JP2003040650A - Colored painting - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored glass which is provided with a coating having extremely excellent alkali resistance so as to be usable as a returnable type, and which can be recycled as a colorless and transparent glass material by re-melting. Providing colored coatings as products (mainly glass bottles). SOLUTION: On a glass substrate, a polysiloxane segment (A) having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom and a polymer segment (B) other than the polysiloxane are constituted. ,and,
A colored coating agent comprising a composite resin (C) having a weight ratio [(A) / (A) + (B)] of 5% or more and less than 50% of (A) and a coloring agent (D). Colored paintings obtained by painting.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a colored coated article obtained by coating a glass substrate with a colored coating agent.
More specifically, a composite resin composed of a specific polysiloxane segment and a polymer segment other than polysiloxane, and a colorant on a glass substrate or on a glass substrate coated with a surface treatment agent in advance. The present invention also relates to a colored coating agent containing the above, or a colored coating material obtained by coating a coloring coating agent obtained by mixing the coating agent with a specific curing agent.

More specifically, a glass product which is provided with a coating having extremely excellent alkali resistance which can be used as a returnable type and which can be recycled as a colorless and transparent glass material by remelting (a glass product ( Mainly glass bottles) related to colored coatings.

[0003]

2. Description of the Related Art Up to now, as a coating material for coloring glass suitable for recycling glass materials, a sol-gel solution obtained by hydrolyzing and condensing phenyltrialkoxysilane as a main component has been colored. A coating agent obtained by adding an agent (JP-A-10-204296, JP-A-10-2
37361, JP-A-11-71552, etc.)
A coating agent (International Publication WO98 / 051752, etc.) comprising a sol-gel solution containing a partial hydrolyzed condensate such as methyl silicate and ethyl silicate as a main component and a colorant has been proposed.

However, since the main component of such a coating agent is a polysiloxane composed of a siloxane bond having poor alkali resistance, when the colored coating product obtained is, for example, a colored glass bottle, a washing and sterilizing step with an alkaline aqueous solution is performed. Accompanied by returnable bottles (these are difficult to use as bottles to be collected, washed, and repeatedly used, and their use is limited to one-way bottles.

[0005]

SUMMARY OF THE INVENTION The present inventors, however, have started earnest research to solve various problems in the conventional technique as described above.

[0006] Therefore, the problem to be solved by the present invention is to recycle as a colorless and transparent glass material which is provided with a coating having extremely excellent alkali resistance so that it can be used as a returnable type and is remelted. Possible colored glassware (mainly glass bottles)
To provide a varnished colored coating.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that
Alternatively, a glass substrate coated with a surface treatment agent in advance, composed of a polysiloxane segment having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom and a polymer segment other than polysiloxane,
In addition, a colored coating agent containing a composite resin in which the weight ratio of the polysiloxane segment is 5% or more and less than 50% and a colorant, or obtained by blending the coating agent with a specific curing agent It has been found that a colored coating material having a coating having extremely excellent alkali resistance can be obtained by applying a colored coating agent, and the present invention has been completed.

That is, the present invention provides a polysiloxane segment (A) having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom and a polymer segment other than the polysiloxane segment on a glass substrate. (B) and the weight ratio of (A) [(A) / (A) + (B)] is 5% or more and 50%.
The present invention provides a colored coated product obtained by coating a colored coating agent containing the composite resin (C) and the colorant (D), which are less than the above, as essential components.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The colored coated article of the present invention has a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom directly on a glass substrate or on a glass substrate coated with a surface treatment agent in advance. It is composed of the polysiloxane segment (A) and the polymer segment (B) other than the polysiloxane segment, and the weight ratio [(A) / (A) + (B)] of (A) is 5% or more and 50 %
It is obtained by applying a colored coating agent containing the composite resin (C), which is less than the above, and the colorant (D) as essential components.

The composite resin (C), which is one of the essential components of such a colored coating composition, means that the polysiloxane segment (A) is chemically bonded to the side chain and / or terminal of the polymer segment (B). This refers to a resin having a bonded graft structure and / or block structure.

In the composite resin (C),
As the bonding mode of the polysiloxane segment (A) and the polymer segment (B), the following structural formula (S-1) is used.

[0012]

[Chemical 3]

[Wherein, the carbon atom constitutes a part of the polymer segment (B), and the two silicon atoms constitute a polysiloxane segment (A) or a part of the polysiloxane segment (A). . ] Or the following structural formula (S-3)

[0014]

[Chemical 4]

[However, in the formula, the carbon atom constitutes a part of the polymer segment (B), and the silicon atom constitutes a part of the polysiloxane segment (A). ] The bonding mode can be adopted, but from the viewpoint of achieving a high degree of alkali resistance, the structural formula (S-
It is preferable to adopt the binding mode of 1).

The polysiloxane segment (A), which is one of the constituents of the composite resin (C), is a hydroxyl group and / or silicon bonded to a silicon atom, which is generally called a silanol group. It has a hydrolyzable group bonded to an atom.

The term "hydrolyzable group bonded to a silicon atom" as used herein means a halogen atom, an alkoxy group, a substituted alkoxy group, an acyloxy group, a phenoxy group, a mercapto group, an amino group or an amide group bonded to a silicon atom, respectively. , An aminooxy group, an iminooxy group, or an alkenyloxy group, which are hydrolyzed to form a silanol group.

If only typical examples of the polysiloxane segment (A) are given, the following general formula (S-2) is given.

[0019]

[Chemical 5]

[Wherein R ¹ represents a monovalent organic group which may or may not have a substituent, such as an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. , R ² is a halogen atom, an alkoxy group, a substituted alkoxy group, an acyloxy group, a phenoxy group,
Mercapto group, amino group, amido group, aminooxy group,
It represents an iminooxy group or an alkenyloxy group, and a is 1 or 2. ]

There is a segment derived from a hydrolyzed condensate or a partial hydrolyzed condensate of silicon compounds containing the silane compound represented by as an essential component.

Then, if only typical examples of the silane compound represented by the general formula (S-2) are given, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-butoxysilane and ethyltrimethoxy are exemplified. Silane, n-propyltrimethoxysilane, is
various organotrialkoxysilanes such as o-butyltrimethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane or 3- (meth) acryloyloxypropyltrimethoxysilane;

Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-butoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane,
Various diorganodialkoxysilanes such as methylcyclohexyldimethoxysilane or methylphenyldimethoxysilane; methyltrichlorosilane, ethyltrichlorosilane, phenyltrichlorosilane, vinyltrichlorosilane, 3- (meth) acryloyloxypropyltrichlorosilane, dimethyldichlorosilane. There are various chlorosilanes such as chlorosilane, diethyldichlorosilane or diphenyldichlorosilane.

Among these silane compounds having a hydrolyzable group, particularly preferred are organotrialkoxysilanes and diorganodialkoxysilanes.

In addition to the above-mentioned various silane compounds, tetrafunctional alkoxysilane such as tetramethoxysilane, tetraethoxysilane or tetra-n-propoxysilane, or a partially hydrolyzed condensate of the tetrafunctional alkoxysilane, Within a range that does not impair the effects of the invention, for example, in a range that the silicon atoms derived from the tetrafunctional alkoxysilane do not exceed 20 mol% in the total silicon atoms constituting the polysiloxane (A). You can

Furthermore, metal alkoxide compounds other than silicon atoms, such as boron, titanium, zirconium, or aluminum, may be used, for example, with respect to all silicon atoms constituting the polysiloxane (A), as long as the effects of the present invention are not impaired. Thus, the metal atom contained in the above-mentioned metal alkoxide compound can be used in combination within a range not exceeding 25 mol%.

From the viewpoint of alkali resistance of the colored coating material of the present invention, the weight ratio of the polysiloxane segment (A) to the composite resin (C) [(A) / (A) + (B)].
Is in the range of 5% or more and less than 50%,
It is preferably in the range of 10% or more and less than 50%, and more preferably 15% or more and 50% or less.
It is appropriate to set it within the range of less than%. When the weight ratio of the polysiloxane (A) is less than 5%, the adhesion between the coating film of the colored coating material of the present invention and the glass substrate is lowered, and accordingly, the water resistance of the colored coating material is significantly lowered.

The polymer segment (B), which is the other component of the composite resin (C), is particularly representative as an acrylic polymer, a fluoroolefin polymer, a vinyl ester polymer, and an aroma. Examples include segments based on various vinyl polymers such as group vinyl polymers or polyolefin polymers, and segments based on other than vinyl polymers such as polyurethane polymers and polyester polymers.

Among these, vinyl-based polymer segments or polyurethane-based polymer segments are particularly preferable. The acrylic polymer segment is particularly desirable among the vinyl polymer segments.

Functional groups other than the hydroxyl group bonded to the silicon atom and the hydrolyzable group bonded to the silicon atom can be introduced into the polymer segment (B). And, of these functional groups, particularly representative ones,
Carboxyl group, blocked carboxyl group, carboxylic anhydride group, tertiary amino group, hydroxyl group bonded to carbon atom, blocked hydroxyl group, cyclocarbonate group, epoxy group, carbonyl group, primary amide group, secondary amide,
Carbamate group and the following structural formula (S-4)

[0031]

[Chemical 6]

And functional groups represented by Of the various functional groups listed above, a hydroxyl group bonded to a carbon atom is particularly desirable.

When such a functional group is introduced into the polymer segment (B), the introduced amount of the functional group is the number of moles of the functional group per 1,000 g of the solid content of the polymer segment (B). , 0.1 mol to 5 mol, preferably 0.2 to 4 mol, and more preferably 0.3 to 3 mol.

Production of the composite resin (C) in which the polysiloxane segment (A) and the polymer segment (B) are bound by the bond represented by the structural formula (S-1). As the method, various known and commonly used methods can be applied. Among them, from the viewpoint of ease of preparation, a polymer (b) having a silicon atom to which a hydroxyl group and / or a hydrolyzable group is bonded and composed of a segment other than polysiloxane, and the above-mentioned general formula The method of subjecting the polysilane (a-1) obtained by subjecting the silane compound represented by (S-2) to a hydrolysis-condensation reaction to a condensation reaction is particularly preferable.

As the silane compound represented by the general formula (S-2) used in preparing the polysiloxane (a-1), organotrialkoxysilane or diorganodialkoxysilane is an essential component. Alkoxysilanes contained as are particularly preferable.

Polysiloxane (a) using an alkoxysilane containing the above-mentioned organotrialkoxysilane or diorganodialkoxysilane as an essential component
As the method for preparing -1), various known and conventional methods can be applied. Then, as a simple method among them, for example, as described in JP-A-9-25455, water and a catalyst are added to the above-mentioned alkoxysilanes to carry out a hydrolysis condensation reaction. There is a way.

As the catalyst used in the above-mentioned method, any of various known and conventional catalysts can be used, and of course, they may be used alone or in combination of two or more kinds. is there.

Typical examples of such a catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; p-toluenesulfonic acid, monoisopropyl phosphate, acetic acid, and the like.
Organic acids; Inorganic bases such as sodium hydroxide or potassium hydroxide; Titanate esters such as tetraisopropyl titanate and tetrabutyl titanate;

1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonene-5 (DBN), 1,4-diazabicyclo [2.2] .2] compounds containing various basic nitrogen atoms such as octane (DABCO), tri-n-butylamine, dimethylbenzylamine, monoethanolamine, imidazole, 1-methylimidazole;
Various quaternary ammonium salts such as tetramethylammonium salt, tetrabutylammonium salt and dilauryldimethylammonium salt, which have a counter anion such as chloride, bromide, carboxylate or hydroxide; dibutyltin Such as diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diacetylacetonate, tin octylate or tin stearate,
Examples include tin carboxylate.

Specific examples of the above-mentioned polymer (b) used in the above-mentioned production method include an acrylic polymer,
Fluoroolefin-based polymers, vinyl ester-based polymers, aromatic vinyl-based polymers, polyolefin-based polymers, various vinyl-based polymers, polyurethane-based polymers, polyester-based polymers, and vinyl-based polymers Polymers other than those mentioned above can be mentioned, but among these, vinyl polymers and polyurethane polymers are particularly preferable. Acrylic polymers are particularly preferable among the vinyl polymers.

Also introduced into the polymer (b),
Specific examples of the silicon atom to which the hydrolyzable group is bonded include, for example, the following general formula (S-5).

[0042]

[Chemical 7] (Wherein R ³ is a monovalent organic group such as an alkyl group, an aryl group or an aralkyl group, and R ⁴ is a halogen atom, an alkoxy group, an acyloxy group, a phenoxy group, an aryloxy group, a mercapto group or an amino group. , An amido group, an aminooxy group, an iminooxy group or an alkenyloxy group, and b is 0 or 1 or 2
Shall be an integer. )

It is a hydrolyzable silyl group represented by: And it is particularly preferable that the hydrolyzable silyl group is bonded to the polymer (b) by a covalent bond with a carbon atom.

The amount of hydrolyzable silyl groups to be introduced into the polymer (b) is to prevent a remarkable increase in viscosity and gelation during preparation of the composite resin (C), and From the viewpoint of the durability of the colored coated product of the invention, the number of moles of hydrolyzable silyl groups per 1,000 grams of the polymer (b) is appropriately in the range of about 0.01 to about 2 moles, Preferably, the range of 0.01 to 1.5 mol is suitable, and even more preferably 0.05 to 1.5 mol.
A range of 1 mol is suitable.

In order to prepare the vinyl polymer (b-1) among the above-mentioned polymers (b), various known and conventional methods can be applied. And, as a simple one of them, a vinyl monomer (m-1) having a hydrolyzable silyl group and another vinyl monomer (m-2) copolymerizable therewith And a solution radical polymerization method as described in JP-A-9-25455.

The hydrolyzable silyl group-containing vinyl monomer (m-1) used when preparing the above-mentioned vinyl polymer (b-1) means the general formula (S-
5), which refers to a monomer having a hydrolyzable silyl group, and only representative examples of such a monomer include vinyltrimethoxysilane,
Vinyltriethoxysilane, vinylmethyldimethoxysilane, 2-trimethoxysilylethyl vinyl ether,
Examples include 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, and 3- (meth) acryloyloxypropylmethyldimethoxysilane.

Further, the above-mentioned vinyl monomer (m-1)
As the other vinyl-based monomer (m-2) copolymerizable with, only typical ones are exemplified by methyl (meth) acrylate, ethyl (meth) acrylate, and n-.
Propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, ter
(meth) acrylic acid esters having an alkyl group of C _{1 to} C ₂₂ , such as t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and lauryl (meth) acrylate; benzyl (meth) acrylate,
Various aralkyl (meth) acrylates such as 2-phenylethyl (meth) acrylate; Various cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate; 2-methoxyethyl (meth) ) Acrylate, 4-
Various types of ω such as methoxybutyl (meth) acrylate
-Alkoxyalkyl (meth) acrylates;

Various aromatic vinyl monomers such as styrene, p-tert-butylstyrene, α-methylstyrene, vinyltoluene; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, etc. Various carboxylic acid vinyl esters; methyl crotonate,
Alkyl esters of various crotonic acids such as ethyl crotonate; Dialkyl esters of various unsaturated dibasic acids such as dimethyl maleate, di-n-butyl maleate, dimethyl fumarate, dimethyl itaconate; Ethylene, propylene Various α-olefins such as;
Fluoroolefins such as vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene; ethyl vinyl ether, n
-Various alkyl vinyl ethers such as butyl vinyl ether; various cycloalkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether; N, N-dimethyl (meth) acrylamide, N- (meth) acryloylmorpholine, N- (meth) There are tertiary amide group-containing monomers such as acryloylpyrrolidine and N-vinylpyrrolidone.

In the preparation of the vinyl polymer (b-1) having a carboxyl group as a functional group other than the hydroxyl group bonded to the silicon atom and the hydrolyzable group bonded to the silicon atom, , Vinyl monomers (m-
Examples of particularly representative carboxyl group-containing vinyl monomers used as one of 2) are (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, crotonic acid, itaconic acid, Various unsaturated carboxylic acids such as maleic acid and fumaric acid;

Monomethyl itaconate, mono-itaconate
n-butyl, monomethyl maleate, mono-maleate
n-butyl, monomethyl fumarate, mono-fumarate
Various monoesters (half esters) of saturated dicarboxylic acids such as butyl and saturated monohydric alcohols; monovinyl esters of various saturated dicarboxylic acids such as monovinyl adipate and monovinyl succinate;

Containing anhydrides of various saturated polycarboxylic acids such as succinic anhydride, glutaric anhydride, phthalic anhydride, trimellitic anhydride, and hydroxyl groups bonded to various carbon atoms as described below. Addition reaction products with vinyl-based monomers; various monomers obtained by subjecting various carboxylic group-containing monomers as described above to lactones.

In addition, when the vinyl polymer (b-1) having a blocked carboxyl group is prepared, it is used as one of the vinyl monomers (m-2). As typical examples of the monomer having a block carboxyl group, trimethylsilyl (meth) acrylate, dimethyl-tert-butylsilyl (meth) acrylate, trimethylsilyl crotonate and the like are disclosed in JP-A-62-254876. Various vinyl monomers containing a silyl ester group as disclosed in Japanese Patent Publication No. 1-ethoxyethyl (meth) acrylate, 2-methoxy-2- (meth) acryloyloxypropane, 2- (meth). Such as acryloyloxytetrahydrofuran, as disclosed in JP-A-5-222134. Various, hemiacetal ester group or hemi ketal ester group-containing monomers; te
There are various tert-butyl ester group-containing monomers such as rt-butyl (meth) acrylate and tert-butyl crotonate.

Further, as the vinyl polymer (b-1), it is used as one of the vinyl monomers (m-2) when preparing a polymer having a carboxylic acid anhydride group,
As typical examples of the carboxylic acid anhydride group-containing monomer, various unsaturated polycarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride; acrylic acid anhydride and methacrylic acid anhydride can be given. And the like, anhydrides of various unsaturated monocarboxylic acids; various unsaturated carboxylic acids such as acrylic acid and methacrylic acid, and various saturated carboxylic acids such as acetic acid, propionic acid, benzoic acid, etc. And mixed acid anhydrides.

Further, as the vinyl polymer (b-1), it is used as one of vinyl monomers (m-2) in the preparation of a polymer having a tertiary amino group, 3 Typical examples of vinyl monomers having a primary amino group are 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-di-n-propylaminoethyl (meth ) Acrylate, 3-dimethylaminopropyl (meth) acrylate, 4-dimethylaminobutyl (meth) acrylate, N- [2- (meth) acryloyloxy] ethylmorpholine, etc., containing various tertiary amino groups (meth). Acrylic esters;

Various aromatic vinyl monomers containing tertiary amino groups such as vinyl pyridine, N-vinyl carbazole, N-vinyl quinoline and the like; N- (2-dimethylamino) ethyl (meth) acrylamide, N -(2-Diethylamino) ethyl (meth) acrylamide, N- (2-
Various tertiary amino group-containing (meth) acrylamides such as di-n-propylamino) ethyl (meth) acrylamide; N- (2-dimethylamino) ethyl crotonic acid amide, N- (4-dimethylamino) Various tertiary amino group-containing crotonic acid amides such as butyl crotonic acid amide;

Various 3 types such as 2-dimethylaminoethyl vinyl ether, 2-diethylaminoethyl vinyl ether, 4-dimethylaminobutyl vinyl ether, etc.
Examples include vinyl ethers containing a primary amino group.

Then, as the vinyl polymer (b-1),
Particularly representative as a hydroxyl group-containing vinyl monomer bonded to a carbon atom, which is used as one of vinyl monomers (m-2) when preparing a compound having a hydroxyl group bonded to a carbon atom. Specific examples thereof include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; 2-hydroxy Hydroxyl group-containing vinyl ethers such as ethyl vinyl ether and 4-hydroxybutyl vinyl ether; hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether and 2-hydroxybutyl allyl ether; various hydroxyl group-containing monomers as described above And a group represented by ε-caprolactone, There are adducts of lactones of people.

As the radical polymerization initiator used in the above-mentioned solution radical polymerization method, various known and commonly used compounds can be used. Of these, only typical ones are 2,2 ′. Various azo compounds such as azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile) or 2,2′-azobis (2-methylbutyronitrile); tert- Butyl peroxypivalate, ter
t-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate or di-t
There are various peroxides such as ert-butyl peroxide.

As the organic solvent that can be used when the radical polymerization method is applied, any of the known and commonly used organic solvents can be used, and they can be used alone or in combination of two or more kinds. The good thing is of course.

Of these, only typical ones will be exemplified. N-hexane, n-heptane,
Aliphatic or alicyclic hydrocarbons such as n-octane, cyclohexane and cyclopentane;

Aromatic hydrocarbons such as toluene, xylene, ethylbenzene; ethyl acetate, n-butyl acetate,
Various esters such as n-amyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate;

Methanol, ethanol, iso-propanol, n-butanol, iso-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether, propylene glycol monomethyl ether, propylene glycol mono-n-propyl ether. Various alcohols such as;

Various ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone and cyclohexanone; ethers such as dimethoxyethane, tetrahydrofuran and dioxane; and further N-methylpyrrolidone, dimethylformamide and dimethyl. Examples include acetamide or ethylene carbonate.

By applying the known solution radical polymerization method using the monomers, the polymerization initiators and the organic solvents as mentioned above, the desired vinyl polymer ( b-1) can be prepared, but as the number average molecular weight of the resulting vinyl polymer (b-1), the durability of the colored coated product of the present invention and the composite resin (C) From the viewpoint of preventing thickening and gelation during preparation, 50
The range of 0 to 200,000 is preferable, and 700 to 1
The range of 100,000 is more preferable, and the range of 1,000 to 50,000 is more preferable.

On the other hand, in order to prepare the polyurethane polymer (b-2) among the above-mentioned polymers (b), various conventionally known methods can be applied. One of them is a simple method, in addition to various dihydroxy compounds and various diisocyanate compounds, as a raw material component for introducing a hydrolyzable silyl group, a diamine compound having a hydrolyzable silyl group or a hydrolyzed silyl group. A monoamine compound having a decomposable silyl group is used, for example, JP-A-51-90391 and JP-A-55-73.
729 or JP-A-60-255817.

The number average molecular weight of the resulting polyurethane polymer (b-2) is the durability of the colored coating material of the present invention, and the viscosity and gel during preparation of the composite resin (C). From the viewpoint of preventing oxidization, the range of 500 to 200,000 is preferable, the range of 700 to 100,000 is more preferable, and the range of 1,000 to 5 is more preferable.
It is in the range of 10,000.

Using the polysiloxane (a-1) and the vinyl polymer (b-1) or polyurethane polymer (b-2) obtained by the above-mentioned method, a composite resin (C) is obtained. As a more specific method of preparing,
For example, as described in JP-A-9-25455 and the like, a vinyl polymer (b-1) and a polysiloxane (a
A method of complexing -1) and -1) in the presence of water and a catalyst is particularly preferable.

In preparing the composite resin (C), as the catalyst used in the specific example of the above-mentioned production method, various catalysts which have already been described as usable in preparing the polysiloxane (a-1) are used. Can be mentioned.

On the other hand, among the composite resins (C), the following method is particularly suitable as a method for preparing a resin having both excellent curability and long-term storage stability.

First, a polysiloxane segment (p-1) having a silicon atom as shown below and / or
And a polymer segment (B) other than polysiloxane are prepared. A silicon atom in which a hydrolyzable group and / or a hydroxyl group and an organic group having a total carbon atom number of 4 or more are bonded together. One hydrolyzable group or hydroxyl group and a methyl group and /
Or a silicon atom in which two ethyl groups are bonded together.

Then, the above-mentioned polymer (M) and the following general formula (S-6)

[Chemical 8] [In the formula, R ⁵ represents an alkyl group having 3 or less carbon atoms, and R ⁶ represents an alkyl group having 4 or less carbon atoms. ] Hydrolyzed condensation reaction of a hydrolyzed condensate of alkoxysilanes and / or polysiloxane (a-2) which is a partially hydrolyzed condensate of the alkoxysilanes containing the organotrialkoxysilane as an essential component Make a composite.

In the composite resin (C) prepared by the above method, the polysiloxane segment (A) is composed of a segment derived from the polysiloxane (a-2) and the polysiloxane segment (p-1). And contained in such a polysiloxane segment (p-1),
By introducing an organic group having a total number of carbon atoms of 4 or more onto a silicon atom to which a hydrolyzable group or a hydroxyl group is bonded, or introducing two methyl groups and / or ethyl groups onto the silicon atom. The reactivity of the hydrolyzable group or hydroxyl group on the silicon atom is reduced by the steric effect. This makes it possible to impart excellent storage stability to the composite resin (C).

From the viewpoint of imparting excellent curability to the composite resin (C), among all the silicon atoms constituting the polysiloxane (a-2), the organotrialkoxysilane represented by the general formula (S-6) is used. The ratio of the derived silicon atoms is 2
It is preferably set so as to be 0 mol% or more, more preferably 30 mol% or more, still more preferably 5 mol% or more.
It is 0 mol% or more.

In addition, as the alkoxysilanes used for preparing the polysiloxane (a-2), diorganodialkoxysilane such as dimethyldimethoxysilane, tetrafunctional alkoxysilane such as tetramethoxysilane, or a partial hydrolysis thereof. The decomposition condensate may be, for example, polysiloxane (a-
Of the total silicon atoms constituting 2), these alkoxysilane-derived silicon atoms can be used in combination within a range not exceeding 50 mol%.

A typical example of the organic group having a total number of carbon atoms bonded to silicon atoms of 4 or more contained in the polysiloxane segment (p-1) is a substituent having 3 or more carbon atoms. A methyl group to which is bonded, an ethyl group to which a substituent having two or more carbon atoms is bonded, and a carbon number of 4
The number of carbon atoms bonded to the above alkyl groups and substituents is 4
The alkyl group, cycloalkyl group, cycloalkyl group having a substituent bonded thereto, alkyl group having a cycloalkyl group substituted therewith, aryl group, substituted aryl group, aralkyl group or aralkyl group having a substituent bonded thereto, and the like can be mentioned.

From the viewpoint of practicality, the upper limit of the number of carbon atoms in the organic group having a total number of carbon atoms of 4 or more is 18
It is about an individual.

More specific examples of the organic group having a total carbon number of 4 or more include a methyl group substituted with a cycloalkyl group such as a cyclopentylmethyl group or a cyclohexylmethyl group; an alkoxy such as a 2-ethoxyethyl group. An ethyl group substituted with a group; 2-cyclopentylethyl group, 2-cyclohexylethyl group or β-
An ethyl group substituted with a cycloalkyl group such as a (3,4-epoxycyclohexyl) ethyl group; an n-propyl group substituted with an alkoxy group such as a 3-methoxypropyl group or a 3-ethoxypropyl group; a 3-cyclopentylpropyl group, 3-cyclohexylpropyl group or γ-
N-propyl group substituted with a cycloalkyl group such as (3,4-epoxycyclohexyl) propyl group; n-butyl group, iso-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n- Alkyl group having 4 or more carbon atoms such as octyl group, n-dodecyl group or n-octadecyl group; 3-glycidoxypropyl group, 3-ureidopropyl group, 3-glycidoxypropyl group, 3-
A substituted propyl group such as an acryloxypropyl group or a 3-methacryloxypropyl group, a cyclopentyl group,
Cycloalkyl group such as cyclohexyl group or cyclooctyl group, phenyl group, 4-methylphenyl group, 1
An aryl group such as a naphthyl group or a substituted aryl group; and an aralkyl group such as a benzyl group or a 2-phenylethyl group.

Of the various organic groups mentioned above, particularly preferred are alkyl groups having 4 to 18 carbon atoms, cycloalkyl groups and aryl groups. Among the alkyl groups having 4 to 18 carbon atoms, particularly preferred are iso-butyl groups, particularly preferred cycloalkyl groups are cyclohexyl groups, and particularly preferred aryl groups. The thing is a phenyl group.

As the method for preparing the above-mentioned polysiloxane (a-2), the method described above as the method for preparing the polysiloxane (a-1) may be followed.

From the viewpoint of preparing a composite resin (C) having both excellent curability and long-term storage stability, the polysiloxane segment (A) constituting the composite resin (C) is
Among them, the weight ratio of the segment derived from (a-2) is preferably set to be 5 to 95% by weight, more preferably 10 to 90% by weight, and further 20 to It is particularly preferable to set it to be 80% by weight.

As an example of a specific method for preparing the composite resin (C) from the polymer (M) and the polysiloxane (a-2) described above, as described in JP-A-9-157369. , An organotrialkoxysilane and / or a diorganodialkoxysilane having an organic group having a total number of carbon atoms of 4 or more in the presence of a hydrolyzable silyl group-containing vinyl polymer (b-1), water and a catalyst. And a polysiloxane (a-2) is hydrolyzed and condensed in the presence of water and a catalyst to form a composite.

The catalyst used in the above specific examples is
The various thing used when preparing polysiloxane (a-1) is mentioned.

As the coloring agent (D), which is the other essential component of the coloring coating material used for preparing the colored coating material of the present invention, any known and commonly used coloring agent can be used. When the glass is reused, it is preferable to use an organic dye, an organic pigment, or carbon black because it decomposes and becomes colorless when the glass is remelted. From the viewpoint of durability of the coated article of the present invention, use of an organic pigment is particularly suitable.

Typical examples of such organic pigments include condensed polycyclic pigments such as perylene, quinacridone, anthraquinone, isoindolinone, isoindoline, diketopyrrolopyrrole and dioxazine. Azo pigments are preferred. Further, phthalocyanine-based pigments such as phthalocyanine blue and phthalocyanine green contain copper, but if the amount is small, there is no problem in terms of colorlessness upon remelting.

As a method of adding such an organic pigment to the composite resin (C), a pigment is previously dispersed in a part of the composite resin (C) to prepare a color base, and the color base is used as the rest of the composite resin (C). The method of adding to
A method in which the pigment is dispersed in the entire composite resin (C) is also suitable. In addition, a resin capable of dispersing such an organic pigment [hereinafter, abbreviated as a pigment-dispersing resin (F)] is used within a range that does not impair the characteristics of the coating agent of the present invention. A method of adding a color base prepared by dispersing a pigment to the composite resin (C) is also suitable.

As the component (F), various known and commonly used resins can be used. Of these, only typical ones are exemplified by vinyl-based polymers, polyurethane-based polymers and polyester-based polymers. There are polymers, etc.

The colored coating agent used in the present invention may be prepared as a type not containing a curing agent or may be preferably prepared as a type containing a curing agent. Then, as the particularly preferable curing agent (E) used for preparing the coating agent, the one contained in the above-mentioned composite resin (C),
Various compounds having at least one functional group that reacts with various functional groups as described above can be mentioned.

As the functional groups contained in the curing agent (E), only typical ones are exemplified. Isocyanate group, blocked isocyanate group, epoxy group, oxazoline group, aziridine group, carbodiimide group, silicon atom. A hydroxyl group bonded to, a hydrolyzable group bonded to a silicon atom, an N-hydroxymethylamino group, an N-alkoxymethylamino group, an N-hydroxymethylcarboxylic acid amide group or an N-alkoxymethylcarboxylic acid amide group.

The functional group contained in the curing agent (E) is appropriately selected according to the type of functional group contained in the composite resin (C). As only such representative combinations are shown, a hydroxyl group bonded to a silicon atom-a hydroxyl group bonded to a silicon atom, a hydroxyl group bonded to a silicon atom-a hydrolyzable group bonded to a silicon atom, and a silicon atom bonded. Hydrolyzable group-hydrolyzable group bonded to silicon atom, carboxyl group-epoxy group, carboxyl group-cyclocarbonate group, carboxyl group-aziridinyl group, carboxyl group-carbodiimide group, tertiary amino group-epoxy group, carboxyl group -N-hydroxymethylamino group, carboxyl group-N-alkoxymethylamino group, hydroxyl group bonded to carbon atom-isocyanate group,
Hydroxyl group bonded to carbon atom-blocked isocyanate group, carboxyl group-oxazoline group, N-hydroxymethylamino group-hydroxyl group bonded to carbon atom, N-alkoxymethylamino group-hydroxyl group bonded to carbon atom, N
-Hydroxymethylcarboxylic acid amide group-a hydroxyl group bonded to a carbon atom, N-alkoxymethylcarboxylic acid amide group-a hydroxyl group bonded to a carbon atom, and the like.

The curing agent (E) may have two or more of the above-mentioned various functional groups depending on the functional groups contained in the composite resin (C). Further, as the curing agent (E), various resins can be used in addition to the compound having a relatively low molecular weight, but if only representative examples of such resins are given, There are various vinyl polymers such as acrylic resin and fluororesin, polyester resin, alkyd resin, polyurethane resin, and epoxy resin. Then, particularly when a compound having two or more kinds of the above-mentioned functional groups is used as the curing agent (E), it is convenient to use a vinyl polymer as the curing agent (E). Is.

As the curing agent (E), only typical ones will be exemplified. A compound having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, an epoxy group in one molecule, There are compounds having both a hydrolyzable group bonded to a silicon atom, a polyisocyanate compound, a blocked polyisocyanate compound, a polyepoxy compound, a polyaziridine compound, a polycarbodiimide compound, a polyoxazoline compound, an amino resin, and the like. As a matter of course, the compounds may be used alone or in combination of two or more kinds.

Of the above-mentioned silicon compounds having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, only typical ones will be exemplified. A silane compound having a hydrolyzable group bonded to a silicon atom; a hydrolyzate or a hydrolytic condensate of these silane compounds; a partial hydrolytic condensate obtained by the partial hydrolytic condensation of one of these silane compounds; Partial co-hydrolysis condensate obtained by partial hydrolysis-condensation of two or more kinds of the silane compound.

Of these, only typical examples of the silane compound are given: tetramethoxysilane, tetraethoxysilane, their partial hydrolyzed condensates, their partial cohydrolyzed condensates, and the above-mentioned compounds. There are various silane compounds such as

As the above-mentioned compounds which are particularly typical as a compound having both an epoxy group and a hydrolyzable group bonded to a silicon atom in one molecule, 3-glycidoxypropyltrimethoxysilane, 3 Epoxy groups such as glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane A silane compound containing; a partial hydrolysis-condensation product obtained by partially hydrolyzing and condensing these silane compounds; a partial co-hydrolysis condensation product obtained by the partial hydrolysis-condensation of two or more of these silane compounds;

[EGM-202] [Cyclic polysiloxane manufactured by Toray Dow Corning Silicone Co., Ltd., having both a methoxy group bonded to a silicon atom and 3-glycidoxypropyl]; 392 "(produced by Shin-Etsu Chemical Co., Ltd., partially hydrolyzed condensate of 3-glycidoxypropyltrimethoxysilane);

Various copolymers composed of an epoxy group-containing vinyl monomer and various hydrolyzable silyl group-containing vinyl monomers as described above, or both of these copolymers, An epoxy group and a hydrolyzable silyl group obtained by copolymerizing with a (meth) acrylic-based, vinyl ester-based, vinyl ether-based, aromatic vinyl-based, fluoroolefin-based, or other vinyl monomer that is copolymerizable with There are also vinyl-based copolymers and the like.

Specific examples of the above-mentioned polyisocyanate compounds are only representative examples. Various aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane-4,4'-diisocyanate; meta-xylylene diisocyanate, α , Α, α ', α'-
Various aralkyl diisocyanates such as tetramethyl-meta-xylylene diisocyanate;

Hexamethylene diisocyanate, lysine diisocyanate, 1,3-bisisocyanatomethylcyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexane, isophorone diisocyanate, etc. Various aliphatic or alicyclic diisocyanates such as;

Various polyisocyanates such as those mentioned above are obtained by addition reaction with polyhydric alcohols, and various prepolymers having an isocyanate group; various polyisocyanates such as those mentioned above are cyclized. Various prepolymers having an isocyanurate ring, which are obtained by quantification; Various polyisocyanates having a biuret structure, which are obtained by reacting the above-mentioned various polyisocyanates with water;

Homopolymers of vinyl monomers having various isocyanate groups such as 2-isocyanatoethyl (meth) acrylate, 3-isopropenyl-α, α-dimethylbenzyl isocyanate and (meth) acryloyl isocyanate;

These (meth) acryl-based vinyl monomers which are copolymerizable with these vinyl monomers containing an isocyanate group,
There are various vinyl copolymers having an isocyanate group, which are obtained by copolymerizing with vinyl monomers such as vinyl ester, vinyl ether, aromatic vinyl, and fluoroolefin.

Among these polyisocyanates, particularly from the viewpoint of weather resistance and the like, various types of polyisocyanates derived from aliphatic, aralkyl or alicyclic diisocyanate compounds and various diisocyanate compounds thereof can be used. The use of a prepolymer or a vinyl polymer containing an isocyanate group is particularly desirable.

As the above-mentioned blocked polyisocyanate compounds, only typical ones will be exemplified. They can be obtained by blocking various polyisocyanate compounds as mentioned above with various blocking agents as mentioned later. As various blocked polyisocyanate compounds and compounds containing a uretdione structure obtained by cyclizing and dimerizing isocyanate groups,
There are compounds that regenerate isocyanate groups by heat.

Then, only typical blocking agents used in the preparation of the block polyisocyanate compound are shown by way of example: various alcohols such as methanol, ethanol and lactate; phenol and salicylic acid. Phenolic hydroxyl group-containing compounds such as esters; various amides such as ε-caprolactam and 2-pyrrolidone; various oximes such as acetone oxime and methyl ethyl ketoxime;
There are various active methylene compounds such as methyl acetoacetate, ethyl acetoacetate, acetylacetone and the like.

Specific examples of the above-mentioned polyepoxy compounds are only representative examples. Ethylene glycol, hexanediol, neopentyl glycol, trimethylolpropane, pentaerythritol, sorbitol,
Polyglycidyl ethers of various aliphatic or alicyclic polyols such as hydrogenated bisphenol A; polyglycidyl ethers of various aromatic diols such as bisphenol A, bisphenol S and bisphenol F;

Polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc.,
Polyglycidyl ethers of various polyether polyols; tris (2-hydroxyethyl) isocyanurate
Polyglycidyl ethers; polyglycidyl esters of various aliphatic or aromatic polycarboxylic acids such as adipic acid, butanetetracarboxylic acid, phthalic acid and terephthalic acid;

Bisepoxides of various hydrocarbon dienes such as cyclooctadiene and vinylcyclohexene; bis (3,4-epoxycyclohexylmethyl)
Adipate, 3,4-epoxycyclohexylmethyl-
Various alicyclic polyepoxy compounds such as 3,4-epoxycyclohexylcarboxylate; "EGM-4
00 "[Cyclic polysiloxane having 3-glycidoxypropyl, manufactured by Toray Dow Corning Silicone Co., Ltd.];

Homopolymers of epoxy group-containing vinyl monomers or copolymers of these epoxy group-containing vinyl monomers with (meth) acrylic, vinyl ester, vinyl ether, aromatic Examples thereof include vinyl-based copolymers containing an epoxy group, which are obtained by copolymerizing with vinyl-based or fluoroolefin-based vinyl monomers.

As a typical example of the above polyoxazoline compound, 2,2'-p-phenylene-
Bis- (1,3-oxazoline), 2,2'-tetramethylene-bis- (1,3-oxazoline), 2,2'-
Low molecular weight poly (1,3-oxazoline) compounds such as octamethylene-bis- (1,3-oxazoline);
Obtained by copolymerizing a homopolymer of a vinyl monomer containing a 1,3-oxazoline group such as 2-isopropenyl-1,3-oxazoline or various vinyl monomers copolymerizable therewith. 1,3-oxazoline group-containing vinyl polymers and the like.

N-hydroxymethylamino group or N-
Representative of compounds containing an alkoxymethylamino group are various amino resins.

Typical examples of such amino resin include melamine, benzoguanamine, acetoguanamine,
Various amino group-containing compounds such as urea and glycouril can be treated with formaldehyde, acetaldehyde and the like,
Various amino resins having an alkylol group obtained by reacting with various aldehyde compounds (or aldehyde supplying substances); amino resins having such an alkylol group can be used as methanol, ethanol, n-butanol, iso-butanol, etc. As described above, there are various alkoxyalkyl group-containing amino resins obtained by reacting with various lower alcohols.

A typical example of the compound containing an N-alkoxymethylcarboxylic acid amide group is vinyl obtained by copolymerizing N-alkoxymethyl (meth) acrylamide with a vinyl-based monomer copolymerizable therewith. A system polymer etc. are mentioned.

Typical compounds containing an N-alkoxymethylcarboxylic acid amide group are N-alkoxymethylcarboxylic acids such as N-methoxymethyl (meth) acrylamide and Nn-butoxymethyl (meth) acrylamide. Examples thereof include vinyl polymers containing an N-alkoxymethylcarboxylic acid amide group, which are obtained by copolymerizing vinyl monomers containing an amide group with vinyl monomers copolymerizing with them.

Next, among the colored coating agents used in the present invention, the ratio of the composite resin (C) to the curing agent (E) used in the case of preparing a coating agent which also contains the curing agent (E) will be described.

When the curing agent (E) is a compound having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, the solid content of the composite resin (C) is 1
The solid content of the curing agent (E) is preferably 0.1 to 200 parts by weight, more preferably 0.5 to 150 parts by weight, and still more preferably 1 to 100 parts by weight. It may be blended so as to be in the range of 100 parts by weight.

When the curing agent (E) is a polyisocyanate compound or a blocked polyisocyanate compound, one of the functional groups which react with the isocyanate group or the blocked isocyanate group contained in the composite resin (C).
The amount of the isocyanate group or blocked isocyanate group contained in the curing agent (E) is preferably in the range of 0.1 to 10 equivalents, and more preferably 0.3 to
The curing agent (E) may be added so as to be within the range of 5 equivalents, and more preferably within the range of 0.5 to 2 equivalents.

When the curing agent (E) is a compound having both an epoxy group and a hydrolyzable group bonded to a silicon atom in one molecule or a polyepoxy compound, it is included in the composite resin (C). The total amount of epoxy groups contained in the curing agent (E) is preferably in the range of 0.2 to 5.0 equivalents, more preferably 1 equivalent of the functional groups that react with the epoxy groups. The curing agent (E) may be added so as to be within the range of 0.5 to 3.0 equivalents, and more preferably within the range of 0.7 to 2 equivalents.

When the curing agent (E) is an amino resin, the solid content of the amino resin is preferably 0.1 to 200 parts by weight with respect to 100 parts by weight of the solid content of the composite resin (C). It may be blended so as to be within the range, more preferably within the range of 0.5 to 150 parts by weight, and even more preferably within the range of 1 to 100 parts by weight.

When the curing agent (E) is a polyoxazoline compound, it is contained in the composite resin (C).
The total amount of the oxazoline group contained in the curing agent (E) is equivalent to 1 equivalent of the functional group that reacts with the oxazoline group.
Curing is preferably within the range of 0.2 to 5.0 equivalents, more preferably within the range of 0.5 to 3.0 equivalents, and even more preferably within the range of 0.7 to 2.0 equivalents. The agent (E) may be blended.

Among the colored coating agents used in the present invention, those containing the composite resin (C) and the coloring agent (D) as essential components, or those containing also the curing agent (E) are prepared. In this case, the use ratio of the colorant (D) can be varied over a wide range according to the type of pigment, the required degree of coloring, and the like. From the viewpoint of coloring effect and the durability of the colored coated product, (D) /
[(C) + (D)] or (D) / [(C) +
(D) + (E)] may be set to preferably 0.1 to 80% by weight, more preferably 0.5 to 60% by weight.

If necessary, the coating agent used in the present invention may be a curing catalyst, a flow control agent, a leveling agent, a rheology control agent, an infrared absorbing agent, an ultraviolet absorbing agent, an antioxidant, a plasticizer, etc. It is also possible to mix known and commonly used various additives. Of these additives, only typical ones as curing catalysts will be exemplified. As catalysts used for preparing the composite resin (C) as described above, various catalysts as already mentioned above are used. In addition, tetramethylphosphonium salt, tetraethylphosphonium salt, tetrabutylphosphonium salt,
Various compounds such as triphenylphosphonium salts having various anions such as fluoride, chloride, bromide, and carboxylate as the counter anion are also included.

The colored coating agent thus obtained is directly applied onto a glass substrate and then cured to obtain the colored coated article of the present invention having excellent alkali resistance and high appearance. Then, for applications requiring a higher degree of alkali resistance, in order to improve the adhesion between the glass substrate and the coating film, after treating the glass substrate with a surface treatment agent in advance, It is preferable to use a colored coated product obtained by applying a coating agent.

As the surface treating agent, any of various known and commonly used surface treating agents can be used.
Of these, particularly typical are compounds having both a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom and an epoxy group in one molecule, and a hydrolyzable group bonded to a silicon atom in one molecule. A compound having a decomposable group and / or a silicon atom-bonded hydroxyl group and an amino group, a compound having a silicon atom-bonded hydrolyzable group and / or a silicon atom-bonded hydroxyl group and an isocyanate group in one molecule, A compound having both a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom and an unsaturated double bond in one molecule, or a hydrolyzable group bonded to a silicon atom in one molecule and / or silicon The compound etc. which have a mercapto group together with the hydroxyl group couple | bonded with the atom can be mentioned.

Particularly preferred as such a surface treating agent are 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane and 3
-Glycidoxypropylmethyldimethoxysilane, 3-
Such as glycidoxypropylmethyldiethoxysilane,
Examples thereof include a compound having both an epoxy group and a hydrolyzable group bonded to a silicon atom in one molecule. Furthermore, compounds in which a part or all of the hydrolyzable groups (alkoxysilyl groups) of these compounds are hydrolyzed to form hydroxyl groups are also suitable.

When the surface treating agent is applied onto the glass substrate, the silane coupling agent as described above can be used as it is, but the coupling agent is contained in an amount of 1% by weight to 10% by weight. It is particularly preferable to use it as the alcoholic solution or aqueous solution.

Next, as one of the methods for producing the colored coated article of the present invention, a coating agent is directly applied onto a glass substrate by a dipping method, a brush coating method, a roller coating method, a spray coating method or an electrodeposition coating. Examples of the method include a method of applying a coating by various known and commonly used coating methods such as a method and then curing (hereinafter abbreviated as method (a)).

The optimum curing condition in the above method (a) depends on the kinds of the composite resin (C) and the colorant (D) constituting the colored coating agent, or when the curing agent (E) is added. Varies depending on the type and amount, but at a temperature of about 150 ° C to 230 ° C for about several minutes
By baking for about 1 hour, a colored coated article coated with a coating film having excellent alkali resistance can be obtained.

On the other hand, a method of producing a colored coated article of the present invention by coating a glass base material coated with the above-mentioned surface treatment agent with a colored coating agent in advance and then curing it (hereinafter referred to as method (b)). A surface treatment agent is first coated on a glass substrate, then a colored coating agent is coated on the surface treatment agent, and then the colored coating film is cured.

At the time of coating the surface treatment agent and the colored coating agent at this time, various coating methods exemplified as those applicable in the above method (a) can be applied as they are.

Further, the drying conditions of the surface treatment agent layer and the curing conditions of the colored coating film in the method (b) are appropriately selected depending on the kind of the surface treatment agent or the colored coating agent to be used. , After coating the surface treatment agent, before coating the colored coating agent, by leaving it at room temperature or by heating, in advance, to dry the treatment agent layer on the substrate, and subsequently, After the coating agent is applied, it can be cured.

Alternatively, after coating the surface treatment agent,
Before the treatment agent layer is dried, a colored coating agent may be applied to cure the colored coating film, and at the same time, the surface treatment agent may be dried.

Then, the coating film applied by the method (b) is
By curing under the same curing conditions as in the above method (a), it becomes possible to obtain a colored coated article having extremely excellent alkali resistance.

The thickness of the coating film in the coated article obtained by the above method (a) or (b) depends on the coloring effect and the transparency of the glass material regenerated by melting the colored coated article. From this point of view, the range of 0.1 to 10 μm is more preferable, and the range of 0.2 to 7 μm is more preferable.

Among the coatings thus obtained, those whose glass base material is a glass bottle can be used as a returnable bottle and can be reused as a colorless glass material by remelting, such as for beverages. It can be widely used for

[0135]

EXAMPLES Next, the present invention will be described with reference to Examples, Examples, Comparative Examples,
The test examples and comparative test examples will be described in more detail, but the present invention is by no means limited to these examples. In the following, all parts and% are based on weight unless otherwise specified.

Reference Example 1 [Preparation Example of Polysiloxane (a-1)] In a reaction vessel equipped with a thermometer, a reflux condenser and a dropping funnel, 1,04 of methyltrimethoxysilane (MTMS) was added.
2 parts, 28 of dimethyldimethoxysilane (DMDMS)
3 parts, 46 of phenyltrimethoxysilane (PTMS)
7 parts and 1,0 of isopropyl alcohol (IPA)
00 parts were charged and the temperature was raised to 60 ° C. Then, at the same temperature, 2.0 parts of "A-3" (iso-propyl acid phosphate manufactured by Sakai Chemical Industry Co., Ltd.) and 6 parts of deionized water were added.
The mixture with 70 parts was added dropwise over a period of 5 minutes. Then, the temperature was raised to 80 ° C., and stirring was carried out at the same temperature for 4 hours. Then, under reduced pressure of 10 to 300 mmHg, at 40 to 60 ° C., it took 4 hours to remove methanol and water produced by vacuum distillation to obtain a number average molecular weight of 1,300 in the reaction solution. As a result, the target polysiloxane was obtained in which the effective component [solid content in the case where the used alkoxysilane was completely hydrolyzed and further completely condensed] was 49.9%. Hereinafter, this is abbreviated as polysiloxane (a-1-1).

Analysis by nuclear magnetic resonance analysis ( ¹ H-NMR) confirmed that hydrolysis of the used alkoxysilane proceeded 100%. Therefore, it was confirmed that the obtained (a-1-1) was a polysiloxane having a hydroxyl group bonded to a silicon atom.

Reference Example 2 [Preparation Example of Polysiloxane (a-2)] In a reaction vessel similar to that of Reference Example 1, 1,000 parts of MTMS was charged and heated to 60 ° C. Then, at the same temperature,
A mixture of 0.12 parts of "A-3" and 146 parts of deionized water was added dropwise over 5 minutes. Then, the temperature was raised to 80 ° C., and stirring was carried out at the same temperature for 4 hours. Then, under reduced pressure of 10 to 300 mmHg, 40 to 60
The number average molecular weight was reduced to 9 by removing methanol and water produced by vacuum distillation at 4 ° C for 4 hours.
At 00, the target polysiloxane was obtained in which the active ingredient in the reaction solution [solid content when MTMS used was completely hydrolyzed and further completely condensed] was 70.0%. Hereinafter, this is abbreviated as polysiloxane (a-2-1).

When analyzed by ¹ H-NMR,
It was confirmed that (a-2-1) was a polysiloxane having both a hydroxyl group bonded to a silicon atom and a methoxy group bonded to a silicon atom.

Reference Example 3 [Preparation of vinyl polymer (b-1)] A reaction vessel equipped with a thermometer, a reflux condenser, a stirrer, a dropping funnel and a nitrogen inlet tube was charged with 950 parts of IPA and charged with nitrogen. The temperature was raised to 80 ° C. under aeration of gas. Then, at the same temperature, 400 parts of methyl methacrylate (MMA), n-
Butyl methacrylate (BMA) 200 parts, 2-hydroxyethyl methacrylate (HEMA) 200 parts, n-
Butyl acrylate (BA) 160 parts, 3-methacryloyloxypropyl trimethoxysilane (MPTMS)
A mixture consisting of 30 parts and 10 parts of acrylic acid (AA), 50 parts of IPA and tert-butylperoxy-2.
A mixture of 50 parts of ethylhexanoate (TBPOEH) was added dropwise separately over 4 hours. After completion of the dropping, the solution was stirred at the same temperature for 16 hours to obtain a solution of a vinyl polymer having a non-volatile content of 50.0% and a number average molecular weight of 11,000 and having a trimethoxysilyl group. Hereinafter, this is abbreviated as (b-1-1).

Reference Example 4 [Preparation Example of Control Resin (R)] The vinyl polymer (b-obtained in Reference Example 3) was placed in a reaction vessel equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel. 1
-1) 1,000 parts and 31 parts of the silicon compound (a-1-1) obtained in Reference Example 1 were charged and heated to 80 ° C,
By stirring for 4 hours at the same temperature, the hydrolysis reaction of the vinyl polymer (b-1-1) and the vinyl polymer (b-1-1) and the silicon compound (a-1-1) A condensation reaction between them was performed. When the reaction solution was analyzed by ¹ H-NMR, it was found that the hydrolysis of the trimethoxysilyl group contained in the vinyl polymer (b-1-1) proceeded 100%.

Then, vacuum distillation was carried out at 40 to 60 ° C. for 2 hours under a reduced pressure of 10 to 300 mmHg to remove the produced methanol and water, and a nonvolatile content of 50.2% was obtained. A resin was obtained. Hereafter, this (R-
Abbreviated as 1).

Reference Example 5 (same as above) In a reaction vessel similar to that of Reference Example 4, 977 parts of PTMS (b-1-1) obtained in Reference Example 3, 141 parts of PTMS and 86 parts of DMDMS were charged, and charged to 80 The temperature was raised to ° C. Then, here, 64 parts of deionized water and "A-3"
2.3 parts of the mixture was added dropwise over 5 minutes, and then the mixture was stirred at the same temperature for 4 hours to obtain PTMS and DMDMS.
Then, a co-hydrolysis condensation reaction of the vinyl polymer (b-1-1) was performed. When the reaction solution was analyzed by ¹ H-NMR, it was found that the hydrolysis of the trimethoxysilyl group contained in the vinyl polymer (b-1-1), PTMS and DMDMS proceeded 100%. found.

Subsequently, 376 parts of the silicon compound (a-2-1) obtained in Reference Example 2 and "MS-" were added to this reaction solution.
51 ”“ [Tetramethoxysilane oligomer manufactured by Mitsubishi Chemical Corporation: Effective solid content = 51%] 210 parts was rapidly added while stirring, and 200 parts of deionized water was further added dropwise over 5 minutes, and then 80 ° C. The mixture was stirred for 20 hours.
Finally, under reduced pressure of 10 to 300 mmHg, 40 to 60
After removing the produced methanol and water by performing vacuum distillation at 4 ° C. for 4 hours, 500 parts of IPA was added to obtain a composite resin having a nonvolatile content of 50.1%. Hereinafter, this is abbreviated as (R-2).

Reference Example 6 [Preparation of Composite Resin (C)] This example shows one example for preparing the composite resin (C). In a reaction vessel equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel, 1,000 parts of the vinyl polymer (b-1-1) obtained in Reference Example 3 and the reference example 1 were obtained. Charge 53 parts of a silicon compound (a-1-1),
By heating to 80 ° C. and stirring at the same temperature for 4 hours, the hydrolysis reaction of the vinyl polymer (b-1-1) and the vinyl polymer (b-1-1) and the silicon compound (a −
The condensation reaction with 1-1) was performed. The reaction solution
^{As a result of 1} H-NMR analysis, a vinyl-based polymer (b-
It was found that the hydrolysis of the trimethoxysilyl group contained in 1-1) proceeded 100%.

Subsequently, vacuum distillation was performed at 40 to 60 ° C. for 2 hours under a reduced pressure of 10 to 300 mmHg to remove the produced methanol and water, and to obtain a nonvolatile content of 50.0%. A composite resin was obtained. Hereinafter, this is abbreviated as (C-1).

Reference Example 7 (Same as above) A reaction vessel equipped with a thermometer, a reflux condenser, a stirrer, a dropping funnel and a nitrogen inlet tube was charged with 283 parts of PTMS and DMDM.
S 172 parts and IPA 500 parts were charged, and the temperature was raised to 80 ° C. under aeration of nitrogen gas. Then at the same temperature,
MMA 280 parts, BMA 140 parts, HEMA 140
Part, BA 112 parts, MPTMS 21 parts and AA 7 parts, IPA 35 parts and TBPOEH 35
And the mixture consisting of 1 part and 4 parts were separately added dropwise over 4 hours.

After completion of dropping, the mixture was stirred at the same temperature for 2 hours, then 4.6 parts of "A-3" and 1 part of deionized water were added.
30 parts of the mixture was added dropwise over 5 minutes, and 4 more
By continuing stirring for a period of time, PTMS,
A co-hydrolysis condensation reaction of DMDMS and the acrylic polymer was performed. When the reaction solution was analyzed by ¹ H-NMR, the hydrolysis of the methoxysilyl group contained in the acrylic polymer, PTMS and DMDMS was 100%.
It turned out to be proceeding.

Then, under reduced pressure of 10 to 300 mmHg, at 40 to 60 ° C. for 4 hours, vacuum distillation was performed to remove the produced methanol and water. Finally, by adding 465 parts of IPA with stirring at room temperature,
A target composite resin having a nonvolatile content of 49.9% was obtained. Hereinafter, this is abbreviated as composite resin (C-2).

Reference Example 8 (Same as above) In a reaction vessel similar to that of Reference Example 7, 500 parts of IPA and P were added.
Charge TMS 141 parts and DMDMS 86 parts,
The temperature was raised to 80 ° C. under aeration of nitrogen gas. Then, while stirring at the same temperature, 240 parts of MMA and 120 parts of BMA.
Part, HEMA 120 parts, BA 96 parts, AA 6 parts and MPTMS 18 parts and a mixture of IPA 30 parts and TBPOEH 30 parts, respectively,
Separately, the solution was added dropwise over 4 hours.

After completion of dropping, the mixture was stirred at the same temperature for 2 hours, then a mixture of 2.3 parts of "A-3" and 64 parts of deionized water was added dropwise over 5 minutes, and stirring was continued for another hour. Thus, the co-hydrolysis condensation reaction of PTMS, DMDMS and the acrylic polymer was performed. Reaction solution, ¹
When analyzed by 1 H-NMR, the acrylic polymer, P
It was found that the hydrolysis of the trimethoxysilyl group contained in TMS and DMDMS proceeded 100%.

Subsequently, 310 parts of the silicon compound (a-2-1) obtained in Reference Example 2 and "MS-" were added to this reaction solution.
51 "84 parts was rapidly added while stirring, and 135 parts of deionized water was further added dropwise over 5 minutes.
The mixture was stirred at 0 ° C for 20 hours. Finally, 10-300mm
After removing methanol and water by vacuum distillation under reduced pressure of Hg at 40 to 60 ° C. for 4 hours, 470 parts of IPA was added to obtain 50.0% of non-volatile content. The following composite resin was obtained. Hereinafter, this is abbreviated as (C-3).

Reference Examples 9 to 16 [Preparation Example of Colored Coating Agent] A mixture of a part of the composite resin (C) obtained in Reference Examples 6 to 8 and a colorant (D) was treated with a paint conditioner.
Pigment weight concentration (PWC) by shaking for 3 hours
Various colored bases with 40% were prepared. Then
This colored base, the rest of the composite resin (C), n-BuOH as a solvent, and, if necessary, a curing agent (E).
By mixing and, PWC becomes 12%,
Various colored coating agents were prepared.

Used in the preparation of the respective colored coating agents,
The amounts of the composite resin (C), colorant (D), n-BuOH or curing agent (E) used are as shown in Table 1.

Reference Examples 17 to 20 A mixture of a part of the control resin (R) obtained in Reference Example 4 or 5 and the colorant (D) was shaken with a paint conditioner for 3 hours to give Various colored bases with a pigment weight concentration (PWC) of 40% were prepared. Next, a comparative coating agent having a PWC of 12% was prepared by mixing the colored base, the rest of the control resin (R), n-BuOH, and the curing agent (E).

The amounts of the control resin (R), the colorant (D), the solvent n-BuOH and the curing agent (E) used in the preparation of the comparative coating agent were as shown in Table 1. is there.

[0157]

[Table 1]

<< Footnote in Table 1 >> Each numerical value showing the usage ratio of raw materials is assumed to be a weight part. * 1) "MLB-3R": Anthraquinone-based blue pigment "Monolight Blue 3R" manufactured by Zeneca Co., Ltd. * 2) "MG-6YCL": Brominated phthalocyanine green pigment "Monas" manufactured by Zeneca Co., Ltd. Tral Green 6YC
L ”* 3)“ L-110 ”: Dainippon Ink and Chemicals, Inc.
Iso-butylated melamine manufactured by "Super Beckamine
L-110-60 "; non-volatile content = 60% * 4)" D-550 ": non-yellowing blocked isocyanate" Bernock D-5 "manufactured by Dainippon Ink & Chemicals, Inc.
50 "; NCO content = 6.0 to 7.0%, nonvolatile content =
55%

[0159]

[Table 2]

<< Footnote in Table 1 >> Each numerical value showing the usage ratio of raw materials is assumed to be the number of parts by weight. * 5) "PY1841K": an isoindoline yellow pigment "Pariol Yellow 1841" manufactured by BASF Ltd.
K "

Examples 1 to 4 and Comparative Examples 1 and 2 Various coloring coating agents prepared in Reference Examples 9 to 12 and Reference Examples 17 to 18 (Coating-1) to (Coating-4) and (Ratio-
1) to (ratio -2) were preliminarily immersed in a 2.5% sodium hydroxide aqueous solution at 60 ° C. for 15 minutes or more for alkali cleaning, and then sufficiently washed with water to obtain a surface of a transparent cylindrical glass bottle of 1 liter. Was coated by the dipping method so that the average dry film thickness was 3 μm. After painting
After leaving at room temperature for 5 minutes for preliminary drying, baking was performed under the conditions as shown in Table 2 below to obtain a colored glass bottle as a coated object on which each coloring coating agent was applied.

Examples 5 to 8 and Comparative Examples 3 to 4 A 1 liter transparent cylindrical glass bottle, which had been subjected to alkali washing and water washing in the same manner as in Example 1, was charged with 3-glycidoxypropyltrimethoxysilane. After dipping in a wt% IPA solution for several seconds, it was left to stand at room temperature for about 10 minutes to be naturally dried. Then, on the surface of the glass bottle thus surface-treated, the colored coating agents (Coating-5) to (Coating-8) and (Ratio-3) to (Ratio-4) were respectively applied to the dried film having an average dry film thickness. It was coated by the dipping method so that the thickness became 3 μm. After coating, leave for 5 minutes at room temperature to perform preliminary drying, and then bake under the conditions shown in Table 2 below.
A colored glass bottle, which was a painted object, was obtained, on which each colored coating agent was applied.

A coating film performance evaluation test was carried out on each of the various colored glass bottles obtained. The test items are adhesion, hot water resistance and alkali resistance. Those results also
Collectively shown in Table 2.

[0164]

[Table 3]

<< Footnotes in Table 2 >>"Adhesiveness" means that a cutter knife is used to make 25 notches on the surface of the coating film at intervals of 2 mm by making 6 notches each in the vertical and horizontal directions. After the adhesive tape is attached, the coating film adhered to the base material when it is peeled off vigorously and remaining is displayed by the number of crosses. A value of "25" indicates 100% adhesion.

"Hot water resistance" means that various coated objects are treated at 90 ° C.
After being immersed in the hot water for 20 minutes, the surface condition was visually evaluated and judged. The criteria for the evaluation judgment are as follows. ◎ ... No abnormality ○ ... Slightly traced △ ... Gloss decreased × ... Peeling of coating film

"Alkali resistance 1" means that various coated objects are
After dipping in a 2.5% sodium hydroxide aqueous solution at 60 ° C. for 60 minutes, the surface condition was evaluated by visual inspection. The criteria for the evaluation judgment are as follows. ◎ ... No abnormality ○ ... Slightly traced △ ... Gloss decreased × ... Peeling of coating film or elution of coating film

"Alkali resistance 2" means that various coated objects are
After immersing in a 2.5% sodium hydroxide aqueous solution at 60 ° C. for 180 minutes, the surface condition was visually evaluated and judged. The criteria for evaluation is "alkali resistance 1"
It is subject to the evaluation judgment of.

[0169]

[Table 4]

[0170]

EFFECTS OF THE INVENTION The colored coated article of the present invention is coated with a coating having excellent alkali resistance that can be used as a returnable material, and can be re-melted to be regenerated as a colorless and transparent glass material. It is a highly painted material.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C03C 17/30 C09D 183/10 C09D 183/10 B05D 7/00 E // B05D 7/00 B65D 1/00 BF Term (Reference) 3E033 AA01 BA01 EA10 4D075 DB13 DC43 EB33 EB38 EB43 EB45 EC07 EC11 EC37 4F100 AG00A AH00B AK02B AK02J AK51B AK51J AB01 A59B07A16 J16A16B20A16B16A16B16A16B16A16B16A16B16B16B16A16B16B16B16B16A16B16B16A16B01BCA16B FA05 FA08 FA11 FA21 FA22 FB03 4J038 CG001 CR001 CR002 DA132 DB002 DG001 DG032 DG262 DG302 DL022 DL031 DL032 DL131 GA03 GA06 GA08 GA11 GA15 HA026 HA156 JA03 JA16 JA34 JB18 JB26 JB27 JB38 JC38 KA03 KA04 NA27 PA01 NA04 KA03

Claims (11)

[Claims] 1. A polysiloxane segment (A) having a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom and a polymer segment (B) other than polysiloxane on a glass substrate. And
A composite resin (C) having a weight ratio of (A) [(A) / (A) + (B)] of 5% or more and less than 50% and a colorant (D) are contained as essential components. A colored coated product obtained by applying the colored coating agent. 2. The colored coating agent also contains a curing agent (E) which reacts with a functional group of the composite resin (C).
The colored coated article described in. 3. The polysiloxane segment (A) and the polymer segment (B) have the following structural formula (S-1): [However, in the formula, the carbon atom is the polymer segment (B).
And two silicon atoms form part of the polysiloxane segment (A) or the polysiloxane segment (A). ] The colored coated article according to claim 1 or 2, wherein the colored coated objects are bonded by the bond shown in [3]. 4. The polysiloxane segment (A) has the following general formula (S-2): [Wherein R ¹ represents a monovalent organic group, which may or may not have a substituent, which is an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group, R ² Is a halogen atom, an alkoxy group, a substituted alkoxy group, an acyloxy group, a phenoxy group, a mercapto group,
Represents an amino group, an amido group, an aminooxy group, an iminooxy group or an alkenyloxy group, and a
Is 1 or 2. ] The segment derived from the hydrolysis-condensation product or partial hydrolysis-condensation product of the silicon compound which has the silane compound shown by these as an essential component.
The colored coated article according to any one of 3 to 3. 5. The colored coated article according to claim 4, wherein the silane compound is at least one alkoxysilane selected from the group consisting of organotrialkoxysilane and diorganodialkoxysilane. 6. The polymer segment (B) is a segment derived from at least one polymer selected from the group consisting of vinyl-based polymers and polyurethane-based polymers. The colored coated article according to item. 7. The colored coated article according to any one of claims 1 to 6, wherein the colorant (D) is an organic pigment. 8. A compound in which the curing agent (E) has a hydroxyl group bonded to a silicon atom and / or a hydrolyzable group bonded to a silicon atom, an epoxy group and a hydrolyzable group bonded to a silicon atom in one molecule. The compound having at least one of, a polyisocyanate compound, a blocked polyisocyanate compound, a polyepoxy compound, a polyoxazoline compound, and at least one compound selected from the group consisting of amino resins, any one of claims 1 to 7. The described colored coating agent. 9. The colored coated article according to claim 1, wherein the glass base material has a surface treatment agent applied thereto in advance. 10. The surface treating agent contains a compound having both a hydrolyzable group bonded to a silicon atom and / or a hydroxyl group bonded to a silicon atom and an epoxy group in one molecule. 9. The colored coated article according to 9. 11. The glass substrate is a glass bottle.
10. The colored coated article according to any one of items 10 to 10.