and durability can be obtained. .

  In the step (III), the resin (A ′), the polyurethane (a1) having a hydrophilic group, and a compound having an epoxy group and a hydrolyzable silyl group and / or silanol group are mixed, In the step of obtaining an organic solvent solution of the composite resin (A) in which the vinyl polymer (a2) and the polyurethane (a1) having a hydrophilic group are bonded via the polysiloxane (a3) by hydrolytic condensation. is there.

  For example, the reaction may be performed by reacting a polyol containing the polyol having the hydrophilic group in the organic solvent solution of the resin (A ′) with the polyisocyanate following the step (II). The polyurethane having a group (a1) is sequentially or collectively supplied, and further, a compound having an epoxy group and a hydrolyzable silyl group and / or silanol group is supplied, and then in the range of 20 to 120 ° C. with stirring. It is preferable to carry out for about 0.5 to 24 hours.

  The composite resin (A) is a mixture of a polyurethane (a1) having a hydrophilic group, the vinyl polymer (a2), an epoxy group, a compound having a hydrolyzable silyl group and / or a silanol group, After hydrolytic condensation, the reaction product is reacted with a condensate obtained by condensing methyltrialkoxysilane and ethyltrialkoxysilane, such as methyltrimethoxysilane and ethyltrimethoxysilane, in order to obtain a composite resin (A). It can also be produced by a step of obtaining an organic solvent solution.

  The organic solvent solution of the composite resin (A) obtained by the above process is, for example, neutralized with the hydrophilic group of the composite resin (A) and dispersed in the aqueous medium to form an aqueous solution. Can be

  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, the aqueous medium is supplied into the organic solvent solution of the neutralized product of the composite resin (A), and then the organic solvent is removed to contain the composite resin (A) used in the present invention. An aqueous composite resin composition can be produced.

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

  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 composite resin composition of the present invention suppresses a sudden increase in viscosity during production, and from the viewpoint of improving the productivity of the aqueous composite resin composition, ease of coating, drying properties, etc. It is preferable to have a non-volatile content of 20 to 70% by mass, and more preferably in the range of 30 to 60% by mass.

  Moreover, the aqueous composite 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 Examples include acids, trichloroacetic acid, phosphoric acid, monoalkyl phosphoric acid, dialkyl phosphoric acid, monoalkyl phosphorous acid, dialkyl phosphorous acid and the like.

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

  In the aqueous composite 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 composite resin composition of the present invention includes a photocatalytic compound, inorganic pigment, organic pigment, extender pigment, wax, surfactant, stabilizer, flow regulator, dye, leveling agent, rheology control agent, if necessary. Various additives such as an ultraviolet absorber, an antioxidant, and a plasticizer can be used.

  Since the said aqueous composite resin composition can form the coating film excellent in base-material followability, it can be used for various uses, such as a coating agent and an adhesive agent. Among these, the aqueous composite 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. More preferably, it is used for an agent or a primer layer-forming coating agent.

  As a base material which can apply | coat the said coating agent and can form a coating film, a metal base material, a plastic base material, a glass base material, paper, a wood base material, a fiber base material etc. are mentioned, for example.

  In addition to the durability, weather resistance, and substrate followability, the coating agent of the present invention 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, the surface of various metal substrates that constitute building members such as exterior walls and roofs, guardrails, soundproof walls, civil engineering members such as drainage grooves, household appliances, industrial machinery, automobile parts, etc. Can be used for coating. In particular, the coating agent obtained by reacting a polyol containing a polyether polyol and a polyol having a hydrophilic group with a polyurethane having a hydrophilic group constituting the composite resin (A) and a polyisocyanate. Can be used exclusively as a coating agent for metal substrates because it has excellent adhesion to metal substrates and substrate followability, and is particularly preferably used for steel sheet surface treatment agents that can replace conventional chromate treatments. be able to. In addition, the coating agent for the metal substrate may be directly applied to the surface of the metal substrate and dried to form a coating film, and a primer layer is formed between the metal substrate and the top layer. May be used for

  Examples of the metal substrate include plated steel plates such as galvanized steel plates and aluminum-zinc alloy steel plates, aluminum plates, aluminum alloy plates, electromagnetic steel plates, copper plates, and stainless steel plates.

  Among the coating agents of the present invention, the polyurethane (a1) having a hydrophilic group constituting the composite resin (A) contained in the coating agent contains a polyol and a polyol containing a polycarbonate polyol and a polyol having a hydrophilic group. The coating agent obtained by reacting isocyanate has excellent adhesion to various types of plastic substrates without impairing the durability, weather resistance, and substrate followability. In particular, the coating agent has excellent adhesion to a substrate made of polymethyl methacrylate resin or polystyrene resin, which is generally known as a difficult-to-adhere substrate. It can be suitably used as a coating agent.

  As the plastic base material, polycarbonate base material, polyester base material, acrylonitrile-butadiene-styrene base material, poly base material, which are generally adopted for plastic molded products such as mobile phones, home appliances, automobile interior and exterior materials, OA equipment, etc. A plastic substrate selected from the group consisting of an acrylic substrate, a polystyrene substrate, a polyurethane substrate, an epoxy resin substrate, a polyvinyl chloride substrate, and a polyamide substrate can be used.

  Moreover, since the coating agent of this invention 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.

  The various base materials described above may be coated in advance, but since the coating agent of the present invention has excellent adhesion to a plastic substrate or the like, surface treatment such as coating is performed in advance. Even if it is not a base material, it can be used without a problem.

  The base materials may be plate-shaped, spherical, film-shaped, and sheet-shaped, respectively. In addition, since the coating agent of the present invention is particularly excellent in substrate followability, a film-like or sheet-like substrate that tends to cause deformation or expansion / contraction due to the influence of external force or temperature, or a substrate having fine irregularities on the surface Can also be used suitably.

  The coating agent of the present invention is applied to the surface of the substrate directly, and then dried and cured, for example, so that the coating film appearance after exposure test, substrate adhesion, surface hardness, solvent resistance, A coating film excellent in cracking property, weather resistance, contamination resistance, substrate followability and the like can be formed.

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

  Examples of the method for applying the coating agent of the present invention include brush coating, roller coating, spray coating, dip coating, flow coater coating, roll coater coating, and electrodeposition coating.

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

  The method for drying and curing may be a method of curing for about 1 to 10 days at room temperature. From the viewpoint of rapidly curing, the temperature is 50 to 250 ° C. for 1 to 600 seconds. A method of heating to a certain extent is preferred. Moreover, when using the plastic base material which is easy to deform | transform and discolor at comparatively high temperature, it is preferable to cure at comparatively low temperature of about 30-100 degreeC.

  The film thickness of the coating film formed using the coating agent of the present invention can be set to 0.5 to 1,000 μm depending on the use of the substrate.

  As an article having a coating film formed by using the coating agent of the present invention by the method as described above, for example, a housing of home appliances such as a television, a refrigerator, a washing machine, an air conditioner; a personal computer, a smartphone, a mobile phone And housings of electronic devices such as digital cameras and game machines; housings of OA devices such as printers and facsimiles; and various plastic members such as various parts used for interior materials of various vehicles such as automobiles and railway vehicles. In addition, interior and exterior materials for buildings such as outer walls, roofs, glass, and decorative panels; civil engineering members such as soundproof walls and drainage grooves; galvanized steel sheets used for household appliances, industrial machinery, automotive parts, and aluminum-zinc Metal members such as plated steel plates such as alloy steel plates, aluminum plates, aluminum alloy plates, electromagnetic steel plates, copper plates, and stainless steel plates are also included. Furthermore, since the coating agent of this invention can form the coating film which is excellent in base material followability, the various functional films etc. which comprise the polarizing plate of a liquid crystal display are also mentioned.

  Next, the present invention will be specifically described with reference to examples and comparative examples.

(Synthesis Example 1: Production of methyltrimethoxysilane condensate (a3′-1))
Into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling tube and a nitrogen gas inlet, 1,421 parts by mass of methyltrimethoxysilane (hereinafter abbreviated as “MTMS”) was charged, and the temperature was raised to 60 ° C. Warm up. Next, a mixture of 0.17 parts by mass of iso-propyl acid phosphate (“A-3” manufactured by Sakai Chemical Co., Ltd.) and 207 parts by mass of deionized water was dropped into the reaction vessel over 5 minutes, and then 80 ° C. The mixture was stirred at temperature for 4 hours to cause hydrolysis and condensation reaction.

  The condensate obtained by the above hydrolysis condensation reaction is subjected to a temperature of 40 to 60 ° C. and a reduced pressure of 40 to 1.3 kPa (the reduced pressure condition at the start of the distillation of methanol is 40 kPa, and finally becomes 1.3 kPa) (Hereinafter, the same shall apply)), and the methanol and water produced in the reaction process are removed to contain the MTMS condensate (a3′-1) having a number average molecular weight of 1,000. 1,000 parts by weight of a liquid (70% by mass of active ingredient) was obtained.

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

(Synthesis Example 2: Production of Composite Resin Intermediate (A′-1))
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser tube and a nitrogen gas inlet, 125 parts by mass of propylene glycol monopropyl ether (hereinafter abbreviated as “PnP”), phenyltrimethoxysilane (hereinafter, “ 168 parts by mass and 102 parts by mass of dimethyldimethoxysilane (hereinafter abbreviated as “DMDMS”) were charged, and the temperature was raised to 80 ° C. Next, at the same temperature, 38 parts by mass of methyl methacrylate (hereinafter abbreviated as “MMA”), 24 parts by mass of butyl methacrylate (hereinafter abbreviated as “BMA”), butyl acrylate (hereinafter abbreviated as “BA”). 36 parts by mass, acrylic acid (hereinafter abbreviated as “AA”) 24 parts by mass, 3-methacryloxypropyltrimethoxysilane (hereinafter abbreviated as “MPTS”) 4 parts by mass, PnP 54 parts by mass And a mixture containing 6 parts by mass of tert-butylperoxy-2-ethylhexanoate (hereinafter abbreviated as “TBPEH”) was dropped into the reaction vessel over 4 hours, and then at the same temperature. Organic of acrylic polymer (a2-1) having a number average molecular weight of 10,200 having a carboxyl group and a hydrolyzable silyl group by reacting for 2 hours A solvent solution was obtained.

  A mixture of 2.7 parts by mass of iso-propyl acid phosphate (“A-3” manufactured by Sakai Chemical Co., Ltd.) and 76 parts by mass of deionized water was added to the acrylic polymer (a2-1) obtained above for 5 minutes. The hydrolyzable silyl group possessed by the acrylic polymer (a2-1) and the hydrolysis possessed by the polysiloxane derived from PTMS and DMDMS are further stirred for 1 hour at the same temperature to cause a hydrolytic condensation reaction. A liquid containing a composite resin intermediate (A ″ -1) bonded with a reactive silyl group and a silanol group was obtained.

  The liquid containing the composite resin intermediate (A ″ -1) obtained above and the liquid containing the MTMS condensate (a3′-1) obtained in Synthesis Example 1 (active ingredient 70% by mass) 291 parts by mass, and further 49 parts by mass of deionized water were added and stirred at the same temperature for 16 hours to cause hydrolysis and condensation reaction, whereby the composite resin intermediate (A ″ -1) and MTMS were mixed. 1,000 parts by mass (non-volatile content: 50% by mass) of a liquid containing a composite resin intermediate (A′-1) bonded with the condensate (a3′-1) was obtained.

(Synthesis Example 3: Production of Composite Resin Intermediate (A′-2))
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser tube and a nitrogen gas inlet, 121 parts by mass of PnP, 267 parts by mass of PTMS and 162 parts by mass of DMDMS were charged and heated to 80 ° C. Next, at the same temperature, a mixture containing 61 parts by mass of MMA, 50 parts by mass of BMA, 7 parts by mass of BA, 4 parts by mass of MPTS, 52 parts by mass of PnP and 6 parts by mass of TBPEH was dropped into the reaction vessel over 4 hours. Then, the mixture was further reacted at the same temperature for 2 hours to obtain an organic solvent solution of an acrylic polymer (a2-2) having a hydrolyzable silyl group and a number average molecular weight of 10,300.

  To the organic solvent solution of the acrylic polymer (a2-2) obtained above, a mixture of 4.3 parts by mass of A-3 and 121 parts by mass of deionized water is added dropwise over 5 minutes, and further at the same temperature for 1 hour. The hydrolyzable silyl group possessed by the acrylic polymer (a2-2) and the hydrolyzable silyl group and silanol group possessed by the polysiloxane derived from PTMS and DMDMS were bonded by agitation and hydrolysis condensation reaction. A liquid containing the composite resin intermediate (A ″ -2) was obtained.

  A liquid containing the composite resin intermediate (A ″ -2) obtained above and a liquid containing an MTMS condensate (a3′-1) (active ingredient 70% by mass) 123 parts by mass were mixed, Furthermore, 21 parts by mass of deionized water was added and stirred at the same temperature for 16 hours, followed by hydrolysis and condensation reaction, whereby the composite resin intermediate (A ″ -2) and MTMS condensate (a3′-1 And 1,000 parts by mass (non-volatile content: 50% by mass) of the liquid containing the composite resin intermediate (A′-2) bonded to the compound.

(Example 1: Production of aqueous composite resin composition (I))
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser tube and a nitrogen gas inlet, 158 parts by mass of polytetramethylene glycol having a number average molecular weight of 2,000 (“PTMG-2000” manufactured by Mitsubishi Chemical Corporation), and 66 parts by mass of isophorone diisocyanate (hereinafter abbreviated as “IPDI”) was 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 by mass of dimethylolpropionic acid (hereinafter abbreviated as “DMPA”), 5 parts by mass of neopentyl glycol (hereinafter abbreviated as “NPG”), and methyl ethyl ketone (hereinafter abbreviated as “DMPA”). , Abbreviated as “MEK”.) 121 parts by mass were put into the reaction vessel, and further reacted at 80 ° C. for 5 hours. Next, the temperature was lowered to 50 ° C., 30 parts by mass of 3-aminopropyltriethoxysilane (hereinafter abbreviated as “APTES”) and 285 parts by mass of isopropyl alcohol (hereinafter abbreviated as “IPA”) were added. An organic solvent solution of polyurethane (a1-1) having a number average molecular weight of 7,400 having a carboxyl group and a hydrolyzable silyl group was produced by charging the reaction vessel into a reaction vessel.

  In the organic solvent solution of the polyurethane (a1-1) obtained above, 158 parts by mass of the liquid (A′-1) containing the composite resin intermediate and 3-glycidoxypropylmethyldiethoxysilane (hereinafter, “ It is abbreviated as “GPMDES”.) 30 parts by mass are mixed and subjected to a hydrolytic condensation reaction with stirring at 80 ° C. for 3 hours, whereby the hydrolyzable silyl group of the polyurethane (a1-1) and the composite resin intermediate ( A liquid containing the composite resin (I ′) bonded to the hydrolyzable silyl group of A′-1) was obtained.

  The neutralization which neutralized the carboxyl group in the said composite resin by mixing the liquid containing composite resin (I ') obtained above, and 10 mass parts of triethylamine (it abbreviates as "TEA" hereafter). After obtaining the product, a mixture of the neutralized product and 610 parts by weight of deionized water was distilled under reduced pressure of 40 to 1.3 kPa at 40 to 60 ° C. for 8 hours to produce methanol or By removing the organic solvent and water, 1,000 parts by mass of an aqueous dispersion of the aqueous composite resin composition (I) having a nonvolatile content of 37.5% by mass was obtained.

(Example 2: Production of aqueous composite resin composition (II))
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel, condenser and nitrogen gas inlet, 142 parts by mass of polytetramethylene glycol having a number average molecular weight of 2,000 ("PTMG-2000" manufactured by Mitsubishi Chemical Corporation), IPDI 60 parts by mass were charged, the temperature was raised to 100 ° C., and the reaction was performed at the same temperature for 1 hour. Next, the temperature was lowered to 80 ° C., 12 parts by mass of DMPA, 4 parts by mass of NPG, and 110 parts by mass of MEK were put into the reaction vessel, and further reacted at 80 ° C. for 5 hours. Next, the temperature was lowered to 50 ° C., and 27 parts by mass of APTES and 258 parts by mass of IPA were introduced into the reaction vessel and reacted, whereby the number average molecular weight having a carboxyl group and a hydrolyzable silyl group was 7,400. An organic solvent solution of polyurethane (a1-2) was obtained.

  The organic solvent solution of polyurethane (a1-2) obtained above was mixed with 209 parts by mass of the liquid containing the composite resin intermediate (A′-1) obtained in Synthesis Example 2 and 34 parts by mass of GPTES. The hydrolyzable silyl group possessed by the polyurethane (a1-2) and the hydrolyzable silyl group possessed by the composite resin intermediate (A′-1) are obtained by carrying out a hydrolytic condensation reaction at 80 ° C. for 5 hours with stirring. A liquid containing the composite resin (II ′) bonded with a hydrolyzable silyl group was obtained.

  A liquid containing the composite resin (II ′) obtained above and 13 parts by mass of TEA were mixed to obtain a neutralized product that neutralized the carboxyl group in the composite resin. A mixture of 610 parts by mass of ionic water was distilled under the same conditions as in Example 1 to obtain an aqueous dispersion of an aqueous composite resin composition (II) having a non-volatile content of 37.5% by mass, 1,000 masses. Got a part.

(Example 3: Production of aqueous composite resin composition (III))
Except for using 216 parts by mass of composite resin intermediate (A'-1) instead of 209 parts by mass of composite resin intermediate (A'-1), and using 7 parts by mass of TEA instead of 13 parts by mass of TEA In the same manner as in Example 2, 1000 parts by mass of an aqueous composite resin composition (III) having a nonvolatile content of 37.5% by mass was obtained.

(Example 4: Production of aqueous composite resin composition (IV))
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel, condenser and nitrogen gas inlet, 122 parts by mass of polytetramethylene glycol having a number average molecular weight of 2,000 ("PTMG-2000" manufactured by Mitsubishi Chemical Corporation), IPDI 51 parts by mass were charged, the temperature was raised to 100 ° C., and the reaction was performed at the same temperature for 1 hour. Next, the temperature was lowered to 80 ° C., 10 parts by mass of DMPA, 4 parts by mass of NPG, and 94 parts by mass 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 23 parts by mass of APTES and 221 parts by mass of IPA are introduced into the reaction vessel and reacted, whereby the number average molecular weight having a carboxyl group and a hydrolyzable silyl group is 7,500. An organic solvent solution of polyurethane (a1-4) was obtained.

  The organic solvent solution of polyurethane (a1-4) obtained above was mixed with 162 parts by mass of the organic solvent solution of acrylic polymer (a2-1) and 28 parts by mass of GPTMS. Iso-propyl acid phosphate manufactured by Co., Ltd.] A mixture of 1.0 part by mass and 20 parts by mass of deionized water was added dropwise over 5 minutes, followed by hydrolysis and condensation reaction at 80 ° C. for 5 hours with stirring. 80 parts by mass of the methoxysilane condensate (a3′-1) is mixed, 14 parts by mass of deionized water is added, and the mixture is stirred at the same temperature for 16 hours to cause a hydrolysis and condensation reaction. A liquid containing IV ′) was obtained.

  By mixing the liquid containing the composite resin (IV ′) obtained above and 14 parts by mass of TEA, a neutralized product obtained by neutralizing the carboxyl group in the composite resin is obtained. A mixture of 610 parts by mass of ionic water was distilled under the same conditions as in Example 1 to obtain 1000 parts by mass of an aqueous composite resin composition (IV) having a nonvolatile content of 37.0% by mass.

(Example 5: Preparation of aqueous composite resin composition (V))
1000 mass parts of aqueous composite resin composition (V) whose non volatile matter is 37.5 mass% like Example 4 except having used the mixture of 15 mass parts of GPMDES and 17 mass parts of GPTES instead of 28 mass parts of GPTMS Got a part.

(Example 6: Preparation of aqueous composite resin composition (VI))
An aqueous composite resin composition having a non-volatile content of 37.3% by mass in the same manner as in Example 4 except that a mixture of 10 parts by mass of GPMDES, 11 parts by mass of GPTES and 9 parts by mass of GPTMS was used instead of 28 parts by mass of GPTMS. (VI) 1000 parts by mass were obtained.

(Example 7: Preparation of aqueous composite resin composition (VII))
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe and a nitrogen gas inlet, 123 parts by mass of a polyester polyol (“obtained by reacting neopentyl glycol, 1,6-hexanediol and adipic acid” Polyester polyol ”(hydroxyl equivalent: 1000 g / equivalent) and IPDI (50 parts by mass) were charged, heated to 100 ° C., and reacted at the same temperature for 1 hour. Subsequently, the temperature was lowered to 80 ° C., 10 parts by mass of DMPA, 4 parts by mass of NPG, and 94 parts by mass 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 by mass of APTES and 221 parts by mass of IPA are introduced into the reaction vessel to cause a reaction, thereby a polyurethane having a number average molecular weight of 7900 having a carboxyl group and a hydrolyzable silyl group. An organic solvent solution of (a1-7) was obtained.

  The organic solvent solution of polyurethane (a1-7) obtained above was mixed with 279 parts by mass of the liquid containing the composite resin intermediate (A′-1) and 17 parts by mass of GPTES. By performing the hydrolytic condensation reaction for a time, the hydrolyzable silyl group of the polyurethane (a1-7) and the hydrolyzable silyl group of the hydrolyzable silyl group of the composite resin intermediate (A′-1) A liquid containing a composite resin (VII ′) bound to was obtained.

  By mixing the liquid containing the composite resin (VII ′) obtained above and 14 parts by mass of TEA, a neutralized product in which the carboxyl group in the composite resin was neutralized was obtained. A mixture of 610 parts by mass of ionic water was distilled under the same conditions as in Example 1 to obtain 1000 parts by mass of an aqueous composite resin composition (VII) having a nonvolatile content of 36.5% by mass.

(Example 8: Preparation of aqueous composite resin composition (VIII))
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel, condenser and nitrogen gas inlet, polytetramethylene glycol having a number average molecular weight of 2000 ("PTMG-2000" manufactured by Mitsubishi Chemical Corporation) 61 parts by mass, IPDI 26 masses The temperature was raised to 100 ° C. and reacted at the same temperature for 1 hour. Subsequently, the temperature was lowered to 80 ° C., 5 parts by mass of DMPA, 2 parts by mass of NPG, and 47 parts by mass 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 by mass of APTES and 110 parts by mass of IPA are introduced into the reaction vessel and reacted to form a polyurethane having a number average molecular weight of 7500 having a carboxyl group and a hydrolyzable silyl group. An organic solvent solution of (a1-8) was obtained.

  The organic solvent solution of polyurethane (a1-8) obtained above is mixed with 489 parts by mass of the liquid containing the composite resin intermediate (A′-1) and 30 parts by mass of GPTES, and stirred at 50 ° C. for 8 hours. Composite resin (VIII ′) in which the hydrolyzable silyl group possessed by the polyurethane (VIII) and the hydrolyzable silyl group possessed by the composite resin intermediate (A′-1) are bonded by a time hydrolysis condensation reaction. A liquid containing was obtained.

  By mixing the liquid containing the composite resin (VIII ′) obtained above and 16 parts by mass of TEA, a neutralized product obtained by neutralizing carboxyl groups in the composite resin was obtained, and then the neutralized product and A mixture of 610 parts by mass of deionized water was distilled under the same conditions as in Example 1 to obtain 1000 parts by mass of an aqueous composite resin composition (VIII) having a nonvolatile content of 36.5% by mass.

(Example 9: Preparation of aqueous composite resin composition (IX))
A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe and a nitrogen gas inlet, a polycarbonate polyol having a number average molecular weight of 2000 having a 1,6-hexanediol skeleton (UH-200, Ube Industries, Ltd.) 61 mass And 26 parts by mass of IPDI were charged, the temperature was raised to 100 ° C., and the mixture was reacted at the same temperature for 3 hours. Subsequently, the temperature was lowered to 80 ° C., 5 parts by mass of DMPA, 2 parts by mass of NPG, and 47 parts by mass 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 by mass of APTES and 110 parts by mass of IPA are introduced into the reaction vessel and reacted to form a polyurethane having a number average molecular weight of 7500 having a carboxyl group and a hydrolyzable silyl group. An organic solvent solution of (a1-9) was obtained.

  The organic solvent solution of polyurethane (a1-9) obtained above was mixed with 489 parts by mass of the liquid containing the composite resin intermediate (A′-1) and 30 parts by mass of GPTES. Composite resin (IX) in which the hydrolyzable silyl group possessed by the polyurethane (a1-9) and the hydrolyzable silyl group possessed by the composite resin intermediate (A′-1) are bonded by a time hydrolysis condensation reaction A liquid containing ') was obtained.

  By mixing the liquid containing the composite resin (IX ′) obtained above and 16 parts by mass of TEA, a neutralized product obtained by neutralizing the carboxyl group in the composite resin (IX ′) was obtained, A mixture of the neutralized product and 560 parts by mass of deionized water was distilled under the same conditions as in Example 1 to obtain 1000 parts by mass of an aqueous composite resin composition (IX) having a non-volatile content of 37.5% by mass. Got.

  Table 1 shows [polysiloxane structure / composite resin] and [vinyl polymer (a2) structure / polyurethane having hydrophilic group (a1) structure] of the composite resins obtained in Examples 1 to 9 above. . In addition, [polysiloxane structure / composite resin] and [vinyl polymer (a2) structure / polyurethane having hydrophilic group (a1) structure] were obtained based on the charged ratio of raw materials used for preparing the composite resin. The mass ratio of [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.

  The storage stability shown in Table 1 shows the viscosity (initial viscosity) of the aqueous dispersion of each composite resin, and the viscosity (viscosity with time) after leaving the aqueous dispersion of each composite resin in a 50 ° C. environment for 30 days. And the value obtained by dividing the viscosity with time by the initial viscosity [viscosity with time / initial viscosity]. If this value is about 0.5 to 3.0, it can be used as a paint.

(Example 10: Evaluation of coating film of aqueous composite resin composition (I))
Using the aqueous composite resin composition (I) obtained in Example 1, the following coating film evaluation was performed.

[Evaluation of coating appearance]
The aqueous composite resin composition (I) obtained above was applied onto a chromate-treated aluminum plate manufactured by Engineering Test Service Co., Ltd. so that the thickness of the cured coating film was 30 μm, and the environment at 23 ° C. The film was dried for 1 week to obtain a cured coating film. Appearance of the cured film immediately after production of the obtained cured coating film and Dew panel light weather meter (manufactured by Suga Test Instruments Co., Ltd., light irradiation: 30 W / m ² , 70 ° C .; wet: 90% or higher humidity, 50 ° C. The film appearance after exposure for 1,000 hours by light irradiation / wetting cycle = 8 hours / 4 hours) was visually observed, and the film appearance was evaluated according to the following criteria.
○: No crack is generated.
Δ: Some cracks are observed.
X: A crack is generated.

[Evaluation of adhesion]
The aqueous composite resin composition (I) obtained above is coated on a glass (JIS 3202R), untreated aluminum (A1050P), or polyethylene terephthalate (Toray Industries, Inc. “Lumirror T60”) and cured. The film was coated to a thickness of 30 μm and dried for 1 week in an environment of 23 ° C. to obtain a cured coating film. About the obtained cured coating film on each base material, it measured based on the 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. The adhesion was evaluated by counting the number of

[Evaluation of pencil hardness]
About the thing similar to the cured coating film used for evaluation of the coating-film external appearance, it measured based on the JISK-5600 scratch hardness (pencil method) test method. A pencil tip is placed on the cured coating film and pressed at a speed of 0.5 to 1 mm / s. Thereafter, the presence or absence of traces was confirmed without the naked eye, and the hardness of the hardest pencil that did not cause scratches was defined as pencil hardness.

[Evaluation of solvent resistance]
About the same thing as the cured coating film used for the evaluation of the coating film appearance, the condition of the cured coating film after rubbing 50 times on the cured coating film with a felt soaked with ethanol is checked by touch and visual inspection. The solvent resistance was evaluated according to the following criteria.
○: Softening and gloss reduction are not recognized.
(Triangle | delta): Some softening or gloss reduction is recognized.
X: Significant softening or gloss reduction is observed.

[Evaluation of bending resistance]
About the thing similar to the cured coating film used for evaluation of the coating-film external appearance, it evaluated based on the JISK-5600 bending resistance test method. The diameter of the mandrel was 2 mm. The evaluation criteria are as follows. In addition, by evaluation of this bending resistance, crack resistance and base material followability can be evaluated together.
○: No cracks are observed on the coating film surface at the bent portion.
(Triangle | delta): Some cracks are recognized by the coating-film surface of a bending part.
X: Remarkable cracks are observed on the coating film surface at the bent portion.

[Evaluation of weather resistance]
About the same thing as the cured coating film used for the evaluation of the coating film appearance, the specular reflectance (gloss value) (%) of the cured coating film immediately after production and the cured coating film were subjected to a dew panel optical weather meter (Suga test). Co., Ltd., Light irradiation: 30 W / m ² , 70 ° C .; Wetting: Humidity 90% or more, 50 ° C., light irradiation / wetting cycle = 8 hours / 4 hours) Retention rate of film specular reflectivity (gloss value) (%) with respect to specular reflectivity (gloss value) of cured coating film before exposure (gloss retention rate:%) [(100 x specular reflection of coating film after exposure Rate) / (specular reflectance of the cured coating film before exposure)]. It shows that a weather resistance is so favorable that the value of a retention rate is large.

[Evaluation of contamination resistance]
About the thing similar to the cured coating film used for evaluation of a coating-film external appearance, it exposed for 3 months in the DIC Corporation Sakai factory of Takaishi-shi, Osaka. 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 of substrate followability]
The aqueous composite resin composition (I) was applied on a polypropylene film so that the thickness of the cured coating film was 200 μm, dried in an environment of 140 ° C. for 5 minutes, and then in an environment of 25 ° C. for 24 hours. A dried coating film was obtained by drying. This cured coating film was peeled off from the polypropylene film of the substrate, and the tensile elongation of the cured coating film was measured to evaluate the substrate followability. The measurement conditions for tensile elongation are as follows.
Measuring equipment: “Autograph AGS-1kNG” manufactured by Shimadzu Corporation
Sample shape: 10mm x 70mm
Between chucks: 20 mm
Tensile speed: 300 mm / min Measurement atmosphere: 22 ° C., 60% RH

(Examples 11 to 18: Coating film evaluation of aqueous composite resin compositions (II) to (IX))
Each coating film evaluation was performed by the same operation as Example 1 using aqueous composite resin composition (II)-(IX). The evaluation results are shown in Table 2.

  It turned out that the thing of Examples 10-18 which is the water-based composite resin composition of this invention has a favorable coating-film external appearance also after an exposure test, and is excellent also in adhesiveness with a base material. Furthermore, it turned out that it is excellent also in solvent resistance, crack resistance, a weather resistance, stain resistance, and base material followability.

(Comparative Synthesis Example 1: Preparation of comparative aqueous composite resin composition (R-1))
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel, condenser and nitrogen gas inlet, 158 parts by mass of polytetramethylene glycol (“PTMG-2000” manufactured by Mitsubishi Chemical Corporation) with a number average molecular weight of 2,000 and IPDI 66 parts by mass were charged, the temperature was raised to 100 ° C., and the reaction was performed at the same temperature for 1 hour.
Next, the temperature was lowered to 80 ° C., 13 parts by mass of DMPA, 5 parts by mass of NPG, and 121 parts by mass of MEK were put into the reaction vessel, and further reacted at 80 ° C. for 5 hours.
Subsequently, the temperature was lowered to 50 ° C., and 30 parts by mass of APTES and 285 parts by mass of IPA were introduced into the reaction vessel and reacted, whereby the number average molecular weight having a carboxyl group and a hydrolyzable silyl group was 7,500. An organic solvent solution of polyurethane (r-1) was obtained.
Next, the total amount of the organic solvent solution of polyurethane (r-1) and 158 parts by mass of the liquid containing the composite resin intermediate (A′-1) obtained in Synthesis Example 2 were mixed, and the mixture was stirred at 80 ° C. A comparative composite in which the hydrolyzable silyl group of the polyurethane (r-1) and the hydrolyzable silyl group of the composite resin intermediate (A′-1) are bonded by performing a hydrolytic condensation reaction for 1 hour. A liquid containing the resin (R′-1) was obtained.
Then, after obtaining the neutralized product which neutralized the carboxyl group in the composite resin for comparison by mixing the liquid containing the composite resin for comparison (R′-1) and TEA 12 parts by mass, A mixture of the neutralized product and 610 parts by mass of deionized water was distilled under the same conditions as in Example 1 to obtain a liquid 1,000 of a composite resin (R-1) having a nonvolatile content of 35% by mass. A mass part was obtained.

(Comparative Synthesis Example 2: Preparation of comparative aqueous composite resin composition (R-2))
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel, condenser and nitrogen gas inlet, polytetramethylene glycol having a number average molecular weight of 2,000 ("PTMG-2000" manufactured by Mitsubishi Chemical Corporation), 122 parts by mass, IPDI 51 parts by mass were charged, the temperature was raised to 100 ° C., and the reaction was performed at the same temperature for 1 hour.
Next, the temperature was lowered to 80 ° C., 10 parts by mass of DMPA, 4 parts by mass of NPG, and 94 parts by mass 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 by mass of APTES and 221 parts by mass of IPA are introduced into the reaction vessel and reacted, whereby the number average molecular weight having a carboxyl group and a hydrolyzable silyl group is 7,500. An organic solvent solution of polyurethane (r-2) was obtained.
Next, the total amount of the organic solvent solution of polyurethane (r-2) and 279 parts by mass of the liquid containing the composite resin intermediate (A′-1) obtained in Synthesis Example 2 were mixed, and the mixture was stirred at 80 ° C. A comparative composite in which the hydrolyzable silyl group possessed by the polyurethane (r-2) and the hydrolyzable silyl group possessed by the composite resin intermediate (A′-1) are bonded by a hydrolytic condensation reaction for 1 hour. A liquid containing the resin (R′-2) was obtained.
Next, after obtaining the neutralized product obtained by neutralizing the carboxyl group in the comparative composite resin by mixing the liquid containing the comparative composite resin (R′-2) and TEA 14 parts by mass in the previous period. A mixture of the neutralized product and 610 parts by mass of deionized water was distilled under the same conditions as in Example 1 to obtain an aqueous composite resin composition (R-2) 1 having a nonvolatile content of 35% by mass. 1,000 parts by mass were obtained.

(Comparative Synthesis Example 3: Preparation of comparative aqueous composite resin composition (R-3))
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel, condenser and nitrogen gas inlet, polytetramethylene glycol having a number average molecular weight of 2,000 ("PTMG-2000" manufactured by Mitsubishi Chemical Corporation) 61 parts by mass, IPDI 26 parts by mass were charged, the temperature was raised to 100 ° C., and the reaction was performed at the same temperature for 1 hour.
Next, the temperature was lowered to 80 ° C., 5 parts by mass of DMPA, 2 parts by mass of NPG, and 47 parts by mass 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 by mass of APTES and 110 parts by mass of IPA are introduced into the reaction vessel and reacted, whereby the number average molecular weight having a carboxyl group and a hydrolyzable silyl group is 7,500. An organic solvent solution of polyurethane (r-3) was obtained.
Next, the total amount of the organic solvent solution of polyurethane (r-3) and 489 parts by mass of the liquid containing the composite resin intermediate (A′-1) obtained in Synthesis Example 2 were mixed, and the mixture was stirred at 80 ° C. Comparative composite in which the hydrolyzable silyl group possessed by the polyurethane (r-3) and the hydrolyzable silyl group possessed by the composite resin intermediate (A′-1) are bonded by hydrolytic condensation reaction for 1 hour. A liquid containing the resin (R′-3) was obtained.
Next, after obtaining the neutralized product obtained by neutralizing the carboxyl group in the composite resin for comparison by mixing the liquid containing the composite resin for comparison (R′-3) and 16 parts by mass of TEA. A mixture of the neutralized product and 560 parts by mass of deionized water was distilled under the same conditions as in Example 1 to obtain an aqueous composite resin composition (R-3) 1 having a nonvolatile content of 35% by mass. 1,000 parts by mass were obtained.

  Table 3 shows mass ratios of [polysiloxane structure / composite resin] and [vinyl polymer structure / polyurethane structure having a hydrophilic group] of the comparative composite resins obtained in Comparative Synthesis Examples 1 to 3 shown above. It was. In addition, [polysiloxane structure / composite resin] and [vinyl polymer (a2) structure / polyurethane having hydrophilic group (a1) structure] were obtained based on the charged ratio of raw materials used for preparing the composite resin. Further, the mass ratio of [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.

  The storage stability described in Table 3 is in agreement with that described in Table 1.

(Comparative Examples 1-3)
After mixing the aqueous composite resin compositions (R1) to (R3) and the curing agent with the blending composition shown in Table 4, to obtain a two-component curable aqueous composite resin composition, the same operation as in Example 1, Each coating film was evaluated. In the table, [polysiloxane structure / total composite resin] is obtained from the total amount of the composite resins (A) and (B) and the comparative composite resin (R).

  Comparative Example 1 is an example of a two-component curable aqueous composite resin composition of [polysiloxane structure / total composite resin] = 17/100, but it was found that the initial substrate followability was low.

  Comparative Example 2 is an example of a two-part curable aqueous composite resin composition of [polysiloxane structure / total composite resin] = 30/100, but the initial substrate followability is low, and the substrate followability is deteriorated over time. I found out.

  Comparative Example 3 is an example of a two-part curable aqueous composite resin composition of [polysiloxane structure / total composite resin] = 53/100, but the initial substrate followability is low, and the substrate followability is very good over time. It was found to be greatly damaged.

Claims (9)

An aqueous composite resin composition comprising a composite resin (A) in which a polyurethane (a1) having a hydrophilic group and a vinyl polymer (a2) are bonded via a polysiloxane (a3) and an aqueous medium, The bond between the polyurethane (a1) having a functional group and the polysiloxane (a3) is a hydrolyzable silyl group and / or a silanol group possessed by the polyurethane (a1) and a hydrolyzable silyl possessed by the polysiloxane (a3). the condensation coupling of the base and / or silanol group, wherein the bond between the vinyl polymer (a2) and said polysiloxane (a3), a hydrolyzable silyl group and / or silanol having the said vinyl polymer (a2) the condensation bonds of the hydrolyzable silyl group and / or silanol group possessed by the the base polysiloxane (a3), the composite resin ( ) The polysiloxane in (a3) is in the range weight ratio of the structure is 15 to 55 mass% from the polysiloxane (a3) The aqueous composite resin composition characterized by containing an epoxy group.   The aqueous composite according to claim 1, wherein the mass ratio [(a2) / (a1)] of the polyurethane (a1) having the hydrophilic group and the vinyl polymer (a2) is in the range of 20/1 to 1/20. Resin composition. Claim wherein the vinyl polymer (a2) is a polymer of one or more vinyl monomers selected from the group consisting of vinyl monomers having a vinyl monomer and a silanol group having a hydrolyzable silyl group 3. The aqueous composite resin composition according to 1 or 2.

  The polysiloxane (a3) has an aromatic cyclic structure bonded to a silicon atom, an alkyl group having 1 to 3 carbon atoms bonded to a silicon atom, and 1 to 3 carbon atoms bonded to a silicon atom. The aqueous composite resin composition according to any one of claims 1 to 3, wherein the aqueous composite resin composition has at least one selected from the group consisting of alkoxy groups. The aqueous composite resin composition according to any one of claims 1 to 4, wherein the polysiloxane (a3) has at least one structure selected from the group consisting of the following general formulas (I) and (II). object.

(R ¹ in the general formula (I) is an organic group having an epoxy group and / or an organic group having 4 to 12 carbon atoms, and R ² and R ³ in the general formula (II) are Each independently a methyl or ethyl group.)   The aqueous composite according to any one of claims 1 to 5, wherein the polysiloxane (a3) is formed using a condensate of an alkyltrialkoxysilane having an alkyl group having 1 to 3 carbon atoms. Resin composition.   The aqueous composite resin composition according to any one of claims 1 to 6, wherein the polysiloxane (a3) has an epoxy group introduced using a compound having an epoxy group and an alkoxysilyl group.   A coating agent comprising the aqueous composite resin composition according to any one of claims 1 to 7.   An article having a coating film formed using the coating agent according to claim 8.