TWI503375B - Organic silane-based compositions - Google Patents

Description

Organic decane-based composition

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

The present application claims priority to Japanese Patent Application No. 2013-013845, filed on Jan. 29, 2013, and the Japanese Patent Application No. 2013-104509, filed on May In this article.

A transparent plastic molded body such as polycarbonate exhibits advantages such as light weight, easy processability, and impact resistance, and is widely used as a substitute for inorganic glass products, but has disadvantages such as being easily corroded by a solvent and being difficult to be surface-modified. Therefore, compared with inorganic glass, the industry has been trying to improve these properties since the past.

For example, it is known that a glycidyloxytrimethoxydecane is hydrolyzed in an alcohol using nitric acid water, and further, a di-ethyltriamine is added to further react and coat, thereby forming an equivalent on a polycarbonate plate. Hard coating with a pencil hardness of 2 H. (Non-Patent Document 1)

[Previous Technical Literature] [Non-patent literature]

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

However, it takes 24 hours for the above coating composition to be hydrolyzed after coating. The hardening also requires 15 hours of workability, and there is also a problem in its storage stability as described below.

The present invention has been made in view of the above circumstances, and an object of the invention is to provide a method for producing a hydrolysis condensate of a trialkoxysilane which is a raw material of the composition A, and an improved product of the composition A which is excellent in long-term storage stability. The composition A can be applied to a wide range of substrates including plastics, can be surface-modified like glass, can be produced in a short time, and can be hardened in a short time to obtain a coating film having sufficient hardness.

The inventors of the present invention have diligently studied to solve the above problems, and as a result, have found that only the epoxy group-containing trialkoxy decane is mixed with a specific polyamine or imidazole in water for a short time to obtain the trialkoxy decane. The hydrolysis condensate and the composition containing the hydrolysis condensate of the trialkoxysilane can be obtained by coating a film having a sufficient hardness after a coating time is also short. Further, it has been found that a combination of an organic acid having a specific pKa or an alcohol having a perfluoroalkyl group or the like is further mixed in a composition containing a hydrolyzed condensate containing an epoxy group and a polyamine. The storage stability of the material is also excellent, thereby completing the present invention.

That is, the present invention relates to the following: (1) A method for producing an epoxy group-containing trialkoxydecane hydrolyzed condensate, which comprises an epoxy group-containing trialkoxy decane and/or a hydrolysis condensate thereof and water And a polyamine or an imidazole having two or more amine groups or imine groups in which one or more hydrogen atoms are bonded in one molecule, and mixing and stirring; (2) an epoxy group-containing trioxane as in (1) a method for producing a oxoxane hydrolysis condensate, which is mixed and stirred at room temperature; (3) a method for producing an epoxy group-containing trialkoxy decane hydrolyzed condensate according to (1), wherein the polyamine is a poly (4) A method for producing an epoxy group-containing trialkoxy decane hydrolyzed condensate, (4), wherein The epoxy group-containing trialkoxy decane is a glycidoxyalkyltrialkoxy decane; (5) The method for producing an epoxy group-containing trialkoxy decane hydrolyzed condensate according to (1), wherein Epoxy trialkoxy decane and/or its hydrolysis condensate 1 mol, using water in a range of 0.5 mol or more; and (6) epoxy containing according to any one of (1) to (5) A method for producing a hydrazinyl decane hydrolyzed condensate, which is mixed with an acid and stirred.

Further, the present invention relates to the following: (7) A composition comprising: (A) a hydrolyzed condensate containing an epoxytrial trialkoxysilane, (B) a polyamine, and (C-1) a positive (8) A composition comprising: (A) a hydrolysis condensate containing an epoxytrial trialkoxysilane, (B) a polyamine, and (C-2) a pKa of 2.0 at 25 ° C An organic acid in the range of ~6.0 or an alcohol having a carbon number of 2 to 5 having a perfluoroalkyl group and/or a perfluoroalkyl group; (9) a composition according to (8), wherein the epoxy group is alkoxylated The z-average particle diameter of the hydrolyzed condensate of the decane which is measured by a dynamic light scattering method is in the range of 5 to 50 nm; (10) The composition according to (8), wherein the polyamine is selected from the group consisting of alkylene group At least one polyamine of the group consisting of an amine, a polyalkylene polyamine, a poly(phenylene alkylene) polyamine, and a cycloalkylalkyl polyamine; (11) a combination of (8) And all of the hydrogen atoms on the entire nitrogen atom of 1/(polyamine 1 molecule) with respect to the epoxy group 1 molar in the epoxy group-containing trialkoxy decane and/or its hydrolysis condensate Number 1) above the mole and 1/(the number of all hydrogen atoms on all nitrogen atoms in the polyamine 1 molecule) Polyamines are used in the range of 0 times moles or less; (12) The composition of (8), which is 0.3 to 1.2 moles relative to the polyamines 1 mole. An organic acid having a pKa in the range of 2.0 to 6.0 is used in the range; (13) a composition according to (8), wherein the alcohol having a perfluoroalkyl group and/or a perfluoroalkyl group having 2 to 5 carbon atoms is a combination The composition of (8), which further contains a carbon number other than the alcohol having a carbon number of 2 to 5 having a perfluoroalkyl group and/or a perfluoroalkyl group. And a (15) film obtained by applying the composition according to any one of (8) to (14) to a substrate and drying it at room temperature and/or heating.

According to the production method of the present invention, the hydrolysis-condensation product containing the epoxy-containing trialkoxy-decane can be produced in a short time, and therefore, the composition containing the hydrolysis-condensation product can be produced in a short time, and further, the combination of the present invention The material can be formed into a coating film excellent in hardness, adhesion, and appearance on a substrate such as plastic by heating for a short period of time, and further imparts insulation and corrosion resistance. Further, a decane-based water repellent or a monomolecular film-forming solution or the like can be treated on the obtained film to impart a modification to the surface of the substrate such as a function of imparting solvent resistance or water repellency.

Moreover, the composition of the present invention has the same function as the composition containing the hydrolysis-condensation product obtained by the method described in Non-Patent Document 1, and a significant improvement in storage stability can be seen.

Fig. 1 is a graph showing the element concentration in the depth direction of a film by X-ray photoelectron spectroscopy (ESCA) of the PC resin substrate (B-1) treated with the composition (A-1) obtained in Example 1.

Fig. 2 is a graph showing the temporal change of the z-average particle diameter of the solid content in the composition using various solvents obtained in Example 5.

Fig. 3 is a graph showing the temporal change of the z-average particle diameter of the solid content in the composition using various solvents obtained in Example 7.

Figure 4 is a graph showing the solid matter in the composition obtained in Example 8 using various solvents. A graph of the change in z-average particle size over time.

Fig. 5 is a graph showing the element concentration in the depth direction of the film by X-ray photoelectron spectroscopy (ESCA) of the PC resin substrate (B-1) treated with the composition (A-1) obtained in Example 9.

Fig. 6 is a graph showing changes with time in the z-average particle diameter of the solid content in the composition in which the content of benzoic acid obtained in Example 10 is different.

Fig. 7 is a graph showing the temporal change of the z-average particle diameter of the solid content in the composition obtained by using various organic acids obtained in Example 11.

(1) Process for producing an epoxy group-containing trialkoxy decane hydrolyzed condensate or a method for producing a composition containing the same

The method for producing an epoxy group-containing trialkoxy decane hydrolyzed condensate of the present invention comprises mixing and stirring an epoxy group-containing trialkoxy decane and/or a hydrolysis condensate thereof with water, a polyamine or an imidazole. By.

The prior production method described in Non-Patent Document 1 is a method of hydrolyzing and condensing an epoxy group-containing trialkoxysilane with an alcohol having 1 to 5 carbon atoms, water, and an acid such as an inorganic acid or an organic acid, and a polyamine. Or an imidazole is usually added afterwards to prepare a composition, but in this method, the step of hydrolytic condensation is carried out for a long period of time, and in the case where the obtained hydrolyzate-containing composition is hardened, The coating film is provided with sufficient hardness, and also requires a long time and high temperature heating, and lacks practicality. The process of the present invention produces a composition which overcomes the aforementioned disadvantages by preparing a hydrolysis condensate of the trialkoxysilane in the presence of a polyamine or an imidazole.

Further, the hydrolysis-condensation product containing an epoxy group-containing trialkoxysilane obtained by the production method of the present invention is a polymer or oligomer obtained by condensing an epoxy group-containing trialkoxysilane. When the raw material is already a hydrolyzed condensate, the product is a hydrolyzed condensate which is further hydrolyzed and condensed.

(Epoxy-containing trialkoxy decane as a raw material and/or its hydrolysis condensate)

The epoxy group-containing trialkoxy decane to be used in the method of the present invention is not particularly limited as long as it is an epoxy group-containing trialkoxy decane other than the functional group moiety lost by hydrolysis or the like, and for example, it can be exemplified. A compound represented by the following formula (I).

R-Si(OR ₁ ) ₃ ...(I)

(wherein R represents a hydrocarbon group having an epoxy group or a glycidoxy group, and R ₁ represents an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms)

In R, the epoxy group or the glycidoxy group may be one or more, preferably one to three, and may contain both an epoxy group and a glycidoxy group.

Specific 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, and an alkynyl group. The aryl group, the aralkyl group, the aralkenyl group or the like is preferably in the range of 1 to 30, more preferably in the range of 1 to 10, as the carbon number.

Specific examples of the "alkyl group" include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, and neopentyl group. Base, n-hexyl, isohexyl, n-heptyl, n-octyl, n-decyl, isodecyl, n-decyl, etc.; lauryl, tridecyl, myristyl, pentadecyl, palmitoyl, ten Heptadecyl, stearyl 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.

Specific examples of the "cycloalkylalkyl group" include a cyclopropylmethyl group, a cyclopropylethyl group, a cyclopropylpropyl group, a cyclobutylmethyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, and a ring. Heptylmethyl, cyclooctylmethyl, etc., preferably a cycloalkyl group having 3 to 10 carbon atoms 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-butene- 2-yl, 1-penten-1-yl, 4-penten-1-yl, 1-penten-2-yl, 4-penten-2-yl, 3-methyl-1-butene- 1-yl, 1-hexen-1-yl, 5-hexen-1-yl, 1-hepten-1-yl, 6-hepten-1-yl, 1-octene-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, 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-butyne-1- , 1-pentyn-1-yl, 4-pentyn-1-yl, 1-hexyn-1-yl, 5-hexyn-1-yl, 1-heptyn-1-yl, 1-octyl Alkyn-1-yl, 7-octyn-1-yl and the like.

"Aryl" means a monocyclic or polycyclic aryl group which, in the case of a polycyclic aryl group, contains a partially saturated group in addition to the fully unsaturated group. Specifically, a phenyl group, a naphthyl group, an anthracenyl group, a fluorenyl group, a dihydroindenyl group, a tetrahydronaphthyl group, etc. are illustrated.

Specific examples of the "aralkyl group" include a benzyl group, a phenethyl group, a 3-phenyl-n-propyl group, a 4-phenyl-n-butyl group, a 5-phenyl-n-pentyl group, and a 8-phenyl group. Phenyl-n-octyl or the like 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 in which an aryl group and an alkenyl group are bonded, and specifically, a styryl group, a 3-phenyl-1-propen-1-yl group, and a 3-phenyl-2-propene group are exemplified. -1-yl, 4-phenyl-1-buten-1-yl, 4-phenyl-3-buten-1-yl, 5-phenyl-1-penten-1-yl, 5-benzene Alkyl-4-penten-1-yl, 8-phenyl-1-octene-1-yl, 8-phenyl-7-octene-1-yl, naphthylvinyl, etc., preferably carbon number A group of 6 to 10 aryl groups bonded to an alkenyl group having 2 to 10 carbon atoms.

Further, the above-mentioned "hydrocarbon group" may have a substituent other than the epoxy group and the glycidoxy group. Specific examples of such a substituent include a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, and Methyl) acryloxy group or the like.

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

Specific examples of the alkoxy group include a methoxy group, an ethoxy group, and a n-propoxy group. Base, isopropoxy, n-butoxy, isobutoxy, tert-butoxy and the like.

Specific examples of the alkyl group and the alkenyl group which are the same as the alkyl group and the alkenyl group in the above R can be exemplified.

The "alkyl group having 1 to 10 carbon atoms" of the "unsubstituted or substituted alkyl group having 1 to 10 carbon atoms" of R ₁ may be the same as the alkyl group in the above R.

Specific examples of the substituent having a "substituent group" include a halogen atom, an alkoxy group, and a (meth) acryloxy group. Specific examples of the halogen atom and the alkoxy group are the same as those exemplified as the halogen atom and the alkoxy group exemplified as the substituent other than the epoxy group and the glycidoxy group in the above R.

Specific examples of the epoxy group-containing trialkoxysilane or the hydrolysis-condensation product thereof include the following compounds, but are not limited thereto. Further, these may be used alone or in combination of two or more.

[Chemical 1]

Among them, a glycidoxyalkyltrialkalkoxydecane or a glycidoxyalkenyl alkoxydecane is preferable, and specifically, a compound represented by the following formula can be exemplified.

[Chemical 2]

These may be used alone or in combination of two or more.

(Alkoxy decane other than epoxy-containing trialkoxy decane)

In the production method of the present invention, a tetraalkoxy decane or a trialkoxy decane other than the epoxy-containing trialkoxy decane may be appropriately added to the epoxy group-containing trialkoxy decane, or Used as a dialkoxy decane. Specific examples of such alkoxydecanes include tetramethoxydecane, tetraethoxydecane, tetra(n-propoxy)decane, tetra(isopropoxy)decane, and tetra(n-butyl). a tetraalkoxynonane such as oxy)decane; methyltrimethoxydecane, methyltriethoxydecane, ethyltrimethoxydecane, ethyltriethoxydecane, n-propyltrimethoxydecane, N-propyl triethoxy decane, isopropyl trimethoxy decane, isopropyl triethoxy decane, n-butyl trimethoxy decane, n-butyl triethoxy decane, n-pentyl trimethoxy decane , n-hexyltrimethoxydecane, n-heptyltrimethoxydecane, n-octyltrimethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane,allyltrimethoxydecane,cyclohexyltrimethyl Oxydecane, cyclohexyltriethoxydecane, phenyltrimethoxydecane, phenyltriethoxydecane, 3-chloropropane Trimethoxy decane, 3-chloropropyltriethoxy decane, 3,3,3-trifluoropropyltrimethoxydecane, 3,3,3-trifluoropropyltriethoxydecane, nonafluoro Hexyltrimethoxydecane, tridecafluorooctyltrimethoxydecane, heptadecafluorodecyltrimethoxydecane,trifluoropropyltriethoxydecane,tridecafluorooctyltriethoxydecane,heptadecafluoro Mercapto triethoxy decane, 3-aminopropyl trimethoxy decane, 3-aminopropyl triethoxy decane, 2-hydroxyethyl trimethoxy decane, 2-hydroxyethyl triethoxy Decane, 2-hydroxypropyltrimethoxydecane, 2-hydroxypropyltriethoxydecane, 3-hydroxypropyltrimethoxydecane, 3-hydroxypropyltriethoxydecane, 3-mercaptopropyltrimethyl Oxydecane, 3-mercaptopropyltriethoxydecane, 3-isocyanatepropyltrimethoxydecane, 3-isocyanatepropyltriethoxydecane, 3-(methyl)propenyloxypropyl Trimethoxydecane, 3-(methyl)methacryloxypropyltriethoxydecane, 3-(methyl)propenyloxypropyltri-n-propoxydecane, 3-(methyl) Propylene methoxypropyl triisopropoxy decane a trialkoxy decane such as 3-ureidopropyltrimethoxydecane or 3-ureidopropyltriethoxydecane; dimethyldimethoxydecane, dimethyldiethoxydecane, and diethyl Dimethoxy decane, diethyl diethoxy decane, di-n-propyl dimethoxy decane, di-n-propyl diethoxy decane, diisopropyl dimethoxy decane, diisopropyl Diethoxydecane, di-n-butyldimethoxydecane, di-n-butyldiethoxydecane, di-n-pentyldimethoxydecane, di-n-pentyldiethoxydecane, di-n-hexyl Methoxydecane, di-n-hexyldiethoxydecane, di-n-heptyldimethoxydecane, di-n-heptyldiethoxydecane, di-n-octyldimethoxydecane, di-n-octyldiethyl Oxy decane, di-n-cyclohexyl dimethoxy decane, di-n-cyclohexyl diethoxy decane, diphenyl dimethoxy decane, diphenyl diethoxy decane, 3-(methyl) propylene oxime As the dialkoxy decane such as oxypropylmethyldimethoxydecane or heptadecafluoromethyldimethoxydecane, the partially hydrolyzed condensate may be used in the same manner. Specific examples of such a partially hydrolyzed condensate include "MKC Silicate MS51", "MKC Silicate MS56", "MKC Silicate MS57", and "MKC Silicate MS60" manufactured by Mitsubishi Chemical Corporation. Condensation of oxydecane "Ethyl Silicate 40" manufactured by Colcoat, "Ethyl Silicate 48" (all condensates of tetraethoxy decane), etc., and as a tetraalkyloxydecane having a different alkyl group. Specific examples of the condensate include: "MKC Silicate MS56B15", "MKC Silicate MS56B30", "MKC Silicate MS58B15", "MKC Silicate MS56I30", and "MKC Silicate MS56F20" manufactured by Mitsubishi Chemical Corporation; manufactured by Colcoat The product name is "EMS-485".

(water)

The amount of water used in the method of the present invention is not particularly limited as long as it is sufficient to hydrolyze or condense the epoxy group-containing trialkoxysilane and/or its hydrolysis-condensation product to some extent. Specifically, it is represented by the case where the epoxy group-containing trialkoxy decane and/or its hydrolysis condensate is used, wherein the epoxy group-containing trialkoxy decane and its hydrolysis condensate are used in combination In the case of a combination of alkoxy decanes other than the epoxy-containing trialkoxy decane, the total of the two is also 1 mol, preferably 0.5 mol or more. It is preferably 1.0 mol or more, 2.0 mol or more, 5.0 mol or more, or 10 mol or more.

(polyamines)

The polyamine to be used in the present invention is not particularly limited as long as it has two or more amine groups or imine groups having one or more hydrogen atoms bonded thereto, and specifically, it can be exemplified: Amine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylidene triamine, triethylidenetetramine, tetraethylamamine, dipropyltriamine, Methylaminopropylamine, ethylaminopropylamine, N,N'-dimethylhexamethylenediamine, bis(2-methylaminoethyl)ether, menthanediamine, iso Vorketone diamine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro(5,5)undecane adduct, bis(4-amino ring Hexyl)methane, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenylanthracene, m-xylylenediamine, etc., which may be used alone or Mix two or more types. Among them, preferred are polyalkylene polyamines, and specific examples thereof include di-ethyltriamine and tri-ethylidene Amine, tetraethylamamine, dipropyltriamine, and the like.

The amount of the polyamine to be used is not particularly limited, and it is preferred to use 1/(polyamine) relative to the epoxy group containing 1 -(epoxy group) in the epoxy group-containing trialkoxy decane and/or its hydrolysis condensate. 1.2 times to 10 times the number of all hydrogen atoms on all nitrogen atoms in one molecule, more than moles, preferably 1/(the total number of hydrogen atoms on all nitrogen atoms in the polyamine 1 molecule) The range of the ear, 1.5 times to 5 times the molar, or 1.8 times to 2.5 times the range of the molar. 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 higher than 1 When 10% of the total number of hydrogen atoms on all nitrogen atoms in the polyamine-based one molecule is 10 moles, there is a case where a polyamine is left and a film having sufficient hardness cannot be obtained.

(imidazole)

Further, as the imidazole to be used in the present invention, specifically, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-n-propylimidazole, 2-111 can be exemplified. Alkyl-1H-imidazole, 2-heptadecyl-1H-imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-1H-imidazole, 4-methyl Benzyl-2-phenyl-1H-imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4 -methylimidazolium trimellitate, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2 ,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-all three 2,4-Diamino-6-(2'-undecylimidazolyl-)-ethyl-all three 2,4-Diamino-6-[2'-ethyl-4-imidazolyl-(1')]-ethyl-all three 2,4-Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-all three Iso-cyanuric acid adduct, 2-phenylimidazolium isocyanurate adduct, 2-methylimidazolium iso-cyanate adduct, 2-phenyl-4,5-dihydroxymethyl Imidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4,5-di(2-cyanoethoxy)methylimidazole, chlorination 1-dodecyl-2-methyl-3-benzylimidazolium, 1-benzyl-2-phenylimidazolium hydrochloride, 1-benzyl-2-phenylimidazolium trimellitate, etc. These may be used alone or in combination of two or more.

The amount of the imidazole to be used is not particularly limited as long as it is at least the amount of the catalyst, and is preferably in the range of 0.001 to 1.0 mol per mol of the epoxy group contained in the trialkoxysilane to be used. Further preferably, it is in the range of 0.001 to 0.5 mol, or 0.01 to 0.1 mol.

(acid)

In the present invention, it is preferred to carry out this step as needed in the hydrolysis step to further coexist acid.

Specific examples of the acid to be used include an organic acid, an inorganic acid, and the like. More specifically, examples of the organic acid include acetic acid, formic acid, oxalic acid, carbonic acid, phthalic acid, trifluoroacetic acid, and p-toluene. Sulfonic acid, methanesulfonic acid, etc., and the inorganic acid may, for example, be hydrochloric acid, nitric acid, boric acid or fluoroboric acid. Among them, an organic acid having a pKa at 20 ° C of 2.0 to 6.0 is preferably used. Specific examples of such an organic acid include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, caproic acid, isohexanoic acid, chloroacetic acid, fluoroacetic acid, and bromoacetic acid. - chloropropionic acid, 2-bromopropionic acid, 2-hydroxybutyric acid, phenylacetic acid, phenylpropionic acid, 4-phenylbutyric acid, phenoxyacetic acid, cyanoacetic acid, oxalic acid, malonic acid, 2,2-dimethyl Malonic acid, adipic acid, succinic acid, pimelic acid, phthalic acid, glutaric acid, oxalic acid, citric acid, isocitric acid, cyclohexane-1,1-dicarboxylic acid, tartaric acid, O-methoxybenzoic acid, m-methoxybenzoic acid, p-methoxybenzoic acid, benzoic acid, o-chlorobenzoic acid, m-fluorobenzoic acid, 2,3-difluorobenzoic acid, o-nitrobenzoic acid, m-nitrobenzene Formic acid, p-nitrobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, salicylic acid, phthalic acid, isophthalic acid, trans-cinnamic acid, 2-furancarboxylic acid, glyoxylic acid, ethanol Acid, crotonic acid, lactic acid, 2-hydroxy-2-methylpropionic acid, pyruvic acid, mandelic acid, malic acid, acetopropionic acid, 2,6-pyridinedicarboxylic acid, nicotinic acid, and the like. The amount of the acid to be used is not particularly limited, and is preferably in the range of 0.3 to 1.2 mol, and more preferably 0.5 to 1.0 mol, or 0.6 to 1 mol of the polyamine or imidazole to be used. 0.9 range of moles.

In the case of less than 0.3 mol, there is a case where the storage stability of the composition is lowered, When it is higher than 1.2 m, there is a case where a coating film of sufficient hardness cannot be formed.

(solvent)

In the production method of the present invention, an organic solvent may be used as needed. The solvent is not particularly limited as long as it can maintain the uniformity and stability of the solution to some extent. Specifically, it can be exemplified: Methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, third butanol, n-pentanol, isoamyl alcohol, second pentanol, third pentanol, neopentyl Alcohol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-ethoxycarbonyl alcohol, etc.; tetrahydrofuran, ethylene glycol An ether such as dimethyl ether, propylene glycol dimethyl ether or tetrahydropyran; a ketone such as acetone, methyl ethyl ketone or acetamidine acetone; an ester such as methyl acetate or ethylene glycol monoacetate; and formamide And N,N-dimethylformamide, N,N-dimethylacetamide, pyrrolidone, N-methylpyrrolidone and the like, wherein the carbon number is preferably from 1 to 5. Alcohol. These may be used alone or in combination of two or more. The alcohol having 1 to 5 carbon atoms may have a substituent such as a halogen atom on a suitable carbon. Specific examples of the alcohol include perfluoroethanol and perfluoropentanol.

These may be used alone or in combination of two or more. In the case of considering the working environment and the residue on the coating film, it is preferably an alcohol having 3 or less carbon atoms, and particularly preferably isopropyl alcohol or n-propanol. In the case where the storage stability of the hydrolysis condensate is considered, n-pentanol is preferably used.

It is preferred to use water as the other solvent. In this case, the organic solvent to be used is preferably an organic solvent dissolved in water. Further, the ratio of water to organic solvent is preferably an amount ratio which becomes a uniform solution after using the respective amounts required. When a solvent having a carbon number of 3 or less or the like is relatively easily dissolved 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 preferably. It is in the range of 50/50~90/10, 60/40~80/20, or 65/35~75/25.

Further, when an organic solvent such as an alcohol having 4 or more carbons is relatively difficult to dissolve in water, since the solubility of water in an organic solvent is low, the amount of water used is preferably It is used in an amount greater than the amount required for the hydrolysis of the trialkoxysilane and the solution is in a uniform range.

The amount of the solvent to be used is not particularly limited, and the appearance of the coating film containing the composition containing the hydrolysis-condensation product produced by the production method of the present invention, the coatability and hardenability of the composition, and the use of the composition are considered. The nature of the coating film, the storage stability of the composition or the hydrolysis condensate, and the like are preferably such that the concentration of the solid content in the reaction liquid is in the range of 0.5 to 50% by mass, 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.

(manufacturing conditions)

In the present invention, the epoxy group-containing trialkoxy decane and/or its hydrolysis-condensation product and water and one or more amine groups or imine groups having one or more hydrogen atoms bonded in one molecule are aggregated. The amine or the imidazole, the acid as needed, and the organic solvent as needed are mixed and stirred to produce a hydrolysis condensate containing an epoxytrial trialkoxysilane. However, the mixing order and the stirring speed are not particularly limited. , can be set in any order or any speed. The temperature at the time of mixing and stirring is not particularly limited, but 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 temperature of the outside air at the place where the mixing is performed, and is preferably a temperature in the range of 15 to 35 °C.

Preferably, the epoxy group-containing trialkoxysilane is coexistent with water and a polyamine or imidazole having two or more amine groups or imine groups having one or more hydrogen atoms bonded in one molecule. In the state, it is stirred at room temperature for 2 hours to 3 hours.

After the hydrolysis, it is diluted with an organic solvent or water as needed.

The concentration of the solid content of the composition containing the hydrolysis-condensation product obtained by the production method of the present invention is not particularly limited, but is preferably used in the range of 0.5 to 50% by mass, 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 3.0% by mass. When it is 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, stability of the composition, coating film A situation in which transparency, appearance, or coatability cause problems. The concentration of the solid component can be initially adjusted to a specific solid component concentration, and can be adjusted to a specific solid component concentration by preparing the composition in a relatively concentrated state.

(2) Composition

The composition of the present invention comprises a composition containing the hydrolysis-condensation products (A), (B) and (C) of the epoxy group-containing trialkoxysilane obtained by the production method of the present invention or other methods.

(A) Hydrolyzed condensate containing epoxy alkoxy oxane

(B) polyamines, and

(C)

(C-1) n-pentanol, or

(C-2) an organic acid having a pKa in the range of 2.0 to 6.0 at 20 ° C or an alcohol having a perfluoroalkyl group and/or a perfluoroalkyl group having 2 to 5 carbon atoms

Hereinafter, the composition containing the components (A), (B), and (C) will be described in detail.

(hydrolysis condensate containing epoxy alkoxy oxane)

The concentration of the solid content component of the hydrolysis-condensation product containing the epoxy-oxytrialkoxide-containing decane in the composition is not particularly limited, but is preferably in the range of 1 to 50% by mass, more preferably 1 to 10% by mass, or 1.5 to 3 mass% range.

The concentration of the solid component can be initially adjusted to a specific solid component concentration, and can be adjusted to a specific solid component concentration by preparing the composition in a relatively concentrated state.

The method for producing the hydrolysis-condensation product of the epoxy group-containing trialkoxy decane of the component (A) is preferably exemplified by the production method of the present invention described in the above (1), and specifically, it can be exemplified. The following method and the like: adding water, optionally a stanol condensation catalyst, to the epoxy group-containing trialkoxy decane and/or its hydrolysis condensate, and reacting at 5 to 100 ° C, preferably 20 to 60 ° C 1 minute to 10 days, preferably 30 minutes to 24 hours.

Adding water to the epoxy-containing trialkoxy decane and/or its hydrolysis condensate, if necessary In the method of the decyl alcohol condensation catalyst, the epoxy group-containing trialkoxy decane and/or its hydrolysis condensate as a raw material can be used in the same manner as those shown in the item of the production method of the present invention. Further, in the same manner as described in the section of the production method of the present invention, a tetraalkoxy decane, a trialkoxy decane or a dioxane other than the epoxy group-containing alkoxy oxane and/or a hydrolysis-condensation product thereof may be used. Oxydecane, or a partially hydrolyzed condensate thereof, is produced by coexistence.

The amount of water is not particularly limited as long as it is sufficient to hydrolyze or condense the epoxy group-containing trialkoxysilane and/or its hydrolysis-condensation product to some extent, and specifically, it is used in comparison with The trialkoxysilane and/or its hydrolysis condensate 1 mole is preferably 0.5 mole or more, more preferably 1.0 mole or more, 2.0 mole or more, 5.0 mole or more, or 10 mole or more.

The amount of the stanol-condensation catalyst to be used is not particularly limited, and the allyl group containing the epoxy group-containing trialkoxy decane and/or its hydrolysis condensate as a raw material in terms of uncondensed The amount 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 catalyst / the alkylene group).

The sterol condensation catalyst is not particularly limited as long as it hydrolyzes the alkoxy group containing the epoxy group-containing trialkoxy decane and condenses the decyl alcohol to form a decane bond. Specifically, it can be exemplified. : Dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexanoate, dibutyltin dioctoate, dibutyltin dimethyl maleate, dibutyltin diethyldibutyl maleate, dibutyl cis-butane Dibutyltin olefinate, dibutyltin diisooctyl maleate, dibutyltin di-tridecylmaleate, dibutyltin dibenzyl maleate, dibutyltin maleate, two Dicarboxylic acid such as dioctyltin acetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethyl succinate, dioctyltin diisooctyl maleate Dialkyltin acid; dialkylalkanol tin such as dibutyl dimethoxide, dibutyltin diphenyl oxide; dioxane such as dibutyltin diacetate or dibutyltin diacetate Base tin chelate; dialkyltin oxide and isophthalic acid such as dibutyltin oxide or dioctyltin oxide a reaction product of an ester compound such as dioctyl formate, diisononyl phthalate or methyl maleate; a tin compound obtained by reacting a dialkyltin oxide, a carboxylic acid, and an alcohol compound, and a double (three) a reaction of a dialkyltin oxide such as dibutyltin ethoxylate or dioctyltin bis(triethoxytin) with a phthalate compound, and an oxygen-containing derivative of the dialkyltin compound a tetravalent tin compound such as a stannoxane compound; a divalent tin compound such as tin octylate, tin naphthenate, tin stearate or tin versatate; or a reaction product and a mixture of an amine compound such as laurylamine; a monobutyltin compound such as monobutyltin trioctoate or monobutyltin trioxide or a monoalkyltin such as a monooctyltin compound; tetrabutyl titanate or titanium; a titanate such as tetrapropyl acrylate, tetrakis(2-ethylhexyl) titanate, isopropoxy bis(acetic acid ethyl acetate) titanium; tris(acetonitrile)aluminum, tris(acetonitrile) Ethyl acetate, aluminum, diisopropoxy (acetic acid ethyl acetate), aluminum, and other organoaluminum compounds; cerium carboxylate, iron carboxylate, carboxylic acid Carboxylic acid carboxylate, vanadium carboxylate, zirconium carboxylate, calcium carboxylate, potassium carboxylate, cerium carboxylate, manganese carboxylic acid, cerium carboxylate, nickel carboxylate, cobalt carboxylate, zinc carboxylate, aluminum carboxylate, etc. a metal salt of an acid (2-ethylhexanoic acid, neodecanoic acid, Versatic acid, oleic acid, naphthenic acid, etc.) or a reaction product and a mixture thereof with an amine compound such as the following laurylamine ; tetrakis(acetonitrile)zirconium, tributoxide (acetonitrile) zirconium, dibutoxy (diacetone) zirconium, acetamidine acetone bis(acetonitrile ethyl acetate) zirconium, four (acetylacetone) chelating compounds such as titanium; methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, octylamine, 2-ethylhexyl An aliphatic primary amine such as an amine, a mercaptoamine, a mercaptoamine, laurylamine, pentadecylamine, cetylamine, stearylamine or cyclohexylamine, dimethylamine, diethylamine, Dipropylamine, diisopropylamine, dibutylamine, dipentylamine, dioctylamine, di(2-ethylhexyl)amine, didecylamine, dilaurylamine, di-cetamine Base amine, distearylamine, methyl stearylamine, ethyl stearin An aliphatic secondary amine such as an amine or a butyl stearylamine; an aliphatic tertiary amine such as a triamylamine, a trihexylamine or a trioctylamine; an aliphatic unsaturated such as a triallylamine or an oleylamine; Amines, aromatic amines such as lauryl aniline, stearyl aniline, triphenylamine, and monoethanolamine, diethanolamine, triethanolamine, di-ethyltriamine, and tri-ethyltetramine as other amines , oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, ethylenediamine, hexamethylenediamine, triethylenediamine, anthracene, diphenylanthracene, 2,4,6-tris(dimethylaminomethyl)phenol, Porphyrin, N-methyl An amine compound such as a porphyrin, 2-ethyl-4-methylimidazole or 1,8-diazabicyclo(5,4,0)undecene (DBU), or a salt of the amine compound and a carboxylic acid or the like a reactant and mixture of an amine compound such as a reaction or mixture of laurylamine and tin octylate with an organotin compound; a low molecular weight polyamine resin obtained from an excess of a polyamine and a polybasic acid; an excess of a polyamine and Reaction product of epoxy compound; γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, γ-aminopropyltriisopropoxydecane, γ-aminopropylmethyl Dimethoxy decane, γ-aminopropylmethyldiethoxy decane, N-(β-aminoethyl)aminopropyltrimethoxydecane, N-(β-aminoethyl) Aminopropylmethyldimethoxydecane, N-(β-aminoethyl)aminopropyltriethoxydecane, N-(β-aminoethyl)aminopropylmethyldiethyl Oxydecane, N-(β-aminoethyl)aminopropyltriisopropoxydecane, γ-ureidopropyltrimethoxydecane, N-phenyl-γ-aminopropyltrimethoxy Decane, N-benzyl-γ-aminopropyltrimethoxydecane, N-vinylbenzyl-γ-amine Silane triethoxysilane and the like. Further, an amine-modified oxime alkyl polymer, a decylated amine-based polymer, an unsaturated amino decane complex, and a phenylamino long-chain alkyl decane which are derivatives which are modified as such may be exemplified. a stanol condensation catalyst such as an amino group-containing decane coupling agent such as an amine group, and a fatty acid such as a branched alkane carboxylic acid or an organic acid phosphate compound, and an alkaline contact. A well-known stanol condensation catalyst or the like.

Specific examples of the organic acid phosphate compound as the acid catalyst include (CH ₃ O) ₂ P(=O)(OH), (CH ₃ O)P(=O)(OH) ₂ , (C) ₂ H ₅ O) ₂ P(=O)(OH), (C ₂ H ₅ O)P(=O)(OH) ₂ , (C ₃ H ₇ O) ₂ P(=O)(OH), ( C ₃ H ₇ O)P(=O)(OH) ₂ , (C ₄ H ₉ O) ₂ P(=O)(OH), (C ₄ H ₉ O)P(=O)(OH) ₂ , (C ₈ H ₁₇ O) ₂ P(=O)(OH), (C ₈ H ₁₇ O)P(=O)(OH) ₂ , (C ₁₀ H ₂₁ O)2P(=O)(OH), (C ₁₀ H ₂₁ O)P(=O)(OH) ₂ , (C ₁₃ H ₂₇ O) ₂ P(=O)(OH), (C ₁₃ H ₂₇ O)P(=O)(OH) ₂ , (C ₁₆ H ₃₃ O) ₂ P(=O)(OH), (C ₁₆ H ₃₃ O)P(=O)(OH) ₂ , (HOC ₆ H ₁₂ O) ₂ P(=O)(OH ), (HOC ₆ H ₁₂ O)P(=O)(OH) ₂ , (HOC ₈ H ₁₆ O) ₂ P(=O)(OH), (HOC ₈ H ₁₆ O)P(=O)(OH ₂ , [(HOCH ₂ CH(OH)O] ₂ P(=O)(OH), [(HOCH ₂ CH(OH)O]P(=O)(OH) ₂ , [(HOCH ₂ CH(OH C ₂ H ₄ O] ₂ P(=O)(OH), [(HOCH ₂ CH(OH)C ₂ H ₄ O]P(=O)(OH) ₂ or the like.

Further, a photoacid generator can also be used as the stanol condensation catalyst. As the photoacid generator, specifically, tetrafluoroborate (BF ₄ ^- ), hexafluorophosphate (PF ₆ ^- ), or fluoroalkyl phosphate (PFm(RF) _6-m ^- (RF) can be used. Alkyl fluoride, m represents an integer from 0 to 5), hexafluoroantimonate (SbF ₆ ^- ), hexafluoroarsenate (AsF ₆ ^- ), hexachloroantimonate (SbCl ₆ ^- ), tetraphenylborate , tetrakis(trifluoromethylphenyl)borate, tetrakis(pentafluoromethylphenyl)borate, perchlorate ion (ClO ₄ ^- ), trifluoromethanesulfonate ion (CF ₃ SO ₃ ^- ), fluorine An anthracene or phosphonium salt having an anion such as a sulfonate ion (FSO ₃ ^- ), a tosylate ion, a trinitrobenzenesulfonate anion or a trinitrotosylate anion.

The stanol condensation catalyst may be used alone or in combination of two or more.

In the composition of the present invention, a polyamine or an imidazole is used as a hardener or a hardening accelerator for an epoxy-containing trialkoxysilane. Therefore, it is preferred to use a polyamine or an imidazole as a decyl alcohol condensation contact. Media. Details of the polyamines and imidazoles are as described in the section of the above-described production method of the present invention.

The z-average particle diameter measured by a dynamic light scattering method for the hydrolysis-condensation product containing an epoxy-containing trialkoxy-decane used in the present invention is based on the viewpoint of the hardness of the film or the uneven coating at the time of coating. In other words, it is preferably in the range of 5 to 50 nm, and more preferably 5 to 30 nm. When it is larger than 50 nm, there is a short service life, there is a problem in storage stability, or a coating spot is formed after coating, and when it is less than 5 nm, the hardness of the coating film obtained from the composition is not Sufficient situation.

(polyamines and other hardeners or hardening accelerators)

Specific polyamines are included in the compositions of the present invention. The polyamines shown in the production method of the above (1) can be exemplified as the polyamines. The amount of use is also as described in the production method of the above (1).

Further, a curing agent or a curing accelerator other than the above may be added as needed.

Specifically, the imidazoles shown in the production method of the above (1); dimethylaminopropylamine, diethylaminopropylamine, trimethylhexamethylenediamine, and pentane are exemplified. Diamine, bis(2-dimethylaminoethyl)ether, pentamethyldiethylideneamine, alkyl-third monoamine, 1,4-diazabicyclo(2,2,2) octyl Alkane (tri-ethylenediamine), N,N,N',N'-tetramethylhexamethylenediamine, N,N,N',N'-tetramethylpropanediamine, N,N , N', N'-tetramethylethylenediamine, N,N-dimethylcyclohexylamine, dimethylaminoethoxyethoxyethanol, dimethylaminohexanol and other aliphatic amines , piperidine, piperazine , menthane diamine, isophorone diamine, methyl Porphyrin, ethyl Porphyrin, N, N', N"-tris(dimethylaminopropyl)hexahydro-all three ,3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro(5,5)undecane adduct, N-aminoethylpipe Trimethylaminoethylpiperine , bis(4-aminocyclohexyl)methane, N,N'-dimethylperazine , 1,8-diazabicyclo(4,5,0) undecene-7 and other alicyclic or heterocyclic amines, benzylmethylamine, dimethylbenzylamine, pyridine, methylpyridine, etc. Amine-based, epoxy compound addition polyamine, methacrylate polyamine, Mannich addition polyamine, thiourea addition polyamine, ketone block polyamine and other modified amines, dicyandiamide, hydrazine An amine compound such as an organic acid hydrazine, a diamine maleimonitrile, an amine sulfimine, a boron trifluoride-piperidine complex, a boron trifluoride-monoethylamine complex, and the like An imidazoline compound such as 2-methylimidazoline or 2-phenylimidazoline; a guanamine compound such as polyamine obtained by condensation of a dimer acid with a polyamine; an aryl group and a thio group of a carboxylic acid; Active carbonyl compounds such as aryl esters; phenol novolacs, cresol novolacs, polyols, polythiols, polysulfides, 2-(dimethylaminomethylphenol), 2,4,6-three (two Phenolic, alcoholic, thiol, and ether systems such as methylaminomethyl)phenol and 2,4,6-tris(dimethylaminomethyl)phenol such as tris-2-ethylhexyl hydrochloride Or a thioether compound; butylated urea, butylated melamine, butylated thiourea a urea-based, thiourea-based or Lewis-acid-based compound such as boron trifluoride; an alkylphosphine such as ethylphosphine or butylphosphine; a primary phosphine such as phenylphosphine; a dialkyl group such as dimethylphosphine or dipropylphosphine; a phosphine, a diphosphine such as diphenylphosphine or a methylphosphine, a phosphorus compound such as a trisphosphine such as trimethylphosphine or triethylphosphine; phthalic anhydride, hexahydrophthalic anhydride, and Tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methyl endomethylenetetrahydrophthalic anhydride, maleic anhydride , tetramethylene maleic anhydride, trimellitic anhydride, chloro-bromic anhydride, pyromellitic dianhydride, dodecenyl succinic anhydride, benzophenone tetracarboxylic dianhydride, ethylene glycol double (dehydration) An acid anhydride compound such as trimellitate), methylcyclohexene tetracarboxylic dianhydride or polysebacic anhydride; aryldiazonium salt, diarylsulfonium salt, triarylsulfonium salt, triphenylstanol - anthracene salt such as aluminum complex, triphenylmethoxy decane-aluminum complex, decyl decyl-aluminum complex, triphenyl decyl alcohol-tris(salicylic acid) aluminum complex Active 矽Compound - complexes of aluminum-based compound and the like.

(organic acid)

The organic acid to be used in the composition of the present invention is not particularly limited as long as it is an organic acid having a pKa in the range of from 2.0 to 6.0, preferably from 3.0 to 5.0, at 25 ° C. Specifically, formic acid is exemplified. , 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, 2-bromopropionic acid, 2-hydroxyl Butyric acid, phenylacetic acid, phenylpropionic acid, 4-phenylbutyric acid, phenoxyacetic acid, cyanoacetic acid, oxalic acid, malonic acid, 2,2-dimethylmalonic acid, adipic acid, succinic acid , pimelic acid, phthalic acid, glutaric acid, oxalic acid, citric acid, isocitric acid, cyclohexane-1,1-dicarboxylic acid, tartaric acid, o-methoxybenzoic acid, m-methoxy Benzoic acid, p-methoxybenzoic acid, benzoic acid, o-chlorobenzoic acid, m-fluorobenzoic acid, 2,3-difluorobenzoic acid, o-nitrobenzoic acid, m-nitrobenzoic acid, p-nitrobenzoic acid, M-aminobenzoic acid, p-aminobenzoic acid, salicylic acid, phthalic acid, isophthalic acid, trans-cinnamic acid, 2-furancarboxylic acid, glyoxylic acid, glycolic acid, crotonic acid, lactic acid, 2-hydroxy -2-methylpropanoic acid, pyruvic acid, mandelic An acid, malic acid, acetopropionic acid, 2,6-pyridinedicarboxylic acid, nicotinic acid or the like, among which an aliphatic monocarboxylic acid or a substituted or unsubstituted benzoic acid can be preferably exemplified.

The amount of the 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, relative to the polyamine 1 mole used. The scope.

In the case of less than 0.3 mol, there is a case where the storage stability of the composition is lowered, and when it is higher than 1.2 mol, there is a case where a coating film having a sufficient hardness cannot be formed.

(alcohols having a perfluoroalkyl group and/or a perfluoroalkyl group having 2 to 5 carbon atoms)

As the alcohol having a perfluoroalkyl group and/or a perfluoroalkylene group having 2 to 5 carbon atoms, which is used in the composition of the present invention, specifically, trifluoromethanol, 2, 2, 2-three can be exemplified. Fluoroethanol, 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, Nonafluorobutanol, 2,2,3,3,4,4,5,5-octafluoro-1-pentanol, and the like.

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

(Organic solvents)

In the composition of the present invention, an organic solvent can be used in order to adjust the concentration of the solid content in the composition. The solvent is not particularly limited as long as it is a solvent capable of maintaining uniformity and stability of the solution. In other words, methanol, ethanol, propanol, isopropanol, n-butanol, second butanol, third butanol, n-pentanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, ethylene Alcohol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether and other alcohols; tetrahydrofuran, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, tetrahydropyran and other ethers; acetone, methyl ethyl ketone, B Ketones such as acetone; esters such as methyl acetate and ethylene glycol monoacetate; formamide, N,N-dimethylformamide, N,N-dimethylacetamide, pyrrole An amide such as ketone or N-methylpyrrolidone is preferred, and among them, an alcohol having 1 to 5 carbon atoms is preferred. These may be used alone or in combination of two or more.

It is preferred to use water as the other solvent. 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 not particularly limited as long as it is a ratio of the amount required to obtain a uniform solution in the form of a composition. When a solvent having a carbon number of 3 or less or the like is relatively easily dissolved 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 preferably. It is in the range of 50/50~90/10, 60/40~80/20, or 65/35~75/25.

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 in an organic solvent is low, the amount of water used is preferably a trialkoxy decane. It is used in an amount greater than the amount required for hydrolysis and the composition is in a uniform range.

(mixing ratio)

The concentration of the solid content component in the composition of the present invention is not particularly limited, and is preferably 0.5 to 0.5 in consideration of the appearance, coatability, hardenability, properties of the coating film, storage stability of the composition, and the like of the coating film. The amount in the range of 50% by mass is more preferably in the range of 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. When it is less than 0.5% by mass, it is difficult to form a film uniformly, and when it is more than 50% by mass, the stability of the composition, the transparency of the coating film, the appearance, or the coating property may cause problems. situation.

The amount of the organic solvent and water to be used can be appropriately determined in consideration of the amount of the fluoroalcohol to be used in combination with the concentration of the solid content.

(other blending ingredients)

In the composition of the present invention, other components may be added depending on the use thereof, and specific examples thereof include inorganic fine particles such as colloidal cerium oxide or colloidal alumina, various surfactants, dyes, pigments, and dispersion materials. Water-repellent materials, sticky materials, spices, anti-drugs Bacterial ingredients, etc.

(Production conditions of the composition)

The method for producing the composition of the present invention is not particularly limited, and specifically, the following methods and the like can be exemplified.

i) mixing and stirring the epoxy-containing trialkoxy decane and/or its hydrolysis condensate, decyl alcohol condensation catalyst, water and optionally an organic solvent (including n-pentanol) at room temperature, and then Polyamines, optionally organic acids or fluoroalcohols are added and diluted with an organic solvent (including n-pentanol) and optionally water.

Ii) mixing and stirring the epoxy group-containing trialkoxy decane and/or its hydrolysis condensate, water, organic solvent (including n-pentanol), and polyamine at room temperature, and further adding an organic acid as needed Or fluoroalcohols, and further diluted with an organic solvent (including n-pentanol) and optionally water.

Iii) an epoxy group-containing trialkoxy decane and/or its hydrolysis condensate, water, a solvent alcohol (including n-pentanol), a polyamine, and optionally an organic acid or a fluoroalcohol at room temperature The mixture is stirred and stirred, and further diluted with an organic solvent (including n-pentanol) and optionally water.

Iv) The epoxy group-containing trialkoxy decane, water, a solvent alcohol (including n-pentanol), a polyamine, and, if necessary, an organic acid or a fluoroalcohol are mixed and stirred at room temperature.

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 becomes the temperature of the outside air at the place where the stirring is performed, and is preferably in the range of 15 to 35 °C.

(3) Use aspect of the composition of the present invention

The composition of the present invention can form a coating film on the surface of the substrate as an object by all known coating methods such as brushing, spraying, dipping, spin coating, bar coating, and gravure printing. 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 20 ° C to 150 ° C for 10 seconds to 24 hours, preferably 30 seconds to 10 hours. Around.

Although not particularly limited, the obtained film 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, and polycarbonate resins. A resin substrate such as an acrylic resin, a polyimide resin, a polyester resin, an epoxy resin, a liquid crystal polymer resin, or a polyether oxime may be coated on the surface with another coating material. Among these, a resin substrate or a metal substrate is particularly preferable.

On the film obtained from the composition of the present invention, a water repellent layer or a layer containing a hydrolysis condensate of a metal surfactant, or a self-assembled monomolecular film or the like may be further laminated.

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. Processing of antennas, towers, electrical communication facilities, road traffic signs, signalling machines, etc. in snowfall areas; reduction of frictional resistance of ships and water, prevention of dirt adhesion of vehicles/aircraft bodies, prevention of various metal materials Corrosion of electrodes such as surfaces or battery materials; treatment of the surface of fish nets; addition to sealants, refractory waterproof sealants, automotive waxes, etc. Further, since the resin substrate treated by the composition of the present invention is hardened on the surface, it can be used as a substitute for the use of glass which has previously been used for a windshield such as a car.

[Examples]

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

[Example 1] 1. Preparation of coating composition

0.44 g of acetic acid was added to 0.54 g of 2-methylimidazole dispersed in 1.25 g of water and Let it dissolve. To the obtained aqueous solution, 16.5 g of 3-glycidoxypropyltrimethoxydecane (GPTMS) was added, and the mixture was stirred at room temperature for 2 hours. 10.0 g of the condensation reaction liquid was diluted with 40.0 g of Solmix (registered trademark) (AP-7, manufactured by Japan Alcohol Trading Co., Ltd.) to obtain a coating composition (A-1) having a solid content of 20% by weight.

2. Film formation and liquid handling of the coating composition

Film formation of the coating composition (A-1) was carried out on a polycarbonate (PC) resin substrate. First, the prepared coating composition (A-1) was immersed on a PC resin substrate. The coated substrate was dried in an oven (120 ° C, 20 min) to obtain a coating composition-treated substrate (B-1). A fluorine-based glass surface liquid repellent agent, Ultra Glaco (registered trademark) (manufactured by Soft 99 Co., Ltd.), was applied onto the obtained substrate to obtain a base film-liquid-repellent treated PC resin substrate (C-1).

3. Evaluation of liquid repellency

The static contact angle of (C-1) obtained was measured using a contact angle measuring device (Drop Master 700, manufactured by Kyowa Interface Science Co., Ltd.). The results are shown in Table 1. For comparison, a soda lime glass (SLG) substrate (cC-1) treated with Ultra Glaco (registered trademark) was produced, and static contact angle measurement was performed in the same manner.

*1: Tetradecane

As a result, it was found that the water-repellent film similar to that on the soda lime glass substrate can be formed on the PC resin substrate by using the coating composition of the present invention.

4. Determination by X-ray photoelectron spectroscopy (ESCA)

The substrate (B-1) for coating the composition was subjected to measurement by an X-ray photoelectron spectroscopy apparatus (Quantera II, manufactured by ULVAC-PHI Co., Ltd.). The cycle was carried out for 100 cycles under a sputtering condition of 1 kV to a depth of about 200 nm. The measurement results are shown in Fig. 1. It is understood from Fig. 1 that a glass-like inorganic film rich in Si component is formed.

5. Checkerboard adhesion test

The checkerboard peeling test of (B-1) was carried out in accordance with the checkerboard tape peeling test method described in JIS K-5400 (1999). The coating film on the PC resin substrate was cross-cut into a checkerboard shape of 1 mm × 1 mm, and a peeling test was performed using a transparent adhesive tape. The coating film of each checkerboard was evaluated by an optical microscope, and as a result, no peeling was observed at all (non-peeling number/test number=100/100). As a result, it was found that the PC resin substrate and the coating film were in good contact with each other.

[Embodiment 2] 1. Preparation of coating composition

The coating composition (A-1) was obtained in the same manner as in Example 1.

2. Film formation on SUS304 mirror panel and Cu mirror panel

The coating composition (A-1) obtained was used to form a film on a SUS304 mirror panel and a Cu mirror panel. First, the prepared coating composition (A-1) was immersed on a SUS304 mirror panel and a Cu mirror panel. The coated substrate was heat-hardened (200 ° C, 20 min) in an oven to obtain treated substrates (B-2) and (B-3). The Cu mirror panel after the heat treatment was visually evaluated. As a result, the untreated product lost its mirror surface due to rust, but the coating composition treated product (B-3) did not change as compared with that before heating, and the mirror surface was maintained.

3. Thermal cycle test

The thermal cycle test of (B-2) and (B-3) was carried out. The test system used a hot air dryer (LC-234, manufactured by Espec Corporation). The sample was placed in a cycle of 25 ° C to 200 ° C for 2 hours, placed in a treated substrate, and subjected to a heat cycle test for 5 weeks. By visually confirming (B-2) and (B-3) There was no cracking or peeling after the test.

[Example 3] 1. Preparation of coating composition

2.0 g of GPTMS, 0.5 g of diethyltriamine, 0.3 g of water and 8.0 g of n-pentanol were mixed and stirred at room temperature for 2 hours. 1.0 g of the reaction solution was diluted with 9.0 g of n-pentanol to prepare a coating composition (A-2) in an amount of 2% by mass of the solid content. The average particle diameter of the GPTMS hydrolysis condensate in the coating composition was measured by a particle size distribution meter (Zetasizer Nano, manufactured by Malvern, measuring conditions: solution viscosity 3.31, particle refractive index 1.50), and as a result, coating composition preparation was carried out. The particle size after 1 day was 11 nm.

2. Film formation on a PC resin substrate

The PC resin substrate (80 × 80 mm) was subjected to ultrasonic cleaning for 10 minutes in each of water, a hydrocarbon-based cleaning agent (NS Clean 100, manufactured by JX Nippon Oil & Energy Co., Ltd.), and isopropyl alcohol. About 0.5 ml of the prepared coating composition (A-2) was dropped on the PC resin substrate after washing, and uniformly coated with Kimwipe, and then allowed to stand in a drying cabinet at a temperature of 25 ° C for 8 hours. The treated substrate (B-4) was obtained. The coating composition (A-2) was coated on the same substrate in the same manner, and then heated in an oven at 120 ° C for 20 minutes to obtain a treated substrate (B-5). For the obtained (B-4) and (B-5), Vickers hardness (HV) was performed using a surface hardness meter (Picodentor, manufactured by Fischer, measuring conditions: maximum load 0.5 mN, creep rate 20 sec). , unit N/mm ² ) and Martens hardness (HM, unit N/mm ² ). The results are shown in Table 2.

[Example 4] 1 Preparation of coating composition

The coating composition (A-2) was prepared in the same manner as in Example 3 using GPTMS and diethylenetriamine.

2 film formation on the substrate

About 0.5 ml of the coating composition (A-2) was dropped onto a polyethylene terephthalate (PET) film and spread by a Kimwipe in a uniform manner. The coating composition-treated PET film (B-6) was obtained by heating at 120 ° C for 20 minutes in an oven.

The same solution was spread on a SUS304 mirror panel by the same method, and then heated at 200 ° C for 20 minutes in an oven to obtain a coating composition-treated SUS304 mirror panel (B-7).

3 Self-assembled monolayer (SAM) processing substrate fabrication

After UV (Ultraviolet) ozone treatment (about 12,000 mJ/cm ² ) was performed on the coated substrates for 10 minutes on the obtained two substrates (B-6) and (B-7), a solution was formed in the SAM ( SAMLAY (registered trademark), manufactured by Nippon Soda Co., Ltd.) was immersed for 5 minutes, and then the surface was subjected to ultrasonic cleaning in a hydrocarbon-based cleaning agent (NS Clean 100, manufactured by JX Nippon Oil & Energy Co., Ltd.) to obtain SAM treatment. Substrate (C-2), (C-3). The static contact angle measurement was performed on each substrate by the same method as described above. The results are shown in Table 3.

The typical contact angle of SAM was observed in the case of water and TD.

[Example 5]

2.0 g of GPTMS, 0.5 g of diethyltriamine, 0.22 g (relative to GPTMS) 2 parts of water and 8.0 g of n-pentanol were mixed and stirred at room temperature for 2 hours, and further diluted with 90 g of n-pentanol to prepare a mass concentration of 2.5 in terms of solid content. % coating composition (A-3). The hydrolysis condensate of GPTMS in the coating composition was measured by a particle size distribution meter (Zetasizer Nano, manufactured by Malvern, measuring conditions: setting the viscosity of the solution to the viscosity of n-pentanol as a main solvent, and the refractive index of the particles was 1.50) The average particle diameter was as follows. The particle size of the coating composition after 1 day of preparation was 11 nm.

The coating composition (A-31) to (A-34) was prepared by the same method as the above method using isopropanol, methanol, ethanol, n-butanol instead of n-pentanol.

(A-3) and (A-31) to (A-34) were placed in a stoppered bottle and stored at 25 ° C. The measurement was carried out under the same conditions as in the case of n-pentanol. The viscosity of each main solvent and the refractive index of the particles were the same as described above. The temporal change of the z-average particle diameter in each composition was measured. The results are shown in Fig. 2.

It is known from Fig. 2 that the storage stability is optimal when n-pentanol is used.

[Example 6] (Confirmation of the effect of z-average particle diameter in the composition of the hydrolysis condensate of GPTMS)

2.0 g of GPTMS, 0.5 g of diethyltriamine, 0.22 g of water, and 8.0 g of n-pentanol were mixed, and then stirred at room temperature to prepare a coating composition. The mixture was sampled immediately after mixing, diluted to 10 times with n-pentanol, and the z-average particle diameter was measured by a particle size distribution meter (Zetasizer Nano, manufactured by Malvern, measuring conditions: same as in Example 3). The remaining coating composition was stirred at room temperature for 1 hour, 8 hours, 1 day, 2 days, and 3 days, and then diluted under the same conditions, and the z-average particle diameter was measured.

On a PC resin substrate (80 × 80 mm) which was washed with ultrasonic waves for 10 minutes in water, a hydrocarbon-based cleaning agent (NS Clean 100, manufactured by JX Nippon Oil & Energy Co., Ltd.), and isopropyl alcohol. Each of the coating compositions sampled was about 0.5 ml and utilized. Kimwipe was uniformly spread, and then heat-hardened in an oven at 120 ° C for 10 minutes to obtain a treated substrate to visually confirm the presence or absence of coating unevenness (appearance evaluation). The case where there was no coating unevenness was judged as ○, and the case where coating unevenness was applied was judged as ×. Further, the obtained film was lightly wiped 10 times with a Kimwipe, and visually confirmed whether or not there was a scratch (friction test). The case where no scratch was caused was judged as ○, and the case where there was scratch was judged as ×. The results are shown in Table 4.

According to the above, when the average particle diameter is 5 nm or less, a film having sufficient hardness cannot be obtained, and when the average particle diameter is 50 nm or more, the coating property of the coating film is inferior, and a coating spot is observed everywhere.

[Example 7] Difference in storage stability caused by ratio of alcohol to water

Mix 2.0 g of GPTMS, 0.5 g of diethyltriamine, 8.0 g of water and isopropyl alcohol (IPA) in a mass ratio (water/IPA) of 5/2, and stir at room temperature. Further, the mixture was diluted with 90 g of a mixed solvent of water/IPA in a mass ratio of 5/2 for 2 hours to prepare a coating composition (A-4) in an amount of 2.5% by mass of the solid content.

Mix 2.0 g of GPTMS, 0.5 g of diethyltriamine, 8.0 g of water and isopropyl alcohol (IPA) in a mass ratio (water/IPA) of 5/2, and stir at room temperature 2 The coating composition (A-41) having a mass concentration of the solid content of 2.5% was prepared by diluting with IPA 90 g in an hour.

(A-4) and (A-41) were placed in a stoppered bottle, and stored at 25 ° C, and the combination was measured by a particle size distribution meter (Zetasizer Nano, manufactured by Malvern, measuring conditions: same as in Example 3). The z-average particle size of the solids component in the material and its change over time. The result is shown in Fig. 3.

[Embodiment 8]

Mix 2.0 g of GPTMS, 0.5 g of diethyltriamine, 8.0 g of water and isopropyl alcohol (IPA) in a mass ratio (water/IPA) of 5/2, and stir at room temperature. 2 hours, further adding 16g, 32g, 48g of 2,2,2-trifluoroethanol (TFE) or 0.5g, 1.0g, 2.0g of 1,1,1,3,3,3-hexafluoro-2- The coating composition (A-51) to (A-56) was prepared by diluting with propanol (HFIP) and further using a mixed solvent of water/IPA mass ratio of 5/2 so that the entire composition became 100 g. Further, the coating composition (A-50) was obtained by the same method as the above method except that TFE and HFIP were not added.

(A-50) to (A-54) were placed in a stoppered bottle, and stored at 25 ° C, and the combination was measured by a particle size distribution meter (Zetasizer Nano, manufactured by Malvern, measuring conditions: same as in Example 3). The z-average particle size of the solids component in the material and its change over time. The result is shown in Fig. 4.

According to the above, it is preferable to use TFE of 30% by mass or more of the entire composition for long-term storage. Further, it has been found that a certain degree of storage stability can be ensured when a small amount of HFIP is added.

[Embodiment 9] 1. Preparation of coating composition

2.0 g of GPTMS, 0.5 g of diethyltriamine, 0.5 g of benzoic acid, 70.0 g of water and 28.0 g of IPA were mixed, and then stirred at room temperature for 2 hours to prepare a solid. The coating composition (A-6) in terms of mass concentration of the component was 3%. The average particle diameter of the solid content in the coating composition was measured by a particle size distribution meter (Zetasizer Nano, manufactured by Malvern Co., Ltd.), and as a result, the particle size of the coating composition after one day of preparation was 8.5 nm.

2. Film formation on a PC resin substrate

The PC resin substrate (80 × 80 mm) was subjected to ultrasonic cleaning for 10 minutes in each of water, a hydrocarbon solvent (NS Clean 100), and IPA. The prepared coating composition was formed into a film on the cleaned PC resin substrate by bar coating, and dried by heating in a circulating oven of 100 ° C for 10 minutes to obtain a coating combination. A substrate (B-8) having a film thickness of about 50 nm of the coating film formed of the object (A-6).

3. Treatment of substrate (B-8) turbidity and color evaluation

The haze ratio (B-8), the L* value, the a* value, and the b* value of (B-8) were respectively determined using a color-turbidity measuring instrument (COH400, manufactured by JEOL Ltd.). For comparison, the untreated PC resin substrate was also measured in the same manner. The results are shown in Table 5.

According to the above, the coating film of the present invention is a colorless, transparent coating film.

4. Evaluation of the adhesion of various substrates

Using various substrates, the coating composition (A-6) was treated under the conditions shown in Table 5, and the treated substrate was tested by a checkerboard tape peeling test described in JIS K5400 (1999). . The results are shown in Table 6.

*1: Polyethylene terephthalate

*2: Glass fiber reinforced plastic

*3: Indicated in parentheses (number of unpeeled/tests).

*4: The coating method is a bar coating.

*5: UV ozone treatment (about 2400 mJ/cm ² ) was carried out before coating.

According to the above, it is known that a coating film excellent in adhesion can be formed on all the substrates regardless of inorganic, organic or metallic.

5. Determination by X-ray photoelectron spectroscopy (ESCA)

The coating composition-treated substrate (B-8) was measured by an X-ray photoelectron spectroscopy apparatus (Quantera II, manufactured by ULVAC-PHI, measuring conditions: voltage: 1 kV, cycle number 100, measured to a depth of about 200 nm) . The measurement results are shown in Fig. 5.

6. Research on surface modification

About 0.5 mL of the coating composition (A-6) was formed into a film on a PET film by bar coating, and heated at 100 ° C for 10 minutes in an oven to obtain a PET film treated with the coated composition (B) -9). Further, a film (B-10) obtained by subjecting the coated surface of (B-9) to UV ozone treatment (about 12000 mJ/cm ² ) for 10 minutes was obtained. Further, (B-10) was immersed in SAMLAY (registered trademark) for 5 minutes, and thereafter, the surface was subjected to ultrasonic cleaning in NS Clean 100 to obtain a SAM-treated film (C-4).

For comparison, a film (cC-4) obtained by treating the untreated PET film with SAMLAY (registered trademark) was prepared.

The static contact angle was measured by the same method as described above for the untreated PET film, (B-9), (B-10), (C-4), and (cC-4) films. The results are shown together in Table 7.

From the above, it is known that the same surface treatment as glass can be carried out on the polymer by using the coating film of the present invention.

[Embodiment 10]

2.0 g of GPTMS, 0.5 g of diethyltriamine, 0.5 g, 0.2 g, 0.08 g of benzoic acid, 70.0 g of water and 28.0 g of IPA were mixed, and then stirred at room temperature for 2 hours. The coating composition (A-71) to (A-73) was prepared. A composition (A-70) which does not use benzoic acid is also prepared in the same manner. The obtained (A-70) and (A-71) to (A-73) were placed in a stoppered bottle, and stored at 25 ° C, and the combination was measured by a particle size distribution meter (Zetasizer Nano, manufactured by Malvern). The z-average particle size of the solids component in the material changes over time. The result is shown in Fig. 6.

[Example 11]

0.5 g of GPTMS, 0.125 g of diethyltriamine, 0.171 g of p-nitrobenzoic acid, 17.5 g of water and 7.0 g of IPA were mixed, and then stirred at room temperature for 2 hours to prepare Coating composition (A-80). By the same operation, a coating composition (A-81) or (A-82) using 0.156 g of p-methoxybenzoic acid or 0.0615 g of acetic acid instead of p-nitrobenzoic acid was prepared.

(A-80), (A-81), and (A-82) were placed in a stoppered bottle, and stored at 25 ° C, and were measured by a particle size distribution meter (Zetasizer Nano, manufactured by Malvern Co., Ltd., measurement conditions: and implementation). Example 3 is the same) determining the z-average particle size of the solid component in the composition and measuring its time-dependent Chemical. The result is shown in Fig. 7.

About 0.5 mL of the coating compositions (A-80), (A-81), and (A-82) were formed into a film on a PET film by bar coating, and heated at 100 ° C for 10 minutes in an oven. The coating compositions were treated with PET films (B-11), (B-12) and (B-13). Further, the coated surface was subjected to UV ozone treatment (about 12,000 mJ/cm ² ) for 10 minutes, and then immersed in SAMLAY (registered trademark) for 5 minutes, and then the surface was ultrasonically cleaned in NS Clean 100 to obtain SAM treated membranes (C-5), (C-6) and (C-7). Each film was subjected to static contact angle measurement by the same method as described above. The results are shown together in Table 8.

[Embodiment 12]

0.5 g of GPTMS, 0.05 g of 3,3,4,4,5,5,6,6,6-nonafluorohexyltrimethoxydecane, 0.125 g of diethyltriamine, 0.125 g of benzoic acid 2.0 g of 2,2,2-trifluoroethanol, 16.0 g of water and 6.5 g of IPA were mixed, and then stirred at room temperature for 24 hours to obtain a coating composition (A-8).

The PC resin substrate (80 × 80 mm) was subjected to ultrasonic cleaning for 10 minutes in each of water, NS Clean, and IPA. The prepared coating composition (A-8) was formed into a film on the cleaned PC resin substrate by bar coating, and dried in a circulating oven having a temperature management of 120 ° C for 20 minutes. The treated substrate (B-11) was obtained.

The static contact angle of the obtained processing substrate (B-11) and the processing substrate (B-12) after the processing substrate (B-11) was rubbed was measured by the same method as described above. For comparison, a processed substrate prepared by adding no fluorotrimethoxydecane was also prepared. (R-1) The same measurement was carried out. The results are shown in Table 9.

[Comparative Example 1] 1 Preparation of coating composition

To 16.5 g of 3-glycidoxypropyltrimethoxydecane (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.), 1.27 g of a 1 vol% aqueous acetic acid solution was added, and the mixture was stirred at room temperature for 3 days. To the obtained reaction liquid, 0.54 g of 2-methylimidazole was added, and 94.3 g of an alcohol-based mixed solvent Solmix (registered trademark) (AP-7, manufactured by Japan Alcohol Trading Co., Ltd.) was added to obtain a solid component. 20% by weight of the coating composition (cA-2).

2 filming and liquid handling of coating composition

The prepared coating composition (cA-2) was dip-coated on a PC resin substrate. The coated substrate was dried in an oven (120 ° C, 20 minutes) to obtain a coating composition-treated substrate (cB-1). A fluorine-based glass surface liquid repellent agent, Ultra Glaco (registered trademark) (manufactured by Soft 99 Corporation), was applied onto the obtained treated substrate to obtain a coating composition-liquid-repellent treated PC substrate (cC-2).

For comparison, a substrate (cC-3) obtained by applying a fluoroglass glass surface liquid treatment agent, Ultra Glaco (registered trademark) (manufactured by Soft 99 Corporation), to a soda lime glass coating was obtained.

3 Evaluation of liquid repellency

The static contact angles of (cC-2) and (cC-3) obtained were measured by the same method as described above. The results are shown in Table 10.

This value is equivalent to the liquid repellency of the case where the soda lime glass (SLG) substrate is subjected to Ultra Glaco treatment, but the preparation of the coating composition takes 3 days.

Claims (13)

A method for producing an epoxy group-containing trialkoxy decane hydrolyzed condensate, which comprises mixing and stirring an epoxy group-containing trialkoxy decane and/or a hydrolysis-condensation product thereof with water and an imidazole. A method for producing an epoxy group-containing trialkoxy decane hydrolyzed condensate according to claim 1, which is mixed and stirred at room temperature. A process for producing an epoxy group-containing trialkoxy decane hydrolyzed condensate according to claim 1, wherein the epoxy group-containing trialkoxy decane is glycidoxyalkyltrialkoxide. The method for producing a hydrolyzed condensate containing an epoxy group-containing trialkoxy decane according to claim 1, wherein the epoxy group is more than 0.5 mole per mole of the epoxy group-containing trialkoxy decane and/or its hydrolysis condensate. Use water within the range. The method for producing an epoxy group-containing trialkoxy decane hydrolyzed condensate according to any one of claims 1 to 4, wherein the acid is mixed and stirred together with the acid. A composition comprising: (A) a hydrolyzed condensate containing an epoxytrial trialkoxy decane, wherein the z-average particle diameter measured by dynamic light scattering is in the range of 5 to 50 nm, and (B) poly Amines, and (C-1) n-pentanol. A composition comprising: (A) a hydrolyzed condensate containing an epoxytrial trialkoxy decane, wherein the z-average particle diameter measured by dynamic light scattering is in the range of 5 to 50 nm, and (B) poly An amine, and (C-2) an organic acid or an alcohol, the substituted or unsubstituted benzoic acid having a pKa at a temperature of from 2.0 to 6.0 at 25 ° C, the alcohol having a perfluoroalkyl group And/or a perfluoroalkylene group having 2 to 5 carbon atoms. The composition of claim 7, wherein the polyamine is selected from the group consisting of an alkylene polyamine, a polyalkylene polyamine, a poly(phenylene alkylene)polyamine, and a cycloalkylalkyl polyamine. At least one polyamine in the group. The composition of claim 7, wherein the total number of nitrogen atoms in the 1/(polyamine 1 molecule) is 1 mol relative to the epoxy group-containing trialkoxysilane and/or the epoxy group thereof. A polyamine is used in the range of 10 times or less of the total number of hydrogen atoms in the above) and 10 or less (the total number of hydrogen atoms on all nitrogen atoms in the polyamine-based one molecule). The composition of claim 7, wherein an organic acid having a pKa in the range of 2.0 to 6.0 is used in the range of 0.3 to 1.2 moles relative to the polyamine 1 molar. The composition of claim 7, wherein the alcohol having 2 to 5 carbon atoms of the perfluoroalkyl group and/or the perfluoroalkylene group is 30% by mass or more of the entire composition. The composition of claim 7, 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 and/or a perfluoroalkylene group. A film obtained by applying the composition according to any one of claims 7 to 12 to a substrate and drying it at room temperature and/or heating.