KR101470858B1

KR101470858B1 - Organic-inorganic composite hybrid resin and Coating Material Using The Resin

Info

Publication number: KR101470858B1
Application number: KR20140093027A
Authority: KR
Inventors: 강병도; 심현호
Original assignee: 주식회사 한국화이어텍
Priority date: 2014-07-23
Filing date: 2014-07-23
Publication date: 2014-12-09

Abstract

The present invention relates to a resin composition comprising 100 parts by weight of an inorganic resin, 20 to 140 parts by weight of an organic resin reactive with the inorganic resin, and 20 to 100 parts by weight of an alcohol as a solvent; Wherein the inorganic resin is obtained by partial hydrolysis reaction of at least one of colloidal alumina or colloidal silica so that a hydroxy group remains using a metal alkoxide or a metal alkoxide partial hydrolyzate; Wherein the organic resin is obtained by reacting an epoxy resin with a metal alkoxide or by further reacting a polyol with the epoxy resin to obtain an organic / inorganic hybrid resin. This resin is excellent in adhesion when applied to paints and is excellent in adhesion to concrete, tiles and metal materials, and can be used as an organic or inorganic paint.

Description

Technical Field [0001] The present invention relates to an organic-inorganic composite hybrid resin and a coating composition using the same,

The present invention relates to an organic / inorganic hybrid resin, and more particularly, to an epoxy resin and a siloxane resin having improved adhesiveness, chemical resistance and hardness which are shortcomings of conventional epoxy resin and siloxane resin, Based hybrid resin and a coating material composition using the same.

Silica sol refers to a colloidal state in which amorphous fine particulate silica has a stable molecular state in a fluid state and is a spherical fine particle having an apparently transparent or milky white color having a diameter of 5 to 100 nm. In 1823 SiCl ₄ was synthesized by Berzelius and in 1860 by Graham, colloidal silica was first produced. Commercialization proceeded with the production of colloids enriched up to 50% by Monsanto's firing method and Dupont's ion exchange method.

Inorganic paints based on inorganic binders such as silica sol have very excellent properties such as heat resistance and hardness which are not obtainable from general paints but their coating properties are too brittle and have poor mechanical properties. The material must be sandblasted and the material must be preheated during the coating process.

On the other hand, organic resins have excellent flexibility and adhesion. Among them, the epoxy resin has chemical resistance, electrical insulation, moldability and the like, but there is a limit to the heat resistance of the epoxy resin itself compared with the inorganic resin, and there are limitations such as water resistance and hardness.

As the organic / inorganic hybrids, the mechanical properties are increased by mixing the inorganic polymer with the organic polymer, but the application is limited. These organic and inorganic composites which control the high functional materials in the molecular unit are characterized by the combination of the characteristics of light, excellent strength, processability and toughness of the organic material and excellent strength, heat resistance and transparency of the inorganic material ceramic.

Techniques for dispersing organic polymer materials into nano-sized materials include nanofiller dispersion method for producing nano-sized ceramic primary particles; Interlayer inserting method of inserting polymer into interlayer and dispersing ceramics by using clay mineral with nano size thick layered structure; And a polymer matrix dispersion method in which the metal alkoxide is subjected to a sol-gel process in the presence of a polymer.

The sol-gel hybrid is a method in which alkoxysilane is added to a molten polymer or polymer solution and the silicate produced in the cured product is dispersed at the nanoscale in a sol-gel hardening process.

Molecular design hybrids have a wide range of polymer selectivity, and there is no difference in the degree of dispersion of silica due to film thickness, so that the hybrid effect can be optimized and the properties of the polymer can be protected by applying silicate to specific sites of the polymer.

On the other hand, Korean Patent Laid-Open Publication No. 10-2014-0060816 discloses a structural unit in which a siloxy group (SiO-) in an organopolysiloxane structure and a metal atom of an organometallic compound are chemically bonded to each other by reacting silane with a metal A novel organometallic polysiloxane and a process for its preparation have been introduced.

An organic-inorganic hybrid coating layer comprising an epoxidized polybutadiene resin, at least one curable epoxy resin, a cured product of an organic silane and nanoparticles as an optical film resin for display; An inorganic gas barrier layer formed on an upper surface of the organic-inorganic hybrid coating layer; And an overcoat layer formed on the upper surface of the inorganic gas barrier layer and having the same constitution as the organic-inorganic hybrid coating layer is disclosed in Korean Patent Application No. 10-2012-0117263.

Korean Patent Application No. 10-2012-0027782 relates to a quick-drying hybrid binder which can be applied to a floor coating material and a method for producing the same, which comprises 30 to 50 parts by weight of pottasium silicate, 2 to 10 parts by weight of an epoxy silane, 40 to 68 parts by weight of an acrylic emulsion resin and 50 to 500 parts by weight of a styrene-acrylic emulsion resin, and the binder composition.

Korean Patent Publication No. 10-2011-0045131 for reaction of epoxy acryl oligomer with silane coupling agent, Korean Patent Registration No. 10-0312176-0000 for copolymer of alkoxysilane and diene, reaction of alkoxysilane acrylic monomer and epoxy acrylate Korean Patent Laid-open Publication No. 10-2007-0080014 concerning the reaction has been disclosed.

The epoxy-silica hybrid has a low elastic modulus at around 100 캜, but is not softened even at high temperatures, and has excellent adhesion and heat resistance, and is used as a component of heat-resistant paints and adhesives.

A related application is disclosed in Korean Patent Application No. 10-2010-0011998, and there is a coating material prepared by reaction of an alkoxy silane hydrolyzate with an epoxy resin. Wherein the silane is composed of ethyl silicate and tetramethoxy silane, methacryloxy silane, and epoxy silane.

However, the above-mentioned technology has limitations on the hardness of the product and on the silane network as well as on the organic and inorganic network.

Korean Patent Publication No. 10-2011-0045131, Korean Patent Registration No. 10-0312176-0000 Korean Patent Publication No. 10-2007-0080014 Korean Patent Application No. 10-2010-0011998

It is an object of the present invention to solve the problems of hardness, water resistance and adhesiveness of conventional organic epoxy coating agents and to solve problems of brittle of inorganic resin, incompatibility with organic polymer, chemical resistance, and salt water resistance. It is an object of the present invention to provide a two-part coating agent which is applied by synthesizing a room temperature curing type and a middle temperature curing type (100 ° C or less) of a base and a curing agent. The subject is composed of organic and inorganic composite resins. Composites such as organic epoxy polymers, polyols, organic silane derivatives, colloidal metals, and curing agents include amines, aminosilanes and mesophilic acid anhydrides which are applied at room temperature.

Particularly, the present invention relates to a polyolefin resin composition which utilizes the characteristics of excellent hardness, workability and excellent heat resistance possessed by the silane derivatives of colloidal alumina sol or colloidal silica resin, which are inorganic resins, and has flexibility, curability, transparency, Which is excellent in workability and heat resistance adhesion property. For this purpose, the present invention aims to synthesize an organic / inorganic hybrid resin in which a network through hydrolysis of a colloidal metal sol and silane and an organic polyol are added to react with an epoxy resin after reacting with an alkoxysilane to further strengthen the network .

The above objects are achieved by a resin composition comprising 100 parts by weight of an inorganic resin, 20 to 140 parts by weight of an organic resin to be reacted with the inorganic resin, and 20 to 100 parts by weight of a solvent;

The inorganic resin is obtained by partial hydrolysis reaction of at least one of colloidal alumina or colloidal silica so that an alkoxy group remains using a metal alkoxide or is obtained by partial hydrolysis of a metal alkoxide;

Wherein the organic resin is obtained by reacting an epoxy resin and an alkoxysilane at an elevated temperature or by adding a polyol thereto.

According to an aspect of the present invention,

Examples of the metal alkoxide include methyltrimethoxysilane, methyltriethoxysilane, tetraethoxysilane, tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, hexylcycloethoxysilane, phenyltriethoxysilane And the alkoxysilane is at least one selected from the group consisting of ethyltriethoxysilane, tetraethylolososilicate, methyltrimethoxysilane, propyltriethoxysilane,? -Aminopropyltrimethoxysilane,? -Glycidyloxypropyltrimethoxysilane (Aminoethyl) -? - aminopropyltrimethoxysilane,? -Glycidyloxypropylmethyldiethoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, propyltrimethoxysilane, propyltrimethoxysilane, a single compound selected from? -aminopropyltriethoxysilane, dimethyldiethoxysilane, tetramethoxysilane, phenyltrimethoxysilane and phenyltriethoxysilane, or May be two or more compounds.

According to another aspect of the present invention,

The polyol may be any one or more of polypropylene glycol, polypropylene glycol, neopentyl glycol, trimethoxypropane, and pentaerythritol.

According to still another aspect of the present invention,

The inorganic resin synthesized by the partial hydrolysis reaction can maintain an alkoxy group at 60 to 80%.

According to still another aspect of the present invention,

The molecular weight of the polypropylene glycol and the polyethylene glycol is 400 to 3,000; The polyol may be at least one of neopentyl glycol, trimethylol propane or pentaerythritol.

Still another object of the present invention is to provide

Based on 100 parts by weight of the organic / inorganic hybrid resin; 20 to 50 parts by weight of an extender pigment such as mica or alumina; And 10 to 30 parts by weight of an inorganic pigment.

Herein, the coating material composition may be prepared by using an organic / inorganic hybrid resin as a base material and adding an amine curing agent and an acid anhydride curing agent as curing agents.

Wherein the amine curing agent comprises at least one of ethylenediamine, triethylenetetramine, piperidine, imidazole, aromatic amine, modified amine, alicyclic amine, or amine diol; The acid anhydride curing agent may include at least one of an aliphatic acid anhydride derivative, an aromatic acid anhydride, an alicyclic acid anhydride, or a halogenated anhydride.

According to the above configuration, an organic-inorganic hybrid resin having excellent workability, heat resistance, and adhesion can be provided by maintaining the organic and inorganic characteristics as they are. Further, a coating material (coating composition) having excellent workability and adhesion can be provided by applying such a resin. In particular, surface protective coatings useful for plastic products, metallic substrates, glass, cement concrete, etc. are provided.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram showing a process for synthesizing an inorganic resin using a colloidal sol according to an embodiment of the present invention. FIG.
Figure 2 shows the partial hydrolysis reaction of tetraalkoxysilane.
3 is a molecular structure of five kinds of polyols which are starting materials of an organic resin.
Fig. 4 illustrates the use of epoxy, alkoxysilane, and polyol as a process of synthesizing an organic resin.
FIG. 5 shows a process of synthesizing epoxy resin and inorganic resin composite resin according to an embodiment of the present invention.
Fig. 6 shows an example of amine curing of the epoxy resin-based composite resin embodiment.
7 is a conventional epoxy hybrid resin composition.
Figure 8 shows the siloxane networking of alkoxysilanes.
Figure 9 shows the partial hydrolysis process of methyltrimethoxysilane.
10 shows the hydrolysis process of the metal alkoxide using silica sol.
Fig. 11 schematically shows the characteristics of the epoxy resin.
Fig. 12 shows classification of epoxy resin.
Figure 13 shows a structural formula that additionally reacts the polyol.
14 is a structural formula showing the use of a curing agent.
15 is a structural formula of an acid anhydride.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

The present invention relates to a hybrid resin comprising an inorganic resin and an organic resin. The organic-inorganic hybrid resin (hereinafter abbreviated as "hybrid resin") of the present invention is prepared by synthesizing an inorganic resin and an organic resin independently and then reacting them.

The inorganic resin is obtained by hydrolyzing the coating composition with colloidal alumina (or colloidal silica) and an organic functional silane compound or partial hydrolysis of the metal alkoxide.

The organic resin may be one obtained by reacting an epoxy resin with an alkoxysilane. The organic resin may also be synthesized by adding a polyol composed of at least one of polypropylene glycol (or polyethylene glycol), neopentyl glycol, trimethylol propane, and pentaerythritol to a reaction product obtained by reacting an epoxy resin with an alkoxysilane.

A process for synthesizing an inorganic resin capable of reacting primarily with an organic resin will be described in detail with reference to FIG. 1 is a reaction formula showing the synthesis process of an inorganic resin, and is a reaction formula of hydrolysis of colloidal alumina or colloidal silica with metal alkoxide. 1, M and M 'are silicon (Si) or aluminum (Al).

A colloidal alumina (or colloidal silica) and an organoleptic silane compound are hydrolyzed to produce an inorganic resin. The colloidal alumina used herein is an aqueous dispersion colloidal sol having a solids content of 10 to 20% by weight and a water-soluble solvent of 80 to 90% by weight and having a pH of 2 to 5. If the solid content of the colloidal alumina sol is less than 10% by weight, the resinization is difficult, while if it exceeds 20% by weight, the stability is degraded. Colloidal silica is difficult to be resinized when the pH is acidic and less than 10% by weight of the solid content, and when it exceeds 30% by weight, the stability is degraded.

The organofunctional silane compounds usable for the hydrolysis reaction with colloidal alumina or colloidal silica include ethyltriethoxysilane, tetraethylolososilicate, methyltrimethoxysilane, propyltriethoxysilane, gamma -aminopropyl (Aminoethyl) -? - aminopropyltrimethoxysilane,? -Glycidyloxypropylmethyldiethoxysilane, dimethyldimethoxy silane,? -Trimethoxysilane, A single compound selected from silane, diethyldiethoxysilane, propyltrimethoxysilane,? -Aminopropyltriethoxysilane, dimethyldiethoxysilane, tetramethoxysilane, phenyltrimethoxysilane and phenyltriethoxysilane, or 2 More than species can be used.

The hydrolysis reaction ratio of the colloidal alumina or colloidal silica and the organoleptic silane compound is preferably 1: 0.3 to 1: 2 equivalent, and if the organoleptic silane compound is the colloidal alumina or colloidal silica 1 equivalent If the amount is less than 0.3 equivalents, the remaining hydroxyl groups after hydrolysis can promote the gelation of the coating. If the amount is more than 2 equivalents, the functional group capable of a second-order reaction is less in the synthesized inorganic resin, The formed film is very fragile and may cause poor adhesion to the resin.

In the hydrolysis reaction product, the siloxane bond gradually becomes stronger as ROH escapes with time, and finally, the gel is formed. To prevent this, the solvent is added to the hydrolysis reaction product. As the solvent, alcohols and aliphatic solvents may be used alone or in combination. The content of such a solvent is preferably 40 to 80 parts by weight of the hydrolysis reaction. If the amount is less than 40 parts by weight, the storage stability is a problem. If the amount is more than 80 parts by weight, the reaction time may be too long or the reaction may not take place have.

The synthesized inorganic resin has excellent heat resistance, but the coating film itself is fragile. Therefore, the flexibility is insufficient and the adhesion with general organic coating film is insufficient. To achieve the object of the present invention, alkoxysilane is added to an epoxy resin to synthesize a composite do. The organic resin is further added with polyol to the mixture to increase the organic or inorganic network. After that, the metal alkoxide partial hydrolyzate or colloidal sol, which is a inorganic resin, is hydrolyzed with metal alkoxide and then reacted, Organic hybrid hybrid resin excellent in physical properties is completed.

On the other hand, in Korean Patent Registration No. 10-0956752, an organic / inorganic hybrid resin was prepared by using alkoxysilane and silane hydrolyzate as an epoxy resin.

This is because the network formation of the silane and the colloid-like metal is small in the inorganic resin portion compared to the present invention. This is because the hydroxyl group capable of reacting with the silane is limited to one, so that the physical properties and the functionality of the self resin tend to be inferior. And there is no extra polyol in the silane partial hydrolyzate, and the network between the organic and inorganic groups is insufficient (see FIG. 7).

The synthesis of the organic resin in the present invention will be described in detail as follows.

Organic resins can react with epoxy resin to metal alkoxide to react with inorganic resin, and additionally polyol can be added to easily form many organic and inorganic networks which can react with inorganic resin. This can be confirmed from FIG.

The metal alkoxide may be methyl silicate and ethyl silicate.

Methyl silicates include polymethyl silicates such as dimers and trimers synthesized by hydrolysis and condensation reaction of tetramethyl orthosilicate (TMOS) or tetramethyl orthosilicate. Examples of the ethyl silicate include polyethyl silicate such as a dimer and a trimer synthesized by hydrolysis and condensation reaction of tetraethyl orthosilicate (TEOS) or tetraethyl orthosilicate. The mixture may be used alone or in combination of two or more.

Hydrolysates and partial condensates of tetraalkoxysilanes are obtained by hydrolysis of tetraalkoxysilanes. The tetraalkoxysilane is hydrolyzed as a water and an acid catalyst to generate a hydrolyzate, and a reaction is continuously performed to obtain a partial condensate by the route shown in the reaction formula of FIG.

FIG. 4 shows a reaction product of an epoxy and an alkoxysilane or a secondary reaction product of an epoxy, an alkoxysilane and a polyol. When a partially hydrolyzed siloxane or siloxane polyol is provided as shown in FIG. 4, an organic / inorganic hybrid resin is synthesized by a route as shown in FIG. Again, the hydrolysis reaction must be done in part. That is, an alkoxide group must partially remain in the reactant. This is for the bonding reaction of concrete floor and minerals.

In the present invention, the difference from the existing technology is that the colloidal metal sol is used in the inorganic resin to improve the hardness and physical properties by stronger networking than the hydrolyzate of the silane, and by combining the epoxy and the alkoxysilane with the reacted organic resin, Of the silane hydrolyzate and the epoxies. In addition, the polyol (polyethylene glycol, polypropylene glycol, neopentyl glycol, trimethylol propane, pentaerythritol) was further reacted to increase the reaction site with the inorganic resin to secure the stability of the resin by covalent bonding between the organic resin. However, the polyalkylene glycol can be used in various molecular weights ranging from 300 to 3000.

Hydrolysis of a conventional inorganic resin, for example, MTES (methyl triethoxy silane), can be seen from the fact that the silane content is low and the networking is small due to the hydrolysis of the silane itself, as shown in FIG.

The conventional sol-gel process involves hydrolysis and condensation. In the case of alkoxysilane, the siloxane is condensed through silanol to form a silsesquioxane of the same species or react with the silica surface. On the other hand, silica reacts only on the surface and volume reduction occurs in the condensation of silanol. In order to minimize the voids of the silica particles, a proper combination of other silica particles is required (see Figs. 9 to 10).

The synthesis of the organic resin in the present invention will be described in more detail as follows.

First, organic reservoirs are to compensate for the disadvantages of alkaline resistance in domestic water, which is a disadvantage of inorganic resins, and which are liable to break down. The organic resin is based on an epoxy resin, and its characteristics are shown in Fig.

The epoxy may be in various forms as shown in Fig. In addition to those shown in FIG. 12, there are hydrogenated epoxy and the like. The alkoxysilane is reacted with the alkoxysilane to introduce the inorganic resin, and the polyol is further reacted to strengthen the networking of the inorganic resin and increase the flexibility of the organic resin (see FIG. 13).

In Fig. 13, R1 is an alkyl group containing an epoxy, acrylic, vinyl, methacrylic, mercapto group, and R, (attached) R2 or R3 are all alkyl or alkyl, hydroxyl group.

The inorganic resin reacts with colloidal silica or colloidal alumina with an alkoxysilane to form a siloxane bond. Then, the resultant is added to and reacted with an organic resin to synthesize the final organic / inorganic hybrid resin.

The colloidal sol and the tetraalkoxysilane listed above are diluted together with an acid catalyst and a solvent, and then reacted while dropping the distilled water required for the hydrolysis reaction while maintaining the temperature at 60 ° C. The decomposition reaction rate of the alkoxysilane is 60 to 80% It is suitable.

When the hydrolysis reaction rate is less than 60%, the reaction with the organic resin in the next step is not performed smoothly. When the hydrolysis reaction rate is 80% or more, 70% to 75% is most suitable because no self-storage property is obtained. When the predetermined equivalent hydrolysis reaction of the alkoxysilane is completed, polyalkylene glycol and other polyol may be added to the reaction vessel again and the temperature may be raised to synthesize an organic resin. These polyol groups (neopentyl glycol, trimethylol propane, pentaerythritol) and the like contribute to the improvement of stability between organic and inorganic resins by multiple bonds between resins.

Meanwhile, the curing agent of the epoxy resin-based composite resin to be used in the present invention can be an amine and an acid anhydride series. Specifically, it is possible to use ethylenediamine, triethylenetetramine series as primary amine, piperidine, Etc. may be used. As other curing agents, aromatic amines, tertiary amines, and modified amines can be used.

Alicyclic amines having the advantages of room temperature curing and transparency can be used as the curing agent, and ketimine and amine ducts are also applicable (see Fig. 14). 15 shows an acid anhydride.

Hereinafter, the constitution and effects of the present invention will be described in more detail with reference to Examples and Test Examples. However, these test examples and examples are provided for illustrative purposes only in order to facilitate understanding of the present invention, and the scope and scope of the present invention are not limited by the following examples.

&Lt; Inorganic resin synthesis &

Colloidal alumina or colloidal silica was fed to the reaction vessel and the metal alkoxide was added dropwise while stirring at 300 rpm to hydrolyze the hydroxyl group of the inorganic binder to the metal alkoxide and the temperature was maintained at 30 to 60 ° C Respectively.

The reaction was terminated when 80% (2.4 -OR / molecule) of the alkoxy group of the metal alkoxide was hydrolyzed while the alkoxy group was being quantified. At this time, the inorganic resin was synthesized by diluting with a solvent.

In the following, inorganic resins were synthesized by five methods.

[Inorganic resin # 1]

220 g of methyltrimethoxysilane is added dropwise slowly to 100 g of colloidal silica a) at 30 to 60 占 폚. After 3 hours, 150 g of 2-propanol was added to synthesize a inorganic resin.

[Inorganic resin # 2]

280 g of methyltriethoxysilane is added dropwise slowly to 100 g of colloidal silica a) at 30 to 60 ° C. After 3 hours, 150 g of ethanol was added to synthesize the inorganic resin.

[Inorganic resin # 3]

To 100 g of colloidal silica a) 270 g of tetraethoxysilane is slowly added dropwise at 30 to 60 ° C. Then, after 3 hours, inorganic resin was synthesized by adding 150 g of Dowanolp.

[Inorganic resin # 4]

50 g of acryloxypropylmethyldimethoxysilane and 200 g of glycidoxypropyltrimethoxysilane are slowly dropped into 100 g of colloidal alumina b) at 30 to 60 ° C. Then, 3 hours later, 50 g of 2-propanol and 100 g of ethanol were added to synthesize an inorganic resin.

[Inorganic resin # 5]

80 g of methacryloxypropylmethyltriethoxysilane and 180 g of vinylmethyldiethoxysilane are slowly dropped into 100 g of colloidal alumina c) at 30 to 60 ° C. After 3 hours, 50 g of 2-propanol, 50 g of ethanol and 50 g of Dowanol p were added to synthesize a inorganic resin.

&Lt; Organic resin synthesis >

(Epoxy equivalent 180 to 190) of glycidyl ether type is introduced into a four-necked flask with alkoxysilane, acid catalyst and ethanol, and the temperature is raised to 80 to 100 DEG C to introduce a silane compound into the epoxy, and further a polyol Glycol, polypropylene glycol, neopentyl glycol, trimethylol propane, pentaerythritol) was added to synthesize an organic resin having a hydroxyl group and an alkoxysilane group introduced therein.

[Organic resin # 1]: Glycidoxy silane synthesis of DEGBA type epoxy

100 g of epoxy (epoxy equivalent: 180 to 190) of DEGBA TYPE and 80 g of glycidoxypropyltrimethoxysilane (GTPMS) are placed in a four-necked reactor equipped with a condenser, and 2 g of hydrochloric acid is added to react at 100 ° C. for 3 hours.

[Organic resin # 2]: Methacryloxy silane synthesis of DEGBF type epoxy

100 g of epoxy (epoxy equivalent: 180 to 190) of DEGBF TYPE, 40 g of methacryloxypropyltriethoxysilane and 0.02 g of hydroquinone were added to a four-necked reactor equipped with a condenser, and 0.2 g of nitric acid was added thereto. And reacts.

[Organic resin # 3]: Synthesis of vinylsilyl polypropylene glycol of phenol novolac type epoxy

100 g of phenol novolak type epoxy (epoxy equivalent) is added and 60 g of vinyl silane is added under stirring. Then, 0.3 g of boric acid was added, the temperature was raised, and the mixture was stirred at 100 ° C for 4 hours. Then, 30 g of polypropylene glycol having a molecular weight of 3000 was added to carry out an additional reaction. Thereafter, the temperature is raised, and the mixture is maintained at 90 DEG C for 5 hours to react and cool to complete the reaction.

[Organic resin # 4] Synthesis of bromohexoxystyrylsilyl neopentyl glycol

90 g of p-styryltrimethoxysilane and 0.1 g of sulfuric acid are added, and the mixture is stirred at 100 ° C. for 4 hours. 15 g of neopentyl glycol is further added to the reaction mixture. Thereafter, the temperature is raised, and the mixture is maintained at 90 DEG C for 5 hours to react and cool to complete the reaction.

[Organic resin # 5] Synthesis of hydrogenated epoxy cyclohexylepoxy silyltrimethylol propane

(Epoxy equivalent) was added, and 63 g of cyclohexylethyltrimethoxysilane and 0.5 g of p-toluenesulfonic acid were added thereto under stirring, and the mixture was heated at 100 ° C for 4 hours, and then 5 g of trimethylolpropane was reacted. Thereafter, the temperature is raised, and the mixture is maintained at 90 DEG C for 5 hours to react and cool to complete the reaction.

[Organic resin # 6] DEGBA Synthesis of epoxy silyl pentaerythritol

Add 100 g of DEGBA epoxy (epoxy equivalent), add 40 g of glycidoxypropyltriethoxysilane and 0.3 g of tetrabutoxy titanate with stirring, stir at 100 ° C for 4 hours, and react with 3 g of pentaerythritol. Thereafter, the temperature is raised, and the mixture is maintained at 90 DEG C for 5 hours to react and cool to complete the reaction.

&Lt; Synthesis of organic / inorganic hybrid resin &

The organic / inorganic hybrid resin can be obtained by final synthesizing the above-prepared inorganic resin and organic resin at 50 to 80 캜 as shown in the following table. Alcohol is added here as a solvent. In the following table, composite resins # 1, # 2, # 3, # 4 and # 5 were used as examples of the organic / inorganic hybrid resin of the present invention.

Synthesis of organic / inorganic hybrid resin Furtherance Composite resin # 1 Composite resin
#2 Composite resin
# 3 Composite resin
#4 Composite resin
# 5 Composite resin
# 6

Inorganic resin

#One 100 100 #2 100 # 3 100 #4 100 # 5 100

Organic resin

#One 55 #2 40 # 3 75 #4 80 # 5 100 # 6 40

&Lt; Evaluation of Physical Properties of Coating Film &

As shown in the table above, the hybrid resin of the present invention was obtained in five types with different mixing ratios of the inorganic resin and the inorganic resin, and then the physical properties of the coating film were tested by adding a curing agent. Comparative Example in the following table shows the result of testing a coating film employing Korean Patent Registration No. 10-0956752 and silica for abrasion resistance thin film coating material (Kyonggi University, Park Jung Hoon, 2004), and comparison with a coating film using the present invention Were tested together. The results of the test show that the present invention is applied to various items.

Coating property sheet division
Test Items Composite resin
#One Composite resin # 2 Composite resin
# 3 Composite resin
#4 Composite resin
# 5 Composite resin
# 6 Comparative Example Attachment 4B 5B 5B 5B 5B 5B 2B Heat resistance
(FLAME TEST) Good Good Good Good Good Good minuteness
crack Pencil hardness 3H 3H 3H 3H 3H 3H 2H Acid resistance Good Good Good Good Good Good Good Alkali resistance Good Good Good Good Good Good Good Chemical resistance

5% hydrochloric acid Good Good Good Good Good Good Poor 10% sulfuric acid Good Good Good Good Good Good Poor of mine
Alkaline Good Good Good Good Good Good Good

- Test Methods-

1) Adhesion: After degreasing the alcohol by pretreating the tile substrate, the resin composition was air-sprayed, then cured at 200 ° C for 20 minutes, and then adhered by a tape test after 1 mm × 1 mm × 10 cross cut.

2) Heat resistance: After degreasing the alcohol with the pretreatment of the tile substrate, the resin composition is air-sprayed, and the surface of the specimen is evaluated after heating with FLAME.

3) Pencil Hardness: The resin composition was air-sprayed on the tile specimen after alcohol degreasing by the pretreatment, and then the specimen was cured at 200 ° C for 20 minutes.

4) Acid resistance: After the alcohol composition was degreased by alcohol pretreatment on the tile substrate, the resin composition was air-sprayed and then evaluated for physical properties of the film after 96 hours of SPOT test on each acid after 1 day of curing.

5) Alkali resistance: Alcohol degreasing with the pretreatment of the tile substrate, air spraying of the resin composition, curing, and evaluation of physical properties of the coating after 70 hours of saturated calcium hydroxide deposition.

The configuration shown and described above is merely a preferred embodiment based on the technical idea of the present invention. It will be understood by those skilled in the art that various changes and modifications may be made without departing from the scope of the present invention.

Claims

100 parts by weight of an inorganic resin, 20 to 140 parts by weight of an organic resin to be reacted with the inorganic resin, and 20 to 100 parts by weight of a solvent;
The inorganic resin is obtained by partial hydrolysis reaction of at least one of colloidal alumina or colloidal silica so that an alkoxy group remains using a metal alkoxide or is obtained by partial hydrolysis of a metal alkoxide;
Wherein the organic resin is obtained by reacting an epoxy resin and an alkoxysilane at a raised temperature or by reacting a reaction product of an epoxy resin and an alkoxysilane with a polyol.

The method according to claim 1,
Examples of the metal alkoxide include methyltrimethoxysilane, methyltriethoxysilane, tetraethoxysilane, tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, hexylcycloethoxysilane, phenyltriethoxysilane And the alkoxysilane is at least one selected from the group consisting of ethyltriethoxysilane, tetraethylolososilicate, methyltrimethoxysilane, propyltriethoxysilane,? -Aminopropyltrimethoxysilane,? -Glycidyloxypropyltrimethoxysilane (Aminoethyl) -? - aminopropyltrimethoxysilane,? -Glycidyloxypropylmethyldiethoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, propyltrimethoxysilane, propyltrimethoxysilane, a single compound selected from? -aminopropyltriethoxysilane, dimethyldiethoxysilane, tetramethoxysilane, phenyltrimethoxysilane and phenyltriethoxysilane, or Is a compound of two or more kinds.

The method according to claim 1,
Wherein the polyol is at least one of polypropylene glycol, polyethylene glycol, neopentyl glycol, trimethoxypropane, and pentaerythritol.

The method according to claim 1,
Wherein the inorganic resin synthesized by the partial hydrolysis reaction maintains an alkoxy group at 60 to 80%.

The method of claim 3,
Wherein the polypropylene glycol and the polyethylene glycol have a molecular weight of 400 to 3,000.

Based on 100 parts by weight of the organic / inorganic hybrid resin of claim 1;
20 to 50 parts by weight of an extender pigment such as mica or alumina;
10 to 30 parts by weight of an inorganic pigment;
&Lt; / RTI > further comprising a coating composition.

The method according to claim 1,
Wherein said organic / inorganic composite hybrid resin is used as a base material, and said curing agent is prepared by using an amine curing agent and an acid anhydride curing agent.

8. The method of claim 7,
Wherein the amine curing agent comprises at least one of ethylenediamine, triethylenetetramine, piperidine, imidazole, aromatic amine, modified amine, alicyclic amine, or amine diol;
Wherein the acid anhydride curing agent comprises at least one of an aliphatic acid anhydride derivative, an aromatic acid anhydride, an alicyclic acid anhydride, or a halogenated anhydride.