JP2000265113A - Production of coating agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a coating agent capable of improving storage stability of a coating agent containing an organosilane compound. SOLUTION: This method comprises producing a coating agent composed of an organosilane compound of the formula RacSi(ORb)d (Ra is an alkyl group which may contain a functional group; Rb is a 1-4C alkyl group; c is an integer of 0-3; d is an integer of 1-4 and c+d is 4) and a solvent in which the concentration of the organosilane compound is C1%; (calculated as RacCSi(ORb)d/2; wt.%). In this case, the organosilane compound is hydrolyzed in a low-concentration solution having C1/3 to 2C1/3% (calculated as RacSi(ORb)d/2; wt.%) organosilane compound concentration, a part of the solvent is distilled away and the concentration of the organosilane compound is adjusted to C1%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a coating agent for coating a film or various substrates, and more particularly, to an organic compound having a hydrolyzable group and having difficulty in controlling a polycondensation reaction. The present invention relates to a method for producing a coating agent containing a silane compound and exhibiting excellent storage stability.

[0002]

2. Description of the Related Art Alkoxysilane compounds are hydrolyzed and condensed with water to form a dense film, and are therefore used in various fields as coating agents and the like. When used as a coating agent, a method is usually employed in which hydrolysis and condensation are carried out to some extent before coating the substrate.
This is to prevent the volatilization of the silane monomer during drying by allowing the hydrolysis reaction to proceed, and to shorten the time required for polycondensation after film formation to suppress the drying and curing step to a short time. In addition, it is very difficult to control the hydrolysis reaction, and it is difficult to ensure storage stability as a coating agent. For example, a silane compound having an alkoxysilyl group such as a methoxysilyl group is extremely liable to undergo a hydrolysis-condensation polymerization reaction, and forms a three-dimensional cured polymer and gels even when sealed and stored. Further, cloudiness often occurs due to the difference in solubility between the polycondensed polymer and the silane monomer. Since a coating agent that has gelled or clouded can no longer form a uniform film as a coating agent, there has been a problem that an expensive organic silane compound is wasted.

[0003]

[SUMMARY OF THE INVENTION] The present invention is an organic silane compound (I) in _{^{R a c Si (OR b)}} d ... (I) ( formula represented by the following general formula (I), R ^a is functional An alkyl group which may have a group,
R ^b represents an alkyl group having 1 to 4 carbon atoms, c is an integer of 0 to 3, d is an integer of 1 to 4, and c + d is 4. )
An object of the present invention was to find a method for producing a coating agent capable of improving the storage stability of a coating agent containing the same.

[0004]

Means for Solving the Problems The method of producing the coating agent of the present invention which solves the above problems, an organic silane compound represented by the following general formula ^{(I) (I) R a} c Si (OR b) d ... ( I) wherein R ^a is an alkyl group which may have ^a functional group,
R ^b represents an alkyl group having 1 to 4 carbon atoms, c is an integer of 0 to 3, d is an integer of 1 to 4, and c + d is 4. )
And a solvent, and the concentration of the organosilane compound (I) is C
_{^{1% (R a c Si (}} OR b) d / 2 terms; wt%) A process for producing a coating agent, in advance, the concentration of the organic silane compound _{(I) C 1 / 3~2C 1} /3 % (R ^a _c Si (O
After performing a hydrolysis reaction of the organic silane compound (I) in a solution having a low concentration of R ^b ) ( _{d / 2} conversion; weight%), a part of the solvent is distilled off, and the concentration of the organic silane compound (I) is reduced. Is adjusted to be C ₁ %. This is because it has been found that by performing the hydrolysis reaction at a low concentration and then increasing the concentration, the storage stability is significantly improved.

[0005] The concentration of C _1% is, 7.5~60% (R ^a _c
Si (OR ^b ) _{d / 2} conversion; weight%) is preferable. Within this range, good storage stability can be ensured.

The coating agent produced by the production method of the present invention includes an organic compound (A) having a functional group (excluding an alkoxysilyl group), and the organic compound (A).
A functional group capable of reacting with the functional group of
R ¹ ) an organic silane compound (B) having a group (R ¹ is an alkyl group having 1 to 4 carbon atoms) and / or a hydrolyzed condensate thereof, and an organic silane compound (C) represented by the following general formula (C) and / or its hydrolytic _{^{condensate, R 2 m Si (oR 3}} ) n ... (C) ( wherein, R ² may be the same or different, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, aryl Represents a functional group directly bonded to a group, a vinyl group or a carbon chain, R ³ may be the same or different, represents an alkyl group having 1 to 4 carbon atoms, m is 0 or a positive integer, and n is 1 or more. An integer and m + n is 4.). Both the organic silane compound (B) and the organic silane compound (C) of the preferred coating agent correspond to the organic silane compound (I).

[0007]

In the manufacturing method of the embodiment of the present invention, an organic silane compound represented by the following general formula (I) (I) in _{^{R a c Si (OR b)}} d ... (I) ( wherein, R ^a is functional An alkyl group which may have a group,
R ^b represents an alkyl group having 1 to 4 carbon atoms, c is an integer of 0 to 3, d is an integer of 1 to 4, and c + d is 4. )
And a solvent, and the concentration of the organosilane compound (I) is C
_{^{1% (R a c Si (}} OR b) d / 2 terms; wt%) In producing the coating agent is, in advance, C ₁ / 3~2C _{1
^{/ 3% (R a c Si}} (OR b) d / 2 terms; wt%) was hydrolyzed reaction at low concentration range of, then adjusted by distilling off part of the solvent in a concentration C _1%. Incidentally, R ^a _c Si in this case
(OR ^b) _{d / 2} in terms of A, computationally, alkoxysilyl group of the organic silane compound (I) all R ^a _c Si (OR ^b)
_{It is d / 2} , that is, the weight% calculated as a state in which the hydrolytic condensation is completed. All the concentrations of the coating agent of the present invention have the above-mentioned meaning, and are hereinafter simply referred to as “%”.

When a hydrolysis reaction is carried out in a high-concentration organic silane compound solution, the hydrolysis reaction does not occur uniformly in the solution, but the reaction may rapidly proceed locally, resulting in cloudiness or gelation. Easily. On the other hand, if the concentration of the coating agent is too low, time and energy for removing the solvent in the drying and film forming process are wasted. Therefore, in the production method of the present invention, the hydrolysis reaction of the organic silane compound (I) is performed in a low concentration range of 1/3 to 2/3 of C ₁ %, which is a concentration suitable for storing the coating agent. After this, it was an essential requirement that the concentration of the coating agent be adjusted to C ₁ % by distilling off part of the solvent. With this configuration, it has become possible to stably perform the hydrolysis reaction and provide a coating agent having excellent storage stability.

[0009] During storage of the coating agent, the organic silanization
Concentration C of compound (I)₁% Should be 7.5-60%
Is preferred. Organic silane compound (I) is lower than 7.5%
For the concentration, it takes time and
Energy is useless. If over 60%, Cotin
The stability of the agent solution becomes extremely poor. More preferred C ₁
% Is 10 to 45%, more preferably 15 to 45%.
30%.

Even if the concentration C ₁ % of the coating agent is adjusted within the above range, if the hydrolysis reaction is carried out at a concentration higher than or the same as the concentration of the coating agent, the storage stability deteriorates. Reaction is 1/3 of C ₁ %
It must be performed in a low concentration range of ２/3 (1.5-20%). The lower concentration than C _1/3, in a subsequent solvent evaporation process over no merit must distilled off much of the solvent, energy is wasted. However, 2C ₁ /
When hydrolysis is performed in a high concentration range exceeding 3, a hydrolysis reaction may occur rapidly and gel may occur. In the present invention,
"Preservation stability is good" means that when the coating agent is stored at 50 ° C. in a closed state, it does not cause clouding or gelation for 2 months or more.

The coating agent suitable for the production method of the present invention contains an organic silane compound (I) as an essential component. This is because the purpose of the production method of the present invention is to stabilize such an organosilane compound (I). Most preferably, the alkoxysilyl group of the organic silane compound (I): Si (OR ^b ) group is a methoxysilyl group, and the stabilizing effect according to the method of the present invention is exhibited, and the coating is performed by the high reactivity of the methoxysilyl group. Since the curing reaction occurs quickly in the process, the curing time can be shortened at the same time.

Examples of the solvent for the coating agent include water necessary for the hydrolysis reaction, alcohols such as methanol, ethanol, 2-propanol, butanol and ethylene glycol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and toluene. , Aromatic hydrocarbons such as benzene and xylene, hydrocarbons such as hexane, heptane and octane, esters such as ethyl acetate and butyl acetate, and others, such as tetrahydrofuran and propyl ether. A mixture of more than one species can be used. Among them, alcohols such as methanol and ethanol are preferable because they are excellent in stability during hydrolysis reaction and storage stability.

The point of the method of the present invention is, as described above,
The hydrolysis reaction is performed in a low concentration range, and then a part of the solvent is distilled off to adjust the concentration to a high concentration. When the solvent is distilled off to obtain a high concentration, the organic silane compound (I)
After the water added for the hydrolysis of is consumed and the organic silane monomer disappears, it is preferable that As the specific time, since the reactivity and the reaction rate of the hydrolysis vary depending on the type of the alkoxysilyl group or the organic silane monomer, it cannot be said unconditionally. The reaction is considered to have reached equilibrium, so it is recommended to use this as a guide.
If 24 hours have passed after the start of the hydrolysis reaction, there is no problem in practical operation because almost equilibrium reaction is reached in a coating agent having a general composition. Conversely, if the hydrolysis reaction is carried out for a longer period of time, the productivity will be reduced, which is not preferable.

On the other hand, with respect to the amount of water, if the amount of water in the solvent is too large during the hydrolysis reaction in a low concentration range, the hydrolysis reaction may occur rapidly and gelation is likely to occur, and the coating agent becomes unstable. Since water tends to be easily formed, the amount of water needs to be an amount that does not cause gelation. However, since the reactivity of hydrolysis is different depending on the type of alkoxysilyl group and monomer, the ease of gelation is also different.Therefore, the amount of water is considered in consideration of the reactivity of the alkoxysilyl group. Since it is the highest, the amount of water may be suppressed, and may be changed as appropriate.

If the amount of water is suppressed too much, the stability as a coating agent is excellent, but the monomer volatilizes before forming a dense polymer chain when the coating agent is formed into a film. It is environmentally dangerous, and the physical properties of the coating agent and the film may be unstable. Therefore, when the amount of the residual silane monomer in the coating agent becomes 10% or less with respect to the amount of the organic silane compound (I) contained before the hydrolysis reaction, the concentration may be increased by distilling off the solvent. It is preferable to adjust the amount of water so that it can be performed. A more preferred residual monomer amount is 4
%, More preferably 1% or less.

In the production method of the present invention, a coating agent containing the organosilane compound (I) represented by the general formula (I) and a solvent as essential components is subjected to a hydrolysis reaction in a specific concentration range. Having a gist in producing a stable high concentration coating agent by distilling off a part of the solvent,
The compounding components other than the above essential components of the coating agent are not particularly limited. However, in order to form a flexible film that is tough and free from cracks, etc., a specific organic silane compound (I) is required. It is preferable to use a compounding component other than the organic silane compound together with the organic silane compound. Such a coating agent will be described below.

The coating agent includes an organic compound (A) having a functional group (excluding an alkoxysilyl group), a functional group capable of reacting with the functional group of the organic compound (A), and Si (OR ¹ ) An organic silane compound (B) having a group (R ¹ is an alkyl group having 1 to 4 carbon atoms) and / or a hydrolytic condensate thereof, and an organic silane compound (C) represented by the following general formula (C) and / or The hydrolysis condensate R ² _m Si (OR ³ ) _n ... (C) (wherein R ² may be the same or different and is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, a vinyl group) Or a functional group directly bonded to a carbon chain, R ³ may be the same or different and represents an alkyl group having 1 to 4 carbon atoms, m is 0 or a positive integer, n is an integer of 1 or more, and m + n is 4.) Things. The organic silane compound (I) may include both the organic silane compound (B) and the organic silane compound (C).

The organic compound (A) is not particularly limited as long as it has a functional group other than the alkoxysilyl group. Since the organic compound (A) does not have an alkoxysilyl group, it does not participate in the hydrolysis condensation reaction of the organic silane compound (B) or the organic silane compound (C).
A film formed only with a silane compound has a drawback of being hard but brittle (poor in impact resistance). However, by adding an organic compound (A) to a coating agent, the film becomes flexible and flexible. Can be provided. Although the organic compound (A) does not participate in the hydrolysis-condensation reaction, it reacts with the organic silane compound (B) by the functional group of (A) and is incorporated into the polymer chain constituting the coating. Thus, a so-called soft segment portion is formed in the polymer chain constituting the coating. Therefore, the impact resistance of the coating can be improved without lowering the hardness, the strength, and the denseness.

The organic compound (A) needs to be a compound having a functional group other than the alkoxysilyl group, but the type of the functional group is not particularly limited. Various functional groups can be used depending on the combination of Among them, a combination of an amino group and an epoxy group is preferable because the reaction rate is high and the coating is quickly cured. As the organic compound (A), the functional group is 2
A compound having more than one compound is also effective for speeding up curing.

In a preferred embodiment of the coating agent,
Organic compound (A) is an epoxy group, an isocyanate group,
Examples of the configuration include a compound having at least one functional group selected from the group consisting of a carboxyl group or an anhydride thereof, an oxazolinyl group, a halogenated alkyl group, and a hydroxyl group. Especially, it is preferable to have an epoxy group. In this case, it is recommended that the organic silane compound (B) has an alkoxysilyl group and an amino group.

In another preferred embodiment of the coating agent, the organic compound (A) is a compound having an amino group, in particular, a polymer compound having a molecular weight of 200 or more provides flexibility to the coating film. It is preferable from the viewpoint of doing. More preferably, they are polyethylene imines. In this case, the organic silane compound (B) is an organic silane compound having a functional group capable of reacting with an amino group together with an alkoxysilyl group, and particularly a compound having an epoxy group. Preferably, there is.

Specific examples of the organic compound (A) having an amino group include allylamine, diallylamine, isopropylamine, diisopropylamine, iminobispropylamine, ethylamine, diethylamine, 2-ethylhexylamine, 3-ethoxypropylamine, and diisobutylamine. , 3-diethylaminopropylamine, di-2-ethylhexylamine, dibutylaminopropylamine, propylamine, dimethylaminopropylamine, methyliminobispropylamine, 3-methoxypropylamine, ethylenediamine, 1,4-diaminobutane, 1, 2-diaminopropane, 1,3-diaminopropane, hexamethylenediamine, ethanolamine,
Low molecular weight organic compounds having one or more amino groups such as diethanolamine; polyethyleneimines, for example, Epomin series (Nippon Shokubai Co., Ltd. (Epomin SP-003, Epomin SP-006, Epomin SP-012, Epomin SP)
-018, Epomin SP-103, Epomin SP-11
0, epomin SP-200, epomin SP-300, epomin SP-1000, epomin SP-1020, etc.),
Polyallylamines (for example, PAA-L manufactured by Nitto Boseki Co., Ltd.
PAA-H, etc.), homopolymers of amino group-containing (meth) acrylates such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate, and these amino group-containing (meth) acrylates and other (meth) acrylates And copolymers with (meth) acrylic acid, and high molecular organic compounds containing amino groups such as polyoxyethylene alkylamines.

Specific examples of the organic compound (A) having an epoxy group include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene glycol diglycidyl ether, Aliphatic diglycidyl ethers such as propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and glycerol diglycidyl ether; Glycerol triglycidyl ether, diglycerol triglycidyl ether, triglycidyl tris (2 (Hydroxyethyl) isocyanurate, polyglycidyl ethers such as trimethylolpropane triglycidyl ether and pentaerythritol tetraglycidyl ether; aliphatic and aromatic diglycidyl esters such as adipic acid diglycidyl ester and o-phthalic acid diglycidyl ester; Bisphenol A diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, bisphenol S diglycidyl ether, bisphenol F
Diglycidyl ether and compounds represented by the following formula

[0024]

Embedded image

Glycidyls having an aromatic ring or a hydrogenated ring thereof (including a nuclear-substituted derivative); or oligomers having a glycidyl group as a functional group (for example, in the case of bisphenol A diglycidyl ether oligomer, Can be expressed);

[0026]

Embedded image

And the like.

Hexamethylene diisocyanate,
Isocyanates such as tolylene diisocyanate, 1,4-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, tolidine diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate; dicarboxylic acids such as tartaric acid and adipic acid; polyacrylic Carboxyl-containing polymers such as acids; oxazolinyl group-containing polymers and the like can also be used as the organic compound (A). One or more of these may be used. Among the organic compounds (A) exemplified above, compounds having an aromatic ring or a hydrogenated ring thereof (including a nuclear-substituted derivative) have an effect of improving the water resistance of the coating.

The organic silane compound (B) has a functional group capable of reacting with the functional group of the organic compound (A) and Si.
It is a compound having an (OR ¹ ) group (R ¹ is an alkyl group having 1 to 4 carbon atoms). It is necessary to determine the functional group of the organic silane compound (B) according to the functional group of the organic compound (A).

Specifically, N-β (aminoethyl) γ-
Aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β
(Aminoethyl) γ-aminopropyltriisopropoxysilane, N-β (aminoethyl) γ-aminopropyltributoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, N
-Β (aminoethyl) γ-aminopropylmethyldiisopropoxysilane, N-β (aminoethyl) γ-aminopropylmethyldibutoxysilane, N-β (aminoethyl) γ-aminopropylethyldimethoxysilane, N-
β (aminoethyl) γ-aminopropylethyldiethoxysilane, N-β (aminoethyl) γ-aminopropylethyldiisopropoxysilane, N-β (aminoethyl) γ-aminopropylethyldibutoxysilane, γ-
Aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropyltributoxysilane, γ-aminopropylmethyldimethoxysilane, γ-
Aminopropylmethyldiethoxysilane, γ-aminopropylmethyldiisopropoxysilane, γ-aminopropylmethyldibutoxysilane, γ-aminopropylethyldimethoxysilane, γ-aminopropylethyldiethoxysilane, γ-aminopropylethyldiiso Propoxysilane, γ-aminopropylethyldibutoxysilane, γ-aminopropyltriacetoxysilane, γ-
(2-ureidoethyl) aminopropyltrimethoxysilane, γ- (2-ureidoethyl) aminopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl)-
Amino group-containing compounds such as γ-aminopropyltrimethoxysilane; β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4
-Epoxycyclohexyl) ethyltriisopropoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane Epoxy group-containing compounds such as, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane; Or γ-isocyanopropyltrimethoxysilane, γ-isocyanopropyltriethoxysilane, γ-
Isocyanopropylmethyldimethoxysilane, isocyanate group-containing compounds such as γ-isocyanopropylmethyldiethoxysilane; mercapto group-containing compounds such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; and the like. One or more kinds can be used. In addition, these organic silane compounds (B) must be selected so that they can react with the functional group of the organic compound (A).

The organic silane compound (B) reacts with the organic compound (A) and has a hydrolyzable group of Si (O
R ¹ ) group (R ¹ has the same meaning as described above), so that it undergoes hydrolytic polycondensation, and also co-hydrolytic polycondensation with the hydrolyzable condensed group of the organosilane compound (C) described below. Therefore, a dense film can be formed quickly. It also has the effect of increasing the adhesion between the coating and the substrate.

The organic silane compound (C) used in the present invention is not particularly limited as long as it is represented by the following general formula (C). R ² _m Si (OR ³ ) _n ... (C) (wherein R ² may be the same or different and is directly connected to a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, a vinyl group or a carbon chain) R ³ may be the same or different and represents an alkyl group having 1 to 4 carbon atoms, m is 0 or a positive integer, n is an integer of 1 or more, and m + n is 4. .).

The organic silane compound (C) can be distinguished from the organic silane compound (B) in that it does not have a functional group capable of reacting with the functional group of the organic compound (A). The organic silane compound (C) enhances the adhesion to the substrate and forms a dense film of the polysiloxane skeleton together with the organic silane compound (B), so that a film having excellent heat resistance can be formed.

As specific examples, tetramethoxysilane,
Tetraethoxysilane, tetraisopropoxysilane,
Tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, dimethyldimethoxysilane, Examples thereof include dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldiisopropoxysilane, and diethyldibutoxysilane. Among them, tetramethoxysilane and tetraethoxysilane are preferable from the viewpoint of the reactivity and the improvement of the water resistance of the film.

An organic metal compound having the same effect as the organic silane compound (C) can be used as one of the components of the coating agent. Specifically, titanium tetraethoxide, titanium tetraisopropoxide, titanium alkoxides such as titanium tetrabutoxide, zirconium tetraethoxide, zirconium tetraisopropoxide, zirconium alkoxides such as zirconium tetrabutoxide, aluminum triethoxide, Aluminum alkoxides such as aluminum triisopropoxide and aluminum tributoxide;

The specific coating agent described above essentially contains an organic compound (A), an organic silane compound (B), an organic silane compound (C) and a solvent. The total amount of each compound other than the solvent in this coating agent was 1
A preferred amount of each compound when the content is set to 00% by weight will be described. The organic compound (A) is preferably 1 to 40% by weight. When the amount of the organic compound (A) is less than 1% by weight, the flexibility of the coating film is insufficient, and the effect of improving the impact resistance may not be exhibited. If the amount is more than 40% by weight, the amount of the organic silane compound (B) or the organic silane compound (C) decreases, so that a dense and strong film cannot be obtained. A more preferred use amount of (A) is in the range of 5 to 30% by weight,
More preferably, it is 5 to 20% by weight.

The content of the organic silane compound (B) is preferably 0.5 to 80% by weight. If the amount of the organic silane compound (B) is less than 0.5% by weight, the adhesion of the film to the substrate is not good, but if it is more than 80% by weight, the moisture resistance of the film tends to be poor. The more preferred amount of the organic silane compound (B) is in the range of 1 to 70% by weight, and more preferably 1 to 6% by weight.
0% by weight.

5 to 90% by weight of the organic silane compound (C)
Is preferred. When the amount of the organic silane compound (C) is less than 5% by weight, the moisture resistance of the coating may be insufficient. But 9
If it is used in excess of 0% by weight, the amount of the organic compound (A) used is reduced, so that the flexibility of the film is reduced. A more preferred amount of the organic silane compound (C) is in the range of 10 to 90% by weight, and further preferably 30 to 80% by weight.
It is.

In the production method of the present invention, a coating agent containing the organic silane compound (I) is produced. In the case of the specific coating agent, the organic silane compound (B) is used.
And either or both of the organic silane compound (C) correspond to the organic silane compound (I). Therefore, in the hydrolysis reaction in a low-concentration solution, a cohydrolysis reaction between the organic silane compound (B) and the organic silane compound (C) is performed (method). Although the procedure is somewhat complicated, the organic silane compound (B) and the organic silane compound (C) are separately hydrolyzed at a low concentration, and then the respective solvents are partially distilled off to obtain a high concentration. It is also possible to employ a method in which both are mixed after the reaction (method), or a method in which both are mixed after the hydrolysis reaction and a part of the solvent is distilled off (method).

Regarding the method of adding the organic compound (A),
After a functional group reaction between the organic compound (A) and the organic silane compound (B) is performed in advance, a method similar to the above-described method 1 or 2 is applied to the reaction product, or an organic compound (A) is used in the presence of the organic compound (A). A method of co-hydrolyzing and condensing the silane compound (B) and the organic silane compound (C) to increase the concentration, co-hydrolyzing and condensing the organic silane compound (B) and the organic silane compound (C), and removing a part of the solvent. Organic compound (A) after distillation
And the reaction is carried out.

The coating agent obtained by the method of the present invention includes:
If necessary, various inorganic and organic additives such as a curing catalyst, a wettability improver, a plasticizer, an antifoaming agent, and a thickener can be added as necessary.

The substrate on which a coating with the coating agent obtained by the method of the present invention can be formed is not particularly limited. It can be coated on anything such as plastic, wood, knit, woven, non-woven, paper, synthetic paper, metal, metal foil. As a widely used base material, not a thin film such as a plastic film or a film,
Examples include resin molded articles such as bottles and containers, and various molded articles.

The type of plastic constituting the film and the molded product is not particularly limited.
Polyester, polyamide resin, poly (meta) such as olefin resin such as polypropylene, styrene resin such as polystyrene, polyethylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalate, polybutylene terephthalate and copolymers thereof.
Acrylic resins such as acrylic acid and its esters, polyoxymethylene, polyacrylonitrile, polyvinyl acetate, ethylene-vinyl acetate copolymer (EVA), polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer Coalescence, polyetherketone, polycarbonate, cellophane, polyethersulfone, polysulfone, polyphenylenesulfone,
Thermoplastic resins such as polyimide, ionomer resin, and fluororesin, and thermosetting resins such as melamine resin, polyurethane resin, epoxy resin, phenol resin, unsaturated polyester resin, alkyd resin, urea resin, and silicon resin can be preferably used. Of course, two or more of these laminates may be used as the base material.

The method of coating the above-mentioned base material with the coating agent is not particularly limited, and examples thereof include roll coating, dip coating, bar coating, nozzle coating, die coating, spray coating, and a combination thereof. Can be adopted. Since the coating agent of the present invention has excellent storage stability, not only a bar coating method but also a dip coating method and a roll coating method can be used, but the coating agent may gel when exposed to air. It is preferable to use a nozzle coating method, a spray coating method, or a die coating method, which can keep the coating agent from contacting air to the outlet. The thickness of the coating is not particularly limited, but is usually in the range of 0.1 to 20 μm after drying.

The coating agent is coated on the entire surface or a part of the resin molded product, or on one or both surfaces of the film. It is recommended that drying after coating be performed in a heating / humidifying step of 50 ° C. or more and RH of 5% or more, since a dense film can be formed with good drying efficiency. Before the coating agent is applied, a known anchor coat layer such as a urethane resin may be provided on the substrate.

Other layers may be laminated on the coating film obtained by the method of the present invention. Laminating means, as a substrate, a coating method, an extrusion method, a dry lamination, a wet lamination, a material laminated in advance by a lamination method such as a hot melt lamination or the like, or after coating the coating agent of the present invention, Means for laminating by a known method such as coating another layer or performing vapor deposition can be adopted. As a material to be laminated, a known material that can be used as the base material can be used. If necessary for lamination, a known adhesive may be used.

The coating film obtained by the method of the present invention has sufficient strength and hardness, and has good abrasion resistance, impact resistance, heat resistance, flexibility, transparency, moisture resistance, solvent resistance and the like. Since it is excellent, it can be applied to various uses for forming a protective film and for various other purposes.

[0048]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which do not limit the present invention.
Modifications and alterations that do not depart from the spirit described below are all included in the technical scope of the present invention.

The storage stability is a result of visually observing a period until the film becomes clouded or gelled when the coating agent is sealed in a sealable container and stored in an atmosphere at 50 ° C.

Example 1 A flask equipped with a stirrer, a thermometer and a cooler was charged with 20 g of tetramethoxysilane, 4.0 g of water, 0.8 g of 0.1N hydrochloric acid and 54.4 g of methanol.
For 24 hours to carry out a hydrolysis reaction. Thereafter, only 39.6 g of methanol was distilled off from this solution to obtain a coating agent 1. Table 1 shows the physical property evaluation results of this coating agent 1. In the table, the concentration at the time of hydrolysis was C ₀
%. Further, for both C ₀ and C ₁ , R ^a _c Si (OR ^b ) _{d / 2}
It is a weight% in conversion.

Example 2 A flask equipped with a stirrer, a thermometer and a cooler was charged with γ-
20 g of methacryloxypropyltrimethoxysilane, 2.0 g of water, 0.2 g of 0.1 N nitric acid and methanol.
1 g and toluene 61.1 g were charged at 30 ° C. for 24 hours.
The hydrolysis reaction was performed by stirring for hours. 72.2 g of the solvent was distilled off from this mixed solution to obtain a coating agent 2. Table 1 shows the evaluation results of the physical properties of this coating agent 2.

Example 3 In a flask equipped with a stirrer, a thermometer and a cooler, γ-
After charging 100 g of aminopropyltrimethoxysilane, 50.0 g of methanol and 30 g of toluene, and heating to 70 ° C., 10 g of bisphenol A diglycidyl ether
Was added dropwise over 30 minutes. Further, the mixture was aged at 70 ° C. for 3 hours and cooled to room temperature.
g of the mixed solution, and the mixture is aged by stirring at room temperature for 1 hour.
Further, 65 g of tetramethoxysilane oligomer “M silicate 51” (manufactured by Tama Chemical Co., Ltd.) and 756 g of methanol
And aged at room temperature for 24 hours. From this mixed solution, 349 g of the solvent was distilled off to obtain a coating agent 3. Table 1 shows the physical property evaluation results of this coating agent 3.

Example 4 A coating agent 4 was obtained in the same manner as in Example 3, except that bisphenol A diglycidyl ether was replaced with resorcinol glycidyl ether. Table 1 shows the results of evaluating the physical properties of this coating agent 4.

Example 5 In a flask equipped with a stirrer, a thermometer and a cooler, 8.0 g of polyethyleneimine “Epomin SP018” (manufactured by Nippon Shokubai Co., Ltd.), 3.0 g of γ-glycidoxypropyltrimethoxysilane, methanol After charging 50 g and heating to 70 ° C., the mixture was aged for 3 hours and then cooled to room temperature. A mixed solution of 0.2 g of water and 5 g of methanol was added, and the mixture was stirred and aged at room temperature for 1 hour. To this solution, 15.0 g of “M silicate 51” and 96.5 g of methanol were further added, and the mixture was aged at room temperature for 24 hours. From this mixed solution, 59.2 g of methanol was distilled off to obtain a coating agent 5. Table 1 shows the results of evaluating the physical properties of this coating agent 5.

Comparative Example 1 In the coating agent of Example 4, the solid concentration was 15
Comparative Example 1 was obtained in the same manner as in Example 4 except that the composition was changed to%. Table 1 shows the results of evaluating the physical properties of this comparative coating agent 1.

Comparative Example 2 In the coating agent of Example 5, the solid content was adjusted to 15
Comparative Example 2 was obtained in the same manner as in Example 4 except that% was changed to%. Table 1 shows the physical property evaluation results of this comparative coating agent 2.

Comparative Example 3 A coating agent for comparison 3 was obtained in the same manner as in Example 4 except that the amount of the solvent distilled off was changed to 720 g. Agent 3 has gelled.

[0058]

[Table 1]

[0059]

The method for producing the coating agent of the present invention comprises:
The hydrolyzable organic silane compound is hydrolyzed at a low concentration in advance, and then a part of the solvent is distilled off to obtain a high-concentration coating agent. Thus, it was possible to provide a coating agent having excellent storage stability without causing aging. Since the coating agent obtained by the method of the present invention quickly forms a dried / cured film in the film forming step, it was possible to prevent environmental pollution and to save energy.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J035 AA01 BA01 BA11 CA061 CA112 CA142 CA192 EB02 LA05 LB01 4J038 DL021 DL022 DL051 DL052 JC32 KA06 PC08

Claims (3)

[Claims] 1. A in the following formula the organosilane compound represented by ^{(I) (I) R a} c Si (OR b) d ... (I) ( wherein, R ^a which may have a functional group alkyl Group,
R ^b represents an alkyl group having 1 to 4 carbon atoms, c is an integer of 0 to 3, d is an integer of 1 to 4, and c + d is 4. )
And a solvent, and the concentration of the organosilane compound (I) is C
_{^{1% (R a c Si (}} OR b) d / 2 terms; wt%) A process for producing a coating agent, in advance, the concentration of the organic silane compound (I) C ₁ / 3~2C _{1
^{/ 3% (R a c Si}} (OR b) d / 2 terms; wt%) After the hydrolysis reaction of the organic silane compound at low concentrations in the solution (I), and distilling off part of the solvent Organosilane compound (I)
A method for producing a coating agent, comprising adjusting the concentration of C to ₁ %. 2. The method according to claim 1, wherein said concentration C ₁ % is 7.5 to 60% (R ^a
_{2. The} method for producing a coating agent according to claim 1, wherein _c Si (OR ^b ) _{d / 2} conversion; 3. A coating agent comprising an organic compound (A) having a functional group (excluding an alkoxysilyl group), a functional group capable of reacting with the functional group of the organic compound (A), and Si (OR ¹ A) an organic silane compound (B) having a group (R ¹ is an alkyl group having 1 to 4 carbon atoms) and / or a hydrolytic condensate thereof, and an organic silane compound (C) and / or Or a hydrolyzed condensate thereof, R ² _m Si (OR ³ ) _n ... (C) (wherein R ² may be the same or different and is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, Represents a vinyl group or a functional group directly bonded to a carbon chain, R ³ may be the same or different and represents an alkyl group having 1 to 4 carbon atoms, m is 0 or a positive integer, and n is an integer of 1 or more. And m + n is 4.) Claim 1
Or the method for producing a coating agent according to item 2.