JP2002226770A - Coating agent composition, cured film of coating agent and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating agent composition excellent in thermostability, thermal decomposition resistance, low thermal expansibilty, adhesion, acid resistance and scratch resistance as well as capable of obtaining a transparent cured film, a cured film of a coating agent obtained from the composition and a manufacturing method of the cured film. SOLUTION: This coating agent composition comprises a silane-modified epoxy resin containing an alkoxy group obtained from dealcoholic condensation reaction of (1) an epoxy resin containing hydroxy groups, (2) an epoxy compound having one hydroxy group in one molecule and (3) a partial condensate of an alkoxysilane, the cured film of a coating agent is obtained by curing the composition; and the manufacturing method of the cured film is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a coating composition containing an alkoxy group-containing silane-modified epoxy resin. In addition, the present invention relates to a cured coating agent film obtained by applying the coating agent composition and then curing the same, and a method for producing the same. In the present specification, the coating agent composition is a resin composition containing an alkoxy group-containing silane-modified epoxy resin, and includes, for example, sealers, primers, surface coating agents for flooring agents, and hard coating agents for plastics. Anchor coating agents such as plating anchor coats and metal deposition anchor coats;
It means a coating agent composition used in at least one application selected from the group consisting of a sealing agent for electronic materials, liquid crystal plates, building materials and the like; and an adhesive for printed circuit boards and building materials.

[0002]

2. Description of the Related Art Hitherto, a so-called bisphenol type epoxy resin produced from bisphenols and epichlorohydrin or β-methylepichlorohydrin has been generally used as a composition in combination with a curing agent, and has a high water resistance and an excellent adhesion. Because of its relatively excellent chemical resistance, it has been awarded in the fields of various coating agents, adhesives, sealing agents and the like. However, in recent years, higher performance has been required in this field, and particularly, improvements in heat resistance, substrate adhesion, and acid resistance have been desired.

As a method for improving the heat resistance of a cured epoxy resin, for example, a method of mixing a filler such as glass fiber, glass particles, mica, etc. in addition to an epoxy resin and a curing agent is known. But with this method,
Since the obtained epoxy resin cured product loses transparency and has poor adhesion at the interface between the filler and the resin, mechanical properties such as elastic modulus and heat resistance are also insufficient.

As a method for improving the heat resistance of a cured film of an epoxy resin composition, a method using a composite of an epoxy resin and silica has been proposed (JP-A-8-10).
0107). The complex is added to the solution of the partially cured film of the epoxy resin, hydrolyzable alkoxysilane,
It is obtained by further curing the cured film, hydrolyzing the alkoxysilane to form a sol, and further performing polycondensation to form a gel. However, although the cured film obtained from such a composite has a somewhat improved heat resistance as compared with the cured film of the epoxy resin alone, the cured film due to water in the composite and water and alcohol generated at the time of curing. Voids (bubbles) are generated inside. Further, when the amount of alkoxysilane is increased for the purpose of further improving heat resistance, the silica produced by the sol-gel curing reaction loses the transparency of the cured film obtained by aggregating and whitens, and a large amount of alkoxysilane is removed. A large amount of water is required to form a sol, and as a result, the cured film may be warped, cracked, or the like.

Further, a composition (JP-A-3-201466) comprising a combination of a silane-modified epoxy resin obtained by reacting a silicone compound with an epoxy resin and a phenol novolak resin as a curing agent, a bisphenol A type epoxy resin, Composition comprising a combination of a silane-modified epoxy resin obtained by reacting tetrabisbromobisphenol A and a methoxy group-containing silicone intermediate, and a phenol novolak resin as a curing agent (JP-A-61-27224).
No. 3, JP-A-61-272244). However, the cured films of these epoxy resin compositions have insufficient heat resistance because the main constituent unit of the silicone compound or the methoxy group-containing silicone intermediate is a diorganopolysiloxane unit and cannot produce silica. .

Further, a cured film obtained by curing an alkoxy-containing silane-modified epoxy resin obtained by subjecting a bisphenol-type epoxy resin and an alkoxysilane partial condensate to a dealcoholation reaction loses the glass transition point, and has a high heat-resistant material. It has been reported that However, according to this method, when a liquid epoxy resin having an epoxy equivalent of 300 or less is used as the bisphenol-type epoxy resin, although the obtained cured film has a high glass transition point,
The glass transition point does not disappear. When a solid epoxy resin having an epoxy equivalent of 800 or more is used, the storage stability of the obtained epoxy resin composition decreases.

[0007]

SUMMARY OF THE INVENTION The present invention relates to a specific coating agent which is excellent in heat resistance, thermal decomposition resistance, low thermal expansion, adhesion, acid resistance, and scratch resistance, and can obtain a transparent cured film. An object is to provide a composition, a cured coating agent film obtained from the composition, and a method for producing the cured film.

[0008]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, have found that a specific epoxy resin and a specific alkoxysilane-containing silane-modified epoxy resin comprising a partial condensate of an alkoxysilane are contained. The present inventors have found that a coating agent composition and a cured coating agent film obtained from the composition meet the above-mentioned object, and have completed the present invention.

That is, the present invention provides an alkoxy group obtained by subjecting a hydroxyl group-containing epoxy resin (1) to an epoxy compound (2) having one hydroxyl group in one molecule and a partial condensate of an alkoxysilane (3) to remove alcohol by condensation. The present invention relates to a coating composition comprising a silane-modified epoxy resin. The present invention also relates to a cured coating material obtained by curing the composition and a method for producing the cured film.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION A hydroxyl group-containing epoxy resin (1) which is a raw material of an alkoxy group-containing silane-modified epoxy resin
The epoxy resin (hereinafter, simply referred to as epoxy resin (1)) is not particularly limited as long as it is an epoxy resin containing a hydroxyl group capable of undergoing a dealcoholization reaction with the alkoxysilane partial condensate (3), but bisphenols and epichlorohydrin or β
Bisphenol-type epoxy resins obtained by reaction with haloepoxides such as -methylepichlorohydrin are suitable in consideration of mechanical properties, chemical properties, electrical properties, versatility and the like. Bisphenols include those obtained by the reaction of phenol with aldehydes or ketones such as formaldehyde, acetaldehyde, acetone, acetophenone, cyclohexanone, and benzophenone, oxidation of dihydroxyphenyl sulfide with peracid, and etherification of hydroquinones. Is raised. Further, as the epoxy resin (1), 2,6-
It is also possible to use a material having flame retardancy, such as a halogenated bisphenol-type epoxy resin derived from a halogenated phenol such as dihalophenol or a phosphorus-modified bisphenol-type epoxy resin obtained by chemically reacting a phosphorus compound. Examples of epoxy resins other than bisphenols include, for example, an alicyclic epoxy resin obtained by hydrogenating the above bisphenol type epoxy resin, and an acid, a part of an epoxy group in a known epoxy resin (a) as described below. A hydroxyl group-containing epoxy resin obtained by reacting an amine or a phenol to open the epoxy group is exemplified. Examples of such an epoxy resin (a) include a phenol novolak resin, a novolak type epoxy resin obtained by reacting a cresol novolak resin with a haloepoxide; phthalic acid,
A glycidyl ester type epoxy resin obtained by reacting polybasic acids such as dimer acid and epichlorohydrin; a glycidylamine type epoxy resin obtained by reacting polyamines such as diaminodiphenylmethane and isocyanuric acid with epichlorohydrin; Examples thereof include linear aliphatic epoxy resins and alicyclic epoxy resins obtained by oxidizing olefin bonds with a peracid such as peracetic acid, and biphenyl type epoxy resins obtained by reacting biphenols with epichlorohydrin.

The epoxy resin (1) has a hydroxyl group capable of forming a silicate ester by a dealcoholization condensation reaction with the alkoxysilane partial condensate (3). The hydroxyl group need not be contained in all the molecules constituting the epoxy resin (1), and it is only necessary that these resins have a hydroxyl group. Epoxy resin as above (1)
Of these, bisphenol-type epoxy resins are preferred in view of versatility, and bisphenol A-type epoxy resins using bisphenol A as bisphenols are preferred because of their low cost.

The bisphenol A type epoxy resin has the general formula (a):

[0013]

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Is a compound represented by the formula:

In the present invention, the epoxy equivalent of the epoxy resin (1) is not particularly limited, and an epoxy equivalent depending on the application can be appropriately selected and used depending on the structure of the epoxy resin (1). However, when an alkoxy group-containing silane-modified epoxy resin is produced without a solvent or when a semi-cured film is produced using a resin composition containing an alkoxy group-containing silane-modified epoxy resin, the epoxy resin (1) Using one or more bisphenol-type epoxy resins, the total epoxy equivalent is 200 to
It is preferable to adjust so as to be 400 g / eq. That is, when an alkoxy group-containing silane-modified epoxy resin is produced in the absence of a solvent, the viscosity in the reaction system is higher than when the reaction is carried out in a solvent system. Therefore, from the viewpoint of adjusting the viscosity, the epoxy resin (1) Is to select the type. In addition, when the purpose of the production of a semi-cured film is as described below, the semi-cured film is required to have a certain degree of flexibility and adhesion even while sol-gel curing is almost completed, This is for selecting the type of the resin (1).
In addition, the said semi-hardened film means the hardened film in the state which carried out the sol-gel hardening reaction of the coating agent composition of this invention.
When the equivalent of the epoxy resin (1) exceeds 400 g / eq, the viscosity tends to be increased during the dealcoholization condensation reaction, and when the epoxy equivalent is less than 200 g / eq, an alkoxy group which is a reaction product is used. The amount of the alkoxysilane partial condensate (3) remaining in the contained silane-modified epoxy resin increases and the semi-cured film becomes brittle, which is not preferable.

In the present invention, the epoxy resins (1) and (1)
Each of the epoxy compounds (2) having one hydroxyl group in the molecule (hereinafter simply referred to as epoxy compound (2)) undergoes a dealcoholization condensation reaction with the alkoxysilane partial condensate (3) to form an alkoxy group-containing silane-modified epoxy. Give resin. Therefore, a hydroxyl group must be present in the epoxy resin (1). For example, in the case of the bisphenol A type epoxy resin of the general formula (a), a molecule having no hydroxyl group (in the general formula (a)) m = 0). Since the epoxy resin molecule having no hydroxyl group does not react with the alkoxysilane partial condensate (3), it is present in the alkoxy group-containing silane-modified epoxy resin unreacted. The molecule is chemically bonded to the silane-modified bisphenol-type epoxy resin molecule via the epoxy resin curing agent when forming the epoxy resin-silica hybrid cured film, but the epoxy resin (1) has no hydroxyl group. When many molecules are contained, the cured film finally obtained does not exhibit sufficient heat resistance.

In the present invention, even when the epoxy resin (1) containing a large number of epoxy resin molecules having no hydroxyl group is used, in order to impart sufficient heat resistance to the obtained cured film, the epoxy compound ( 2) is an essential component. That is, the epoxy compound (2) has an effect of preventing a decrease in heat resistance of the cured film. In the production of the alkoxy group-containing silane-modified epoxy resin, the amount of the epoxy compound (2) used is not particularly limited, and may be appropriately determined according to the content of the molecule having no hydroxyl group in the epoxy resin (1). From the viewpoint of the heat resistance of the cured film,
When the epoxy equivalent of the epoxy resin (1) is less than 200 g / eq, the weight of the epoxy compound (2) / the weight of the epoxy resin (1) is 0.05 or more, and the epoxy equivalent is 200 to 300 g / eq. In the case of the above, the weight ratio is 0.03 or more, and the epoxy equivalent is 300 g / e.
When it exceeds q, the weight ratio is preferably 0.01 or more. Since many of the epoxy compounds (2) have some toxicity, it is preferable to minimize the residual amount of the epoxy compound (2) in the alkoxy group-containing silane-modified epoxy resin. When the weight ratio is more than 0.3, the production time of the alkoxy group-containing silane-modified epoxy resin is increased in order to reduce the unreacted epoxy compound (2), and the production efficiency is reduced.

The number of epoxy groups is not particularly limited as long as the epoxy compound (2) is an epoxy compound having one hydroxyl group in one molecule. As the epoxy compound (2), the smaller the molecular weight, the better the compatibility with the epoxy resin (1) and the alkoxysilane partial condensate (3) and the higher the effect of imparting heat resistance. Are preferred. Specific examples thereof include monoglycidyl ethers having one hydroxyl group at the molecular terminal obtained by reacting epichlorohydrin with water, a dihydric alcohol or a phenol having two hydroxyl groups; epichlorohydrin; Polyglycidyl ethers having one hydroxyl group at the molecular terminal obtained by reacting a trihydric or higher polyhydric alcohol such as glycerin or pentaerythritol; molecular terminal obtained by reacting epichlorohydrin with aminomonoalcohol And an alicyclic hydrocarbon monoepoxide having one hydroxyl group in the molecule (eg, epoxidized tetrahydrobenzyl alcohol). Among these epoxy compounds, glycidol is the most excellent in terms of the effect of imparting heat resistance, and has high reactivity with the alkoxysilane partial condensate (3).

As the alkoxysilane partial condensate (3) constituting the alkoxy group-containing silane-modified epoxy resin, the following alkoxysilane compound and water are added in the presence of an acid or base catalyst to partially hydrolyze and condense. Can be used.

Examples of the alkoxysilane compound include:
For example, general formula (b): R¹ _pSi (OR^Two)_4-p  (In the formula, p represents 0 or 1. R¹Is directly
A lower alkyl group which may have a linked functional group,
A hydroxyl group or an unsaturated aliphatic residue. R^TwoIs a methyl group
Or an ethyl group;^TwoEach other is the same or different
It may be. ) Can be exemplified.

Specific examples of the alkoxysilane which is a constituent material of the alkoxysilane partial condensate (3) include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltrimethoxysilane. Ethoxysilane, n-
Examples thereof include propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane.

As the alkoxysilane partial condensate (3), a product obtained from methoxysilanes of the alkoxysilane compound as the constituent material is not reactive with the epoxy resin (1) or the epoxy compound (2). Rich in
It is preferable because a cured film can be prepared at a relatively low temperature, and tetramethoxysilane and methyltrimethoxysilane are more preferable particularly in consideration of versatility.

The alkoxysilane partial condensate (3) is represented, for example, by the following general formula (c) or (d). General formula (c):

[0024]

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(Wherein, R ¹ represents a lower alkyl group, an aryl group or an unsaturated aliphatic residue which may have a functional group directly bonded to a carbon atom. R ² represents a methyl group or an ethyl group. may be different from each R ² together are the same.)

General formula (d):

[0027]

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(In formula (d), R ² is the same as R ^{2 in} formula (c).)

The alkoxysilane partial condensate (3) has a number average molecular weight of about 230 to 2,000, and in formulas (c) and (d), the average number of repeating units n is 2 to 11
Is preferred. If the value of n exceeds 11, the solubility becomes poor, the compatibility with the epoxy resin (1) is significantly reduced at the reaction temperature, and the reactivity with the epoxy resin (1) and the epoxy compound (2) is reduced. It is not preferable because of the tendency. If n is less than 2, the alcohol is distilled out of the reaction system together with the alcohol during the reaction, which is not preferable.

The alkoxy group-containing silane-modified epoxy resin is obtained by subjecting the epoxy resin (1), the epoxy compound (2) and the alkoxysilane partial condensate (3) to a dealcoholization condensation reaction in the presence or absence of a solvent. can get. The weight ratio of the epoxy resin (1) and the epoxy compound (2) to the alkoxysilane partial condensate (3) is such that the alkoxy groups are substantially left in the alkoxy group-containing silane-modified epoxy resin. Although there is no particular limitation, the total equivalent of the hydroxyl group of the epoxy resin (1) and the hydroxyl group of the epoxy compound (2) / the equivalent of the alkoxy group of the alkoxysilane partial condensate (3) (equivalent ratio) = 0.1 to It is preferably 0.6. More preferably, it is 0.13 to 0.5. The equivalent ratio is 0.1
If it is less than 3, unreacted alkoxysilane partial condensate (3)
When it exceeds 0.6, sufficient heat resistance cannot be obtained, which is not preferable.

As the epoxy resin (1), a high molecular weight resin having an average epoxy equivalent of 400 or more, or as the alkoxysilane partial condensate (3), an average number of repeating units n> 7 of the above general formula (C) is used. In such a case, when the alcohol-condensation reaction is performed until the hydroxyl group of the epoxy resin (1) is completely eliminated, a tendency to increase the viscosity and gel may be observed. In such a case, the dealcoholation reaction is stopped during the reaction, or the epoxy compound (2) /
High viscosity and gelation can be prevented by a method such as selecting a condition such that the epoxy resin (1) (hydroxyl equivalent ratio) exceeds 0.33. For example, as a method of stopping the reaction in the middle, when the viscosity increases, the reaction system is changed to a reflux system, the amount of methanol removed from the reaction system is adjusted, or the reaction system is cooled to terminate the reaction. A method can be adopted.

In the dealcoholization condensation reaction of the present invention, the reaction temperature is about 50 to 130 ° C., preferably 70 to 130 ° C.
110 ° C. and the total reaction time is about 1 to 15 hours. This reaction is preferably performed under substantially anhydrous conditions in order to prevent a polycondensation reaction of the alkoxysilane partial condensate (3) itself. The production of the alkoxy group-containing silane-modified epoxy resin can also be performed under reduced pressure as long as the epoxy compound (2) does not evaporate in order to shorten the reaction time.

In the above dealcoholization condensation reaction, among the conventionally known catalysts, those which do not open the epoxy ring can be used to promote the reaction. Examples of the catalyst include lithium, sodium, potassium,
Metals such as rubidium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese; oxides of these metals, organic acids Salts, halides, alkoxides and the like can be mentioned. Among these, organic tin and organic acid tin are particularly preferable, and specifically, dibutyltin dilaurate, tin octylate and the like are effective.

The above dealcoholization condensation reaction can be carried out in the presence or absence of a solvent. However, when the molecular weight of the epoxy resin (1) or the alkoxysilane partial condensate (3) is large, at the reaction temperature,
It is preferable to use a solvent because the reaction system may become non-uniform and the reaction hardly proceeds. The solvent is not particularly limited as long as it is an organic solvent that dissolves the epoxy resin (1) and the partial condensate of the alkoxysilane (3) and is inactive against these. Examples of such an organic solvent include aprotic polar solvents such as dimethylformamide, dimethylacetamide, methyl ethyl ketone, methyl isobutyl ketone, and propylene glycol dimethyl ether.

The alkoxy group-containing silane-modified epoxy resin thus obtained is mainly composed of an alkoxysilane partially condensed product obtained by substituting an alkoxy group with an epoxy resin residue or a glycidyl group. An unreacted epoxy resin (1), epoxy compound (2), and alkoxysilane partial condensate (3) may be contained. The unreacted alkoxysilane partial condensate (3) can be converted into silica by a sol-gel curing reaction.

The alkoxy group-containing silane-modified epoxy resin has an alkoxy group derived from the alkoxysilane partial condensate (3) in its molecule. The content of the alkoxy group is not particularly limited, but the alkoxy group is subjected to a sol-gel reaction or dealcohol condensation by evaporation or heat treatment of a solvent or by reaction with water (moisture),
The alkoxy group-containing silane-modified epoxy resin is usually required to form a mutually bonded cured film,
30 to 95 mol%, preferably 40 to 80 mol% of the alkoxy group of the alkoxysilane partial condensate (3) as the reaction raw material.
It is better to keep mol% unreacted. Such a cured film has a gelled fine silica site (high-order network structure of siloxane bonds). In such a cured film, the Si content in the solid residue of the alkoxy group-containing silane-modified epoxy resin is 2 to 60% by weight in terms of silica weight.
It is preferable that Silica weight conversion S in solid residue
The i content is the weight percentage of the silica site when the alkoxysilyl site in the alkoxy group-containing silane-modified epoxy resin is cured to the silica site through the above sol-gel curing reaction. If it is less than 2% by weight, it is difficult to obtain the effects of the present invention such as heat resistance, thermal decomposition resistance, low thermal expansion, adhesion, acid resistance, and scratch resistance. If it exceeds 60% by weight, the cured film becomes too brittle. However, it tends to be difficult to obtain a thick cured film.

The coating composition of the present invention may contain an alkoxy group-containing silane-modified epoxy resin, and other components are not particularly limited, and various known epoxy resins may be used in combination. In addition,
When applied to various uses, it is preferable to contain a curing agent for epoxy resin and a curing accelerator.

As the epoxy resin that can be used in combination, the epoxy resin (1) described as a component of the present invention, an ortho-cresol novolak type epoxy resin,
Novolak type epoxy resins such as phenol novolak type epoxy resins; glycidyl ester type epoxy resins obtained by reacting polybasic acids such as phthalic acid and dimer acid and epichlorohydrin; polyamines such as diaminodiphenylmethane and isocyanuric acid Glycidylamine type epoxy resins obtained by reacting chlorohydrin; linear aliphatic epoxy resins and alicyclic epoxy resins obtained by oxidizing olefin bonds with a peracid such as peracetic acid.

Examples of the epoxy resin curing agent include phenol resin curing agents, polyamine curing agents, polycarboxylic acid curing agents, and imidazole curing agents which are usually used as epoxy resin curing agents. It can be used without any particular restrictions. Specifically, phenolic resin-based ones include phenol novolak resin, cresol novolak resin, poly p-vinylphenol, and the like, and polyamine-based curing agents such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dicyandiamide, Polyamidoamine (polyamide resin), melamine resin, ketimine compound, isophoronediamine, m
-Xylenediamine, m-phenylenediamine, 1,3
-Bis (aminomethyl) cyclohexane, N-aminoethylpiperazine, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, diaminodiphenylsulfone, dicyandiamide and the like, and polycarboxylic acids Examples of the system curing agent include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, hexachloroendmethylenetetrahydrophthalic anhydride, and methyl-3,6-endomethylenetetrahydro. Phthalic anhydride; and examples of imidazole-based curing agents include 2-methylimidazole,
2-ethylhexylimidazole, 2-undecylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate,
-Phenylimidazolium isocyanurate and the like. The epoxy resin curing agent not only reacts with the epoxy ring to effect ring-opening curing, but also serves as a catalyst for a reaction in which alkoxysilyl sites and alkoxy groups in the alkoxy group-containing silane-modified epoxy resin undergo siloxane condensation with each other. When a semi-cured film is obtained, a latent curing agent that reacts with the epoxy resin at a high temperature is preferable. For example, a phenol novolak resin among the above exemplified compounds,
Cresol novolak resins and acid anhydrides are preferred. In addition, when a long-term stability is required as a one-pack coating composition containing at least both an alkoxy group-containing silane-modified epoxy resin and a curing agent for an epoxy resin, a phenol novolak resin among the above exemplified compounds, Cresol novolak resins, dicyandiamide, imidazoles and acid anhydrides are preferred.

The proportion of the epoxy resin curing agent used is usually 0.2 to 1.5 equivalents of the functional group having active hydrogen in the curing agent per 1 equivalent of epoxy group in the alkoxy group-containing silane-modified epoxy resin. It is prepared by blending in such a ratio as to give a degree.

Further, the above-mentioned coating composition contains:
A curing accelerator for accelerating the curing reaction between the epoxy resin and the curing agent can be contained. For example, tertiary amines such as 1,8-diaza-bicyclo [5.4.0] undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol;
-Methylimidazole, 2-phenylimidazole, 2
Imidazoles such as -phenyl-4-methylimidazole and 2-heptadecylimidazole; organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine and phenylphosphine; tetraphenylphosphonium tetraphenylborate; Examples thereof include tetraphenylboron salts such as ethyl-4-methylimidazole / tetraphenylborate and N-methylmorpholine / tetraphenylborate.

The curing accelerator is used in an amount of 0.1 to 5 parts by weight with respect to the epoxy group of the alkoxy group-containing silane-modified epoxy resin and the total epoxy group of the epoxy resin used as an optional component. Is preferred. In addition, in order to promote siloxane condensation of an alkoxysilyl moiety or an alkoxy group in an alkoxy group-containing silane-modified epoxy resin, a conventionally known acid or basic catalyst or a sol-gel curing catalyst such as a metal catalyst can be blended. . Among these, tin octylate and dibutyltin dilaurate,
A metal-based catalyst such as tetrapropoxytitanium is preferable because of its high activity.

Also, the coating composition of the present invention
Depending on the intended use, a conventionally known polymer compound can be contained. For example, in order to impart flexibility or flexibility to the coating composition, a conventionally known acrylic resin, urethane resin, or a rubber material such as polybutadiene can be used in combination, and the coating composition has a low dielectric constant. In order to impart properties and slip properties, a silicone resin or the like can be used in combination. In the coating agent composition of the present invention, the alkoxysilane partial condensate (3)
May be added to increase the Si content of the coating composition, but considering the heat resistance, adhesion, acid resistance, etc. of the obtained cured film, the weight of silica in the solid residue of the coating composition is considered. The converted Si content is 2 in terms of silica weight.
It is preferably about 60% by weight. In this case, the compounded alkoxysilane partial condensate (3) is integrated with the silica portion of the alkoxy group-containing silane-modified epoxy resin by a sol-gel curing reaction.

Further, the coating composition of the present invention comprises
Depending on the intended use, the concentration and viscosity can be appropriately adjusted by the solvent. As the solvent, those similar to those used for producing the alkoxy group-containing silane-modified epoxy resin can be used. In addition, the coating composition may contain a filler, a release agent, a surface treatment agent, a flame retardant, a viscosity modifier, a plasticizer, an antibacterial agent, and / or the like, as long as the effects of the present invention are not impaired. Fungicides, leveling agents, defoamers, coloring agents, stabilizers,
A coupling agent or the like may be blended.

In order to obtain a cured film directly from the coating composition of the present invention, the composition is cured at room temperature to 250 ° C. The curing temperature is appropriately determined depending on the type of the epoxy resin curing agent. When using a phenolic resin-based curing agent or a polycarboxylic acid-based curing agent as the curing agent, a sol-gel curing catalyst is used in combination with the curing agent in an amount of 0.1% or more in addition to the curing agent to perform processing such as coating and impregnation. After application, it is preferable to cure at 150 to 250 ° C. When a polyamine-based curing agent is used, curing at a low temperature of from room temperature to 100 ° C. is possible, but it is preferable to use a highly active sol-gel curing catalyst such as tin octylate in combination with 0.3% or more for curing. Because the alcohol is generated in the sol-gel curing reaction of the alkoxysilyl moiety, the curing by the ring-opening / crosslinking reaction of the epoxy group in the alkoxy group-containing silane-modified epoxy resin and the curing agent for the epoxy resin proceeds. Later, when the alcohol is generated, foaming or cracking occurs. Therefore, it is necessary to adjust the sol-gel curing reaction rate by appropriately selecting the catalyst.

Hereinafter, a method for obtaining a cured film from the coating composition of the present invention through a semi-cured film will be described. In order to obtain the final cured film from the coating composition through the semi-cured film, carefully consider the type of curing agent and epoxy polymerization catalyst for the epoxy resin in the resin composition, as well as the semi-cured conditions. The choice is important. As a curing agent for the epoxy resin, a latent curing agent such as a phenolic resin-based curing agent or a polycarboxylic acid-based curing agent is used, and a tin-based sol-gel curing catalyst is added in an amount of 0 to the solid residue of the alkoxy group-containing silane-modified epoxy resin. It is preferable to mix about 0.05 to 5%. To produce a semi-cured film using the coating composition, preferably by heating at 40 to 150 ° C., if the solvent is contained, evaporating the solvent, contained in the resin composition The sol-gel curing of the alkoxysilyl moiety of the alkoxy group-containing silane-modified epoxy resin to be carried out needs to be advanced by 70% or more, preferably 90% or more to generate a siloxane bond. Because alcohol is generated in the sol-gel curing reaction at the alkoxysilyl site, if the progress of sol-gel curing during the production of a semi-cured film is small, curing shrinkage, cracking, and foaming may occur in the subsequent complete curing reaction It is because there is. The semi-cured film thus obtained is 60 to 150
Heating to ° C. softens and enables adhesion of various substrates and the like. In the alkoxy group-containing silane-modified epoxy resin which is an essential component of the coating composition, when a methyltrimethoxysilane partial condensate is used as the alkoxysilane partial condensate (3), the semi-cured film is appropriately softened when heated. It is preferable because it is easy to adhere. Thereafter, by heating the processed semi-cured film at 150 to 250 ° C., the epoxy group and the curing agent for epoxy resin are cured, and a desired cured film is obtained.

The coating composition of the present invention includes paints such as sealers, primers, surface coating agents for flooring agents, and hard coating agents for plastics; anchor coats for plating;
Anchor coating agents such as metal deposition anchor coatings; sealing agents for electronic materials, liquid crystal plates, building materials, etc .; suitable for adhesives for printed circuit boards, building materials, etc .; Thus, a cured film can be easily formed.

Examples of application of the coating composition of the present invention to various uses are described below. The coating composition of the present invention is particularly useful as a coating (sealer) applied to the first layer of an inorganic substrate. Here, the inorganic base material includes not only ceramic base materials such as concrete, mortar and glass, but also metal base materials such as iron, stainless steel, magnesium alloy and zinc alloy. When the sealer is applied outdoors, it is preferable to cure by a method of obtaining a directly cured film using a polyamine-based curing agent that can be cured at room temperature because heat curing is difficult. On the other hand, when baking is possible, a cured film can be obtained under the predetermined heating conditions using the above-mentioned various curing agents for epoxy resins. As a method of applying the coating material to the substrate, any method such as brush coating, spray coating, roll coating, dip coating can be applied, and usually about 5 to 100 μm by adjusting the viscosity with an organic solvent as needed. Coated to form a cured film. In addition, in order to improve rust prevention properties, etc.,
Various fillers may be blended. The type of the filler is not particularly limited, but coloring pigments such as titanium white, yellow iron oxide, and carbon black; extender pigments such as silica, talc, and precipitated barium; rust-preventive pigments such as zinc white and aluminum phosphate; Can be illustrated.

When the coating composition of the present invention is used as a primer, for example, it is disclosed in JP-A-6-1283.
No. 53, a method of using a primer for flooring materials can be applied. A coating composition containing a solvent having a boiling point of less than 150 ° C. is applied on a base material such as concrete so that the thickness of a cured film is about 3 to 50 μm, and left at room temperature for 1 hour to 2 days to cure. Since curing is performed at room temperature, it is preferable to use a polyamine-based curing agent as a curing agent for an epoxy resin. The curing time can be determined in consideration of the pot life of the polyamine-based curing agent as the curing agent. After curing the primer, for example, an epoxy resin for flooring is applied according to a conventional method. Since the coating agent composition of the present invention has particularly good adhesion to an inorganic base material such as concrete, it becomes a cured product having high durability and free of blisters.

When the coating composition of the present invention is applied to the surface coating of flooring materials, for example, Japanese Patent Application Laid-Open No.
224858 and JP-A-6-128353 can be employed. That is, on the concrete treated with the primer of the coating composition of the present invention, so that the thickness of the cured film is about 100 to 5000 μm,
Apply using a roller and cure at room temperature for 1-7 days. In the coating composition, an alkoxy group-containing silane-modified epoxy resin manufactured without solvent, and a polyamine-based curing agent as a curing agent for the epoxy resin is an essential component. The filler and the plasticizer used in the above can be appropriately compounded.

When the coating composition of the present invention is used as a hard coating agent for plastics, the coating composition is coated on a plastic substrate by a known method so that the cured film has a thickness of about 5 to 50 μm. May be applied and cured by a method of directly obtaining a cured film. Since the curing temperature needs to be set to be equal to or lower than the thermal deformation temperature of the base plastic, it is preferable to use a curing agent for a polyamine-based epoxy resin as a curing agent and cure at a low temperature.

When the coating composition of the present invention is used as an anchor coating agent, it is applied on a substrate in the same manner as the above-mentioned coating method so that the thickness of the cured film is about 2 to 100 μm. What is necessary is just to harden by the method of obtaining a hardened film directly. When plating is performed on the cured film, the surface is treated with a roughening agent, and the surface is washed with hot water to form irregularities, and the metal is plated. As the plating method, electroless plating and electrolytic plating are preferable, and at least one selected from sulfuric acid, dichromic acid, oxidizing agent, and alkali is used as the roughening agent. The cured film obtained from the coating composition of the present invention has a moderately roughened surface by these roughening agents, and thus has excellent adhesion to the plating layer. When metal deposition is performed, a conventionally known metal or metal oxide such as silica, aluminum, and alumina may be deposited with the cured film facing upward.

When the coating composition of the present invention is used as a sealing or adhesive for building materials, the method described in JP-A-10-204152 can be exemplified. That is, in order to prepare a sealing material and an adhesive for building materials, it is preferable to use a coating composition containing an alkoxy group-containing silane-modified epoxy resin manufactured under no solvent, and to this, a filler or a plasticizer is added, What is necessary is just to intensively knead using a well-known kneader. As the filler, various types of organic or inorganic fillers can be used, but it is preferable to select an acidic or neutral filler. As the filler, fumed silica, calcined silica, precipitated silica, ground silica, fused silica; diatomaceous earth; iron oxide, zinc oxide,
Titanium oxide; pyroxene clay, kaolin clay, calcined clay; or carbon black; calcium carbonate. Note that a filler exhibiting basicity is not preferred because it excessively promotes sol-gel curing of the sealing agent and does not provide a sufficient pot life. The amount of the filler is from 50 to 50 parts by weight of the solid residue of the alkoxy group-containing silane-modified epoxy resin from the viewpoint of the physical properties of the cured product.
Preferably, it is 150 parts by weight. As the epoxy resin curing agent to be used, a polyamine curing agent capable of curing at room temperature is preferable. From the viewpoint of workability, using a plasticizer such as dioctyl phthalate or dibutyl phthalate, the viscosity of the sealing or adhesive for building materials is 1000 to 1000 at 25 ° C.
It is preferable to adjust so as to be about 00 mPa · s.

When the coating composition of the present invention is used as an adhesive for printed circuit boards, for example, Japanese Patent Application Laid-Open No.
No. 5,1571, and the method described in JP-A-6-145628 can be applied. That is, the adhesive for a printed circuit board contains an alkoxy group-containing silane-modified epoxy resin and a curing agent for an epoxy resin as essential components. In addition to these components, polyamide resin, acrylic resin, phenolic resin, imide resin, rubber Resin components such as resin,
It can be prepared by appropriately using various inorganic and organic fillers. From the viewpoint of workability, an organic solvent, preferably one having a boiling point of less than 150 ° C., may be appropriately blended. Since the adhesive for a printed circuit board needs to be bonded to a copper foil through a semi-cured film, the curing agent for an epoxy resin used for the adhesive may be a phenolic resin-based curing agent, a polycarboxylic acid-based curing agent, or the like. Curing agents are preferred. As a specific method of using the adhesive for a printed board, a coating composition is applied on an insulating film such as polyimide, and a semi-cured film of about 5 to 50 μm is formed according to the above method. A laminated board can be obtained by laminating a copper foil on top and laminating the laminate at 60 to 150 ° C. and curing the laminate at 150 to 250 ° C.

[0055]

According to the present invention, heat resistance, heat decomposition resistance,
It is possible to provide a coating composition which is excellent in low thermal expansion property, adhesion, acid resistance, and scratch resistance and can obtain a transparent cured film.

[0056]

The present invention will be specifically described below with reference to examples and comparative examples. In each case,% is based on weight unless otherwise specified.

Production Example 1 (Production of Alkoxy Group-Containing Silane-Modified Epoxy Resin) A solid bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd.) was equipped with a stirrer, a water separator, a thermometer, and a nitrogen inlet. Trade name “Epototo YD-011”, epoxy equivalent 475 g / eq, m = 2.2) 180 g, liquid bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd.
Product name "Epototo YD-127", epoxy equivalent 19
05.6 g / eq, m = 0.1) 455.6 g, and glycidol (trade name “Epiol O” manufactured by NOF Corporation)
H "), and melt-mixed at 80 ° C. Furthermore, poly (methyltrimethoxysilane) (manufactured by Tama Chemical Co., Ltd.)
Product name "MTMS-A", average number of repeating units 3.2)
348 g and 1.0 g of dibutyltin dilaurate as a catalyst were added under a nitrogen stream at 100 ° C. for 8 hours.
A methanol removal reaction was performed. After further cooling to 60 ° C, 13k
The pressure was reduced to Pa, and the dissolved methanol was completely removed to obtain an alkoxy group-containing silane-modified epoxy resin containing 94% of the active ingredient (after curing). The equivalent of the epoxy resin (1) at the time of preparation was 267 g / eq, the total equivalent of the hydroxyl group of the epoxy resin (1) and the hydroxyl group of the glycidol (2) / the equivalent of the alkoxy group of the alkoxysisilane partial condensate (3). (Equivalent ratio) is 0.22, weight of glycidol (2) / weight of epoxy resin (1) = 0.08
Met. From the ¹ H-NMR (CDCl ₃ solution) of this resin, the methine peak of the epoxy ring (around 3.3 ppm) was 10
It was confirmed that it was maintained at 0% and that the peak (around 3.85 ppm) of the hydroxyl group in the epoxy resin had disappeared. The epoxy equivalent of the obtained alkoxy group-containing silane-modified epoxy resin was 274 g / eq.

Production Example 2 In a reactor similar to that of Production Example 1, Epotote YD-011 was added.
180 g, Epotote YD-127 456.7 g,
83.2 g of epoxidized tetrahydrobenzyl alcohol (trade name “ETHB” manufactured by Daicel Chemical Industries, Ltd.) was added, and the mixture was melted and mixed at 80 ° C. Further. MTMS-
348.0 g of A and 1.0 g of dibutyltin dilaurate were added, and a methanol removal reaction was performed at 100 ° C. for 8 hours under a nitrogen stream. After further cooling to 60 ° C, 13kP
The pressure was reduced to a, and the dissolved methanol was completely removed to obtain an alkoxy group-containing silane-modified epoxy resin having an active ingredient (after curing) of 94%. At the time of preparation,
The equivalent of the epoxy resin (1) is 267 g / eq, the total equivalent of the hydroxyl group of the epoxy resin (1) and the hydroxyl group of the epoxy compound (2) / the equivalent of the alkoxy group of the alkoxysilane partial condensate (3) (equivalent ratio). Is 0.23, weight of epoxy compound (2) / weight of epoxy resin (1) = 0.13
Met. From the ¹ H-NMR (CDCl ₃ solution) of this resin, the methine peak of the epoxy ring (around 3.3 ppm) was 10
It was confirmed that it was maintained at 0% and that the peak (around 3.85 ppm) of the hydroxyl group in the epoxy resin had disappeared. The epoxy equivalent of the obtained alkoxy group-containing silane-modified epoxy resin was 290 g / eq.

Preparation Example 3 Semi-solid bisphenol A was placed in the same reactor as in Preparation Example 1.
Type epoxy resin (trade name “Epicoat 834”, manufactured by Yuka Shell Epoxy Co., Ltd.), epoxy equivalent 250 g / eq,
m = 0.6) 300 g, and glycidol 55.9 g
And melt-mixed at 80 ° C. Further, 160.2 g of MTMS-A and 0.5 g of dibutyltin dilaurate were added.
g was added and a methanol removal reaction was performed at 100 ° C. for 8 hours under a nitrogen stream. After further cooling to 60 ° C., the pressure was reduced to 13 kPa, and the dissolved methanol was completely removed, whereby an alkoxy group-containing silane-modified epoxy resin having an active ingredient (after curing) of 97% was obtained. The equivalent of the epoxy resin (1) at the time of preparation was 250 g / eq, the total equivalent of the hydroxyl group of the epoxy resin (1) and the hydroxyl group of the glycidol (2) / the equivalent of the alkoxy group of the alkoxysisilane partial condensate (3). (Equivalent ratio) is 0.44, glycidol (2)
Weight / weight of epoxy resin (1) = 0.19. From the ¹ H-NMR (CDCl ₃ solution) of the present resin, 100% of the methine peak of the epoxy ring (around 3.3 ppm) is retained, and the peak of the hydroxyl group in the epoxy resin (around 3.85 ppm) disappears. I was able to confirm. The epoxy equivalent of the obtained alkoxy group-containing silane-modified epoxy resin was 235 g / eq.

Production Example 4 Epototote YD-011 was placed in the same reactor as in Production Example 1.
300 g, 275.7 g Epicoat 834, 51.4 g glycidol, and 600 g methyl ethyl ketone
Was added and dissolved at 80 ° C. In addition, 37 MTMS-A
1.9 g and 1.5 g of dibutyltin dilaurate were added, and the mixture was subjected to a desolvation reaction with methanol produced at 80 ° C. for 6 hours under a nitrogen stream, whereby the active ingredient (after curing) became 6
9% of an alkoxy group-containing silane-modified epoxy resin was obtained. The equivalent of the epoxy resin (1) at the time of preparation was 36.
7 g / eq, the total equivalent of the hydroxyl group of the epoxy resin (1) and the hydroxyl group of the glycidol (2) / the equivalent of the alkoxy group of the alkoxysilane partial condensate (3) (equivalent ratio) is 0.
30, weight of glycidol (2) / epoxy resin (1)
Was 0.09. ¹ H-NMR (C
DCI ₃ solution) to the methine peak of the epoxy ring (3.3)
It was confirmed that 100% (near ppm) was maintained at 100% and that the peak of hydroxyl groups in the epoxy resin (near 3.85 ppm) had disappeared. The epoxy equivalent of the obtained alkoxy group-containing silane-modified epoxy resin is 510 g.
/ Eq.

Production Example 5 Epototote YD-011 was placed in the same reactor as in Production Example 1.
380 g, 636.4 g of Epotote YD-127,
181.8 g of glycidol was added and melt-mixed at 80 ° C. Further, 815.3 g of poly (tetramethoxysilane) (manufactured by Tama Chemical Co., Ltd., trade name "methyl silicate 51", average number of repeating units 4.0) and 0.5 g of dibutyltin dilaurate were added, and the mixture was added under a nitrogen stream. At 90 ° C. for 6 hours. After further cooling to 50 ° C., the pressure was reduced to 13 kPa, and the dissolved methanol was completely removed to obtain an alkoxy group-containing silane-modified epoxy resin having an active ingredient (after curing) of 83%. The equivalent of the epoxy resin (1) at the time of preparation was 293 g / e.
q, hydroxyl group of epoxy resin (1) and glycidol (2)
Of hydroxyl group / equivalent of alkoxy group of alkoxysilan partial condensate (3) (equivalent ratio) is 0.20, weight of glycidol (2) / weight of epoxy resin (1) =
0.18. From the ¹ H-NMR (CDCl ₃ solution) of the present resin, 100% of the methine peak of the epoxy ring (around 3.3 ppm) is retained, and the peak of the hydroxyl group in the epoxy resin (around 3.85 ppm) disappears. I was able to confirm. The epoxy equivalent of the obtained alkoxy group-containing silane-modified epoxy resin was 280 g / eq.

Comparative Production Example 1 Epotote YD-127 was used as it was.

Comparative Production Example 2 Epototote YD-127 was placed in the same reactor as in Production Example 1.
Was added and dissolved at 80 ° C. 296 g of MTMS-A and 1.0 g of dibutyltin dilaurate were added, and a methanol removal reaction was performed at 90 ° C. for 8 hours under a nitrogen stream. After further cooling to 60 ° C., the pressure was reduced to 13 kPa, and the dissolved methanol was completely removed.
An alkoxy group-containing silane-modified epoxy resin having an active ingredient (after curing) of 93% was obtained. The equivalent of the epoxy resin (1) at the time of preparation was 185 g / eq, and the epoxy resin (1) was used.
Equivalent of hydroxyl group / partial condensate of alkoxy silane (3)
The equivalent weight (equivalent ratio) of the alkoxy group was 0.05.
From the ¹ H-NMR (CDCl ₃ solution) of the present resin, 100% of the methine peak of the epoxy ring (around 3.3 ppm) is retained, and the peak of the hydroxyl group in the epoxy resin (around 3.85 ppm) disappears. I was able to confirm. The epoxy equivalent of the obtained alkoxy group-containing silane-modified epoxy resin was 250 g / eq.

Comparative Production Example 3 In the same reactor as in Production Example 1, Epotote YD-011 was added.
300.0 g, Epotote YD-127 1250 g
In addition, it was dissolved at 80 ° C. Furthermore, MTMS-A is 58
1.4 g and 1.0 g of dibutyltin dilaurate were added, and a methanol removal reaction was performed at 100 ° C. for 8 hours under a nitrogen stream. After further cooling to 60 ° C., the pressure was reduced to 13 kPa, and the dissolved methanol was completely removed.
An alkoxy group-containing silane-modified epoxy resin containing 95% of an active ingredient (after curing) was obtained. At the time of preparation, the equivalent of the epoxy resin (1) was 210 g / eq, and the epoxy resin (1) was used.
Equivalent of hydroxyl group / partial condensate of alkoxy silane (3)
The equivalent weight (equivalent ratio) of the alkoxy group was 0.112. From the ¹ H-NMR (CDCl ₃ solution) of the present resin, 100% of the methine peak of the epoxy ring (around 3.3 ppm) is retained, and the peak of the hydroxyl group in the epoxy resin (around 3.85 ppm) disappears. I was able to confirm. The epoxy equivalent of the obtained alkoxy group-containing silane-modified epoxy resin was 280 g / eq.

Examples 1 to 5 (Preparation of Coating Composition) Each of the resins obtained in Production Examples 1 to 5 was diluted with methyl ethyl ketone, and dimethyl formamide of dicyandiamide was added.
% Solution was added so that the equivalent of the amino group of dicyandiamide / the equivalent of the epoxy group in the resin solution = 1.0 to prepare each coating agent composition.

Comparative Examples 1 to 3 A 15% solution of dicyandiamide in dimethylformamide was added to each of the resin solutions obtained in Comparative Production Examples 1 to 3, by the equivalent of amino group of dicyandiamide / equivalent of epoxy group in resin solution = 1. Each epoxy resin composition was prepared so as to be 0.

Examples 6 and 7 and Comparative Examples 4 and 5 (Preparation of Coating Composition) Each of the resins obtained in Production Examples 1 and 5 and Comparative Production Examples 1 and 2 was added to a phenol novolak resin (Arakawa Chemical Industries, Ltd.). stock)
Made, trade name "Tamanol 759", phenol equivalent 106
g / eq) of a 60% solution of methyl ethyl ketone so that the equivalent of the hydroxyl group of the phenolic resin / the equivalent of the epoxy group in the resin solution = 1.0. Further, 0.5% of tin octylate per solid residue is added. , 2-methylimidazole in 0.1
% Of each was added to prepare a coating composition.

Examples 8 to 12 and Comparative Examples 6 and 7 (Preparation of Coating Composition) Each resin obtained in Production Examples 1 to 5 and Comparative Production Examples 1 and 2
Methyl isobutyl ketone 6 of aminopolyamide resin (trade name “Goodmide G-725” manufactured by Toto Kasei Co., Ltd.)
The 0% solution was added to the equivalent of the amino group of the aminopolyamide resin /
A coating agent composition was prepared by adding so that the equivalent of the epoxy group in the resin solution = 0.9, and further adding 0.5% of tin octylate per solid residue.

Examples 13 to 17 and Comparative Examples 8 and 9 (Preparation of Coating Composition) To each of the resins obtained in Production Examples 1 to 5, 4-methylhexahydrophthalic anhydride was added to the hydroxyl group of the phenol resin. Equivalent /
A coating agent composition was prepared by adding so that the equivalent of the epoxy group in the resin solution = 0.9, and further adding 0.5% of tin octylate per solid residue.

Examples 18 and 19 and Comparative Examples 10 and 11
(Preparation of Coating Agent Composition) A heterocyclic amine curing agent (trade name “Epomate RX2”, manufactured by Yuka Shell Epoxy Co., Ltd.) was added to each resin obtained in Production Examples 1 and 5 using a heterocyclic amine. The coating agent composition was prepared by adding the equivalent of the amino group of the curing agent / the equivalent of the epoxy group in the resin solution to 0.9, and further adding 0.5% of tin octylate per solid residue. did.

(Shrinkage / Appearance) Each of the resin compositions obtained in Examples 1 to 19 and Comparative Examples 1 to 11 was applied to a glass plate and applied with a bar coater # 30. Examples 1 to 5 were cured at 100 ° C. for 15 minutes and further at 210 ° C. for 2 hours, and Examples 8 to 12 and Comparative Examples 6 and 7 were cured at 130 ° C. 2
0 minutes, further cured at 170 ° C. for 1 hour, Examples 13 to 17,
And Comparative Examples 8 and 9 were cured at 200 ° C. for 5 hours.
8, 19 and Comparative Examples 10 and 11 were cured at room temperature for one day. The state (shrinkage, appearance) of the obtained cured film was evaluated according to the following criteria. The results are shown in Tables 1 and 2.

Criteria for shrinkage evaluation ○: No crack or warpage in cured product. Δ: Warpage is present in the cured product. X: The cured product has cracks.

Criteria for evaluation of appearance ○: Transparent. Δ: Cloudy. ×: Whitened.

[0074]

[Table 1]

[0075]

[Table 2]

As is clear from the comparison between Tables 1 and 2, all of the coating compositions of the respective examples could produce transparent cured films without voids and cracks. The epoxy resin compositions of 5, 7, 9, and 11 were whitened due to phase separation between the epoxy resin and silica, were very brittle, and had cracks in the cured film.

(Stability) When the coating compositions of Examples 6, 7 and 13 to 17 were stored at room temperature, the change in viscosity after one month was within 20%, and the so-called one-part As a type of resin composition, it is recognized that it is useful for paints such as sealers, primers, hard coat agents for plastics, anchor coats for plating, anchor coats for metal deposition, adhesives for printed circuit boards, and the like.

(Heat Resistance) Examples 1 to 7 and Comparative Examples 1 and 3
The coating composition obtained in the above was poured into an aluminum container (length × width × depth = 10 cm × 10 cm × 1.5 cm), and cured under the same curing conditions as in the item of “Appearance / shrinkage”. A cured film of 400 μm is cut into 6 mm × 25 mm, and a viscoelasticity measuring device (trade name “DVE-V” manufactured by Rheology Co., Ltd.)
4 ", measurement conditions: amplitude 1 μm, frequency 10 Hz, slope 3 ° C./min), the dynamic storage modulus E ′ and Tan δ were measured to evaluate the heat resistance. The measurement results are shown in FIGS.

As is clear from FIG. 1, in Comparative Example 1,
The storage elastic modulus of the cured film (epoxy resin cured film) is significantly reduced at around 90 ° C. In Comparative Example 3, an improvement is seen but not enough. In Examples 1 to 3, it is recognized that the storage elastic modulus of the cured film does not decrease sharply and is excellent in heat resistance.

As is clear from FIG.
No. 6 maintains a high elastic modulus at a high temperature and is recognized to be excellent in heat resistance. In Examples 5 and 7, no decrease in the elastic modulus was observed.

As apparent from FIGS. 2 and 4, in Comparative Example 1, the glass transition point of the cured film (epoxy resin cured film) was observed, and in Comparative Example 3, the glass transition point was increased. Not enough. In all of Examples 1 to 7, the glass transition point was high, as judged from the Tan δ value,
It tends to disappear and is recognized as having excellent heat resistance. Therefore, the coating composition of Examples 1 to 7 is suitable as a paint requiring heat resistance or a heat-resistant adhesive for printed circuit boards.

(Heat Decomposition) The coating compositions obtained in Examples 1 and 5 and Comparative Examples 1 to 3 were applied to aluminum foil and cured at 100 ° C. for 15 minutes and at 210 ° C. for 1 hour to form a film. A cured film having a thickness of about 30 μm was produced. The thermogravimetric loss of the cured product peeled from the aluminum foil was measured by a differential thermogravimetric / thermogravimetric simultaneous measuring device (trade name “TG / DTA220” manufactured by Seiko Instruments Inc., measurement condition: slope 10).
° C / min). Table 3 shows the results.

[0083]

[Table 3]

As is clear from Table 3, Examples 1 and 5 have a sufficiently high temperature at a weight loss of 10% as compared with Comparative Examples 1 to 3, and are excellent in thermal decomposition resistance. It is suitable as a heat-resistant adhesive for substrates.

(Low thermal expansion) The coating compositions obtained in Examples 6 and 7 and Comparative Example 1 were applied to aluminum foil and cured at 100 ° C. for 15 minutes and at 210 ° C. for 1 hour to obtain a film having a film thickness of about A cured film of 30 μm was produced. Examples 6 and 7
The coefficient of linear expansion at 40 to 100 ° C. of the cured film obtained in Comparative Example 4 was measured by a thermal stress / strain measuring device (same as above). Table 4 shows the results.

[0086]

[Table 4]

As is clear from Table 4, Examples 6 and 7 are particularly useful as adhesives for printed circuit boards, since they have lower thermal expansion properties and better thermal decomposition resistance than Comparative Example 4.

(Adhesion) Examples 6 to 8, 11 to 13, 1
The coating compositions of 6 to 19 and Comparative Examples 4, 6, 8, and 11 were further blended as follows. The mixture was kneaded for 1 hour with a paint shaker to obtain a solid residue of 5%.
The coating composition (paint) was 0%. Each obtained paint is applied to the substrate using a bar coater,
Cured under the same curing conditions as in item
m was obtained.

Each coating composition 100 parts Yellow iron oxide (trade name “TAROXLL-XLO” manufactured by Titanium Industry Co., Ltd.) 8 parts Aluminum hydrogen tripolyphosphate (trade name “K-white” manufactured by Teikoku Chemical Co., Ltd.) # 82 ") 6 parts Talc (Tsuchiya Kaolin Industries, Ltd., trade name" Crown Talc SC ") 10 parts Calcium carbonate (Maruo Calcium Co., Ltd., trade name" Super SSS ") 16 parts Diluent solvent (MEK) Predetermined amount

A cellophane tape peeling test was conducted according to the general test method of JIS K-5400, and the evaluation was made according to the following criteria. Table 5 shows the evaluation results. ◎ ―――― 100/100 ○ ―――― 99 ~ 95/100 △ ――― 94 ~ 70/100 × ――― 69〜0 / 100

[0091]

[Table 5]

As is evident from Table 5, the cured films obtained from the coating compositions of the examples had better adhesion to metal and ceramic substrates than those of the comparative examples. It is suitable for coating agents, adhesives for building materials and printed circuit boards.

(Scratch resistance) Using the cured film on the glass plate used in the above item (Adhesion), JIS K-5
A pencil scratch test was carried out using 400 paint general test methods. Table 6 shows the results.

[0094]

[Table 6]

Since the cured films of these examples are more excellent in scratch resistance than those of the comparative examples, they are suitable for paints, anchor coating agents and the like.

Examples 20 and 21, and Comparative Example 12 The alkoxy group-containing silane-modified epoxy resins and epoxy resins obtained in Production Examples 1 and 5 and Comparative Production Example 1 were further blended as follows. The materials were kneaded with a mixer for one hour. Then, a ketimine curing agent (trade name “Epicure H30”, manufactured by Yuka Shell Epoxy Co., Ltd.) was added to the kneaded product such that the equivalent of amino group / the equivalent of epoxy group = 1/1, The mixture was further kneaded for 1 minute to obtain a coating composition. 100 parts of each alkoxy group-containing silane-modified epoxy resin Talc (trade name "Crown Talc SC" manufactured by Tsuchiya Kaolin Industries, Ltd.) 10 parts Calcium carbonate (trade name "Super SSS" manufactured by Maruo Calcium Co., Ltd.) 100 parts

(Acid resistance) The composition was applied on a mortar plate with a roller and left in a constant temperature room at a temperature of 23 ° C. and a humidity of 65% for 3 days to obtain a cured film having a thickness of about 1 mm. The mortar plate with the cured film was subjected to a 48-hour spot test in accordance with JIS A5707. In addition, 10% sulfuric acid was used as the acid.
The sample after the test was visually judged and evaluated according to the following criteria. Table 7 shows the evaluation results. ：: No abnormality △: Discoloration ×: Blister, swelling

[0098]

[Table 7]

The cured films of the examples are excellent in acid resistance and are suitable as sealing agents and anchor coating agents for plating.

[Brief description of the drawings]

FIG. 1 shows the evaluation results of the dynamic (tensile) viscoelasticity of the cured films obtained in Examples 1 to 3 and Comparative Examples 1 and 3.

FIG. 2 shows evaluation results of tan δ of cured films obtained in Examples 1 to 3 and Comparative Examples 1 and 3.

FIG. 3 shows the evaluation results of the dynamic (tensile) viscoelasticity of the cured films obtained in Examples 4 to 7 and Comparative Example 1.

FIG. 4 is an evaluation result of tan δ of the cured films obtained in Examples 4 to 7 and Comparative Example 1.

Continued on front page F-term (reference) 4H017 AA04 AA31 AB08 AB15 AD06 4J036 AA05 AB07 AB17 AD07 AD08 AD09 AD14 AD22 AG07 AH07 AJ08 AK01 AK17 CA06 CA15 CB03 DB08 DB09 DB19 DB21 DB22 DC03 DC04 DC05 DC06 DC09 DC10 DC12 FB02 GA06 JA01 4J038 DB031 DB041 DB061 DB071 DB111 DB151 DB161 DB411 DL052 DL102 GA03 JA35 JA41 JA63 JA69 JB01 JB32 JC12 KA03 KA04 NA04 NA09 NA11 NA12 NA14 PA19 PB05 PB09 PB12 PC08

Claims (12)

[Claims] 1. An alkoxy group-containing silane modified resin obtained by subjecting a hydroxyl group-containing epoxy resin (1) to an alcohol compound having one hydroxyl group in one molecule (2) and an alkoxysilane partial condensate (3) by a dealcoholization condensation reaction. A coating composition comprising an epoxy resin. 2. The coating composition according to claim 1, wherein the hydroxyl group-containing epoxy resin (1) is a bisphenol type epoxy resin. 3. The coating composition according to claim 2, wherein the hydroxyl group-containing epoxy resin (1) is a bisphenol A type epoxy resin. 4. The coating composition according to claim 1, wherein the epoxy compound (2) having one hydroxyl group in one molecule is glycidol. 5. The coating composition according to claim 1, wherein the alkoxysilane partial condensate (3) is a partial condensate of methyltrimethoxysilane or a partial condensate of tetramethoxysilane. 6. An epoxy compound having a hydroxyl group of a hydroxyl group-containing epoxy resin (1) and one hydroxyl group in one molecule (2).
Of the alkoxy group of the alkoxysilan partial condensate (3) (equivalent ratio) is 0.1 to
The coating composition according to any one of claims 1 to 5, which is 0.6. 7. The coating composition according to claim 1, further comprising a curing agent for an epoxy resin. 8. The coating according to claim 7, wherein the curing agent for the epoxy resin is at least one selected from the group consisting of a phenolic resin-based curing agent, a polyamine-based curing agent, a polycarboxylic acid-based curing agent, and an imidazole-based curing agent. Composition. 9. A cured coating agent obtained by curing the coating agent composition according to claim 1. 10. A method for producing a cured coating agent film obtained by curing the coating agent composition according to claim 1 at room temperature to 250 ° C. 11. The coating composition according to claim 1, which is applied on an adherend (A) to obtain a coating composition.
After performing sol-gel curing at 0 ° C. to obtain a semi-cured film, the adherend (B) is superimposed on the semi-cured film, and then 150 to 250
A method for producing a cured coating agent film that is completely cured at ℃. 12. The coating composition according to any one of claims 1 to 8, wherein the coating composition is an anchor coating agent.
A coating composition used in at least one application selected from the group consisting of a sealing agent and an adhesive.