TW201606009A - Silane coating composition - Google Patents

Abstract

The problem of the present invention is to provide a coating composition that can be applied to a wide range of base materials, including plastics, the coating composition permitting glass-type surface modification, being capable of being produced in a short time, exhibiting sufficient hardness after curing for a short time, resulting in a coating film having exceptional adhesiveness due to an anchoring effect, and having exceptional long-term storage stability. A composition is used that contains: (A) a hydrolysis condensate of an epoxy-group-containing trialkoxysilane; (B) polyamines; (C) an organic acid having a pKa within a range of 2.0-6.0 at 25 DEG C, or C2-5 alcohols having a perfluoroalkyl group or perfluoroalkylene group; and (D) metal compound particles.

Description

Decane-based coating composition

The present invention relates to an organic decane-based composition, and more particularly to a composition excellent in adhesion to a plastic substrate or a metal substrate, and further excellent in storage stability.

The present application claims priority to Japanese Patent Application No. 2014-146252, filed on Jul. 16, 2014, which is incorporated herein.

A transparent plastic molded body such as polycarbonate exhibits the advantages of light weight, easy processability, and impact resistance, and is widely used as a substitute for inorganic glass products, but has the disadvantage of being easily invaded by a solvent and being difficult to be surface-modified. . Therefore, there is still a point that is inferior to that of inorganic glass, and attempts to improve these properties have been continuously conducted since the past.

For example, it is known that glycidyloxytrimethoxydecane is hydrolyzed with an aqueous solution of nitric acid in an alcohol, and further, di-ethyltriamine is added to further react, and coating can be formed on a polycarbonate plate. Hard coating film with a pencil hardness of 2 H. (Non-Patent Document 1)

Further, there is known a thermosetting resin composition which contains a general formula of NH ₂ -R ¹ -NH-R ¹ -NH ₂ (R ¹ represents a straight or branched alkyl group having 6 or less carbon atoms) An amino group compound, a glycidoxy group C1-6 linear or branched alkyltrial trialkoxy decane monomer or a polymer thereof, and a tetraalkoxy decane or an alkyltrialkoxy decane The mixture is obtained by hydrolysis, and it is known that it is applied to a metal surface and hardened by heating, and a film excellent in physical properties such as abrasion resistance, surface hardness, and chemical resistance can be obtained. Further, it is described that a hydrohalic acid, a carboxylic acid, a sulfonic acid or the like can be used as the hydrolysis catalyst. (Patent Document 1)

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 55-25469

[Non-patent literature]

[Non-Patent Document 1] J. Korean Ind. Eng. Chem., Vol17, No2, April 2006, 170-176.

However, the coating composition described in Non-Patent Document 1 requires a hydrolysis time of 24 hours, and the workability after the coating film is required to be as long as 15 hours, and further, as described later, in terms of storage stability. There is a problem.

Further, in Patent Document 1, a strong acid such as perchloric acid is preferably used as a hydrolysis catalyst, and the amount used is 1% by mass or less based on the entire composition. However, the long-term storage stability of the composition is not described. Inspiration, in addition, there is no description or suggestion about the adhesion between the undercoat layer and the upper layer.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a coating composition which can be adapted to a wide range of substrates including plastics, which can be surface-modified into a glass shape and can be used in a short time. In addition, it is produced by coating with a sufficient hardness by hardening for a short period of time, and a coating film such as an undercoat layer having excellent adhesion to a substrate or excellent adhesion to an upper layer can be obtained.

The inventors of the present invention conducted intensive studies to solve the above problems, and as a result, found that by applying a hydrolysis-condensation product containing an epoxy group-containing trialkoxydecane, a polyamine, a specific organic acid or a specific alcohol, and The composition of the metal compound particles is dried and the above problems can be solved, so that the present invention can be completed.

That is, the present invention relates to: (1)

A decane-based coating composition comprising: (A) a hydrolysis condensate of an epoxy group-containing trialkoxy decane, (B) a polyamine, and (C) a pKa of from 2.0 to 6.0 at 25 ° C An organic acid, or an alcohol having a carbon number of 2 to 5 having a perfluoroalkyl group or a perfluoroalkylene group, and (D) a metal compound particle; (2) a decane-based coating composition according to (1), wherein The z-average particle diameter of the hydrolyzed condensate of the epoxy group-containing trialkoxydecane determined by dynamic light scattering is in the range of 5 to 50 nm; (3) the decane-based coating composition as (1) Wherein the polyamine is at least one selected from the group consisting of an alkylene polyamine, a polyalkylene polyamine, a poly(phenylene alkylene)polyamine, and a cycloalkylalkylpolyamine. a polyamine; (4) a decane-based coating composition according to (1), which is 1/m of the epoxy group-containing trialkoxy decane and/or its hydrolysis condensate. (the total number of hydrogen atoms on all nitrogen atoms in the polyamine 1 molecule) is 10 or less per mole of 1/(all hydrogen atoms on all nitrogen atoms in the polyamine 1 molecule) Polyamines are used internally; (5) decane coating group such as (1) a compound which uses an organic acid having a pKa in the range of 2.0 to 6.0 in the range of 0.3 to 1.2 mols, and (6) a decane-based coating composition as in (1), with respect to the polyamine 1 mol. The alcohol having 2 to 5 carbon atoms of the perfluoroalkyl group or the perfluoroalkylene group is 30% by mass or more of the entire composition; (7) The decane-based coating composition of (1), which further comprises a perfluoroalkyl group or a perfluoroalkylene group having an alcohol having a carbon number of from 2 to 5 and an alcohol having a carbon number of from 1 to 5; (8) a decane-based coating composition of (1), wherein the metal compound particles The metal element is at least one selected from the group consisting of ruthenium, aluminum, titanium, and iron; (9) the decane-based coating composition of (1), wherein the metal compound particles are cerium oxide; (10) a decane-based coating composition of (1), wherein the metal compound particles are averaged once (11) The decane-based coating composition of (1), wherein the metal compound particles are contained in the range of 20 to 83% by mass of the total solid content of the composition; (12) a film. The decane-based coating composition according to any one of (1) to (11) is applied onto a substrate and dried at room temperature and/or heated.

By using the decane-based coating composition of the present invention and coating on a substrate, the surface of the substrate can be modified into a glassy surface having sufficient hardness in a short time, and further, the surface can be finely formed. Bump. The film obtained by using the composition of the present invention can be used as an undercoat layer excellent in adhesion to a resin layer provided thereon, and is generally used as a primer layer for providing a resin layer on the surface of a substrate having poor adhesion. And useful.

Hereinafter, the composition containing the above components (A), (B), (C) and (D) of the present invention will be described in detail.

(A) Hydrolyzed condensate of an epoxy group-containing trialkoxy decane

The hydrolysis-condensation product of the epoxy group-containing trialkoxysilane used in the present invention can be produced by using an epoxy group-containing trialkoxysilane and/or a hydrolysis-condensation product thereof as a raw material.

The trialkyloxydecane containing an epoxy group is not particularly limited as long as it is a trialkoxysilane containing an epoxy group other than a functional group moiety converted by hydrolysis or the like.

In the case of the general formula, a compound represented by the following formula (I) can be mentioned.

R-Si(OR ¹ ) ₃ . . . (I)

In the formula, R represents a hydrocarbon group having an epoxy group or a glycidoxy group, and R ¹ represents an alkyl group.

In R, the epoxy group or the glycidoxy group may be contained in one or more, preferably in the range of 1 to 3, and may include both an epoxy group and a glycidoxy group.

Examples of the "hydrocarbon group" of the "hydrocarbon group having an epoxy group or a glycidoxy group" of R include an alkyl group, a cycloalkyl group, a cycloalkylalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, and an aryl group. Arylalkyl, arylalkenyl, and the like. The carbon number is preferably in the range of 1 to 30, and more preferably in the range of 1 to 10.

Specific examples of the "alkyl group" include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, second butyl group, tert-butyl group, n-pentyl group and isoprene. Base, neopentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, n-decyl, isodecyl, n-decyl, etc., dodecyl, tridecyl, tetradecyl, fifteen Alkyl, hexadecyl, heptadecyl, octadecyl, and the like.

Specific examples of the "cycloalkyl group" include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

The "cycloalkylalkyl group" is a group in which a cycloalkyl group is bonded to an alkyl group, and is preferably a group in which a cycloalkyl group having 3 to 10 carbon atoms is bonded to an alkyl group having 1 to 10 carbon atoms.

Specific examples of the "alkenyl group" include a vinyl group, a 1-propen-1-yl group, an allyl group, a 1-buten-1-yl group, a 2-buten-1-yl group, and a 3-butene group. 1-yl, 1-buten-2-yl, 3-buten-2-yl, 1-penten-1-yl, 4-penten-1-yl, 1-penten-2-yl, 4 -penten-2-yl, 3-methyl-1-buten-1-yl, 1-hexen-1-yl, 5-hexen-1-yl, 1-hepten-1-yl, 6 -hepten-1-yl, 1-octen-1-yl, 7-octene-1-yl, 1,3-butadien-1-yl and the like.

Specific examples of the "cycloalkenyl group" include 1-cyclopenten-1-yl, 2-cyclopenten-1-yl, 1-cyclohexen-1-yl, and 2-cyclohexene-1. -yl, 3-cyclohexen-1-yl and the like.

Specific examples of the "alkynyl group" include an ethynyl group, a 1-propyn-1-yl group, a 2-propyn-1-yl group, a 1-butyn-1-yl group, and a 3-butyn-1-yl group. , 1-pentyn-1-yl, 4-pentyn-1-yl, 1-hexyn-1-yl, 5-hexyn-1-yl, 1-heptyn-1-yl, 1-octyne -1-yl, 7-octyn-1-yl and the like.

"Aryl" means a monocyclic or polycyclic aryl group, and in the case of a polycyclic aryl group, in addition to a fully unsaturated ring, a group having a partially saturated ring. Specific examples thereof include a phenyl group, a naphthyl group, an anthracenyl group, an anthracenyl group, a dihydroindenyl group, and a tetrahydronaphthyl group.

The "arylalkyl group" is a group in which an aryl group is bonded to an alkyl group, and is preferably a group in which an aryl group having 6 to 10 carbon atoms is bonded to an alkyl group having 1 to 10 carbon atoms.

The "arylalkenyl group" is a group formed by bonding an aryl group and an alkenyl group, and is preferably a group of an aryl group having 6 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms.

The above "hydrocarbon group" may have a substituent other than the epoxy group and the glycidoxy group, and examples of such a substituent include a halogen group, an alkyl group, an alkenyl group, an alkoxy group, and a (meth) propylene group. Oxyl and the like.

Here, examples of the halogen group include a fluorine group, a chlorine group, a bromine group, and an iodine group.

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

Examples of the alkyl group and the alkenyl group include the same hydrocarbon groups as the alkyl group and the alkenyl group in the above R.

Examples of the "alkyl group" of R ¹ include the same hydrocarbon groups as the alkyl group in the above R.

The above "alkyl group" may have a substituent, and examples of such a substituent include a halogen group, an alkoxy group, and a (meth)acryloxy group.

The epoxy group-containing trialkoxysilane or a hydrolysis condensate thereof as a raw material is preferably a glycidoxyalkyltrialkoxide or a glycidoxyalkenyl alkoxydecane. These may be used alone or in combination of two or more.

Specific examples of the compound represented by the formula (I) include methyl-triglycidyloxydecane, methyltris(3-methyl-3-oxetanylmethoxy)decane, and 2- (3,4-Epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxy-n-propyltrimethoxydecane, 3-glycidoxy-n-propylmethyldiethoxydecane 3-glycidoxypropyltriethoxydecane.

The hydrolysis condensate of the epoxy group-containing trialkoxy decane may be mixed and stirred by the epoxy group-containing trialkoxy decane and/or its hydrolysis condensate, water, and, if necessary, a decyl alcohol condensation catalyst. preparation. The mixing order and the stirring speed are not particularly limited, and any order or arbitrary speed can be set. The temperature during mixing and stirring is not particularly limited, It is preferably carried out at a temperature ranging from room temperature to the boiling point of the solvent to be used, and more preferably at room temperature. The room temperature is, in this case, the external atmospheric temperature at the place where the mixing is performed, and is preferably in the range of 15 to 35 °C.

It is preferred to stir at room temperature for 2 hours to 3 hours in a state in which all of the epoxy group-containing trialkoxy decane, water, and, if necessary, a decyl alcohol condensation catalyst are present. In the preparation, it is diluted with an organic solvent or water as necessary.

The amount of the water to be used is not particularly limited as long as it can liquefy or condense the epoxy group-containing trialkoxysilane and/or its hydrolysis-condensation product to some extent, and specifically, With respect to the epoxy group-containing trialkoxysilane and/or its hydrolysis condensate 1 mole, it is preferably 0.5 mole or more, more preferably 1.0 mole or more, 2.0 mole or more, or 5.0. Above the mole, or above 10 moles.

The amount of the decyl alcohol condensation catalyst to be used is not particularly limited, and is equivalent to all uncondensed trialkoxy decane in the epoxy group-containing trialkoxy decane and/or its hydrolysis condensate. The amount of the base is preferably in the range of 0.001 to 1.0, more preferably 0.01 to 1.0, or 0.1 to 0.5, based on the molar ratio (the stanol condensation catalyst / the alkylene group).

Examples of the decyl alcohol condensation catalyst include a metal alkoxide, a metal chelate compound, an organic acid metal salt, or a metal compound such as the hydrolysis condensate, and more specifically, titanium tetraisopropoxide or the like. Titanium isopropoxide, acetoacetone, or a hydrolysis condensate thereof.

Examples of the stanol condensation catalyst include an acid, a base, and the like in addition to the above metal compound.

Examples of the acid include an organic acid and an inorganic acid. Examples of the organic acid include acetic acid, formic acid, oxalic acid, carbonic acid, phthalic acid, trifluoroacetic acid, p-toluenesulfonic acid, methanesulfonic acid, and the like; and as the inorganic acid, Examples thereof include hydrochloric acid, nitric acid, boric acid, and hydrofluoroboric acid.

Here, as the acid, a photoacid generator which generates an acid due to light irradiation, specifically Examples thereof include diphenylphosphonium hexafluorophosphate and triphenylsulfonium hexafluorophosphate.

Examples of the base include a strong base such as tetramethylguanidine or tetramethylguanidinopropyltrimethoxydecane; an aliphatic first amine; an aliphatic second amine; an aliphatic third amine; and an aliphatic group. Unsaturated amines; aromatic amines; di-ethyltriamine, tri-ethyltetramine, diethylaminopropylamine, xylylenediamine, ethylenediamine, hexamethylenediamine, triethylene a polyamine such as an amine; a salt of the amine compound with a carboxylic acid or the like; a carboxylic acid neutralizing salt of an organic amine; a quaternary ammonium salt; an imidazole, 2-ethyl-4-methylimidazole, 2-phenyl Imidazoles such as 4-methyl-5-hydroxyimidazole;

The sterol condensation catalyst may be used singly or in combination of two or more.

In the composition of the present invention, in the case of using a polyamine or an imidazole as a hardener or a hardening accelerator for an epoxy group-containing trialkoxysilane, it is preferred to use a polyamine for the decyl alcohol condensation catalyst. Or imidazoles.

The hydrolysis condensate of the epoxy group-containing trialkoxy decane used in the present invention is preferably a z-average particle diameter of 5 to 50 nm as measured by dynamic light scattering, and more preferably 5 to 5 30nm. When it is larger than 50 nm, there is a case where the service life is short, and there is a problem in storage stability, and there is a case where coating unevenness occurs after coating. Further, in the case of less than 5 nm, the hardness of the obtained film may be insufficient.

(B) Polyamines

The polyamine to be used is not particularly limited as long as it has two or more amine groups or imine groups in which one or more hydrogen atoms are bonded to one molecule, and specific examples thereof include ethylenediamine and Sanya. Methyldiamine, tetramethylenediamine, hexamethylenediamine, diethylidene triamine, triethylidenetetramine, tetraethylidene pentaamine, dipropyltriamine, methylamine Propylamine, ethylaminopropylamine, N,N'-dimethylhexamethylenediamine, bis(2-methylaminoethyl)ether, menthanediamine, isophoronediamine, 3 ,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro(5,5)undecane adduct, bis(4-aminocyclohexyl)methane, o-benzene Diamine, m-phenylenediamine, P-phenylenediamine, diaminodiphenylmethane, diaminodiphenylanthracene, m-xylylenediamine, and the like. These may be used alone or in combination of two or more. Among them, an alkylene polyamine, a polyalkylene polyamine, a poly(phenylene alkylene)polyamine, and a cycloalkylalkylpolyamine are preferred, and a polyalkylene polyamine is preferred. Specific examples thereof include di-ethyltriamine, tri-extension ethyltetramine, tetra-extension ethylpentamine, di-propyltriamine, and the like.

The amount of the polyamine to be used is not particularly limited, and it is preferably 1/(polyamine) relative to the epoxy group-containing trialkoxysilane and/or the epoxy group 1 molar thereof in the hydrolysis condensate thereof. The number of all hydrogen atoms on all nitrogen atoms in the class 1 molecule is more than 2 moles, preferably 1 / 10 times to 10 times the number of all hydrogen atoms on all nitrogen atoms in the polyamine 1 molecule. The range, 1.5 times to 5 times the range of moles, or 1.8 times to 2.5 times the range of moles. In the case of less than 1/(the total number of hydrogen atoms on all nitrogen atoms in the polyamine 1 molecule), there is a case where the hardening is insufficient and a film having a higher hardness cannot be obtained, which is greater than 1/(poly) In the case where the number of all hydrogen atoms on all the nitrogen atoms in the amine molecule is 10 times the molar amount, there is a case where the polyamine remains and the film having a sufficient hardness cannot be formed.

(C) an organic acid or an alcohol having a perfluoroalkyl group or a perfluoroalkyl group having 2 to 5 carbon atoms

The organic acid to be used is not particularly limited as long as it has an organic acid having a pKa of from 2.0 to 6.0 at 25 ° C, preferably from 3.0 to 5.0. Specific examples thereof include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, caproic acid, isohexanoic acid, chloroacetic acid, fluoroacetic acid, bromoacetic acid, 3-chloropropionic acid, and 2- Bromopropionic acid, 2-hydroxybutyric acid, phenylacetic acid, phenylpropionic acid, 4-phenylbutyric acid, phenoxyacetic acid, cyanoacetic acid, oxalic acid, malonic acid, 2,2-dimethylmalonic acid, hexane Acid, succinic acid, pimelic acid, phthalic acid, glutaric acid, oxalic acid, citric acid, isocitric acid, cyclohexane-1,1-dicarboxylic acid, tartaric acid, o-anisic acid, fennel Acid, p-anisic acid, benzoic acid, o-chlorobenzoic acid, m-fluorobenzoic acid, 2,3-difluorobenzoic acid, o-nitrobenzoic acid, m-nitrobenzoic acid, p-nitrobenzoic acid, m-aminobenzene Formic acid, p-aminobenzoic acid, salicylic acid, phthalic acid, irophthalic acid, trans cinnamic acid, 2-furancarboxylic acid, glyoxylic acid, glycolic acid, crotonic acid, lactic acid, 2-hydroxy-2- Methylpropionic acid, pyruvic acid, mandelic acid, malic acid, acetopropionic acid, 2,6-pyridinedicarboxylic acid, nicotinic acid, etc., among which aliphatic monocarboxylic acid or benzoic acid or substituted is preferred. benzoic acid.

The amount of the organic acid to be used is not particularly limited, and is preferably in the range of 0.3 to 1.2 mol, more preferably 0.5 to 1.0 mol, or 0.6 to 0.9 mol, based on the polyamine 1 mole used. The range of the ear.

When it is less than 0.3 mol, the storage stability of the decane-based coating composition may be lowered, and when it is more than 1.2 mol, there is a case where a coating film having a sufficient hardness cannot be formed.

The alcohol (perfluorinated alcohol) having a carbon number of 2 to 5 having a perfluoroalkyl group or a perfluoroalkylene group to be used, specifically, 2,2,2-trifluoroethanol, 1, 1,2,2,2-pentafluoroethanol, 3,3,3-trifluoro-1-propanol, 2,2,3,3,3-pentafluoro-1-propanol, 1,1,2, 2,3,3,3-heptafluoro-1-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2-trifluoromethyl-2-propanol, 2- Methyl-1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,4,4,4-heptafluoro-1-butanol, nonafluoro-third Butanol, 2,2,3,3,4,4,5,5-octafluoro-1-pentanol, and the like.

The amount of the perfluorinated alcohol to be used is not particularly limited, but is preferably 30% by mass or more, and more preferably 40% by mass or more based on the entire decane-based coating composition. When it is less than 30% by mass, there is a case where the long-term storage stability of the composition is lowered.

(mixing ratio of ingredients (A) and (B))

The concentration of the solid content component in the decane-based coating composition is not particularly limited, and it is preferably used in consideration of the appearance, coatability, curability, properties of the film, storage stability of the composition, and the like of the film. The concentration of the solid content of the hydrolyzed condensate of the epoxy group-containing trialkoxy decane and (B) the polyamine is in the range of 0.5 to 50% by mass based on the total mass thereof, and more preferably 1.0 to 30% by mass. %, 1.0 to 20% by mass, 1.0 to 10% by mass, 1.5 to 5.0% by mass, or 1.8 to 3% by mass. In the case of less than 0.5% by mass, there is a case where it is difficult to form a film homogeneously, and in the case of more than 50% by mass, the composition is present. The stability, the transparency of the film, the appearance, or the coating property cause problems.

The amount of the organic solvent and water to be used can be appropriately determined within a range in which the concentration of the solid content component can be adjusted.

(D) metal compound particles

Specific examples of the metal of the metal compound particles include ruthenium, tungsten, osmium, zirconium, aluminum, titanium, magnesium, iron, tin, zinc, cadmium, nickel, copper, ruthenium, osmium, iridium, osmium, mercury, ruthenium. , chromium, antimony, lead, indium, antimony, cadmium, antimony, gallium, magnesium, etc.

Specific examples of the metal compound include cerium oxide, tungsten oxide, cerium oxide, zirconium oxide, aluminum oxide, titanium oxide, magnesium oxide, tin oxide, zinc oxide, cadmium oxide, cerium oxide, nickel oxide, copper oxide, and oxidation. Lanthanum, cerium oxide, cerium oxide, oxidized mercury, cerium oxide, chromium oxide, lead oxide, indium oxide, cerium oxide, cadmium oxide, cerium oxide, gallium oxide (III), ferrous oxide or other metal oxide or magnesium fluoride .

Preferably, it is a metal compound containing at least one metal element selected from the group consisting of a Group 4 element, a Group 5 element, a Group 13 element, a Group 14 element, and a Group 8 to 10 element of the periodic table; The particles are more preferably metal compound particles containing at least one metal element selected from the group consisting of ruthenium, aluminum, titanium, and iron, and more preferably metal compound particles containing ruthenium.

The particle diameter of the metal compound is not particularly limited, and is preferably in the range of 1 nm to 500 nm, and more preferably in the range of 10 nm to 100 nm, in terms of the average primary particle diameter.

Further, the properties of the metal compound particles may be a sol or a powder, and it is usually preferred to use a sol. Since the sol is usually a colloid-like dispersion, it is easy to form a uniform dispersion by merely mixing with other components, and there is also a problem that unevenness is caused by precipitation or the like.

In addition, a surface modification of the surface of each metal compound particle by a decane coupling agent or the like can be used, and specific examples thereof include a cerium oxide sol which has been subjected to a hydrophobic treatment with a hydrocarbon group or the like.

The content of the metal compound particles is preferably from 20 to 83% by mass, and more preferably from 65 to 75% by mass based on the total solid content of the composition.

(solvent)

The decane-based coating composition can be an organic solvent in order to adjust the concentration of the solid content component in the composition. The solvent is not particularly limited as long as it can maintain the uniformity and stability of the solution, and examples thereof include alcohols, ethers, ketones, esters, guanamines, and the like, and carbon is preferred. Number 1 to 5 alcohol. These may be used alone or in combination of two or more.

As the other solvent, water is preferably used. In this case, the organic solvent to be used is preferably an organic solvent dissolved in water. Further, the ratio of the water to the organic solvent is preferably a ratio of the amount of the solution to be uniform after using the respective amounts required. When a solvent having a carbon number of 1 to 3 or the like is dissolved relatively well in an organic solvent of water, the mass ratio of water to the organic solvent (water/organic solvent) is preferably in the range of 30/70 to 95/5, and further It is preferably in the range of 50/50 to 90/10, 60/40 to 80/20, or 65/35 to 75/25.

Further, when an organic solvent such as an alcohol having 4 or more carbon atoms is relatively difficult to dissolve in water, since the solubility of water with respect to the organic solvent is low, the amount of water used is preferably a trialkoxy decane. The amount required for hydrolysis is above the amount and is in the range that makes the composition uniform.

(other components)

In the decane-based coating composition of the present invention, other components may be added depending on the use thereof, and examples of the other components include various surfactants, dyes, pigments, dispersion materials, liquid-repellent materials, viscosity-increasing materials, and perfumes. Antibacterial ingredients, etc.

(Preparation method of composition)

The method for producing the decane-based coating composition of the present invention is not particularly limited, and specific examples thereof include the following methods.

i) water, polyamines, and organic or perfluorinated alcohols, and organically soluble if necessary The agent is mixed and stirred at room temperature, and then an epoxy group-containing trialkoxysilane and/or a hydrolysis condensate thereof, a metal compound particle sol or a powder are added, and the mixture is diluted with an organic solvent.

Ii) mixing water, an epoxy group-containing trialkoxy decane and/or its hydrolysis condensate, polyamines, and optionally an organic solvent at room temperature, stirring, and then adding an organic acid or perfluorination The alcohol, the metal compound particle sol or the powder is diluted with an organic solvent.

Iii) mixing and stirring water, an epoxy group-containing trialkoxy decane and/or a hydrolysis condensate thereof, a polyamine, an organic acid or a perfluorinated alcohol, and optionally an organic solvent at room temperature. Then, a metal compound particle sol or powder is added and diluted with an organic solvent.

The stirring temperature is not particularly limited, and is preferably from room temperature to the boiling point temperature of the solvent to be used, and is more preferably carried out at room temperature. In this case, the room temperature is the external atmospheric temperature at the place where the stirring is performed, and is preferably in the range of 15 to 35 °C.

(Use of the composition of the present invention)

The decane-based coating composition of the present invention can be coated with the above-described decane-based coating composition on the surface of the substrate by any known coating method such as brushing, spraying, dipping, spin coating, bar coating, or gravure printing. And thereby forming a film. Drying can be carried out by drying and/or heating at room temperature. Specifically, it is carried out at 20 ° C to 250 ° C, preferably at 20 ° C to 150 ° C for 10 seconds to 24 hours, preferably 30 seconds to 10 hours.

The film to be obtained is not particularly limited, but is preferably more than 10 nm and 5 μm or less.

The substrate to which the composition of the present invention is treated is not particularly limited as long as it can be treated, and specific examples thereof include iron, stainless steel, copper, aluminum, and other metals, ceramics, cement, glass, polycarbonate resin, and acrylic acid. A resin substrate such as a resin, a polyimide resin, a polyester resin, an epoxy resin, a liquid crystal polymer resin, or a polyether oxime, and the like, and the substrate may be coated with a surface of another coating material. Among these, it is especially preferred to be a resin substrate or a metal base. material.

Further, an organic monomolecular film such as a resin layer such as a liquid-repellent layer or a layer containing a hydrolysis-condensation product of a metal-based surfactant may be laminated on the film formed of the composition of the present invention. Since the composition of the present invention contains metal compound particles, the surface of the film becomes uneven, and the adhesion to the laminated film is improved.

The composition of the present invention can be used, for example, for a heat exchanger, a heat sink for a heat exchanger, a building material, a roof, a window glass, a windshield, various mirrors, a plastic lens, a lens, a tire, a rubber, a magnetic recording medium, a surface of a semiconductor material. Treatment of antennas, towers, electrical communication facilities, road traffic signs, signalling devices, etc.; reduction of frictional resistance of ships and water; prevention of contamination of vehicles and aircraft bodies; various metals Prevention of corrosion of electrodes on the surface of materials or battery materials; treatment of the surface of fishing nets; addition of sealants, refractory waterproof sealants, car waxes, etc. Further, since the resin substrate treated with the composition of the present invention is hardened by its surface, it can also be used as a substitute for the use of glass which has been previously used for a windshield of an automobile.

[Examples]

The examples are described below, but the technical scope of the present invention is not limited to the examples.

[Evaluation method]

(adhesiveness)

According to the grid tape peeling test method described in JIS K-5400 (1999), the film on the substrate was cross-cut into a grid shape of 1 mm × 1 mm, and a peeling test was performed using a transparent adhesive tape.

(surface roughness)

The surface roughness was measured using a scanning white interferometer (VertScan (registered trademark) 2.0, manufactured by Ryoka Systems Co., Ltd.).

Sa represents the arithmetic mean of the absolute values of Z(x, y) in the measurement area. Sq indicates the determination The root mean square of Z(x, y) in the region.

(liquid repellency)

The static contact angle of the film was measured using a contact angle measuring device (Drop Master 700, manufactured by Kyowa Interface Science Co., Ltd.).

[Example 1] ~ [Example 5]

(Preparation of decane-based coating composition)

2.0 g of 3-glycidoxy-n-propyltrimethoxydecane (GPTMS), 0.5 g of diethyltriamine, 0.5 g of benzoic acid, 70 g of water and 28 g of isopropanol were mixed. The mixture was stirred at room temperature for 2 hours to obtain a composition (A-1). Isopropanol-dispersed cerium oxide sol (solid content concentration: 30%, particle size: 70-100 nm, trade name: IPA-ST-ZL, manufactured by Nissan Chemical Industries, Ltd.) was added to 10.0 g of the composition (A-1). g, 0.5 g, 1.0 g, 2.0 g, and 3.0 g, the decane-based coating compositions (B-1) to (B-5) were obtained.

(formation of film)

Next, the prepared decane-based coating compositions (B-1) to (B-5) were formed into a film by bar coating using a PET film (COSMOSHINE (registered trademark) A4300, manufactured by Toyobo Co., Ltd.). The oven was heated and dried at 100 ° C for 10 minutes to obtain a decane-based coating composition-treated film (C-1) to (C-5). The results of measuring the adhesion and surface roughness of (C-1) to (C-5) are shown in Table 1.

(layer of organic monomolecular film)

The film surface of (C-1) to (C-5) was subjected to UV ozone treatment (about 12,000 mJ/cm ² ) for 10 minutes, and further immersed in a self-assembled monomolecular film (SAM) to form a solution (SAMLAY ( In the case of a chemical-based detergent (NS CLEAN (registered trademark) 100, manufactured by JX Nippon Oil & Energy Corporation), ultrasonic cleaning was carried out at 60 ° C for 10 minutes. The oven was dried in an oven to obtain a SAM treated film (C-6) to (C-10). The results obtained by measuring the static contact angles of (C-6) to (C-10) are shown in Table 1.

According to the above results, a fine uneven surface can be formed on the PET film, and a monomolecular film can be laminated on the film. Higher liquid repellency was observed based on the fractal effect produced by the higher surface roughness.

[Embodiment 6] ~ [Example 10]

The decane-based coating composition (B-1) to (B-5) were coated with a Ni substrate to obtain a coating composition-treated Ni substrate (D-1) to (D-5), and a grid tape was obtained. Peel test. The results are shown in Table 2.

According to the above results, it is known that a coating film excellent in adhesion to various substrates can be formed without being limited to a resin or a metal.

Claims (12)

A decane-based coating composition comprising: (A) a hydrolysis condensate of an epoxy group-containing trialkoxy decane, (B) a polyamine, and (C) a pKa of from 2.0 to 6.0 at 25 ° C An organic acid, or an alcohol having a perfluoroalkyl group or a perfluoroalkyl group having 2 to 5 carbon atoms, and (D) a metal compound particle. The decane-based coating composition of claim 1, wherein the z-average particle diameter of the hydrolyzed condensate of the epoxy group-containing trialkoxysilane is determined by a dynamic light scattering method to be in the range of 5 to 50 nm. The decane-based coating composition of claim 1, wherein the polyamine is selected from the group consisting of an alkylene polyamine, a polyalkylene polyamine, a poly(phenylene alkylene)polyamine, and a cycloalkylalkyl group. At least one polyamine of the group consisting of polyamines. The decane-based coating composition of claim 1, which is 1 mol of the epoxy group in the epoxy group-containing trialkoxy decane and/or its hydrolysis condensate, 1/(polyamine 1 molecule) Polyamines are used in the range of 10 times or less of the total number of hydrogen atoms on all nitrogen atoms in the middle of the nitrogen atom and 1/(the total number of hydrogen atoms on all nitrogen atoms in the polyamine 1 molecule). The decane-based coating composition of claim 1, which is an organic acid having a pKa of from 2.0 to 6.0 in a range of from 0.3 to 1.2 mol per mol of the monoamine. The decane-based coating composition of claim 1, wherein the alcohol having 2 to 5 carbon atoms of a perfluoroalkyl group or a perfluoroalkylene group is 30% by mass or more of the entire composition. The decane-based coating composition of claim 1, which further comprises an alcohol having 1 to 5 carbon atoms and water other than the alcohol having 2 to 5 carbon atoms of a perfluoroalkyl group or a perfluoroalkylene group. The decane-based coating composition of claim 1, wherein the metal element of the metal compound particle The element is selected from at least one selected from the group consisting of bismuth, aluminum, titanium, and iron. The decane-based coating composition of claim 1, wherein the metal compound particles are cerium oxide. The decane-based coating composition of claim 1, wherein the metal compound particles have an average primary particle diameter of from 1 to 500 nm. The decane-based coating composition according to claim 1, wherein the metal compound particles are contained in the range of 20 to 83% by mass based on the total solid content of the composition. A film obtained by applying a decane-based coating composition according to any one of claims 1 to 11 to a substrate and drying it at room temperature and/or heating.