JPH11302528A - Solution composition for phenoxy resin-silicon hybrid material, surface modifying agent for substrate, its use and surface-modified substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject solution composition having excellent adhesivity to various substrates, especially transparent plastics, and capable of forming a cured film having excellent surface characteristics such as hardness and scratch resistance on the surface of a substrate by dissolving a phenoxy resin and an alkoxysilane in a common solvent. SOLUTION: This solution composition is produced by dissolving (A) a phenoxy resin synthesized from bisphenol A compound and an epihalohydrin and having a weight-average molecular weight of preferably 5,000-100,000, e.g. a polymer having the recurring unit of formula and (B) an alkoxysilane such as an organic silicon compound of formula R<1> p Si(OR<2> )q ((p) is 0-3; (q) is 1-4; p+q=4; R<1> is a lower alkyl; R<2> is H or the like) (e.g. tetramethoxysilane) in (C) a solvent capable of dissolving the components (e.g. ethylene glycol monomethyl ether). In the case of using the above composition as a primer, it is preferable to mix about 5-200 pts.wt. of the component B into 100 pts.wt. of the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a phenoxy resin
The present invention relates to a solution composition for a silicon-based hybrid material, a surface modifier for a substrate using the solution composition, a method for modifying the surface of a substrate, and a surface-modified substrate. The phenoxy resin-silicon hybrid material of the present invention is useful as a surface modifier for forming a cured film (protective film) on the surface of various substrates such as metal, glass, ceramics, and plastics. It is used as a surface coating agent capable of direct protective coating, as a primer (undercoat layer) for surface coating agents (overcoat layer) for various substrates, and the like. Above all,
It is useful as a coating agent on plastic surfaces that are easily damaged, and modified plastics with improved surface properties are
It can be used for various molded products, for example, sundries, daily necessities, aircraft windows and doors, motorcycle windshields, headlights and various lighting fixture covers, large structures such as signboards and displays, meter panels, and equipment covers.

[0002]

2. Description of the Related Art In general, various protective films are formed on the surface of a base material such as metal, glass, ceramics, plastics, and the like in order to maintain aesthetic appearance, impart corrosion resistance, weather resistance, abrasion resistance, and scratch resistance. . For example, the metal surface is coated with a protective film to maintain a highly polished surface for a long time,
In addition to being protected from abrasion and abrasion by various objects, resistance to corrosion by acids, salts and the like is given. In addition, the protective film formed on the surface of glass, ceramics, plastics, etc. not only protects from scratches and abrasion, but also when the substrate surface requires transparency, the protective film also has transparency. It is positioned as an important performance.

[0003] In particular, among the above-mentioned substrates, plastic materials are generally used in a wide range of applications because of their light weight, ease of molding, and excellent impact resistance. Above all, transparent plastic substrates such as polycarbonate, methacrylic resin and polyvinyl chloride are widely used in various applications requiring transparency such as glass replacement. However, although these plastic base materials have excellent performance of transparency, the surface hardness is insufficient, so that the surface is easily scratched by wiping work to remove dust and dirt, friction, scratching, etc., There is a disadvantage that gloss and transparency are easily lost during use. Further, these plastic substrates are easily attacked by an organic solvent, lack chemical resistance, and have a problem in weather resistance such as light deterioration.

The disadvantages of such plastic substrates are
Usually, the problem is solved by coating the surface of the substrate with a thermosetting resin or a UV-curable resin having high hardness. For example, as a conventionally known method, an inexpensive thermosetting resin such as a melamine resin is directly applied and baked and cured (Japanese Patent Publication Nos. 40-7392 and 46-109). A method in which a cured film obtained by polymerizing a polyfunctional acrylic monomer such as dimethacrylate on the inner surface of a mold is transferred at the time of cast polymerization of methacrylic resin (Japanese Patent Publication Nos. 35-17847 and 37-9827). and so on.

However, the melamine-based resin coating requires a long time to cure and has poor weather resistance. Recently, the influence of acid rain has become a problem. In addition, the thermosetting of the polyfunctional acrylic monomer also requires a long time. For this reason, recently, a method of using ultraviolet irradiation polymerization (UV curing) or electron beam irradiation of a polyfunctional acrylic monomer such as diethylene glycol dimethacrylate or a phosphazene derivative has become mainstream (Kurahashi: Painting and Paint, 39-47N).
o. 485 (1991)). However, in methods using ultraviolet irradiation polymerization (UV curing), problems such as reduced adhesion and insufficient coating film hardness due to shrinkage strain due to rapid curing, and discoloration due to photodegradation of the surface layer in outdoor use, etc. There is a problem in weather resistance such as generation of cracks. In addition, there is a problem that equipment and processing methods for performing high-energy irradiation in an inert atmosphere require advanced technology.

Various organopolysiloxane-based coating agents have long been proposed as coating agents for various substrate surfaces. Organopolysiloxane-based coating agents have the characteristics of a siloxane bond,
Easy to form high crosslink density, excellent weather resistance and very hard layer can be obtained by simple method, so it is used as a coating agent for large molded products and molded products with complicated shapes Have been. Such an organopolysiloxane-based coating is one in which alkoxysilanes are hydrolyzed to form an organopolysiloxane through polycondensation through the formation of silanol groups and are cured. The structural unit of an organosilane such as an alkoxysilane has a monofunctional property. From monofunctional to tetrafunctional.

A cured film made of a tetrafunctional alkoxysilane is not used as it is because it has poor film-forming properties and lacks adhesiveness. In order to fuse the formed silica particles. An example of practical application is a composite of an organic polymer consisting of a copolymer of a hydrolysis / polycondensate of a tetrafunctional alkoxylane and a fluorinated olefin such as tetrafluoroethylene with vinyl acetate or hydroxyalkyl vinyl ether. The body is known (US Pat. Nos. 3,429,845 and 3,429,843).
No. 6).

Further, as a method using a trifunctional alkoxysilane, a resin having a curable ladder structure which is first heated to 80 ° C. or higher and hydrolyzed and condensed is then redissolved in a solvent to obtain a curing catalyst. And a method of heat-curing is known (U.S. Pat. Nos. 3,451,838, 35).
54698).

However, these organosiloxane-based coating agents generally have a considerably slow curing rate, and have poor wettability with various substrates, especially plastic substrates such as polycarbonate resins. It has a drawback that it is easily peeled off due to poor adhesion to the material, and thus lacks abrasion resistance. In order to avoid these drawbacks, treatment with a general silane coupling agent such as a silane coupling agent such as 3-glycidoxypropyltrimethoxysilane or 3-aminopropyltrimethoxysilane, or a silane containing an amino group Reaction product comprising a compound and an acid anhydride (JP-A-56
No. 16573), a reaction product comprising an amino group-containing silane compound and an epoxy resin (JP-A-51-2).
No. 736), a thermoplastic acrylic resin (Japanese Unexamined Patent Publication No.
It is indispensable to select and use appropriate primers such as 138565, JP-A-58-196237).

[0010] However, the primers proposed so far have poor balance of adhesion, weather resistance and the like. For example,
A primer using a thermoplastic acrylic resin or the like has a problem in weather resistance if the adhesion is improved, or the interpenetration with the overcoat layer progresses, and the performance of the coating film cannot be maintained. In addition, primers using silicon compounds,
There are many problems, such as a decrease in the level of improvement in adhesion when trying to increase the weather resistance, and an inadequate long-term stability due to the aging of the resulting sol solution composition.

In recent years, as a method of dealing with such a drawback of the primer, an attempt has been made to directly apply a coating agent to a substrate and form a protective film with one coat. For example, using a copolymer of an acrylic monomer or the like and a monomer having an alkoxysilyl group such as vinyltrimethoxysilane to form a composite of an acrylic resin and a polysiloxane to improve adhesion to a plastic substrate such as a polycarbonate. However, they have not yet achieved sufficient adhesion and scratch resistance. Another problem is that it is difficult to copolymerize an acrylic monomer or the like with a monomer having an alkoxysilyl group. Furthermore, a method of imparting adhesiveness together with hardness and abrasion resistance by gradually changing the composite composition and performing multilayer coating has been proposed, but since the process becomes complicated, except for special applications, There are many problems in practical use.

[0012]

SUMMARY OF THE INVENTION The present invention relates to various substrates,
In particular, it has excellent adhesion to plastic materials, especially to transparent plastics such as polycarbonate, and forms a cured film with excellent surface properties such as high hardness and scratch resistance on the surface of the substrate. An object is to provide a material whose surface can be modified.

[0013]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that phenoxy resin (A) which is a thermoplastic polyhydroxy polyether synthesized from bisphenol A and epihalohydrin (A) Phenoxy resin-silicon hybrid obtained by heating and drying a colorless and transparent solution composition prepared by uniformly mixing the silane and the alkoxysilanes (B) with a solvent (C) in which both are soluble. The material has excellent adhesion to various substrate surfaces such as metal, glass, ceramics and plastics, especially to transparent plastic surfaces such as polycarbonate, and has excellent surface properties such as high hardness and scratch resistance. The cured film (protective film) can be formed, and the cured film has excellent adhesion to the coating agent used as an overcoat layer. It found that for may also become a primer or the like to form an undercoat layer, and have completed the present invention.

That is, the present invention relates to a phenoxy resin (A) synthesized from bisphenol A and epihalohydrin.
And a solution composition for a phenoxy resin-silicon hybrid material in which the alkoxysilanes (B) are dissolved in a solvent (C) in which they are soluble; a surface modifier using the solution composition; Phenoxy resin-silicon hybrid material obtained by curing by heating and drying; after applying the surface modifier to the surface of the substrate, curing by heating and drying, and curing of the substrate surface by the phenoxy resin-silicon hybrid material A method for modifying the surface of a substrate for forming a film;
Further, the present invention relates to a surface-modified base material in which the surface modifier is applied to the surface of a substrate, cured by heating and drying, and a cured film of a phenoxy resin-silicon hybrid material is formed on the surface of the substrate.

[0015]

DETAILED DESCRIPTION OF THE INVENTION The phenoxy resin (A) used in the present invention is a thermoplastic polyhydroxy polyether synthesized from bisphenol A and epihalohydrin (for example, epichlorohydrin). It has a unit. For example, a typical phenoxy resin is represented by the general formula (1):

[0016]

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A compound having a repeating unit represented by the following formula: Such a phenoxy resin (A) has a self-forming property, is excellent in corrosion resistance, adhesion to various substrates (metal, glass, ceramics, plastics, etc.) and toughness,
It is a thermally stable resin because it has no reactive epoxy group at the terminal. In the present invention, attention is paid to characteristics such as excellent adhesiveness and toughness of the phenoxy resin (A), and an alkoxysilane (B) is combined with the phenoxy resin (A) and cured by heat to improve the adhesiveness to a plastic substrate. In addition to the application, the formation of a cured film having high hardness and scratch resistance due to curing of the silane compound is realized.

The phenoxy resin (A) generally preferably has a weight average molecular weight of about 5,000 to 100,000. It is more preferable to use those having a weight average molecular weight of 10,000 or more and 80,000 or less. As a commercially available product of such a phenoxy resin,
For example, a phenothot YP series (trade name) manufactured by Toto Kasei Co., Ltd. may be mentioned.

Various alkoxysilanes (B) can be used in the present invention. For example, the general formula (2): in ^{_{R 1 p Si (OR 2)}} q ( wherein, p is an integer of 0 to 3, q is an integer of from 1 to 4, shows what satisfying p + q = 4, R ¹ Is a lower alkyl group, an aryl group, or an unsaturated aliphatic residue which may have a functional group directly bonded to a carbon atom, which may be the same or different, and R ² represents a hydrogen atom or a lower alkyl group. The organosilicon compounds represented and / or their partial hydrolysates can be exemplified. The lower alkyl group refers to a linear or branched alkyl group having 6 or less carbon atoms.

Specific examples of the organosilicon compound include:
Tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetra-i-propoxysilane, tetrabutoxysilane, tetra-i-butoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, n-
Propyltrimethoxysilane, i-propyltrimethoxysilane, 3-chloropropyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane,
Methyltriethoxysilane, ethyltriethoxysilane, n-propyltriethoxysilane, i-propyltriethoxysilane, 3-chloropropyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, methyltripropoxysilane, methyltrii-
Propoxysilane, ethyltri i-propoxysilane,
n-propyltrii-propoxysilane, i-propyltrii-propoxysilane, 3-chloropropyltrii
-Propoxysilane, vinyltri-i-propoxysilane, phenyltri-i-propoxysilane, methyltributoxysilane, ethyltributoxysilane, n-propyltributoxysilane, i-propyltributoxysilane, 3-chloropropyltributoxysilane, vinyl Tributoxysilane, phenyltributoxysilane, 3,
3,3-trifluorotrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3,4-epoxycyclohexyltrimethoxysilane, 3,3 3-trifluorotriethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltriethoxysilane,
3,4-epoxycyclohexyltriethoxysilane,
3,3,3-trifluorotri-i-propoxysilane,
3-methacryloxypropyltrii-propoxysilane, 3-glycidoxypropyltrii-propoxysilane, 3-mercaptopropyltrii-propoxysilane, 3,4-epoxycyclohexyltrii-propoxysilane, 3,3,3 -Trifluorotributoxysilane, 3-methacryloxypropyltributoxysilane,
3-glycidoxypropyltributoxysilane, 3-mercaptopropyltributoxysilane, 3,4-epoxycyclohexylbutoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, Diphenyldiethoxysilane, 3-
Aminoethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminophenyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminoethyltriethoxysilane, 3-amino Propyltriethoxysilane, 3-
Aminophenyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3
-Aminoethylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminophenylmethyldimethoxysilane, N- (2-aminoethyl) -3
-Aminopropylmethyldimethoxysilane, 3-aminoethylmethyldiethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminophenylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxy Examples thereof include silane, 3-aminoethyldimethylmethoxysilane, 3-aminopropyldimethylmethoxysilane, 3-aminophenyldimethylmethoxysilane, and N- (2-aminoethyl) -3-aminopropidimethylmethoxysilane. These can be used alone or in combination of two or more.

As the alkoxysilanes (B), a partial hydrolyzate of the aforementioned organosilicon compound can also be used. As the partial hydrolyzate, MKC silicate MS51 (trade name, manufactured by Mitsubishi Chemical Corporation),
M silicate 51, silicate 40 (both trade names,
Commercially-available products represented by Tama Chemical Industry Co., Ltd.) and those obtained by partially hydrolyzing the organosilicon compound by various methods can be used without limitation, but the partially hydrolyzed product is used as the alkoxysilane (B). In this case, a solvent, an acid catalyst and water (typically 50 mol% or less based on the organosilicon compound) are added to the organosilicon compound,
The reaction solution composition prepared by stirring at 0 ° C. is preferably obtained by further adding the organosilicon compound and water (typically 50 mol% or less based on the organosilicon compound) and mixing. It is preferable because it has excellent curability and storage stability of the partial hydrolyzate.

The acid catalyst used for preparing the partial hydrolyzate is not particularly limited as long as it can be used as a catalyst for the hydrolysis reaction of the organosilicon compound used, and various known ones can be used. Specific examples include a hydrogen chloride alcohol solution, phosphoric acid (usually a 94% aqueous solution), inorganic acids such as boric acid, and organic acids such as acetic acid, citric acid, and paratoluenesulfonic acid. The amount of these catalysts can be appropriately determined depending on the kind of the organosilicon compound and the kind of the catalyst, but is usually 0.01 to 50 mol% based on the organosilicon compound used. Further, the solvent is a solvent (C) used for preparing the solution composition of the present invention.
Can be used.

The alkoxysilanes (B) include:
From the viewpoint of versatility and storage stability of the solution composition for hybrid materials, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, -Aminopropyltrimethoxysilane, N- (2-aminoethyl)-
3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and partial hydrolysates thereof are preferred.

The solution composition for a phenoxy resin-silicon hybrid material of the present invention comprises the phenoxy resin (A)
And alkoxysilanes (B) dissolved and mixed in a solvent (C) capable of dissolving both. The mixing ratio of the phenoxy resin (A) and the alkoxysilanes (B) is appropriately adjusted according to the type of the alkoxysilanes (B) used and the purpose of using the solution composition of the present invention.

Usually, when the solution composition is used as a primer, it is preferable to use about 5 to 200 parts by weight of alkoxysilane with respect to 100 parts by weight of the phenoxy resin (A). When the amount of the alkoxysilanes (B) used is small, the performance of the overcoat layer, such as hardness and abrasion resistance, tends to appear due to mutual penetration with the overcoat layer and excessive or insufficient hardness of the cured film. More preferably, the amount of the class (B) used is 10 parts by weight or more. When the amount of the alkoxysilanes (B) used increases, the adhesion to the overcoat layer and the bending resistance as a primer due to the increase in the elasticity tend to decrease. More preferably, it is 200 parts by weight or less.

When the solution composition is used as a hard coating agent such as a surface coating for a substrate such as a plastic, the phenoxy resin (A) 1 is usually used.
The alkoxysilane (B) is added in an amount of 50 to 100 parts by weight.
It is preferable to use about 2000 parts by weight. The amount of the alkoxysilanes (B) used is 100 parts by weight or more, and more preferably 200 parts by weight, in order for a cured film obtained by curing the solution composition to exhibit more properties as a surface coating film. The amount is more preferably at least part by weight. When the amount of the alkoxysilanes (B) used increases,
Since the coating film after drying tends to crack, the amount of the alkoxysilanes (B) used is 1500 weight in consideration of the balance between the hardness of the coating film and the adhesion to the plastic substrate. Parts by weight, more preferably 1000 parts by weight or less.

Solvent (C) used in the above solution composition
Although various solvents that dissolve the phenoxy resin (A) and the alkoxysilanes (B) can be used, those having a boiling point of 100 ° C. or higher are preferable for forming a good cured film. When the boiling point of the solvent (C) is lower than 100 ° C.,
When the phenoxy resin (A) and the alkoxysilanes (B) are complexed while the solvent in the solution composition is volatilized and the curing reaction proceeds to form a cured film, before the complexing and curing reaction sufficiently proceed. The solvent volatilizes, and the phenoxy resin in the composition tends to be insolubilized and separated, which is difficult to control. The solution composition has a solid content of 0.1 to 3%.
About 0% by weight, more preferably 1% by weight or more,
% By weight or less.

Specific examples of the solvent (C) include toluene,
Aromatic compounds such as xylene, ether compounds such as 1,4-dioxane, nitrogen-containing compounds such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, alcohols such as tetrahydrofurfuryl alcohol, ethylene glycol monomethyl Ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,
Examples thereof include glycol ether compounds such as diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate. These solvents (C) can be used alone or in combination of two or more. Among these solvents (C), glycol ether compounds can form a loose hydrogen bond-like interaction by interaction with the alkoxysilanes (B) to suppress gelation. In consideration of the storage stability of the composition, it is preferable that the glycol ether compound be contained in 20% or more of the total solvent. .

In order to cure the solution composition by heating and drying, various catalysts capable of decomposing and polycondensing the alkoxysilanes (B) in the solution composition are usually used. For example, acid catalysts such as hydrogen chloride alcohol solution, phosphoric acid (usually a 94% aqueous solution), inorganic acids such as boric acid, and organic acids such as acetic acid, citric acid, and paratoluenesulfonic acid; alcoholic potassium hydroxide, alcoholic water Alkali catalysts such as various amines such as sodium oxide, ethanolamine, diethanolamine, triethanolamine and dimethylethanolamine; β-diketone complexes such as Al (III) triacetylacetone complex; organic tin compounds such as dibutyltin octylate; can give.

The amount of the catalyst to be used can be appropriately determined depending on the activity of the catalyst to be used. Usually, the catalyst is used in a molar ratio with respect to the alkoxysilane to be used, such as 0.001 to 5 mol with paratoluenesulfonic acid having high catalytic ability. %, Boric acid, acetic acid or the like having a low catalytic ability is used in an amount of about 1 to 50 mol%. If the amount of the catalyst used is small, the wettability of the cured film at the time of film formation is poor. If the amount is too large, the water resistance of the formed film may be deteriorated or coloring may occur. These catalysts can be used alone or in combination of two or more depending on the alkoxysilanes (B) used, the physical properties (hardness, etc.) of the target cured film, and the like. The timing of addition of the catalyst is not particularly limited, and may be added when the phenoxy resin (A) and the alkoxysilanes (B) are dissolved in the solvent (C) to prepare the solution composition. You may add immediately before apply | coating to a base material. Further, it can be present in the partial hydrolyzate used as the alkoxysilanes (B). Alternatively, a catalyst having a low activity may be added first, and a catalyst may be further added immediately before application to the base material in order to accelerate the curing reaction.

The solution composition of the present invention contains a viscosity modifier, a leveling agent, and the like within a range that does not impair the effects of the present invention.
Various organic and inorganic additives such as an antifoaming agent, a coloring agent, a stabilizer, and a solvent for adjusting the solubility can be added as necessary.

The solution composition thus prepared comprises a metal,
It has good wettability to various substrates such as glass, ceramics and plastics, and has excellent coating workability because the leveling property can be freely adjusted by the characteristics of the phenoxy resin (A). Such a solution composition can be used, for example, as a surface modifier for various substrates such as metals, glasses, ceramics, and plastics.

The surface modifier of the present invention can be used specifically as a coating agent applied directly or via a primer to the surface of a substrate. The substrate can be applied to various materials and forms. However, since the cured film is excellent in transparency, it is suitable for plastic molded articles, especially transparent plastic among various substrates. Examples of transparent plastics include polymethyl methacrylate, polycarbonate, polyvinyl chloride, and the like.

The surface modifier of the present invention can be used as a primer (undercoat) for various coating agents (overcoat). Examples of the coating agent applicable as the overcoat layer include an organosiloxane composition and the hybrid composition of the present invention.

The surface modifier applied to the substrate is rapidly cured by dehydration and / or dealcoholization / polycondensation of the alkoxysilanes (B) by heating and drying, and the phenoxy resin-silicon is added to the surface of the substrate. A cured film is formed using a hybrid material.

Although the curing temperature varies depending on the base material used, it is usually carried out at about 50 to 250 ° C. When the substrate is plastic, curing is performed at a temperature lower than the deformation temperature of the plastic. If the temperature is lower than 50 ° C., it takes a long time for curing, which is not preferable. The curing time is usually 1 minute or more, more preferably 5 minutes.
~ 60 minutes. As the application method, for example, various ordinary application methods such as dip coating, roll coating, bar coating, curtain flow coating, spray coating, and spin coating can be adopted. The thickness of the cured film formed of the hybrid material formed on the surface of the base material is usually about 1 to 50 microns.

[0037]

The cured film obtained from the solution composition for a phenoxy resin-silicon hybrid material of the present invention has excellent adhesion to various substrates. Such a solution composition can be used as a surface modifier for various substrates, for example,
When used as a hard coating agent on the surface of a substrate such as plastic, a primer is not necessarily required, and the substrate can be directly coated, so that productivity can be improved and cost can be reduced. It also has good adhesion to various coating agents (overcoat layer) and can be used as a primer (undercoat layer).

Further, the cured film obtained from the solution composition of the present invention has a high hardness, and the surface hardness of the cured film is usually H or more in pencil hardness. On the other hand, 0000 steel wool can achieve a level with almost no damage.

Further, the cured film obtained from the solution composition of the present invention can significantly improve and improve the water resistance, scratch resistance, abrasion resistance, weather resistance, chemical resistance, heat resistance, etc. of the substrate surface. it can. For example, transparent plastics such as polycarbonate, which are widely used as plastic base materials, are often susceptible to organic solvents and their transparency is often impaired, but the coating film of the surface-modified plastic of the present invention has solvent resistance. Is significantly improved, and transparency is impaired even when rubbed with a cloth containing various organic solvents, for example, ketone solvents such as methyl ethyl ketone, aromatic solvents such as toluene, hexane, and aliphatic solvents such as cyclohexane. Never. In addition, since the cured film is colorless and transparent, it is possible to apply a colorant and paint various hues.

Further, conventionally, the cured film having a high hardness on the surface and having abrasion resistance tends to have a considerably poor adhesion to the substrate surface, but the cured film of the present invention has a good hardness. Because of the excellent adhesion, the hardness and scratch resistance are realized, and the cured film does not peel off even when the substrate is considerably bent.

[0041]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In addition, the characteristic evaluation in an Example was performed using the following method.

"Hardness (Empitz hardness)": JIS-K5
400.

"Scratch resistance": The coating film was rubbed five times with # 0000 steel wool. Evaluation was performed based on the following criteria. ：: No scratches at all, or slight scratches when rubbed very strongly. ×: Damaged by weak friction.

"Adhesion (cross-cut test)": 100 (10.times.10) cross-sections of 1 mm square reaching the plastic substrate were cut into a coating film with a steel knife, and cellophane tape (Nichiban) was applied. After pressure bonding, the film was rapidly peeled off in the direction of 90 ° C., and the degree of peeling of the coating film was evaluated. 100/100: no peeling. 0/100: All peeled.

"Transparency": Evaluation was made visually. ：: colorless and transparent. Δ: translucent, slightly cloudy. X: No transparency.

"Chemical resistance": The coating film surface was rubbed with a cloth impregnated with xylene and left at room temperature for 15 minutes. ：: No change in the coating film. ×: The coating film is whitened, dissolved or peeled.

Example 1 Erlenmeyer flask with a stopcock containing a stirrer (100 ml)
Phenoxy resin (manufactured by Toto Kasei Co., Ltd., trade name: Phenotote TP-50S, weight average molecular weight = 46,000)
5 g and 30 g of N-methyl-2-pyrrolidone were added, and after dissolving the phenoxy resin, 20 g of tetramethoxysilane was gradually added while stirring the phenoxy resin solution at room temperature using a magnetic stirrer. Next, 0.24 g (3 mol% of tetramethoxysilane) of boric acid (crystal) was added, and the mixture was stirred and mixed at room temperature for 30 minutes to prepare a colorless, transparent, and uniform surface modifier 1.

Examples 2 to 13 and Comparative Examples 1 and 2 In Example 1, the composition or composition ratio of the surface modifier was
Surface modifiers 2 to 13 were prepared in the same manner as in Example 1 except that the surface modifiers were changed as shown in Table 1.

Example 14 (1) Preparation of Alkoxysilane Partial Hydrolyzate 10 g of tetramethoxysilane, 10 g of ethylene glycol monomethyl ether, 1.2 g of water, paratoluenesulfonic acid were placed in a stoppered Erlenmeyer flask (100 ml) containing a stirrer. 0.8 g was added and mixed, and the mixture was stirred at room temperature. After generating heat rapidly to form a uniform transparent solution, the mixture was stirred for 10 minutes. Next, 30 g of methyltrimethoxysilane and 1.2 g of water were added to this solution, and the mixture was stirred and mixed at room temperature for 30 minutes to obtain a colorless and transparent uniform solution. This solution is referred to as composition liquid A.

(2) Preparation of Solution Composition for Hybrid Material Phenoxy resin (manufactured by Toto Kasei Co., Ltd., trade name: Phenotote TP-50S, weight average molecular weight = 46,000) 10
g in a mixed solvent consisting of 30 g of N-methylpyrrolidone and 20 g of ethylene glycol monomethyl ether. This solution is referred to as composition liquid B. At room temperature, while stirring the composition liquid A, the composition liquid B was slowly dropped. At the beginning of the dropping, the solution became cloudy, and at the end of the dropping, it became a colorless, transparent and uniform solution. After the completion of the dropwise addition, the mixture was stirred and mixed at room temperature for 30 minutes to prepare a surface modifier 14.

Examples 15 and 16 Surface modifiers 15 and 16 were prepared in the same manner as in Example 14 except that the composition or composition ratio of the surface modifier was changed as shown in Table 1. did.

[0052]

[Table 1]

In Table 1, TMOS: tetramethoxysilane, TEOS: tetraethoxysilane, MTMOS: methyltrimethoxysilane, PhTEOS: phenyltriethoxysilane, NMP: N-methyl-2-pyrrolidone, EGMME: ethylene glycol monomethyl ether, DEGGMME: diethylene glycol monomethyl ether, p-TsOH: p-toluenesulfonic acid, E
A: Ethanolamine is shown.

Practical examples of the above surface modifier are shown below.

Practical Example 1 A surface-modifying agent 1 prepared in Example 1 was applied to a polycarbonate sheet (PC sheet; manufactured by Nippon GE Plastics Co., Ltd., trade name: Lexan, with a 0.5 mm thick double-sided protective film). On the test piece with the protective film removed,
After coating using a YBA type applicator manufactured by Yoshimitsu Seiki Co., Ltd. (coating gap: 150 micrometers), heating and drying were performed at 120 ° C. for 30 minutes. The above-mentioned evaluation was performed about the obtained coating film. Table 2 shows the results.

Practical example 2 In practical example 1, the surface modifier 2 prepared in Example 2 was used as the surface modifier, and the surface modifier 2 was added to the surface modifier 2 immediately before coating on the PC sheet. Practical Example 1 except that 0.01 mol% of paratoluenesulfonic acid was further added to the molar amount of tetramethoxysilane in the composition 2.
The coating was carried out in the same manner as described above, followed by heating and drying at 120 ° C. for 30 minutes. The above-mentioned evaluation was performed about the obtained coating film. Table 2 shows the results.

Practical Examples 3 to 15 and Comparative Practical Examples 1 and 2 Coatings were formed in the same manner as in Practical Examples 1 and 2 except that the surface modifier used and the type of the added catalyst were changed as shown in Table 2. Then, heating and drying were performed at 120 ° C. for 30 minutes.
Table 2 shows the results. In addition, Example 1 was applied when the surface modifier was directly coated on the PC sheet, and Example 2 was applied when the catalyst was added immediately before coating.

[0058]

[Table 2]

In Table 2, p-TsOH: paratoluenesulfonic acid, KOH: alcoholic potassium hydroxide solution are shown.

Practical Example 16 The surface modifier 11 prepared in Example 11 was applied to a polycarbonate sheet (hereinafter referred to as PC sheet; manufactured by Nippon GE Plastics Co., Ltd., trade name: Lexan, with a 0.5 mm thick double-sided protective film). The test piece from which the protective film was peeled off was applied (undercoated) using a YBA type applicator manufactured by Yoshimitsu Seiki Co., Ltd. (coating gap: 50 micrometers), and then heated and dried at 120 ° C. for 5 minutes. After cooling, the surface of the composition A prepared in Example 14 (1) was
Was similarly coated (overcoated) using a YBA type applicator manufactured by Yoshimitsu Seiki Co., Ltd. (coating gap 50 micrometers), and then heated and dried at 120 ° C. for 30 minutes. The above-mentioned evaluation was performed about the obtained coating film. Table 2 shows the results.

Practical Examples 17 and 18 Coatings were performed in the same manner as in Practical Example 13 except that the type of the top coating agent or the undercoat coating agent used in Table 16 was changed as shown in Table 3. The above coating film was evaluated as described above. Table 2 shows the results. Table 3 shows the results.

[0062]

[Table 3]

Claims (8)

[Claims] 1. A solution for a phenoxy resin-silicon hybrid material obtained by dissolving a phenoxy resin (A) and an alkoxysilane (B) synthesized from bisphenol A and epihalohydrin in a soluble solvent (C). Composition. 2. An alkoxysilane (B) is represented by the general formula (2): R ¹ _p Si (OR ₂ ) _q (wherein R ¹ is a lower alkyl which may have a functional group directly bonded to a carbon atom. R ² represents a hydrogen atom or a lower alkyl group, p represents an integer of 0 to 3, q represents an integer of 1 to 4, and satisfying p + q = 4. The solution composition according to claim 1, which is an organosilicon compound represented by the formula (1) and / or a partial hydrolyzate thereof. 3. The solution composition according to claim 1, wherein the solvent (C) is a solvent having a boiling point of 100 ° C. or higher. 4. The solvent (C) contains at least 20% by weight of a glycol ether compound.
Or the solution composition according to 3. 5. A surface modifier for a substrate, comprising the solution composition according to claim 1. 6. A phenoxy resin-silicon hybrid material obtained by curing the solution composition according to claim 1 by heating and drying. 7. After the surface modifier according to claim 5 is applied to the surface of the base material, the composition is cured by heating and drying.
A method for modifying the surface of a substrate for forming a cured film using a phenoxy resin-silicon hybrid material. 8. A surface modification in which the surface modifier according to claim 5 is applied to the surface of a substrate and cured by heating and drying to form a cured film of a phenoxy resin-silicon hybrid material on the surface of the substrate. Base material.