JP4403312B2 - Aqueous composite resin composition, coating agent containing the same, and laminate using the same - 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.

  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.

  Examples of the coating agent that can form a coating film having excellent durability and weather resistance as described above include a specific polysiloxane segment (A) and a polymer segment (B) having a hydrophilic group. An aqueous resin obtained by mixing a composite resin (C) and a specific polysiloxane (D) and condensing a part thereof as necessary is dispersed in an aqueous medium (for example, (See Patent Document 1).

  However, since the coating film formed using the water-based resin is relatively hard, the coating film is based on the surface coating of a substrate that is likely to be deformed or stretched due to the influence of external force or temperature change. The deformation of the material could not be followed, and as a result, peeling of the coating film, generation of cracks, and the like may occur.

JP-A-11-279408

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

The present inventors proceeded with the study based on the aqueous resin described in Patent Document 1 and studied the use of a urethane resin in combination as a method for imparting good substrate followability to the aqueous resin.
Specifically, various physical properties of a coating film formed using a resin composition containing the aqueous resin described in the above-mentioned literature 1 and a general hydrophilic group-containing polyurethane were examined.

  However, since the resin composition is not sufficiently compatible with the water-based resin and the urethane resin, it may cause a significant decrease in durability and weather resistance of the formed coating film. Moreover, the substrate follow-up property of the coating film is still not sufficient.

In addition, the present inventors examined an aqueous dispersion of a resin obtained by chemically bonding the water-based resin and the hydrophilic group-containing polyurethane as described above, instead of mixing them.
Specifically, a composition of an aqueous composite resin in which the vinyl polymer constituting the aqueous resin described in Patent Document 1 and the hydrophilic group-containing polyurethane were chemically bonded via a polysiloxane structure was studied. .

  The coating film formed using the aqueous composite resin composition had good substrate followability, but it still has a practically sufficient level in terms of durability and weather resistance. There wasn't.

  However, when an aqueous composite resin in which the mass ratio of the polysiloxane-derived structure in the entire aqueous composite resin is adjusted to a range of 15 to 55 mass% was studied, unexpectedly, durability and weather resistance were significantly improved. It was found that a coated film can be formed, and further, a coated film excellent in excellent substrate followability can be formed.

That is, the present invention is a composite resin hydrophilic group-containing polyurethane (a1) and the vinyl polymer (a2) and is linked via a polysiloxane (a3) (A), and, and also contains an aqueous medium, the hydrophilic The bond between the functional group-containing polyurethane (a1) and the polysiloxane (a3) is the hydrolyzable silyl group and / or silanol group possessed by the hydrophilic group-containing polyurethane (a1) and the hydrosiloxane possessed by the polysiloxane (a3). It is formed by a reaction with a decomposable silyl group and / or silanol group, and the bond between the vinyl polymer (a2) and the polysiloxane (a3) is added to the water that the vinyl polymer (a2) has. By reaction between the decomposable silyl group and / or silanol group and the hydrolyzable silyl group and / or silanol group of the polysiloxane (a3). It is those formed Te, and the aqueous hybrid resin composition, wherein the weight ratio of the polysiloxane (a3) derived from the structure relative to the entire hybrid resin (A) is in the range of 15 to 55 wt% It is about.

The present invention also relates to a method for producing an aqueous composite resin composition comprising the following steps (I) to (IV).
(I) In the presence of an organic solvent, a vinyl monomer is polymerized by polymerizing a vinyl monomer containing at least one selected from the group consisting of a hydrolyzable silyl group-containing vinyl monomer and a silanol group-containing vinyl monomer. A step of obtaining an organic solvent solution of the combined (a2),
(II) The polysiloxane (a3) is bonded to the vinyl polymer (a2) by reacting the vinyl polymer (a2) with a silane compound in the presence of an organic solvent solution of the vinyl polymer (a2). A step of obtaining an organic solvent solution of the obtained resin (C),
(III) The resin (C) and the hydrophilic group-containing polyurethane (a1) are mixed and reacted, whereby the vinyl polymer (a2) and the hydrophilic group-containing polyurethane (a1) are converted into the polysiloxane (a3). A step of obtaining an organic solvent solution of the composite resin (A) bonded via
(IV) neutralizing the hydrophilic group having the of the composite resin (A) in an organic solvent, dissolving the neutralized product in an aqueous medium by mixing the organic solvent solution and water containing neutralized product Or the step of dispersing.

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.
In addition, the aqueous composite resin composition of the present invention can form a coating film having excellent durability and weather resistance, as well as excellent rust prevention, so that, for example, building members such as outer walls and roofs, guardrails, soundproof walls, drainage Galvanized steel sheets, aluminum-zinc alloy steel sheets, etc., aluminum plates, aluminum alloy plates, electromagnetic steel plates, copper plates, stainless steel plates, etc. used for civil engineering members such as grooves, home appliances, industrial machinery, automobile parts, etc. It can be suitably used as a coating agent for coating the surface of a metal substrate or a primer coating layer forming agent between the 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 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 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), an aqueous medium, and other additives as required. The aqueous composite resin composition is characterized in that 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 mass%. .

  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 mass of the polysiloxane (a3) with respect to the entire composite resin (A) when forming a coating film excellent in durability and weather resistance. It is important to have. 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 is the mass 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 mass ratio of the structure derived from the polysiloxane (a3) to the entire composite resin (A) is in the range of 20% by mass to 35% by mass, 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 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 production of the composite resin (A). And a value calculated in consideration of the formation of by-products such as 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 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 them, a carboxylate group partially or wholly neutralized with a basic compound or the like It is preferable to use a sulfonate group in producing a composite resin having good water dispersibility.

  Examples of basic compounds that can be used for neutralization of the anionic group include organic amines such as ammonia, triethylamine, pyridine, morpholine, alkanolamines such as monoethanolamine, Na, K, Li, and Ca. A metal base 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). This is preferable for maintaining water dispersion stability.

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), mass ratio [(a2) / (a1)] of said hydrophilic group containing polyurethane (a1) and said vinyl polymer (a2) is 1/1 to 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 composite 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 contained in the hydrophilic group-containing polyurethane (a1) is introduced into the hydrophilic group-containing polyurethane (a1), for example, by using the hydrophilic group-containing polyol as one component constituting the polyol. be able to.

  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 can 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. 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 composite 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.

  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 aqueous composite 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 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 hydrophilic group-containing polyurethane (a1) include aromatic diisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and 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. For example, a functional group represented by the following general formula: Groups.

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 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, and 3- (meth) acryloyloxypropylmethyldimethoxysilane. Among them, it is preferable to use 3- (meth) acryloyloxypropyltrimethoxysilane.

  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 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 hydrophilic group-containing polyurethane (a1) and the vinyl polymer (a2).

  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.

  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.

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 a step of producing a composite resin (A) and a step of dispersing the composite resin (A) in an aqueous medium.

  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, supplying the aqueous medium into the organic solvent solution of the neutralized product of the composite resin (A) and then removing the organic solvent can produce the aqueous composite resin composition of the present invention. it can.

  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.

  In the aqueous composite resin composition of the present invention, a curing agent may be used in combination as necessary.

  As said hardening | curing agent, the compound which has the functional group which reacts with the hydrophilic group and silanol group which the said composite resin (A) 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 within a range of 0.1 to 50 parts by weight of solid content, for example, within a range of 0.5 to 30 parts by weight with respect to 100 parts by weight of the composite resin (A). It is more preferable to use within the range of 1 to 20 parts by weight.

  Further, when the composite resin (A) has a carboxyl group as a hydrophilic group, the curing agent is an epoxy group or cyclocarbonate that the curing agent has for 1 equivalent of the carboxyl group in the composite resin (A). The equivalent of a reactive functional group such as a group, a hydroxyl group, an oxazoline group, a carbodiimide group, or a hydrazino group is preferably within a range of 0.2 to 5.0 equivalents, and within a range of 0.5 to 3.0 equivalents It is more preferable that it is in the range of 0.7 to 2.0 equivalents.

  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 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 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.

  The photocatalytic compound is a compound that oxidizes and decomposes organic substances by light irradiation, and has recently been attracting attention in fields where a self-cleaning function is required, such as for building exteriors. In addition, the photocatalytic compound can decompose harmful gases such as NOx in the atmosphere and environmental hormones in the water, and can also exhibit air purification, water purification, deodorization and antibacterial functions. It is also attracting attention as an environmentally useful material.

  Examples of the photocatalytic compound include titanium oxide, zinc oxide, iron oxide, zirconium oxide, tungsten oxide, chromium oxide, molybdenum oxide, germanium oxide, copper oxide, vanadium oxide, manganese oxide, nickel oxide, and ruthenium oxide. can do. Specifically, for example, “ST-01” [Ishihara Sangyo Co., Ltd. titanium oxide, average particle size 7 nm], “ST-21” [Ishihara Sangyo Co., Ltd. titanium oxide, average particle size 20 nm], “ AMT-100 "[Titanium Co., Ltd., titanium oxide, average particle diameter 6 nm]," TKD-701 "[Taika Co., Ltd. titanium oxide dispersion, average particle diameter 6 nm]," TKD-702 "[Taika Corporation ) Titanium oxide dispersion, average particle size 6 nm], “STS-21” (Ishihara Sangyo Co., Ltd. titanium oxide water dispersion, average particle size 20 nm), “TKS-203” (Taika Co., Ltd.) Titanium aqueous dispersion, average particle diameter of 6 nm] and the like can be used. Among them, it is preferable to use titanium oxide or zinc oxide that is chemically stable, harmless, and has high photocatalytic activity.

  The photocatalytic compound is preferably in the form of particles, and the average particle diameter is usually 3 to 100 nm, preferably 3 to 50 nm, and particularly preferably 4 to 30 nm.

  As the photocatalytic compound, the fine particle powder may be used as it is, but from the viewpoint of imparting good dispersibility, a sol form in which the photocatalytic compound is dispersed in advance in an organic solvent or an aqueous medium. Are preferably used.

  The photocatalytic compound is preferably in the range of 0.01 to 20 parts by mass and more preferably in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the composite resin (A). preferable. By using the photocatalytic compound within the above range, the effect of decomposition and degradation of the resulting coating film due to oxide fine particles is small, and the self-cleaning function of the coating film due to the hydrophilization of the coating surface layer portion is exhibited. Can do.

  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 for a coating agent because it can form a coating film excellent in durability and weather resistance as well as the substrate follow-up property. It is more preferable to use it as 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. Surface coatings of various metal base materials constituting, for example, building members such as outer walls and roofs, civil engineering members such as guardrails, soundproof walls, drainage grooves, home appliances, industrial machinery, and automobile parts Can be used for 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. 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
As said metal base material, galvanized steel plates, such as a galvanized steel plate and an aluminum zinc alloy steel plate, an aluminum plate, an aluminum alloy plate, an electromagnetic steel plate, a copper plate, a stainless steel plate etc. can be used, for example.

Among the coating agents of the present invention, the hydrophilic group-containing polyurethane (a1) constituting the composite resin (A) contained in the coating agent includes a polyol and a polyisocyanate containing a polycarbonate polyol and a hydrophilic group-containing polyol. The coating agent obtained by reacting 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 can form a coating film excellent in durability, weather resistance, substrate followability, and the like, for example, by directly applying the coating agent to the substrate surface and then drying and curing the coating agent. it can.

  Examples of the method for applying the coating agent on the substrate include a spray method, a curtain coater method, a flow coater method, a roll coater method, a brush coating method, and a dipping method.

  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 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 coating agent of this invention can be suitably adjusted according to the use etc. which a base material is used, it is preferable that it is normally about 0.5 micrometer-20 micrometers.

  Moreover, when obtaining the laminated body which has a coating film which further consists of the coating agent for top layer formation on the coating-film surface formed using the coating agent of this invention on the said base material, for the said top layer formation Conventionally known acrylic resin paints, polyester resin paints, alkyd resin paints, epoxy resin paints, fatty acid-modified epoxy resin paints, silicone resin paints, polyurethane resin paints, etc. are used as coating agents. be able to.

  As described above, a laminate in which the base material and a coating film formed using the coating agent of the present invention are laminated includes, for example, mobile phones, home appliances, office automation equipment, automobile interior and exterior materials, and the like. It can be used for parts, parts of various home appliances, building material products and the like.

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

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 by mass of methyltrimethoxysilane (MTMS) was charged and heated to 60 ° C.

  Next, a mixture of 0.17 parts by mass of “A-3” (iso-propyl acid phosphate 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 The mixture was stirred at a temperature of 4 ° C. 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. In the same manner, the methanol and water produced in the reaction process are removed to remove the methanol and water, thereby containing a condensate (a3′-1) of methyltrimethoxysilane having a number average molecular weight of 1000 (active ingredient) 70 mass%) 1000 mass parts was obtained.

  In addition, with the said active ingredient, the theoretical yield (mass part) when all the methoxy groups of silane monomers, such as methyltrimethoxysilane (MTMS), carried out condensation reaction was remove | divided by the actual yield (mass part) after condensation reaction. It is calculated from the value [theoretical yield (mass part) when all methoxy groups of the silane monomer undergo a condensation reaction / actual yield (mass part) after the condensation reaction].

Synthesis Example 2 [Preparation Example of Condensate of Ethyltrimethoxysilane (a3′-2)]
Into a reaction vessel equipped with a stirrer, thermometer, dropping funnel, condenser and nitrogen gas inlet, 1296 parts by mass of ethyltrimethoxysilane (ETMS) was charged and heated to 60 ° C.

  Next, a mixture of 0.14 parts by mass of “A-3” (iso-propyl acid phosphate manufactured by Sakai Chemical Co., Ltd.) and 171 parts by mass of deionized water was dropped into the reaction vessel over 5 minutes, and then 80 The mixture was stirred at 4 ° C. for 4 hours to cause hydrolysis and condensation reaction.

  The condensate obtained by the hydrolysis condensation reaction was distilled at a temperature of 40 to 60 ° C. and a reduced pressure of 300 to 10 mmHg to remove methanol and water, thereby removing ethyl trimethoxysilane having a number average molecular weight of 1100. 1000 parts by mass of a mixed solution (active ingredient 70% by mass) containing the condensate (a3′-2) was obtained.

Abbreviations in Table 1 are described below. “MTMS”: Methyltrimethoxysilane “ETMS”: Ethyltrimethoxysilane

Synthesis Example 3 [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 by mass of propylene glycol monopropyl ether (PnP), 168 parts by mass of phenyltrimethoxysilane (PTMS) and dimethyldimethoxysilane (DMDMS) ) 102 parts by mass were charged and heated to 80 ° C.

  Next, at the same temperature, 38 parts by mass of methyl methacrylate (MMA), 24 parts by mass of butyl methacrylate (BMA), 36 parts by mass of butyl acrylate (BA), 24 parts by mass of acrylic acid (AA), 3-methacryloxypropyltrimethoxysilane (MPTS) A mixture containing 4 parts by mass, 54 parts by mass of PnP and 6 parts by mass of tert-butylperoxy-2-ethylhexanoate (TBPEH) was dropped into the reaction vessel over 4 hours, and then the same. By reacting at a temperature for 2 hours, 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 by mass of “A-3” [iso-propyl acid phosphate manufactured by Sakai Chemical Co., Ltd.] and 76 parts by mass of deionized water was added dropwise over 5 minutes, and further stirred at the same temperature for 1 hour. The hydrolytic condensation reaction 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 A composite resin intermediate containing liquid (C′-1) was obtained.

  Next, the composite resin intermediate-containing liquid (C′-1) and 291 parts by mass of the methyltrimethoxysilane condensate (a3′-1) are mixed, and 49 parts by mass of deionized water is added. By stirring at the same temperature for 16 hours to cause a hydrolysis condensation reaction, a condensate (a3′-1) of methyltrimethoxysilane was further bonded to the composite resin intermediate in the liquid containing (C′-1). 1000 mass parts of composite resin intermediate containing liquid (C-1) was obtained.

Synthesis Example 4 [Preparation Example of Composite Resin Intermediate Containing Liquid (C-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 (c2) of an acrylic polymer having a carboxyl group and a hydrolyzable silyl group and a number average molecular weight of 10300.

  Next, a mixture of 4.3 parts by mass of “A-3” (iso-propyl acid phosphate manufactured by Sakai Chemical Co., Ltd.) and 121 parts by mass of deionized water was added dropwise over 5 minutes, and the mixture was further stirred at the same temperature for 1 hour. By carrying out hydrolytic condensation reaction, a composite resin-containing liquid (C′-) in which the hydrolyzable silyl group of the acrylic polymer in the organic solvent solution (c2) and the polysiloxane derived from PTMS and DMDMS are combined. 2) 1000 mass parts was obtained.

  Next, 123 parts by mass of a methyltrimethoxysilane condensate (a3′-1) is added, 21 parts by mass of deionized water is further added, and the mixture is stirred at the same temperature for 16 hours. A composite resin intermediate-containing liquid (C-2) in which a condensate (a3′-1) of methyltrimethoxysilane was further bonded to the composite resin intermediate in the liquid containing (C′-2) was obtained.

Synthesis Example 5 [Preparation Example of Composite Resin Intermediate Containing Liquid (C-3)]
Except for using 291 parts by mass of ethyltrimethoxysilane condensate (a3′-2) instead of 291 parts by mass of methyltrimethoxysilane condensate (a3′-1), the same method as in Synthesis Example 3, 1000 parts by mass of a composite resin intermediate containing liquid (C-3) in which the composite resin intermediate in the containing liquid (C'-1) and a condensate of ethyltrimethoxysilane (a3'-2) were combined were obtained. .

Synthesis Example 6 [Preparation Example of Composite Resin Intermediate Containing Liquid (C-4)]
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser tube and a nitrogen gas inlet, 129 parts by mass of PnP, 283 parts by mass of PTMS and 171 parts by mass of DMDMS were charged and heated to 80 ° C.

  Next, at the same temperature, a mixture containing 21 parts by mass of MMA, 13 parts by mass of BMA, 20 parts by mass of BA, 13 parts by mass of AA, 2.1 parts by mass of MPTS, 58 parts by mass of PnP and 3.5 parts by mass of TPEHE, An organic solvent solution of an acrylic polymer having a number average molecular weight of 9900 (c4) having a carboxyl group and a hydrolyzable silyl group by allowing the reaction vessel to drop in 4 hours and further reacting at the same temperature for 2 hours. Got.

  Next, a mixture of 4.6 parts by mass of “A-3” (iso-propyl acid phosphate manufactured by Sakai Chemical Co., Ltd.) and 129 parts by mass of deionized water was added dropwise over 5 minutes, and further stirred at the same temperature for 1 hour. Then, a hydrolytic condensation reaction is performed, whereby the hydrolyzable silyl group of the acrylic polymer in the organic solvent solution (c4) and the polysiloxane derived from PTMS and DMDMS are combined (C ′ -4) 1000 mass parts was obtained.

  Next, the composite resin intermediate (C′-4) and 130 parts by mass of the methyltrimethoxysilane condensate (a3′-1) are mixed, and further 22 parts by mass of deionized water is added at the same temperature. The composite resin intermediate-containing liquid in which a methyltrimethoxysilane condensate (a3′-1) is further bonded to the composite resin intermediate (C′-4) by stirring for 16 hours at a hydrolytic condensation reaction. (C-4) was obtained.

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

  Subsequently, the temperature was lowered to 80 ° C., 13 parts by mass of dimethylolpropionic acid (DMPA), 5 parts by mass of neopentyl glycol (NPG), and 121 parts by mass of methyl ethyl ketone (MEK) were added into the reaction vessel, and then further The reaction was carried out at 80 ° C. for 5 hours.

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

  Next, the total amount of the organic solvent solution (i) of polyurethane and 158 parts by mass 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. Liquid containing composite resin in which hydrolyzable silyl group possessed by polyurethane in organic solvent solution (i) and hydrolyzable silyl group possessed by composite resin intermediate in said containing liquid (C-1) are combined ( I ').

Next, a neutralized product obtained by neutralizing the carboxyl group in the composite resin is obtained by mixing the composite resin-containing liquid (I ′) and 10 parts by mass of triethylamine (TEA), and then the neutralized product and What was mixed with 610 parts by mass of deionized water was distilled under reduced pressure of 300 to 10 mmHg for 4 hours under the condition of 40 to 60 ° C., and the generated methanol, organic solvent and water were removed, so that the nonvolatile content was reduced. 1000 mass parts of 35.0 mass% aqueous composite resin composition (I) was obtained.
Table 2 shows mass ratios of [polysiloxane structure / composite resin] and [vinyl polymer structure / hydrophilic group-containing polyurethane structure] of the composite resin in the obtained aqueous composite resin composition.

Example 2 [Preparation 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 2000 (PTMG-2000 manufactured by Mitsubishi Chemical Corporation), 60 parts by mass of IPDI Was heated to 100 ° C. and reacted 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 put into the reaction vessel and reacted, whereby the polyurethane having a number average molecular weight of 7400 having a carboxyl group and a hydrolyzable silyl group was obtained. An organic solvent solution (ii) was obtained.

  Next, the total amount of the organic solvent solution (ii) of polyurethane and 209 parts by mass 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, Liquid containing composite resin (II) in which hydrolyzable silyl group of polyurethane in organic solvent solution (ii) and hydrolyzable silyl group of composite resin intermediate in said liquid containing (C-1) are combined ') Got.

  Next, a neutralized product obtained by neutralizing the carboxyl group in the composite resin was obtained by mixing the composite resin-containing liquid (II ′) and 13 parts by mass of TEA, and then the neutralized product and deionized water. A mixture of 610 parts by mass was distilled under the same conditions as in Example 1 to obtain 1000 parts by mass of an aqueous composite resin composition (II) having a nonvolatile content of 35.0% by mass.

Example 3 [Preparation of aqueous composite resin composition (III)]
Example 2 with the exception of using 216 parts by mass of composite resin intermediate (C-2) instead of 209 parts by mass of composite resin intermediate (C-1) and 7 parts by mass of TEA instead of 13 parts by mass of TEA In the same manner, 1000 parts by mass of an aqueous composite resin composition (III) having a nonvolatile content of 35.1% by mass was obtained.

Example 4 [Preparation of aqueous composite resin composition (IV)]
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser tube and a nitrogen gas inlet, 122 parts by mass of polytetramethylene glycol having a number average molecular weight of 2000 (PTMG-2000 manufactured by Mitsubishi Chemical Corporation), 51 parts by mass of IPDI Was heated to 100 ° C. and reacted 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 put into the reaction vessel and reacted, whereby a polyurethane having a number average molecular weight of 7500 having a carboxyl group and a hydrolyzable silyl group is obtained. An organic solvent solution (iv) was obtained.

  Next, the total amount of the organic solvent solution (iv) of polyurethane and 279 parts by mass 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. Liquid containing composite resin (IV) in which hydrolyzable silyl group of polyurethane in organic solvent solution (iv) and hydrolyzable silyl group of composite resin intermediate in said liquid containing (C-1) are combined Got.

  Next, the composite resin-containing liquid (IV) and 14 parts by mass 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 610 mass of deionized water. Then, the mixture 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 non-volatile content of 35.0% by mass.

Example 5 [Preparation of aqueous composite resin composition (V)]
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 A mass part and 50 parts by mass of IPDI 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 was lowered to 50 ° C., and 23 parts by mass of APTES and 221 parts by mass of IPA were put into the reaction vessel and reacted, whereby the polyurethane having a number average molecular weight of 7300 having a carboxyl group and a hydrolyzable silyl group was obtained. An organic solvent solution (v) was obtained.

  Next, the whole organic solvent solution (v) of polyurethane and 279 parts by mass 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. Liquid containing composite resin (V ′) in which hydrolyzable silyl group possessed by polyurethane in solvent solution (v) and hydrolyzable silyl group possessed by composite resin intermediate in said containing liquid (C-1) are combined. Got.

  Next, by mixing 14 parts by mass of the composite resin-containing liquid (V ′) and TEA, a neutralized product obtained by neutralizing the carboxyl group in the composite resin is obtained, and then the neutralized product and the neutralized product are removed. 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 (V) having a nonvolatile content of 35.0% by mass.

Example 6 [Preparation of aqueous composite resin composition (VI)]
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 (vi) was obtained.

  Next, the total amount of the organic solvent solution (vi) of polyurethane and 279 parts by mass 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. Liquid containing composite resin in which hydrolyzable silyl group of polyurethane in organic solvent solution (vi) and hydrolyzable silyl group of composite resin intermediate in said containing liquid (C-1) are combined (VI ′ )

  Next, a neutralized product in which the carboxyl group in the composite resin was neutralized was obtained by mixing the composite resin-containing liquid (VI ′) and 14 parts by mass of TEA, and then the neutralized product and deionized water 610 were obtained. By mixing the mixture with parts by mass under the same conditions as in Example 1, 1000 parts by mass of the aqueous composite resin composition (VI) having a non-volatile content of 35.0% by mass was obtained.

Example 7 [Preparation of aqueous composite resin composition (VII)]
Implemented except that 288 parts by mass of composite resin intermediate containing liquid (C-2) was used instead of 279 parts by mass of composite resin intermediate containing liquid (C-1) and 6 parts by mass of TEA was used instead of 14 parts by mass of TEA In the same manner as in Example 4, 1000 parts by mass of an aqueous composite resin composition (VII) having a nonvolatile content of 35.1% by mass was obtained.

Example 8 [Preparation of aqueous composite resin composition (VIII)]
An aqueous composite having a non-volatile content of 35.1% by mass in the same manner as in Example 4 except that 279 parts by mass of the composite resin intermediate (C-1) was used instead of 279 parts by mass of the composite resin intermediate (C-1). 1000 mass parts of resin compositions (VIII) were obtained.

Example 9 [Preparation of aqueous composite resin composition (IX)]
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel, condenser and nitrogen gas inlet, 61 parts by mass of polytetramethylene glycol having a number average molecular weight of 2000 (PTMG-2000 manufactured by Mitsubishi Chemical Corporation), 26 parts by mass of IPDI Was heated 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 (ix) was obtained.

  Next, the total amount of the organic solvent solution (ix) of polyurethane and 489 parts by mass 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, Liquid containing composite resin (IX ′) in which hydrolyzable silyl group of polyurethane in organic solvent solution (ix) and hydrolyzable silyl group of composite resin intermediate in said liquid containing (C-1) are combined )

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

Example 10 [Preparation of aqueous composite resin composition (X)]
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel, condenser and nitrogen gas inlet, 77 parts by mass of polytetramethylene glycol having a number average molecular weight of 2000 (PTMG-2000 manufactured by Mitsubishi Chemical Corporation), 32 parts by mass of IPDI Was heated to 100 ° C. and reacted at the same temperature for 1 hour.

  Subsequently, the temperature was lowered to 80 ° C., 6 parts by mass of DMPA, 2 parts by mass of NPG, and 60 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 15 parts by mass of APTES and 140 parts by mass of IPA are introduced into the reaction vessel and reacted to form a polyurethane having a number average molecular weight of 7600 having a carboxyl group and a hydrolyzable silyl group. An organic solvent solution (x) was obtained.

  Next, the total amount of the organic solvent solution (x) of polyurethane and 476 parts by mass of the composite resin intermediate-containing liquid (C-4) 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 (x) and hydrolyzable silyl group of composite resin intermediate in said containing liquid (C-4) are bonded (X ′ )

  Next, the composite resin-containing liquid (X ′) and 11 parts by mass 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 deionized water. A mixture of 560 parts by mass was distilled under the same conditions as in Example 1 to obtain an aqueous composite resin composition, and then 0.9 parts by mass of GPTMS was added to the composition, whereby the nonvolatile content was reduced. 1000 mass parts of 35.1 mass% aqueous composite resin composition (X) were obtained.

Comparative Example 1 [Preparation of Comparative Aqueous Composite Resin Composition (XI)]
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser tube and a nitrogen gas inlet, 60 parts by mass of PnP, 365 parts by mass of MTMS and 32 parts by mass of DMDMS were charged and heated to 80 ° C.

  Next, 93 parts by mass of MMA, 53 parts by mass of BA, 27 parts by mass of MPTS, 7 parts by mass of AA, 20 parts by mass of 2-hydroxyethyl methacrylate (2-HEMA), 10 parts by mass of PnP, and 10 parts by mass of TBPEH at the same temperature. The mixture containing the acrylic polymer having a number average molecular weight of 16000 having a carboxyl group and a hydrolyzable silyl group is further dropped for 2 hours at the same temperature after dropping into the reaction vessel over 4 hours. An organic solvent solution (xi) was obtained.

  Next, in a reaction vessel containing the organic solvent solution (xi) of the acrylic polymer, 4.6 parts by weight of “A-3” [iso-propyl acid phosphate manufactured by Sakai Chemical Co., Ltd.] and 154 parts by weight of deionized water. The mixture is added dropwise to the hydrolyzable silyl group of the acrylic polymer in the organic solvent solution (xi) by stirring at 80 ° C. for 10 hours to cause a hydrolytic condensation reaction. A liquid (XI ′) containing a composite resin for comparison to which polysiloxane derived from DMDMS was bonded was obtained.

  Next, the comparative composite resin containing liquid (XI ′) and 21 parts by mass of TEA were mixed to obtain a neutralized product obtained by neutralizing the carboxyl group in the comparative composite resin, and then the neutralization A mixture of the product and 530 parts by mass of deionized water was distilled under the same conditions as in Example 1 to obtain 1000 parts by mass of a comparative aqueous composite resin composition (XI) having a nonvolatile content of 40.3% by mass. Got.

Comparative Example 2 [Preparation of comparative aqueous composite resin composition (XII)]
A reaction vessel equipped with a stirrer, thermometer, dropping funnel, condenser and nitrogen gas inlet was charged with 36 parts by mass of PnP, 80 parts by mass of IPA, 32 parts by mass of PTMS, and 19 parts by mass of DMDMS, and the temperature was raised to 80 ° C. Warm up.

  Next, at the same temperature, a mixture containing 9 parts by mass of MMA, 86 parts by mass of BMA, 67 parts by mass of BA, 14 parts by mass of MPTS, 16 parts by mass of AA, 14 parts by mass of PnP, and 14 parts by mass of TBPEH was added to the reaction vessel. After dropwise addition to 4 hours, the mixture was further reacted at the same temperature for 2 hours to obtain an organic solvent solution (xii) of an acrylic polymer having a carboxyl group and a hydrolyzable silyl group and having a number average molecular weight of 13100.

  Next, in a reaction vessel containing the organic polymer solution (xii) of the acrylic polymer, 0.9 part by mass of “A-3” (iso-propyl acid phosphate manufactured by Sakai Chemical Co., Ltd.) and 24 parts by mass of deionized water. The hydrolyzable silyl group of the acrylic polymer in the organic solvent solution (xii) is subjected to a hydrolytic condensation reaction by adding a mixture containing a part in 5 minutes and further stirring at 80 ° C. for 10 hours. A liquid (XII ′) containing a composite resin for comparison in which polysiloxane derived from PTMS and 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 (XII ′) and 18 parts by mass of TEA, and then the neutralized product. And 124 parts by mass of methyltrimethoxysilane condensate (a3′-1) are reacted, mixed with 550 parts by mass of deionized water, and distilled under the same conditions as in Example 1 to obtain a nonvolatile content. 40.0% by mass of a comparative aqueous composite resin composition (XII) (1000 parts by mass) was obtained.

Comparative Example 3 [Preparation of comparative aqueous composite resin composition (XIII)]
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe and a nitrogen gas inlet, polytetramethylene glycol having a number average molecular weight of 2000 (PTMG-2000 manufactured by Mitsubishi Chemical Corporation) and 171 parts by mass of IPDI Was heated to 100 ° C. and reacted at the same temperature for 1 hour.

  Next, the temperature was lowered to 80 ° C., 14 parts by mass of DMPA, 5 parts by mass of NPG, and 132 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 33 parts by mass of APTES and 309 parts by mass of IPA are charged into the reaction vessel and reacted, whereby the number average molecular weight having a carboxyl group and a hydrolyzable silyl group is 7,500. Next, the total amount of the polyurethane organic solvent solution (xiii) and 112 parts by mass of the composite resin intermediate containing liquid (C-1) were mixed and stirred at 80 ° C. The composite liquid for comparison (XIII ′) in which the polyurethane in the organic solvent solution (xiii) and the composite resin intermediate in the liquid containing (C-1) are bonded together by hydrolytic condensation reaction at )

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

Comparative Example 4 [Preparation of comparative aqueous composite resin composition (XIV)]
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser tube and a nitrogen gas inlet, polytetramethylene glycol having a number average molecular weight of 2000 (PTMG-2000 manufactured by Mitsubishi Chemical Corporation) 187 parts by mass, IPDI 78 parts by mass Was heated to 100 ° C. and reacted at the same temperature for 1 hour.

  Subsequently, the temperature was lowered to 80 ° C., 15 parts by mass of DMPA, 6 parts by mass of NPG, and 144 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 36 parts by mass of APTES and 339 parts by mass of IPA were put into the reaction vessel and reacted, whereby the polyurethane having a number average molecular weight of 7400 having a carboxyl group and a hydrolyzable silyl group was obtained. An organic solvent solution (xiv) was obtained.
Next, the total amount of the organic solvent solution (xiv) of polyurethane and 56 parts by mass 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 (XIV ′) in which the polyurethane in the solvent solution (xiv) and the composite resin intermediate in the containing liquid (C-1) were combined was obtained.

  Next, by mixing the composite resin-containing liquid (XIV ′) and 11 parts by mass of TEA, a neutralized product in which the carboxyl group in the comparative composite resin was neutralized 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 (XIV) having a nonvolatile content of 35.0% by mass.

Comparative Example 5 [Preparation example of comparative aqueous composite resin composition (XV)]
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel, condenser and nitrogen gas inlet, 27 parts by mass of polytetramethylene glycol having a number average molecular weight of 2000 (PTMG-2000 manufactured by Mitsubishi Chemical Corporation), 11 parts by mass of IPDI Was heated to 100 ° C. and reacted at the same temperature for 1 hour.

  Subsequently, the temperature was lowered to 80 ° C., 2 parts by mass of DMPA, 1 part by mass of NPG, and 144 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 5 parts by mass of APTES and 49 parts by mass of IPA were put into the reaction vessel and reacted, whereby the polyurethane having a number average molecular weight of 7400 having a carboxyl group and a hydrolyzable silyl group was obtained. An organic solvent solution (xiv) was obtained.
Next, the total amount of the organic solvent solution (xiv) of polyurethane and 676 parts by mass 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 (XIV ′) in which the polyurethane in the solvent solution (xiv) and the composite resin intermediate in the containing liquid (C-1) were combined was obtained.

  Next, by mixing the composite resin-containing liquid (XIV ′) and 12 parts by mass of TEA, a neutralized product obtained by neutralizing the carboxyl group in the comparative 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 (XIV) having a nonvolatile content of 35.0% by mass.

Comparative Example 6 [Preparation example of aqueous composite resin composition for comparison (XVI)]
In a reaction container similar to that of Synthesis Example 1, 150 parts by mass of PnP was charged and heated to 80 ° C.
Next, a mixture containing 60 parts by mass of MMA, 45 parts by mass of BMA, 57 parts by mass of BA, 38 parts by mass of AA, 50 parts by mass of PnP, and 9 parts by mass of TBPEH at the same temperature was added into the reaction vessel over 4 hours. After the dropwise addition, the mixture was further reacted at the same temperature for 2 hours to obtain an acrylic polymer (xvi-1) having a carboxyl group and a number average molecular weight of 16000.

  Further, in another reaction vessel similar to Synthesis Example 1, 260 parts by mass of polytetramethylene glycol (PTMG-2000 manufactured by Mitsubishi Chemical Corporation) and 110 parts by mass of IPDI were charged, and the temperature was raised to 100 ° C. For 1 hour.

  Next, the temperature is lowered to 80 ° C., and 22 parts by mass of DMPA, 8 parts by mass of NPG, and 400 parts by mass of MEK are put into the reaction vessel, and further reacted at 80 ° C. for 5 hours, thereby having a carboxyl group. A polyurethane (xvi-2) having a number average molecular weight of 7,600 was obtained.

  By mixing 109 parts by mass of the above-mentioned acrylic polymer (xvi-1), 656 parts by mass of polyurethane (xvi-2), and 235 parts by mass of a condensate of methyltrimethoxysilane (a3′-1), for a plastic substrate The coating agent (XVI) 1000 parts by mass was obtained.

  The storage stability described in Tables 2 to 4 shows the viscosity (initial viscosity) of the aqueous composite resin composition and the viscosity after standing the aqueous composite resin composition in an environment of 50 ° C. 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 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.

  Various physical properties of the coating film composed of the above-described aqueous composite resin compositions (I) to (X) and comparative aqueous composite resin compositions (XI) to (XVI) were evaluated according to the following evaluation methods.

  Moreover, various hardening | curing agents are mixed and mixed with the said aqueous composite resin composition (I)-(X) and the aqueous composite resin composition (XI)-(XVI) for a comparison according to the compounding composition of Tables 5-11. Various physical properties of the coating film made of each aqueous composite resin composition obtained were also evaluated according to the following evaluation methods.

The following curing agents were used.
“GPTMS”; 3-glycidoxypropyltrimethoxysilane “MS-51”; “MKC silicate MS-51” manufactured by Mitsubishi Chemical Corporation (polymethoxysiloxane having a condensation degree of 2 to 9)
“EX-614B”; “Denacol EX-614B” (epoxy compound having an epoxy equivalent of 173 g / eq) manufactured by Nagase ChemteX Corporation
“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% by mass)
“V-02”; “Carbodilite V-02” manufactured by Nisshinbo Co., Ltd. (aqueous solution of carbodiimide group-containing water-soluble resin having an equivalent carbodiimide group of 600 g / eq, nonvolatile content 40% by mass)

[Durability of coating film (solvent resistance, acid resistance, crack resistance), weather resistance, adhesion evaluation method]
[Test plate preparation method]
The aqueous composite resin composition was applied to a chromate-treated aluminum plate manufactured by Engineering Test Service Co., Ltd. so that the film thickness was 10 μm, dried in an environment of 80 ° C. for 5 minutes, and further A test plate (1) in which a coating film was laminated on an aluminum plate was obtained by drying for 10 minutes in an environment of 140 ° C.
Moreover, on the zinc (Zn) -iron (Fe) molten steel plate (surface untreated) manufactured by Nippon Test Panel Co., Ltd., the aqueous composite resin composition is applied so that the dry film thickness is 2 μm. By drying at 150 ° C. for 5 minutes, a test plate (2) in which a coating film was laminated on the zinc (Zn) -iron (Fe) molten steel plate was obtained.
In addition, on the polycarbonate (PC) substrate manufactured by Engineering Test Service Co., Ltd., the aqueous composite resin composition is applied so that the dry film thickness is 10 μm, and dried at 80 ° C. for 20 minutes, A test plate (3) in which a coating film was laminated on the polycarbonate substrate was obtained.

[Evaluation method of solvent resistance]
Using the felt impregnated with methyl ethyl ketone, the same part of the surface of the test plates (1) to (3) was rubbed back and forth 50 times. The state of the coating film before rubbing and after rubbing was confirmed by finger touch and visual observation, and evaluated according to the following evaluation criteria.

○: Softening and gloss reduction are not observed before and after rubbing.
Δ: Some softening or gloss reduction is observed before and after rubbing.
X: Significant softening or gloss reduction is observed before and after rubbing.
In addition, the water-based composite resin composition did not adhere to the substrate surface and could not produce a test plate, and the solvent resistance evaluation test was not performed. What was shown by "-" in the table | surface shows that the evaluation test was not performed for the said reason.

[Evaluation method of acid resistance]
After leaving the surfaces of the test plates (1) to (3) in a 5% by mass sulfuric acid aqueous solution for 24 hours at a temperature of 25 ° C., the coating film is washed with water and then dried. The state was visually confirmed and evaluated according to the following evaluation criteria.

○: There is no etching mark.
Δ: There is a slight etching mark.
X: Remarkable etching.
In addition, the water-based composite resin composition did not adhere to the substrate surface and could not produce a test plate, and did not perform an acid resistance evaluation test. What was shown by "-" in the table | surface shows that the evaluation test was not performed for the said reason.

[Evaluation method of crack resistance]
The aqueous composite resin composition is applied on a glass plate so that the film thickness is 10 μm, dried in an environment of 80 ° C. for 5 minutes, and then dried in an environment of 140 ° C. for 10 minutes. A coating film was obtained.

Dew panel light weather meter [manufactured by Suga Test Instruments Co., Ltd., light irradiation: 30 W / m ² , 60 ° C., wetting: humidity 90% or more, 40 ° C., light irradiation / wetting cycle = 4 hours / 4 hours], and 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.
In addition, the thing which the said water-based composite resin composition did not contact | adhere to the said base-material surface but could not produce a test board did not perform the crack resistance evaluation test. What was shown by "-" in the table | surface shows that the evaluation test was not performed for the said reason.

[Evaluation method of weather resistance]
Dew panel light weather meter [manufactured by Suga Test Instruments Co., Ltd., light irradiation: 30 W / m ² , 60 ° C., wet: humidity 90% or more, 40 ° C., light irradiation / Wetting cycle = 4 hours / 4 hours].

  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 greater the gloss retention value, the better the weather resistance. % Or more is preferable.
In addition, the thing which the said water-based composite resin composition did not adhere | attach on the said base-material surface, and was not able to produce a test board did not perform the weather resistance evaluation test. What was shown by "-" in the table | surface shows that the evaluation test was not performed for the said reason.

[Adhesion evaluation method]
The test plates (1) to (2) were used and evaluated based on the JIS K-5400 cross cut test method. The evaluation criteria are as follows.
Further, the aqueous composite resin composition was prepared by using a polycarbonate (PC) base material, a polyethylene terephthalate (PET) base material, an acrylonitrile-butadiene-styrene (ABS) base material, polymethyl methacrylate (manufactured by Engineering Test Service Co., Ltd.) PMMA) substrate, polystyrene (PS) substrate, polyvinyl chloride (PVC) substrate, and 6-nylon (NR) substrate were coated so that the dry film thickness was 10 μm, and 20 ° C. at 20 ° C. By drying for a minute, a test plate in which a coating film was laminated on each plastic substrate was produced.
The adhesion of the coating film formed on the surface of the test plate to the plastic substrate was evaluated according to the JIS K-5400 cross-cut test method as described above.

(Double-circle): The peeling of the coating film was not seen at all.
○: The peeled area of the coating film was less than 30% of the total grid area.
(Triangle | delta): The area where the coating film peeled was 30 to less than 95% of the total grid area.
X: The area where the coating film peeled was 95% or more of the total grid area.

[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 80% or more.

[Evaluation method for corrosion resistance]
On the zinc (Zn) -iron (Fe) molten steel sheet (surface untreated) manufactured by Nippon Test Panel Co., Ltd., the aqueous composite resin composition was applied to a dry film thickness of 2 μm, and 150 ° C. Was measured based on the JIS K-5400 9.1 salt spray resistance test, using the test plate (2) obtained by drying at 5 ° C. for 5 minutes. Specifically, the coating film surface of the test plate (2) is scratched with a cutter knife to a depth that reaches the base material (cross cut part), and salt water is tested with a salt spray tester manufactured by Suga Test Instruments Co., Ltd. A spray test was carried out, and the rust generation area after 240 hours was visually evaluated. The evaluation was performed separately for a flat portion not damaged by the cutter knife and a peripheral portion of the cross cut portion.
<Plane>
(Double-circle): The area where the generation | occurrence | production of rust and the swelling and peeling of the coating film resulting from rust were less than 5% with respect to the whole plane part.
◯: The area where the occurrence of rust and the swelling or peeling of the coating film due to rust occurred was 5% or more and less than 30% with respect to the entire plane portion.
(Triangle | delta): The area where the generation | occurrence | production of rust and the swelling and peeling of the coating film resulting from rust were 30% or more and less than 60% with respect to the whole plane part.
X: The area where the occurrence of rust and the swelling and peeling of the coating film due to rust occurred was 60% or more with respect to the entire plane portion.
<The peripheral part of the crosscut part>
(Double-circle): Generation | occurrence | production of rust was not seen in the peripheral part of a crosscut part, and peeling of the coating film etc. resulting from rust was not seen.
◯: A very small amount of rust was observed in the periphery of the crosscut part, but no peeling or swelling of the coating film due to it was observed.
Δ: Rust was widely observed in the periphery of the crosscut portion, and although peeling or swelling of the coating film was observed due to this, no flow rust was observed.
X: Rust was widely generated in the periphery of the crosscut part, and peeling and swelling of the coating film due to the rusting were observed.

[Contamination resistance evaluation method]
The test coating film was subjected to an exposure test for 3 months in DIC Corporation Sakai Factory in Takaishi City, Osaka Prefecture.

  Here, the color difference (ΔE) between the unwashed test coating film after the exposure test and the test 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.

Claims (9)

The hydrophilic group-containing polyurethane (a1) and the vinyl polymer (a2) are combined via a polysiloxane (a3) and an aqueous medium, and the hydrophilic group-containing polyurethane ( the bond between a1) and the polysiloxane (a3) is a hydrolyzable silyl group and / or silanol group of the hydrophilic group-containing polyurethane (a1) and a hydrolyzable silyl group of the polysiloxane (a3); And / or a bond between the vinyl polymer (a2) and the polysiloxane (a3) is formed by a reaction with a silanol group, and the hydrolyzable silyl group of the vinyl polymer (a2) and It is formed by the reaction of silanol groups with hydrolyzable silyl groups and / or silanol groups of the polysiloxane (a3). And than, and the aqueous hybrid resin composition mass ratio of the polysiloxane (a3) derived from the structure relative to the entire hybrid resin (A) is characterized in that in the range of 15 to 55 wt%. 2. The aqueous solution according to claim 1, wherein a mass ratio [(a2) / (a1)] of the hydrophilic group-containing polyurethane (a1) and the vinyl polymer (a2) is in a range of 1/1 to 1/20. Composite resin composition. The vinyl polymer (a2) is obtained by polymerizing a vinyl monomer containing at least one selected from the group consisting of a hydrolyzable silyl group-containing vinyl monomer and a silanol group-containing vinyl monomer. The aqueous composite resin composition according to claim 1, wherein 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 claim 1, which has at least one selected from the group consisting of alkoxy groups having. The polysiloxane (a3) is a polysiloxane (a3-1) having at least one structure selected from the group consisting of the following general formulas (I) and (II), and the alkyl group has 1 to 3 carbon atoms. The aqueous composite resin composition of Claim 1 which is a reaction product with the condensate (a3-2) of the alkyl trialkoxysilane which is individual.

[R ¹ in the general formulas (I) and (II) is an organic group having 4 to 12 carbon atoms bonded to a silicon atom, and R ² and R ³ are each independently a methyl group or silicon bonded to a silicon atom. Represents an ethyl group bonded to an atom. ] Coating agent comprising an aqueous composite resin composition according to any of claims 1-5. Primer coat agent comprising an aqueous composite resin composition according to any of claims 1-5. The laminated body which has a primer layer obtained using the primer coating agent of Claim 7 on a base material, and has a topcoat layer on this primer layer. The method for producing an aqueous composite resin composition according to claim 1, comprising the following steps (I) to (IV).
(I) In the presence of an organic solvent, a vinyl monomer is polymerized by polymerizing a vinyl monomer containing at least one selected from the group consisting of a hydrolyzable silyl group-containing vinyl monomer and a silanol group-containing vinyl monomer. A step of obtaining an organic solvent solution of the combined (a2),
(II) The polysiloxane (a3) is bonded to the vinyl polymer (a2) by reacting the vinyl polymer (a2) with a silane compound in the presence of an organic solvent solution of the vinyl polymer (a2). A step of obtaining an organic solvent solution of the obtained resin (C),
(III) The resin (C) and the hydrophilic group-containing polyurethane (a1) are mixed and reacted, whereby the vinyl polymer (a2) and the hydrophilic group-containing polyurethane (a1) are converted into the polysiloxane (a3). A step of obtaining an organic solvent solution of the composite resin (A) bonded via
(IV) neutralizing the hydrophilic group having the of the composite resin (A) in an organic solvent, dissolving the neutralized product in an aqueous medium by mixing the organic solvent solution and water containing neutralized product Or the step of dispersing.