JP2011111490A - Curable coating composition and coating agent containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable coating composition forming a coating film excellent in conformability to a base material and excellent also in durability such as crack resistance, weather resistance and shielding property in an ultraviolet region. <P>SOLUTION: The curable coating composition contains a composite resin (ABC) in which polyurethane (a1) and a vinyl polymer (a2) are combined via polysiloxane (a3), and an ultraviolet absorber, wherein a weight ratio of a structure derived from the polysiloxane (a3) to the entire composite resin (ABC) is 15-55 wt.%. A coating agent containing the composition and a method for producing the aqueous curable coating composition are also provided. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a curable coating composition that can be used in various applications including coating agents and adhesives.

  The coating agent is required to have a role of protecting the substrate surface from external factors in addition to the role of imparting design properties to various substrate surfaces. Specifically, excellent water resistance, etc. at a level that can prevent deterioration of the base material and generation of rust when exposed to water, organic solvents, acid rain, etc. or exposed to wind and rain for a long time The coating agent which can form the coating film which has the durability of this, a weather resistance, etc. is calculated | required from the industry.

  Examples of the coating agent include a composite resin (C) composed of a specific polysiloxane segment (A), a polymer segment (B) having a hydrophilic group, and a specific polysiloxane (D). It is known that a cured product excellent in durability and resistance to exposure contamination can be formed by an aqueous resin obtained by reaction (see, for example, Patent Document 1).

  However, since the coating film formed using the water-based resin is relatively hard, for example, when applied to a substrate that is likely to cause deformation or expansion / contraction due to the influence of external force or temperature change, the coating film is deformed. As a result, peeling of the coating film or generation of cracks may occur.

  In particular, when a coating film is formed on a plastic base material such as PET constituting a solar cell or various outdoor base materials, the shielding property in the ultraviolet region is poor even though the weather resistance of the coating film is excellent. In some cases, it may be difficult to protect the substrate from ultraviolet light.

JP-A-11-279408

  The problem to be solved by the present invention is a curable coating composition capable of forming a coating film having excellent substrate followability and durability such as crack resistance, weather resistance, and excellent shielding properties in the ultraviolet region. Is to provide.

  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 Document 1 and a general hydrophilic group-containing polyurethane were examined.

  However, although the coating film made of the resin composition has excellent durability and weather resistance, it still does not have excellent substrate followability.

  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, an aqueous composite resin composition in which a vinyl polymer and the hydrophilic group-containing polyurethane were chemically bonded via a polysiloxane structure was examined.

  However, even with the curable coating composition, it was still difficult to form a coating film having a practically sufficient level in terms of durability and weather resistance.

  However, when an aqueous composite resin in which the weight ratio of the polysiloxane-derived structure in the aqueous composite resin is adjusted to 15% by weight or more was examined, a coating film having excellent durability and weather resistance was unexpectedly obtained. The present inventors have found that it is possible to form a coating film that is excellent in substrate followability.

  That is, the present invention comprises a composite resin (ABC) in which a polyurethane (a1) and a vinyl polymer (a2) are bonded via a polysiloxane (a3), and an ultraviolet absorber (D). The bond between a1) and the polysiloxane (a3) is a hydrolyzable silyl group and / or silanol group of the polyurethane (a1) and a hydrolyzable silyl group and / or silanol group of the polysiloxane (a3). And 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 hydrolyzable silyl group and / or silanol group possessed by the polysiloxane (a3). And, to a curable coating composition and a coating agent, wherein the weight ratio of the polysiloxane (a3) derived from the structure with respect to the entire composite resin (ABC) is in the range of 15 to 55 wt%.

  Moreover, this invention relates to the laminated body which has the hardened | cured material of the said coating agent as a topcoat layer on the primer layer obtained using a primer coat agent on a base material.

Moreover, this invention relates to the manufacturing method of the curable coating composition which consists of the process of the following (I)-(V).
The manufacturing method of the curable coating composition of Claim 1 which consists of the process of the following (I)-(V).
(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) A composite resin in which the vinyl polymer (a2) and the polyurethane (a1) are bonded via the polysiloxane (a3) by mixing and reacting the resin (C) and the polyurethane (a1). Obtaining an organic solvent solution of (ABC),
(IV) dissolving or dispersing the resin in the medium by mixing the organic solvent solution containing the composite resin (ABC) in the organic solvent and the medium;
(V) A step of adding an ultraviolet absorber during resin dispersion or dissolution of the composite resin (ABC).

  Since the curable coating composition of the present invention is excellent in crack resistance, durability, weather resistance, stain resistance, and ultraviolet shielding retention, it is based on metals, minerals, plastics, fibers, cloth, paper, wood, concrete, etc. It can be used for coating materials and adhesives.

  In addition, the curable coating composition of the present invention exhibits an excellent effect particularly in terms of substrate followability, and thus, for example, is applied to adhesives of various functional films constituting a polarizing plate, or to the functional films. It can be used as a coating agent. In addition, since the curable coating composition of the present invention can form a coating film excellent in weather resistance and durability, for example, a coating agent for surface treatment of a steel sheet, particularly a coating for forming a primer coat layer between a steel sheet and a top coat. Can be used in the preparation.

  Moreover, since the curable coating composition of this invention is excellent in the shielding property of an ultraviolet-light area | region, it is useful for the coating agent which prevents deterioration of a base material from exposure to an ultraviolet-ray.

  The present invention includes a composite resin in which a polyurethane (a1) and a vinyl polymer (a2) are bonded via a polysiloxane (a3), an ultraviolet absorber, and a medium, the polysiloxane (a3) The curable coating composition is characterized in that the derived structure is contained in the range of 15 to 55% by weight with respect to the entire composite resin.

  The composite resin is dissolved or dispersed in a medium, but a part of the composite resin may be dissolved in the medium. The composite resin dispersed in the medium preferably has an average particle diameter of 10 to 500 nm in order to form a coating film excellent in substrate followability and excellent in durability such as crack resistance and weather resistance. . 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.

  Moreover, when forming the coating film excellent in durability and weather resistance, it is important that the composite resin has a structure derived from 15 to 55% by weight of polysiloxane (a3) with respect to the entire composite resin. . For example, a composite resin in which the polysiloxane (a3) has a weight ratio of 10% by weight cannot form a coating film excellent in durability and weather resistance, and the coating film may peel off over time.

  On the other hand, if it is a composite resin-containing composition in which the weight ratio of the structure derived from the polysiloxane (a3) is 65% by weight, it is possible to form a coating film excellent in durability, but the polyurethane (a1) and the above Since the weight ratio of the structure derived from the vinyl polymer (a2) is low, there are problems such as a decrease in substrate followability and the occurrence of cracks on the coating film surface over time.

  The weight ratio of the structure derived from polysiloxane (a3) to the whole composite resin is in the range of 20% by weight to 35% by weight, and it has excellent durability, weather resistance, and substrate followability. Is preferable in forming.

  The composite resin is dissolved or dispersed in a medium. In the case of dispersion, it is essential to have a hydrophilic group for stable dispersion particularly 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, but may be present in the vinyl polymer (a2) as necessary. .

  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 hydrophilic group, they are present in the range of 50 to 1000 mmol / kg with respect to the entire composite resin, thereby maintaining good water dispersion stability of the aqueous composite resin particles. This is preferable.

  In the composite resin, the weight ratio [(a2) / (a1)] of the polyurethane (a1) and the vinyl polymer (a2) is in the range of 20/1 to 1/20. It is preferable for forming a coating film excellent in material followability and excellent in durability such as crack resistance and weather resistance, and more preferably in the range of 3/1 to 1/12.

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

  First, the polyurethane (a1) constituting the composite resin will be described.

  The polyurethane (a1) is an essential component for imparting excellent substrate followability to the curable coating composition of the present invention.

  As the polyurethane (a1), various types can be used, for example, those having a number average molecular weight of 3000 to 100,000, more preferably 5000 to 50000, and particularly preferably 5000 to 20000. It is preferable for forming a coating film excellent in substrate followability and excellent in durability such as crack resistance and weather resistance.

  The polyurethane (a1) preferably has a hydrophilic group for imparting water dispersion stability to the composite resin when used in an aqueous medium. The hydrophilic group is preferably present in the range of 50 to 1000 mmol / kg with respect to the entire polyurethane (a1) in order to impart better water dispersibility to the composite resin.

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

  As the polyol that can be used for the production of the 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 or can be used alone, as appropriate depending on the characteristics required for the curable coating composition of the present invention, the application to which the curable coating composition is applied, and the like. For example, polyether polyol, polycarbonate polyol, and polyester polyol can be used.

  Since the polyether polyol can impart particularly excellent substrate followability to the curable coating composition of the present invention, it is preferably used alone or 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.

  Further, as the polycarbonate polyol, those obtained by reacting glycol such as 1,4-butanediol and 1,5-pentanediol with dimethyl carbonate, phosgene and the like can be used.

  Examples of the polyester polyol include those obtained by esterifying low molecular weight polyols (polyhydric alcohols) and polycarboxylic acids, and ring-opening polymerization reactions of cyclic ester compounds such as ε-caprolactone. Polyesters, copolymerized polyesters thereof, and the like can be used.

  Examples of the low molecular weight polyol include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, polyethylene glycol, and 2-methyl-1,3-propanediol. 1,3-butanediol, neopentyl glycol, hydrogenated bisphenol A, 1,4-cyclohexanedimethanol, 1,4-butanediol, 1,6-hexanediol, adduct of bisphenol A and propylene oxide or ethylene oxide, Etc. can be used.

  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.

  As the other polyol, for example, an aliphatic cyclic structure-containing polyol such as cyclohexanediol or an aromatic cyclic structure-containing polyol may be used in combination with the various polyols described above.

  Examples of the polyisocyanate used for producing the parent group-containing polyurethane (a1) include aromatic diisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, and cyclohexane. Aliphatic or aliphatic cyclic structure-containing diisocyanates such as 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 polyurethane resin (a1) has a functional group, and has a functional group in addition to the hydrophilic group as described above. Examples of the functional group include polysiloxane (a3) described later. Hydrolyzable silyl groups, silanol groups, amino groups, imino groups, hydroxyl groups, etc., which can react with hydrolyzable silyl groups, among which hydrolyzable silyl groups are preferable because a coating film having excellent long-term weather resistance can be formed. .

  The hydrolyzable silyl group that the polyurethane (a1) may have is a functional group in which the hydrolyzable group is directly bonded to a silicon atom, and examples thereof include a functional group represented by the following general formula. .

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 which the polyurethane (a1) may have is a functional group in which a hydroxyl group is directly bonded to a silicon atom, and is a functional group which is mainly generated by hydrolysis of the hydrolyzable silyl group described above. is there.

  The hydrolyzable silyl group and silanol group are preferably present in an amount of 10 to 400 mmol / kg, more preferably 20 to 300 mmol / kg, based on the entire polyurethane (a1). It is preferable in securing the above.

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

  As the vinyl polymer (a1), use of a polymer having a number average molecular weight of 3000 to 100,000 is excellent in substrate followability and excellent in durability such as crack resistance and weather resistance. It is preferable in forming. More preferably, the number average molecular weight is 5,000 to 50,000.

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

  As the vinyl monomer, a functional group capable of reacting with the hydrolyzable silyl group or the like of the polysiloxane (a3), for example, a hydrolyzable silyl group or a hydroxyl group is introduced into the vinyl polymer (a1). Therefore, it is preferable to use a hydrolyzable silyl group-containing vinyl 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 is 10% by weight or less with respect to the total amount of vinyl monomers used in the production of the vinyl polymer (a2). It is preferable.

Next, polysiloxane (a3) constituting the composite resin will be described.
The polysiloxane (a3) constitutes a connecting portion between the 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, and has, for example, a structure represented by the general formula (I) exemplified in the description of the polyurethane (a1). Those having a structure represented by the following general formula (II) or (III) can be used.

[R ¹ in the general formulas (II) and (III) 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. ]

  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.

Next, the manufacturing method of the curable coating composition used by this invention is demonstrated.
The method for producing a curable coating composition of the present invention mainly comprises a step of producing a composite resin and a step of dissolving or dispersing the composite resin in a medium.

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

The manufacturing method of the curable coating composition of Claim 1 which consists of the process of the following (I-1)-(I-5).
(I-1) 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 in the presence of an organic solvent. Obtaining an organic solvent solution of the vinyl polymer (a2);
(I-2) By reacting the vinyl polymer (a2) with a silane compound in the presence of an organic solvent solution of the vinyl polymer (a2), the vinyl polymer (a2) is reacted with the polysiloxane (a3). A step of obtaining an organic solvent solution of resin (C) bonded with
(I-3) The vinyl polymer (a2) and the polyurethane (a1) were bonded via the polysiloxane (a3) by mixing and reacting the resin (C) and the polyurethane (a1). Obtaining an organic solvent solution of the composite resin (ABC);
(I-4) a step of dissolving or dispersing in a medium by mixing an organic solvent solution containing the composite resin (ABC) and the medium;
(I-5) A step of adding an ultraviolet absorber (D) to the solution or dispersion of the composite resin (ABC).

The manufacturing method of the curable coating composition of Claim 1 which consists of the process of the following (II-1)-(II-5).
(II-1) 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 in the presence of an organic solvent. Obtaining an organic solvent solution of the vinyl polymer (a2);
(II-2) a step of mixing the organic solvent solution of the vinyl polymer (a2) and the polyurethane (a1),
(II-3) By reacting the polyurethane (a1) and the vinyl polymer (a2) with a silane compound in the presence of an organic solvent solution of the mixture, the vinyl polymer (a2) and the polyurethane (a1) A step of obtaining an organic solvent solution of a composite resin (ABC) bonded with polysiloxane (a3) through
(II-4) a step of dissolving or dispersing in a medium by mixing an organic solvent solution of the composite resin (ABC) and the medium;
(II-5) A step of adding an ultraviolet absorber (D) to the solution or dispersion of the composite resin (ABC).

The manufacturing method of the curable coating composition of Claim 1 which consists of the process of the following (III-1)-(III-5).
(III-1) 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 in the presence of an organic solvent. Obtaining an organic solvent solution of the vinyl polymer (a2);
(III-2) Resin (E) in which polysiloxane (a3) is bonded to polyurethane (a1) by reacting polyurethane (a1) with a silane compound in the presence of an organic solvent solution of polyurethane (a1). Obtaining an organic solvent solution of
(III-3) The resin (E) and an organic solvent solution of the vinyl polymer (a2) are mixed and reacted, whereby the vinyl polymer (a2) and the polyurethane (a1) are converted into the polysiloxane (a3). A step of obtaining an organic solvent solution of the composite resin (ABC) bonded via
(III-4) A step of dissolving or dispersing in the medium by mixing the organic solvent solution of the composite resin (ABC) in the organic solvent and the medium,
(III-5) A step of adding an ultraviolet absorber (D) to the solution or dispersion of the composite resin (ABC).

  When the hydrophilic group is present, neutralization is not necessarily performed, but in the case of an aqueous medium, it is preferably performed from the viewpoint of improving the water dispersion stability of the composite resin. 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 and stirring.

  After the neutralization, an aqueous curable coating composition can be produced by supplying an aqueous medium to the organic solvent solution of the composite resin neutralized product and then removing the organic solvent.

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

  Examples of the medium include water, organic solvents, 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 and an organic solvent may be used, or 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 curable coating composition of the present invention suppresses an abrupt increase in viscosity during production, and from the viewpoint of improving the productivity of the curable coating composition, ease of coating, drying properties, etc. It preferably has a non-volatile content (solid content) of 20 to 70% by weight, more preferably in the range of 30 to 60% by weight.

  Although it does not specifically limit as an ultraviolet absorber (D) used for this invention, For example, metal oxides, such as a titanium oxide, a zinc oxide, a tin oxide, a cerium oxide, a benzotriazole type ultraviolet absorber, a triazine type ultraviolet absorber Indole ultraviolet absorbers, benzophenone ultraviolet absorbers, azomethine ultraviolet absorbers, hindered amines and the like.

  Examples of the benzotriazole UV absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -1, 4-dihydroxybenzene], 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (hydroxymethyl) phenol], 2,2′-methylenebis [6- (2H-benzotriazole- 2-yl) -4- (2-hydroxyethyl) phenol and the like.

  Examples of the triazine ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol, 2- (4,6-diphenyl-1,3, 5-triazin-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxyphenol, 2- (4,6- Diphenyl-1,3,5-triazin-2-yl) -5-propyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-butyloxyphenol, etc. Is exemplified. Further examples include 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol.

  Examples of the indole ultraviolet absorber include 5-indoleol, 4-aminoindole, 4-methoxyindole and the like.

Examples of the benzophenone-based ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone. 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-octa Decyloxybenzophenone, sodium 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 5-chloro -2-hydroxy Benzophenone, resorcinol monobenzoate, 2,4-dibenzoyl resorcinol, 4,6-dibenzoyl resorcinol, hydroxydodecylbenzophenone, 2,2'-dihydroxy-4 (3-methacryloxy-2- Hydroxypropoxy) benzophenone and the like.

Examples of hindered amine ultraviolet absorbers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate. Bis (1,2,2,6,6-pentamethyl-4-piperidyl) [{3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl} methyl] butyl malonate and the like. .

  As a blending ratio of the ultraviolet absorber, an ultraviolet shielding effect is sufficiently expressed with respect to 100 parts by weight of the solid content of the composite resin (ABC). In view of ensuring transparency, the content is preferably 20 parts by weight or less, and more preferably in the range of 0.1 to 10 parts by weight.

  A curing agent may be used in combination with the curable coating composition of the present invention as necessary.

  As the curing agent, a compound having a functional group that reacts with the hydrophilic group or silanol group of the composite resin 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 having a structure derived from an aliphatic polyol or alicyclic polyol such as ethylene glycol, hexanediol, neopentyl glycol, trimethylolpropane, pentaerythritol, sorbitol, hydrogenated bisphenol A, and the like. Ethers; 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) ) Isocyanurate polyglycidyl ethers; aliphatic or aromatic polycarboxylic acids such as adipic acid, butanetetracarboxylic acid, phthalic acid, terephthalic acid Liglycidyl esters; bisepoxides of hydrocarbon dienes such as cyclooctadiene and vinylcyclohexene; bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxy Examples thereof include alicyclic polyepoxy compounds such as a rate.

  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 aqueous composite resin. Is more preferable, and it is particularly preferable to use within the range of 1 to 20 parts by weight.

  In addition, when the aqueous composite resin has a carboxyl group as a hydrophilic group, the curing agent is an epoxy group, a cyclocarbonate group, a hydroxyl group, a curing agent with respect to 1 equivalent of the carboxyl group in the aqueous composite resin, The equivalent of the reactive functional group such as oxazoline group, carbodiimide group, hydrazino group is preferably in the range of 0.2 to 5.0 equivalent, and in the range of 0.5 to 3.0 equivalent. More preferably, it is particularly preferably within the range of 0.7 to 2.0 equivalents.

  Moreover, the curable coating 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 curable coating composition of the present invention can contain various resins 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 curable coating composition of the present invention, various inorganic particles such as clay mineral, metal, metal oxide, and glass can be added and 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 curable coating composition of the present invention includes an inorganic pigment, an organic pigment, an extender pigment, a wax, a surfactant, a stabilizer, a flow regulator, a dye, a leveling agent, a rheology control agent, an antioxidant, if necessary. Various additives such as a plasticizer can be used.

  Since the said curable coating composition can form the coating film excellent in durability, such as crack resistance, weather resistance, and base material followability | trackability, it can be used for various uses, such as a coating agent and an adhesive agent. Among them, the curable coating composition of the present invention has excellent substrate followability as compared with conventional products, so that it can be used as a coating agent for substrates that are likely to cause deformation and expansion / contraction due to external factors such as temperature. It can be preferably used.

  Examples of the substrate that can be applied as a coating agent or primer coating agent comprising the curable coating composition of the present invention include metals, glass, paper, wood, various plastic substrates, concrete, asphalt and the like.

  As a plastic substrate, ABS (acrylonitrile-butadiene-styrene) resin, PC (polycarbonate) resin, a material generally used for plastic molded products such as mobile phones, home appliances, automobile interior and exterior materials, OA equipment, etc. ABS / PC resin, PS (polystyrene) resin, acrylic resin, polypropylene resin, polyethylene resin and the like can be mentioned. As the plastic substrate, polyethylene terephthalate, polyester, polyethylene, polypropylene, TAC (triacetyl cellulose), polycarbonate, polychlorinated A substrate made of vinyl or the like can be used.

  The various base materials described above may be coated in advance, but as will be described later, since the coating agent of the present invention can be suitably used as a primer coating agent, the surface of the present invention is directly applied to the surface of the base material. It is preferable to apply a coating agent to form a coating film.

  The base materials may be plate-shaped, spherical, film-shaped, and sheet-shaped, respectively. As described above, since the coating agent of the present invention is particularly excellent in substrate followability, a film-like or sheet-like substrate that easily causes deformation or expansion due to the influence of external force, temperature, etc., or fine irregularities on the surface. It can use suitably also to the substrate which has. Moreover, it is suitable also for the base material which deteriorates easily by exposure to ultraviolet rays.

  The coating agent may form a coating film having excellent durability such as crack resistance, weather resistance, and substrate followability by, for example, applying it on the substrate, followed by drying and curing. 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.

  In addition, the method of drying and proceeding with curing may be a method of curing for about 1 to 10 days at room temperature, but from the viewpoint of rapidly proceeding curing, at a temperature of 50 to 250 ° C., 1 to A method of heating for about 600 seconds is preferable.

  On the other hand, the curable coating composition of the present invention can be suitably used as a primer coating agent that requires particularly excellent substrate followability among the coating agents.

  Therefore, the primer coating agent of the present invention can be suitably used, for example, for the production of a laminate having a primer layer on the substrate and a topcoat layer on the primer layer.

  The primer coat layer constituting the laminate can be formed by applying and drying the primer coat agent of the present invention on the surface of the substrate in the same manner as described above.

  The top coat layer may be formed by, for example, acrylic resin-based paint, polyester resin-based paint, alkyd resin-based paint, epoxy resin-based paint, fatty acid-modified epoxy resin-based paint, silicone resin-based paint, polyurethane resin-based paint, etc. Various top coats can be used.

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

  Next, a mixture of 0.17 parts by weight of “A-3” (iso-propyl acid phosphate manufactured by Sakai Chemical Co., Ltd.) and 207 parts by weight 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 (the reduced pressure condition at the start of the distillation of methanol is 300 mmHg, and finally the pressure is reduced to 10 mmHg. In the same manner, the methanol and water produced in the reaction process are removed by distillation, and a mixed solution (active ingredient) containing a condensate (a3′-1) of methyltrimethoxysilane having a number average molecular weight of 1000 70 wt%) 1000 parts by weight were obtained.

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

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

  Next, a mixture of 0.14 parts by weight of “A-3” (iso-propyl acid phosphate manufactured by Sakai Chemical Co., Ltd.) and 171 parts by weight 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.

  Ethyltrimethoxysilane having a number average molecular weight of 1100 is obtained by distilling the condensate obtained by the hydrolysis condensation reaction at a temperature of 40 to 60 ° C. and a reduced pressure of 300 to 10 mmHg to remove the generated methanol and water. 1000 parts by weight of a mixed solution (active ingredient 70% by weight) 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 weight of propylene glycol monopropyl ether (PnP), 168 parts by weight of phenyltrimethoxysilane (PTMS) and dimethyldimethoxysilane (DMDMS) ) 102 parts by weight were charged and the temperature was raised to 80 ° C.

  Next, at the same temperature, 38 parts by weight of methyl methacrylate (MMA), 24 parts by weight of butyl methacrylate (BMA), 36 parts by weight of butyl acrylate (BA), 24 parts by weight of acrylic acid (AA), 3-methacryloxypropyltrimethoxysilane (MPTS) A mixture containing 4 parts by weight, 54 parts by weight of PnP and 6 parts by weight 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 weight of “A-3” [iso-propyl acid phosphate manufactured by Sakai Chemical Co., Ltd.] and 76 parts by weight of deionized water was added dropwise over 5 minutes, and further stirred at the same temperature for 1 hour. By carrying out the hydrolysis condensation reaction, a composite resin intermediate-containing liquid in which the hydrolyzable silyl group of the acrylic polymer in the organic solvent solution (c1) and the polysiloxane derived from PTMS and DMDMS are combined ( C′-1) was obtained.

  Next, the composite resin intermediate-containing liquid (C′-1) and 291 parts by weight of the methyltrimethoxysilane condensate (a3′-1) are mixed, and 49 parts by weight 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 weight part 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 cooling pipe and a nitrogen gas inlet, 121 parts by weight of PnP, 267 parts by weight of PTMS and 162 parts by weight of DMDMS were charged and heated to 80 ° C.

  Subsequently, at the same temperature, a mixture containing 61 parts by weight of MMA, 50 parts by weight of BMA, 7 parts by weight of BA, 4 parts by weight of MPTS, 52 parts by weight of PnP and 6 parts by weight 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 weight of “A-3” (iso-propyl acid phosphate manufactured by Sakai Chemical Co., Ltd.) and 121 parts by weight 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 parts by weight were obtained.

  Next, 123 parts by weight of methyltrimethoxysilane condensate (a3′-1) is added, 21 parts by weight 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 weight of ethyltrimethoxysilane condensate (a3′-2) instead of 291 parts by weight of methyltrimethoxysilane condensate (a3′-1), the same method as in Synthesis Example 3, 1000 parts by weight of a composite resin intermediate containing liquid (C-3) in which the composite resin intermediate in the containing liquid (C′-1) and the condensate (a3′-2) of ethyltrimethoxysilane were combined was obtained. .

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

  Next, at the same temperature, a mixture containing 21 parts by weight of MMA, 13 parts by weight of BMA, 20 parts by weight of BA, 13 parts by weight of AA, 2.1 parts by weight of MPTS, 58 parts by weight of PnP and 3.5 parts by weight 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 weight of “A-3” (iso-propyl acid phosphate manufactured by Sakai Chemical Co., Ltd.) and 129 parts by weight of deionized water was added dropwise over 5 minutes, followed by stirring 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 parts by weight were obtained.

  Next, the composite resin intermediate (C′-4) and 130 parts by weight of the methyltrimethoxysilane condensate (a3′-1) were mixed, and 22 parts by weight of deionized water was 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.

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

  Next, the temperature was lowered to 80 ° C., 13 parts by weight of dimethylolpropionic acid (DMPA), 5 parts by weight of neopentyl glycol (NPG), and 121 parts by weight of methyl ethyl ketone (MEK) were charged 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 weight of 3-aminopropyltriethoxysilane (APTES) and 285 parts by weight of isopropyl alcohol (IPA) are put into the reaction vessel and reacted, thereby hydrolyzing the 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 whole amount of the organic solvent solution (i) of polyurethane and 158 parts by weight of the composite resin intermediate-containing liquid (C-1) are mixed, and subjected to a hydrolysis condensation reaction at 80 ° C. for 1 hour with stirring. Liquid containing composite resin in which hydrolyzable silyl group 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 ').

  Subsequently, the liquid containing the composite resin (I ′) and 10 parts by weight of triethylamine (TEA) were mixed to obtain a liquid containing a neutralized product obtained by neutralizing the carboxyl group in the composite resin. A mixture of the hydrate-containing liquid and 610 parts by weight of deionized water is distilled under reduced pressure of 300 to 10 mmHg for 4 hours under conditions of 40 to 60 ° C. to remove the generated methanol, organic solvent and water. As a result, 1000 parts by weight of the composite resin water dispersion (I) having a nonvolatile content of 35.0% by weight was obtained. In addition, when manufacturing the said composite resin water dispersion (I), methanol and ethanol are produced | generated as a by-product by the hydrolysis and condensation reaction of polysiloxane (a3'-1). Since these by-products are volatilized in the production process of the composite resin water dispersion (I), the charging ratio of raw materials used for the production of the composite resin and the composite contained in the composite resin water dispersion (I) The weight ratio of the structure derived from polyurethane, vinyl polymer (a2), or polysiloxane (a3) constituting the resin was different. The same applies to the production of the following composite resin aqueous dispersions (II) to (XV). Tables 2 to 4 show the weight ratios of [polysiloxane structure / composite resin] and [vinyl polymer structure / polyurethane structure] constituting the composite resin in the obtained composite resin aqueous dispersion.

Preparation Example 2 [Preparation of aqueous composite resin dispersion (II)]
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser tube and a nitrogen gas inlet, 142 parts by weight of polytetramethylene glycol having a number average molecular weight of 2000 (PTMG-2000 manufactured by Mitsubishi Chemical Corporation), 60 parts by weight 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 weight of DMPA, 4 parts by weight of NPG, and 110 parts by weight 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 weight of APTES and 258 parts by weight 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 whole amount of the organic solvent solution (ii) of polyurethane and 209 parts by weight 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 weight of TEA, and then the neutralized product and deionized water. A mixture of 610 parts by weight was distilled under the same conditions as in Preparation Example 1 to obtain 1000 parts by weight of a composite resin aqueous dispersion (II) having a nonvolatile content of 35.0% by weight.

Preparation Example 3 [Preparation of aqueous composite resin dispersion (III)]
Example 2 with the exception of using 216 parts by weight of composite resin intermediate (C-1) instead of 209 parts by weight of composite resin intermediate (C-1) and using 7 parts by weight of TEA instead of 13 parts by weight of TEA By the same method, 1000 weight part of composite resin water dispersion (III) whose non volatile matter is 35.0 weight% was obtained.

Preparation Example 4 [Preparation of aqueous composite resin dispersion (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 weight of polytetramethylene glycol having a number average molecular weight of 2000 (PTMG-2000 manufactured by Mitsubishi Chemical Corporation), 51 parts by weight 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 weight of DMPA, 4 parts by weight of NPG, and 94 parts by weight 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 weight of APTES and 221 parts by weight 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 whole amount of the organic solvent solution (iv) of polyurethane and 279 parts by weight 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 (iv) and hydrolyzable silyl group of composite resin intermediate in said containing liquid (C-1) are bonded (IV ′ )

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

Preparation Example 5 [Preparation of aqueous composite resin dispersion (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 Part by weight and 50 parts by weight of IPDI were charged, the temperature was raised to 100 ° C., and the mixture was reacted at the same temperature for 1 hour.

  Next, the temperature was lowered to 80 ° C., 10 parts by weight of DMPA, 4 parts by weight of NPG, and 94 parts by weight 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 weight of APTES and 221 parts by weight 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.

  Subsequently, 279 parts by weight of the total amount of the organic solvent solution (v) of the polyurethane and 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.

  Subsequently, the composite resin containing liquid (V ′) and 14 parts by weight of TEA were mixed to obtain a neutralized product containing liquid neutralizing the carboxyl group in the composite resin, and then the neutralization A mixture of the product-containing liquid and 610 parts by weight of deionized water was distilled under the same conditions as in Preparation Example 1 to obtain 1000% by weight of a composite resin water dispersion (V) having a nonvolatile content of 35.0% by weight. Got a part.

Preparation Example 6 [Preparation of aqueous composite resin dispersion (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 weight of polyester polyol (“obtained by reacting neopentyl glycol, 1,6-hexanediol and adipic acid” Polyester polyol (hydroxyl group equivalent: 1000 g / equivalent)) and 50 parts by weight of IPDI were charged, the temperature was raised to 100 ° C., and the mixture was reacted at the same temperature for 1 hour.

  Subsequently, the temperature was lowered to 80 ° C., 10 parts by weight of DMPA, 4 parts by weight of NPG, and 94 parts by weight 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 weight of APTES and 221 parts by weight of IPA are put into the reaction vessel and reacted to form 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 whole amount of the organic solvent solution (vi) of polyurethane and 279 parts by weight 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 ′ )

  Subsequently, the liquid containing the neutralized product obtained by neutralizing the carboxyl group in the composite resin by mixing the composite resin-containing liquid (VI ′) and 14 parts by weight of TEA, and then containing the neutralized product The mixture of the liquid and 610 parts by weight of deionized water was distilled under the same conditions as in Preparation Example 1 to obtain 1000 parts by weight of a composite resin water dispersion (VI) having a nonvolatile content of 35.0% by weight. It was.

Preparation Example 7 [Preparation of aqueous composite resin dispersion (VII)]
Implemented except that 288 parts by weight of composite resin intermediate-containing liquid (C-2) was used instead of 279 parts by weight of composite resin intermediate-containing liquid (C-1) and 6 parts by weight of TEA was used instead of 14 parts by weight of TEA In the same manner as in Example 4, 1000 parts by weight of an aqueous composite resin dispersion (VII) having a nonvolatile content of 35.0% by weight was obtained.

Preparation Example 8 [Preparation of aqueous composite resin dispersion (VIII)]
A composite resin having a nonvolatile content of 35.0% by weight in the same manner as in Example 4 except that 279 parts by weight of the composite resin intermediate (C-3) was used instead of 279 parts by weight of the composite resin intermediate (C-1). 1000 parts by weight of an aqueous dispersion (VIII) was obtained.

Preparation Example 9 [Preparation of aqueous composite resin dispersion (IX)]
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel, condenser and nitrogen gas inlet, 61 parts by weight of polytetramethylene glycol having a number average molecular weight of 2000 (PTMG-2000 manufactured by Mitsubishi Chemical Corporation), 26 parts by weight of IPDI Was heated to 100 ° C. and reacted at the same temperature for 1 hour.

  Next, the temperature was lowered to 80 ° C., 5 parts by weight of DMPA, 2 parts by weight of NPG, and 47 parts by weight 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 weight of APTES and 110 parts by weight 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 (ix) was obtained.

  Subsequently, the total amount of the organic solvent solution (ix) of polyurethane and 489 parts by weight 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, 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, the composite resin-containing liquid (IX ′) and 16 parts by weight of TEA were mixed to obtain a neutralized product-containing liquid in which the carboxyl groups in the composite resin (II ′) were neutralized. A mixture of the neutralized product-containing liquid and 560 parts by weight of deionized water is distilled under the same conditions as in Preparation Example 11 to obtain a composite resin water dispersion (IX) having a non-volatile content of 35.0% by weight. 1000 parts by weight were obtained.

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

  Next, the temperature was lowered to 80 ° C., 6 parts by weight of DMPA, 2 parts by weight of NPG, and 60 parts by weight 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 weight of APTES and 140 parts by weight of IPA are put 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.

  Subsequently, the total amount of the organic solvent solution (x) of polyurethane and 476 parts by weight of the composite resin intermediate-containing solution (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, by mixing the composite resin-containing liquid (X ′) and 11 parts by weight of TEA, a neutralized product-containing liquid in which the carboxyl groups in the composite resin were neutralized was obtained. A mixture of the liquid containing and 560 parts by weight of deionized water is distilled under the same conditions as in Preparation Example 1 to obtain an aqueous composite resin composition, and then 0.9 part by weight of GPTMS is mixed with the composition. As a result, 1000 parts by weight of the composite resin water dispersion (X) having a nonvolatile content of 35.0% by weight was obtained.

Comparative Preparation Example 1 [Preparation of aqueous composite resin dispersion (XI)]
PnP 60 parts by weight, MTMS 365 parts by weight and DMDMS 32 parts by weight were charged into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser tube and a nitrogen gas inlet, and the temperature was raised to 80 ° C.

  Next, 93 parts by weight of MMA, 53 parts by weight of BA, 27 parts by weight of MPTS, 7 parts by weight of AA, 20 parts by weight of 2-hydroxyethyl methacrylate (2-HEMA), 10 parts by weight of PnP, and 10 parts by weight 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.

  Subsequently, 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 weights 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.

  Subsequently, the liquid containing the comparative composite resin (XI ′) and 21 parts by weight of TEA were mixed to obtain a liquid containing a neutralized product obtained by neutralizing the carboxyl group in the comparative composite resin, A mixture of the neutralized product-containing liquid and 530 parts by weight of deionized water was distilled under the same conditions as in Preparation Example 1 to obtain a composite resin water dispersion (XI) having a nonvolatile content of 40.0% by weight. ) 1000 parts by weight were obtained.

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

  Next, at the same temperature, a mixture containing 9 parts by weight of MMA, 86 parts by weight of BMA, 67 parts by weight of BA, 14 parts by weight of MPTS, 16 parts by weight of AA, 14 parts by weight of PnP and 14 parts by weight of TBPEH was placed in 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 solvent solution (xii) of the acrylic polymer, 0.9 part by weight of “A-3” (iso-propyl acid phosphate manufactured by Sakai Chemical Co., Ltd.) and 24 parts by weight 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.

  Subsequently, the liquid containing the comparative composite resin (XII ′) and 18 parts by weight of TEA were mixed to obtain a liquid containing a neutralized product obtained by neutralizing the carboxyl group in the comparative composite resin. After reacting the liquid containing the neutralized product with 124 parts by weight of the methyltrimethoxysilane condensate (a3′-1), it is mixed with 550 parts by weight of deionized water and distilled under the same conditions as in Preparation Example 1. As a result, 1000 parts by weight of a composite resin water dispersion (XII) having a nonvolatile content of 40.0% by weight was obtained.

Comparative Preparation Example 3 [Preparation of aqueous composite resin dispersion (XIII)]
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) and 171 parts by weight 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 weight of DMPA, 5 parts by weight of NPG, and 132 parts by weight 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 33 parts by weight of APTES and 309 parts by weight of IPA were put into the reaction vessel and reacted, whereby the number average molecular weight having a carboxyl group and a hydrolyzable silyl group was 7,500. Next, the total amount of the polyurethane organic solvent solution (xiii) was mixed with 112 parts by weight of the composite resin intermediate containing liquid (C-1), and the mixture was 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 )

  Subsequently, the liquid containing the neutralized product obtained by neutralizing the carboxyl group in the composite resin for comparison (XIII ′) was obtained by mixing the liquid containing the composite resin for comparison (XIII ′) and 12 parts by weight of TEA. Subsequently, a mixture of the neutralized product-containing solution and 610 parts by weight of deionized water is distilled under the same conditions as in Preparation Example 1 to disperse the composite resin in water with a non-volatile content of 35.0% by weight. 1000 parts by weight of body (XIII) was obtained.

Comparative Preparation Example 4 [Preparation of aqueous composite resin dispersion (XIV)]
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) 187 parts by weight, IPDI 78 parts by weight 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 weight of DMPA, 6 parts by weight of NPG, and 144 parts by weight 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 weight of APTES and 339 parts by weight 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 polyurethane organic solvent solution (xiv) and 56 parts by weight of the composite resin intermediate-containing solution (C-1) are mixed, and the mixture is 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, the composite resin-containing liquid (XIV ′) and 11 parts by weight of TEA were mixed to obtain a neutralized product-containing liquid that neutralized the carboxyl group in the comparative composite resin. A mixture of the liquid containing the hydrate and 610 parts by weight of deionized water was distilled under the same conditions as in Preparation Example 1 to obtain a composite resin water dispersion (XIV) 1000 having a nonvolatile content of 35.0% by weight. Part by weight was obtained.

Comparative Preparation Example 5 [Preparation Example of Composite Resin Water Dispersion (XV)]
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) 27 parts by weight, 11 parts by weight 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 weight of DMPA, 1 part by weight of NPG, and 144 parts by weight 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 weight of APTES and 49 parts by weight 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 (xv) was obtained.
Next, the total amount of the organic solvent solution (xv) of polyurethane and 676 parts by weight 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 (XV ′) 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, the composite resin-containing liquid (XV ′) and TEA 12 parts by weight were mixed to obtain a neutralized product-containing liquid that neutralized the carboxyl group in the comparative composite resin. A mixture of the liquid containing the hydrate and 610 parts by weight of deionized water was distilled under the same conditions as in Example 1 to obtain a composite resin water dispersion (XV) 1000 having a nonvolatile content of 35.0% by weight. Part by weight was obtained.

Comparative Preparation Example 6 [Preparation Example of Composite Resin Solution (XVI)]
In the same reaction vessel as in Synthesis Example 1, 150 parts by weight of PnP was charged and heated to 80 ° C.

  Next, a mixture containing 60 parts by weight of MMA, 45 parts by weight of BMA, 57 parts by weight of BA, 38 parts by weight of AA, 50 parts by weight of PnP, and 9 parts by weight 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 weight of polytetramethylene glycol (PTMG-2000 manufactured by Mitsubishi Chemical Corporation) and 110 parts by weight 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 weight of DMPA, 8 parts by weight of NPG, and 400 parts by weight of MEK are put into the reaction vessel, and further reacted at 80 ° C. for 5 hours to have a carboxyl group. A polyurethane (xvi-2) having a number average molecular weight of 7,600 was obtained.

  By mixing 109 parts by weight of the acrylic polymer (xvi-1), 656 parts by weight of polyurethane (xvi-2), and 235 parts by weight of the condensate of methyltrimethoxysilane (a3′-1), the composite resin solution ( XVI) 1000 parts by weight were obtained.

  The storage stability described in Tables 2-4 includes the viscosity of the composite resin aqueous dispersion (initial viscosity) and the viscosity (viscosity with time) of the composite resin solution after being left in an environment of 50 ° C. for 30 days. Was evaluated by a 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.

  Composite resin aqueous dispersions (I) to (XV) and composite resin solution (XVI) obtained above and an ultraviolet absorber (manufactured by BASF Japan Ltd .: TINUVIN477-DW (hydroxyphenyltriazine-based ultraviolet absorber dispersed in water) Agent, active ingredient 20%), TINUVIN 928 (benzotriazole ultraviolet absorber, powder), manufactured by Big Chemie Japan Co., Ltd .: NANOBYK-3820 (zinc oxide dispersed in water, active ingredient 40%), manufactured by ALDRICH: 5 -A curable composition was obtained by mixing the indoleol) and various curing agents, which will be described later, if necessary, according to the blending composition described in Tables 5 to 11 below. A coating film was formed using the obtained curable composition, and various physical properties of the coating film were evaluated according to the following evaluation methods.

In the following evaluation, the coating composition was applied on a PET film so that the thickness of the cured coating film was 10 μm, dried in an environment of 80 ° C. for 5 minutes, and then in an environment of 140 ° C. for 20 minutes. It performed using the cured coating film obtained by making it dry.

[Evaluation method of substrate followability]
The substrate followability of the coating film was evaluated based on crack resistance and the elongation of the coating film.

(Crack resistance evaluation method)
The appearance (presence or absence of cracks) immediately after forming the cured coating film 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: Cracks are observed in the entire coating film surface, particularly in the concave portions of the corrugated slate plate.

Further, the coating film was subjected to Dew panel light weather meter [manufactured by Suga Test Instruments Co., Ltd., light irradiation: 30 W / m ² , 60 ° C., humidity: 90% humidity, 40 ° C., light irradiation / wetting cycle = The appearance of the coating film after a 1000 hour exposure test using 4 hours / 4 hours] was visually evaluated according to the same evaluation criteria as described above.

(Evaluation method of coating film elongation)
The aqueous composite resin composition is coated on a base material made of polypropylene film so that the film thickness becomes 200 μm, dried in an environment of 140 ° C. for 5 minutes, and further dried in an environment of 25 ° C. for 24 hours. The test film (10 mm × 70 mm) was peeled off from the substrate.

  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.

[Method for evaluating durability of coating film]
The durability of the coating film was evaluated based on the solvent resistance, weather resistance and stain resistance.

(Evaluation method of solvent resistance of coating film)
Using a felt soaked with methyl ethyl ketone, the same portion of the test coating film surface 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.

(Method for evaluating weather resistance of coating film)
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 hour] for 1000 hours exposure test. Here, the specular gloss reflectance 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. Larger gloss retention values indicate better weather resistance, preferably approximately 70% or more.

  [100 × (specular reflectance of coating film after exposure test) / (specular reflectance of coating film before exposure test)]

(Evaluation method for stain resistance of coating film)
The test coating film was subjected to an exposure test for 3 months in DIC Corporation Sakai Factory in Takaishi City, Osaka Prefecture.

  Contamination resistance was evaluated by using CM-3500d manufactured by Konica Minolta Sensing Co., Ltd., the color difference (ΔE) between the unwashed test coating film after the exposure test and the test coating film before the exposure test. The smaller the color difference (ΔE), the better the stain resistance.

[Method for evaluating UV shielding property of coating film]
The ultraviolet shielding property of the coating film was evaluated based on the ultraviolet shielding rate and the ultraviolet shielding retention rate.

(Evaluation method of UV shielding rate of coating film)
The aqueous coating composition is coated on a substrate made of PET film so that the film thickness is 10 μm, dried in an environment of 80 ° C. for 5 minutes, and further dried in an environment of 140 ° C. for 20 minutes. The cured coating film obtained in this way was used.

  Using an ultraviolet-visible spectrophotometer “V-570” manufactured by JASCO Corporation, the UV transmittance (%) of the PET film as a blank was measured, and the UV transmittance (%) of the cured coating film at 360 nm. ) Was measured, and the ultraviolet shielding rate [100- (UV transmittance of cured coating film at 360 nm (%))] was determined. It shows that an ultraviolet shielding factor is so favorable that the value of a shielding factor is large.

(Evaluation method of UV shielding retention rate of coating film)
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 hour] for 1000 hours exposure test. Here, the ultraviolet shielding ratio (%) before and after the exposure test was calculated in the same manner as described above, and the ultraviolet shielding retention was determined based on the following formula. The larger the value of the ultraviolet shielding retention rate, the better the ultraviolet shielding property, and it is preferably approximately 80% or more.

  [100 × (UV shielding rate of the coating film after exposure) / (UV shielding rate of the coating film before exposure)]

(Measurement of number average molecular weight)
In addition, the number average molecular weight in this invention is a measured value of the number average molecular weight (polystyrene conversion) by GPC, and was performed on condition of the following using the HLC8220 system by Tosoh Corporation.
Separation column: 4 TSKgelGMH _HR- N manufactured by Tosoh Corporation are used. Column temperature: 40 ° C. Moving layer: Tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd. Flow rate: 1.0 ml / min. Sample concentration: 1.0% by weight. Sample injection volume: 100 microliters. Detector: differential refractometer.

Abbreviations of the curing agents described in Tables 5 to 10 will be described.
“GPTMS”; 3-glycidoxypropyltrimethoxysilane “TINUVIN477-DW”; hydroxyphenyltriazine UV absorber dispersed in water, active ingredient 20%
“TINUVIN 928”; benzotriazole UV absorber, powdered “NANOBYK-3820”; zinc oxide dispersed in water, active ingredient 40%

Claims (11)

The polyurethane (a1) and the vinyl polymer (a2) contain a composite resin (ABC) bonded via a polysiloxane (a3) and an ultraviolet absorber (D). The bond with the siloxane (a3) is formed by the reaction between the hydrolyzable silyl group and / or silanol group of the polyurethane (a1) and the hydrolyzable silyl group and / or silanol group of the polysiloxane (a3). And the bond between the vinyl polymer (a2) and the polysiloxane (a3) is such that the vinyl polymer (a2) has a hydrolyzable silyl group and / or silanol group and the polysiloxane ( a3) is formed by a reaction with a hydrolyzable silyl group and / or silanol group, and the compound Resin (ABC) said polysiloxane (a3) curable coating composition, wherein the weight ratio of the structure derived from is in the range of 15 to 55 wt% of the whole. The curable coating composition according to claim 1, wherein a weight ratio [(a2) / (a1)] of the polyurethane (a1) and the vinyl polymer (a2) is in a range of 20/1 to 1/20. . 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 curable coating composition according to claim 1. 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 curable coating composition of Claim 1 which has 1 or more types chosen from the group which consists of the alkoxy group which has. The polysiloxane (a3) is a polysiloxane (a3-1) having at least one structure selected from the group consisting of the following general formulas (II) and (III), and the alkyl group has 1 to 3 carbon atoms. The curable coating composition of Claim 1 which is a reaction material with the condensate (a3-2) of the alkyl trialkoxysilane which is individual.

[R ¹ in the general formulas (II) and (III) 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. ] The curable coating composition according to any one of claims 1 to 5, wherein a blending ratio of the ultraviolet absorber (D) is 0.01 to 20 parts by weight with respect to 100 parts by weight of the composite resin (ABC). . The ultraviolet absorber (D) is selected from the group consisting of titanium oxide, zinc oxide, tin oxide, cerium oxide, benzotriazole ultraviolet absorber, triazine ultraviolet absorber, indole ultraviolet absorber, and azomethine ultraviolet absorber. The curable coating composition according to claim 1, which is one or more selected compounds. A coating agent comprising the curable coating composition according to claim 1. The manufacturing method of the curable coating composition of Claim 1 which consists of the process of the following (I-1)-(I-5).
(I-1) 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 in the presence of an organic solvent. Obtaining an organic solvent solution of the vinyl polymer (a2);
(I-2) By reacting the vinyl polymer (a2) with a silane compound in the presence of an organic solvent solution of the vinyl polymer (a2), the vinyl polymer (a2) is reacted with the polysiloxane (a3). A step of obtaining an organic solvent solution of resin (C) bonded with
(I-3) The vinyl polymer (a2) and the polyurethane (a1) were bonded via the polysiloxane (a3) by mixing and reacting the resin (C) and the polyurethane (a1). Obtaining an organic solvent solution of the composite resin (ABC);
(I-4) a step of dissolving or dispersing in a medium by mixing an organic solvent solution containing the composite resin (ABC) and the medium;
(I-5) A step of adding an ultraviolet absorber (D) to the solution or dispersion of the composite resin (ABC). The manufacturing method of the curable coating composition of Claim 1 which consists of the process of the following (II-1)-(II-5).
(II-1) 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 in the presence of an organic solvent. Obtaining an organic solvent solution of the vinyl polymer (a2);
(II-2) a step of mixing the organic solvent solution of the vinyl polymer (a2) and the polyurethane (a1),
(II-3) By reacting the polyurethane (a1) and the vinyl polymer (a2) with a silane compound in the presence of an organic solvent solution of the mixture, the vinyl polymer (a2) and the polyurethane (a1) A step of obtaining an organic solvent solution of a composite resin (ABC) bonded with polysiloxane (a3) through
(II-4) a step of dissolving or dispersing in a medium by mixing an organic solvent solution of the composite resin (ABC) and the medium;
(II-5) A step of adding an ultraviolet absorber (D) to the solution or dispersion of the composite resin (ABC). The manufacturing method of the curable coating composition of Claim 1 which consists of the process of the following (III-1)-(III-5).
(III-1) 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 in the presence of an organic solvent. Obtaining an organic solvent solution of the vinyl polymer (a2);
(III-2) Resin (E) in which polysiloxane (a3) is bonded to polyurethane (a1) by reacting polyurethane (a1) with a silane compound in the presence of an organic solvent solution of polyurethane (a1). Obtaining an organic solvent solution of
(III-3) The resin (E) and an organic solvent solution of the vinyl polymer (a2) are mixed and reacted, whereby the vinyl polymer (a2) and the polyurethane (a1) are converted into the polysiloxane (a3). A step of obtaining an organic solvent solution of the composite resin (ABC) bonded via
(III-4) A step of dissolving or dispersing in the medium by mixing the organic solvent solution of the composite resin (ABC) in the organic solvent and the medium,
(III-5) A step of adding an ultraviolet absorber (D) to the solution or dispersion of the composite resin (ABC).