JP2003183577A - Organic-inorganic hybrid hard coat coating - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic-inorganic hybrid hard coat coating which has hardness, flexibility and water-resistance at the same time. <P>SOLUTION: The organic-inorganic hybrid hard coat coating comprises a siloxane polymer to be synthesized from a polysiloxane oligomer and an alkoxysilane having an organic functional group including a phenyl group by the sol-gel method and a phenol group-containing organic polymer uniformly dispersed in its matrix. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an organic-inorganic hybrid hard coat having surface hardness, flexibility and water resistance, which is useful for various plastic materials, and a method for producing the same.

[0002]

2. Description of the Related Art A wide variety of thermoplastic base materials are commercially available, and the material to be selected depends largely on the nature of the material. For example, polycarbonate is known to have the very attractive properties of dimensional stability as well as transparency, high ductility and high heat deflection temperature. Of these materials, transparent ones are used as glass substitutes in a wide variety of applications. Most of thermoplastics such as polycarbonate and acrylic resin have an advantage that they are relatively lightweight and difficult to be crushed as compared with glass.

However, many plastic materials are prone to scratching and abrasion, which tends to reduce transparency.

Protective coatings are commonly used to protect thermoplastic substrates from damage. Such coatings often contain silicon compounds to improve abrasion resistance and are usually heat or UV cured. The coating material may include a UV absorber to reduce the incidence of yellowing.

The most common protective coating system is based on a colloidal silica dispersion in a lower aliphatic alcohol-water mixture of silanol partial condensates. Many other compositions containing silica dispersion and various silanes have been developed. Most of them required the use of primer coatings on the substrate to increase the adhesion of the protective coating. Such primer coatings are typically polyacrylic resins in solvent blends,
It was an acrylic type.

[0006] For example, in JP-A-11-43646, polyester polyol and acrylic polyol are
A method of using it as an adhesion improver for a colloidal silica-filled organopolysiloxane hard coat composition is described, and although a primerless silicone-based hard coat composition containing an acrylate or methacrylate ester is proposed, its Various physical properties such as surface hardness and flexibility are not yet satisfactory, and they have not reached industrial popularity.

Although the silicone hard coat composition protects the base material thereunder from scratches and decomposition, since the base material has come to be used in many more commercial applications such as building materials and automobiles, Further superior functions are required.

There are many other performance requirements for silicone hard coats. For example, when used on transparent substrates, the hardcoat should remain substantially transparent after being subjected to abrasion. Furthermore, the hard coat must be flexible. Also, it often has to have good strain-microcrack properties. Furthermore, it is desirable that the coating exhibit good adhesion without the primer layer, and it is preferred that it be relatively simple to apply and cure.

In view of these circumstances, many hard coat materials have been developed. For example, JP-A-3-28763
Japanese Patent Laid-Open No. 4 (1994) discloses a polycarbonate molded article coated with a cured coating of a ladder-type silicone oligomer containing a silicone-based surfactant through a coating of a carboxyl group-containing (meth) acrylic acid ester copolymer. ing. Since this ladder type silicone oligomer has a high molecular weight and has a small volume reduction upon curing, defects such as cracks can be improved, but since the degree of polymerization of polysiloxane is too high, the adhesion to polycarbonate is poor, Flexibility against bending is also unsatisfactory.

An organic-inorganic hybrid polymer material can be mentioned as a hard coat material which has improved such drawbacks. The dispersed particle size of each component is in the order of submicron to nanometer, and dispersion at the molecular level is also possible. The preparation method includes a method of radically copolymerizing an organic monomer or an organic polymer and an inorganic skeleton-containing compound such as an alkylsiloxane, and an inorganic functional group such as an alkoxysilane as a side chain in the organic polymer. A method of binding and then cross-linking the same is known.

For example, in JP-A-8-104710 and JP-A-8-104711, an alkoxysilyl group-terminated vinyl obtained by radically polymerizing a vinyl monomer using an alkoxysilyl group-terminated azo initiator is disclosed. A method for obtaining an organic-inorganic hybrid polymer material by hydrolyzing and condensing a polymer is described.

As the vinyl polymers, polystyrene, polyvinyl chloride, acrylic resin and the like are described therein. However, when the content of the vinyl polymer increases, the heat resistance and mechanical strength decrease. Therefore, it is desirable that most of the components be siloxane-bonded in order to produce a high-performance hard coat.

Macromolecules, No. 25
Vol. 4, pg. 4309, 1992 describes a method in which an alkoxysilyl group is bonded to the main chain of polyalkylene oxide, followed by hydrolysis and condensation. Furthermore, M
acromol. Chem. Macromol. Sym
p. 42/43, page 303, 1991, polyoxazoline as the main chain, and J. App
l. Polym. Sci. Volume 58, pp. 1263, 1
In 995, cellulose polymers are described. However, the polymers disclosed in these prior art as backbones are all hydrophilic. Since the hydrophilic polymer is hygroscopic and has poor water resistance, it is unsuitable for use in plastic moldings, sealing materials, raw materials for paints, structural materials, hard coating materials and the like.

Organic-inorganic hybrid materials containing a large number of covalent bonds such as polyaddition and polycondensation in the reaction process can obtain a strong binding force, but on the other hand, they are difficult to control the reaction by radicals and have poor reproducibility of various physical properties. Also, there is a problem that the volume change due to the condensation of organic components causes residual stress and cracking.

Further, JP-A No. 11-302528 describes a method for obtaining a phenoxy resin-silicon hybrid material solution composition from bisphenol A, epihalohydrin and alkoxysilane.

Although it has excellent hardness, there is still room for improvement in flexibility, which is a very important factor for use in transparent plastics, and the composition can be changed to broaden the balance between hardness and flexibility. It is not enough in terms of adjusting the range.

In order to solve the above problems, an industrially popular hard coat film having excellent physical properties such as surface hardness and bending flexibility, and a simple and practical production method thereof have been earnestly desired.

[0018]

SUMMARY OF THE INVENTION The present invention is intended to solve the above-mentioned conventional problems, and its object is to:
By uniformly dispersing a small amount of an organic polymer in a silica matrix, it is possible to provide an organic-inorganic hybrid hard coat coating having excellent surface hardness, bending flexibility and water resistance, and a simple and practical production method thereof. is there.

[0019]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have selected a phenyl group-containing organic polymer as an organic polymer to be uniformly dispersed in a silica matrix. In order to ensure uniform dispersion, it was found that use of an alkoxysilane having an organic functional group containing a phenyl group is effective in forming a siloxane polymer matrix from a polysiloxane oligomer by a sol-gel method. Completed the invention. The gist of the present invention is a siloxane polymer synthesized by a sol-gel method from a polysiloxane oligomer and an alkoxysilane having an organic functional group containing a phenyl group, and a phenyl group-containing organic polymer uniformly dispersed in the matrix. An organic-inorganic hybrid hard coat coating composition characterized by containing

The organic-inorganic composite material of the present invention is obtained by hydrolyzing a polysiloxane oligomer and an alkoxysilane having an organic functional group containing a phenyl group by a sol-gel method.
A step of obtaining a siloxane polymer in which the phenyl group-containing organic functional group is uniformly dispersed by polycondensation, and a step of uniformly dispersing the phenyl group-containing organic polymer in the siloxane polymer by π-π electron interaction. It is preferably produced by the method including.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION In a preferred embodiment for producing the organic-inorganic hybrid hard coat coating composition of the present invention , first, a polysiloxane oligomer and an organic functional group containing a phenyl group are incorporated into the molecule. A siloxane polymer modified with an organic functional group containing a phenyl group is produced by a step of dissolving at least one alkoxysilane in an organic solvent and subjecting it to hydrolysis and polycondensation by a sol-gel method. Next, an organic-inorganic hybrid hard coat paint uniformly dispersed by π-π electron interaction is obtained by the step of adding a phenyl group-containing organic polymer to this dispersion and mixing them well.

In the present invention, the alkoxysilane having an organic functional group containing π electrons is used as an interface modifier for the purpose of making the polysiloxane oligomer and the phenyl group-containing organic polymer fit together by π-π electron interaction. It is used.

Therefore, an alkoxysilane having an organic functional group containing a phenyl group is generally required to have an affinity for both the incompatible polysiloxane oligomer and the phenyl group-containing organic polymer. Further, in the hard coat of the present invention, a polymer excellent in flexibility has a basic structure of increasing the crosslink density of the siloxane polymer to increase the surface hardness and imparting flexibility by dispersing the phenyl group-containing organic polymer. Preference is given to using compounds.

Phenyl Group-Containing Organic Polymer Specific examples of the main skeleton of the phenyl group-containing organic polymer include polystyrene, polyamide, polycarbonate, polyester, polyphenylene ether, polysulfone,
Thermoplastic resins and thermoplastic elastomer precursors such as polyether sulfone, polyphthalamide, polyphenylene sulfide, polyarylate, polyimide, polyetherimide, or phenol resin, epoxy resin, acrylic resin, melamine resin, alkyd resin, urea resin,
Examples include thermosetting resin precursors such as silicone resins.

Of these, thermoplastic resins are preferable, and π-
Polystyrene and polyphenylene ether are more preferable in terms of affinity due to π electron interaction.

The phenyl group-containing organic polymer may be a polymer having one component of the above-mentioned polymer or precursor as a main skeleton, or a copolymer skeleton of these multi-components. Further, a mixture of a plurality of types may be used, and a branched shape or a linear shape may be used. The phenyl group-containing organic polymer may be synthesized by any method.

The molecular weight of the phenyl group-containing organic polymer is preferably such that it exhibits good compatibility with the siloxane polymer modified with an organic functional group containing a phenyl group. It is not preferable that the molecular weight is too high, since it is desirable that the silica matrix meshes. That is, if the molecular weight is too large, phase separation easily occurs. On the other hand, if the molecular weight is too small, the stability of the phenyl group-containing organic polymer component will decrease, and problems such as volatilization or bleeding out to the surface will occur. Therefore, generally, the polystyrene-converted GPC weight average molecular weight is about 1000 to 1000.
00, preferably in the range of about 1000 to 10,000.

Polysiloxane Oligomer The polysiloxane oligomer used as a raw material for a siloxane polymer modified with an organic functional group containing a phenyl group is a commercially available product prepared by hydrolyzing and polycondensing an alkoxysilane compound. It is also possible to use an existing polysiloxane oligomer. It is more preferable to use a commercially available polysiloxane oligomer because the time required for the steps and the synthesis can be significantly reduced.

The polysiloxane oligomer has a GPC weight average molecular weight of about 20 in terms of polypropylene glycol.
Desirably, it is in the range of 0 to 5000, preferably about 500 to 2000. If the molecular weight is too high, the alkoxysilane component having an organic functional group containing a phenyl group is prevented from being uniformly dispersed in the siloxane polymer, and the number of hydroxyl groups present on the surface and inside is too small. Adhesion to the material is poor, which is not preferable. Further, bending flexibility is also reduced. On the contrary, when the molecular weight is low, it takes time to synthesize the sol solution, which is industrially undesirable.

Al having an organic functional group containing a phenyl group
The alkoxysilane having an organic functional group containing a coxylsilane phenyl group uniformly disperses a phenyl group-containing organic polymer in a siloxane polymer by a π-π electron interaction, and therefore, at least one π group is conjugated or unconjugated. It is necessary to have an electron in the molecule. The alkoxysilane may be synthesized by any method.

The alkoxysilane may be one having at least π-π electron interaction with the main skeleton of the phenyl group-containing organic polymer, and does not necessarily have the same skeleton as the organic polymer. Considering the cost, it is desirable that the product be on the market.

As the alkoxysilane, any type can be used alone or in combination as long as it has an organic functional group containing π electrons. The first type is a phenyl group-containing alkoxysilane, which is a compound represented by the following formula (1). Formula (1): XaYbSi (OR) c [In the formula, X is at least one selected from a phenyl group-containing group, preferably a phenyl group, a phenethyl group, a phenoxy group, a phenoxyalkyl group and an N-phenylaminoalkyl group. Yes, Y is an alkoxy group having 1 to 5 carbon atoms or a hydroxyl group, R is an alkyl group having 1 to 5 carbon atoms,
A plurality of X and R may be the same or different. a is 1
Or 2, c is 2 or 3, and a + b + c is
It is 4. ]

Specific examples of the most preferred phenyl group-containing alkoxysilanes are phenyltrimethoxysilane, phenyltriethoxysilane, phenethyltrimethoxysilane, phenethyltriethoxysilane, phenoxytrimethoxysilane and phenoxytriethoxysilane. , 3-phenoxypropyltrimethoxysilane, 3-phenoxypropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane,
Examples include trialkoxysilanes such as N-phenylaminopropyltriethoxysilane.

The second type is a silane coupling agent, and when a substrate such as polycarbonate is coated without using a primer, a known silane coupling agent can be used according to the purpose. Thereby, the adhesion and other physical properties can be adjusted. It is desirable that the silane coupling agent is commercially available from the viewpoint of cost. Exemplifying is a compound represented by the following formula (2). Formula (2): ZSi (OR) ₃ [Z is a coupling functional group, preferably a (meth) acryl group, an epoxy group, an isocyanate group, an amino group,
A group selected from a thiol group, a vinyl group, a carboxyl group, an acid halide group, an acid anhydride group and a halogen group, R is an alkyl group having 1 to 5 carbon atoms, and a plurality of Rs are the same or different. May be. ]

Specific examples of the silane coupling agent include (alkyl) alkoxysilanes having an isocyanate group such as 3-isocyanatepropyltriethoxysilane and 2-isocyanateethyltri-n-propoxysilane, and 3-glycid. (Alkyl) alkoxysilanes having epoxy groups such as xypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3,4-epoxybutyltrimethoxysilane, and carboxyls such as carboxymethyltriethoxysilane. (Alkyl) alkoxysilane having a group, alkoxysilane having an acid anhydride group such as 3- (triethoxysilyl) -2-methylpropylsuccinic anhydride, 2- (4-chlorosulfonylphenyl)
Alkoxysilanes having acid halide groups such as ethyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-
(Alkyl) alkoxysilane having amino group such as 2- (aminoethyl) -3-aminopropyltriethoxysilane N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane,
(Alkyl) alkoxysilane having thiol group such as 2-mercaptoethyltriethoxysilane, (alkyl) alkoxysilane having vinyl group such as vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3 A (alkyl) alkoxysilane having a methacryl group such as methacryloxypropyltriethoxysilane, triethoxyfluorosilane, 3-chloropropyltrimethoxysilane,
Mention may be made of (alkyl) alkoxysilanes having halogen groups such as 3-bromopropyltriethoxysilane.

The sol - gel method sol - hydrolysis by gel method, a polycondensation, the polymer having a metal alkoxide compound or a metal alkoxy group to convert the alkoxy group into a hydroxyl group by reaction with water, then the hydroxyl group A compound or polymer having a silanol group (metal hydroxide group, for example, -SiOH) undergoes a dehydration reaction or a dealcohol reaction with an adjacent molecule by simultaneous polycondensation, through an inorganic covalent bond. Three
Refers to the reaction of dimensional crosslinking. At this time, the polycondensation reaction is most likely to be a dehydration reaction of two hydroxy metal groups, but not only that, it may also occur with a functional group having active hydrogen such as another hydroxyl group, an amino group or a carboxyl group.

Water used in the hydrolysis reaction may be added in an amount necessary for converting all alkoxy groups into hydroxyl groups, or the water in the reaction system may be used or the water in the atmosphere may be absorbed. You may let me go. The reaction conditions are preferably room temperature to 80 ° C. for about 1 to 96 hours. At that time,
Acid catalysts such as hydrochloric acid, sulfuric acid, acetic acid, benzenesulfonic acid, p-toluenesulfonic acid, etc., sodium hydroxide, potassium hydroxide, ammonia, ammonium salts, triethylamine, piperidine, 1,8-diazabicyclo [5,4,4]
A basic catalyst such as 0] -7-undecene (DBU), a metal chelate catalyst, or the like may be used.

The solvent used in the sol-gel reaction is capable of dissolving the polysiloxane oligomer as a raw material, the alkoxysilane having an organic functional group containing π electrons, the siloxane polymer to be synthesized and the phenyl group-containing organic polymer. If so, there is no particular limitation. As a specific example, tetrahydrofuran, 1,4-dioxane, 1,3
-Ether solvents such as dioxane, diethyl ether, dibutyl ether, hydrocarbon solvents such as benzene, toluene, n-hexane, chloroform, dichloromethane,
Halogenated hydrocarbon solvents such as dichloroethane and chlorobenzene, ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone, ester solvents such as ethyl acetate and butyl acetate, alcohol solvents such as methanol, ethanol, n-propanol and isopropanol, and the above. Examples thereof include mixed solvents of the above solvents, but are not limited thereto. In general, a polar solvent such as an alcohol solvent is often used, but in the synthesis of the coating liquid of the present invention, tetrahydrofuran, 1 or 2 is used because of the solubility of the phenyl group-containing organic polymer and the polyorganosiloxane oligomer. , 4-dioxane, 1,3-dioxane, or a mixed solvent containing them is preferably used.

In the hydrolysis and polycondensation process in the present invention, the sol-gel reaction may be carried out after the polysiloxane oligomer and the alkoxysilane having an organic functional group containing a phenyl group are mixed and dissolved in a solvent in advance. ,
After hydrolyzing either one of the components first, the other component may be added and the hydrolysis may be continued. In any case, the amount of added water is preferably in the range of 80 to 150% with respect to the minimum amount (hereinafter referred to as stoichiometric ratio) required for converting all the alkoxy groups into siloxane bonds. If it is less than this range, hydrolysis becomes insufficient,
On the other hand, if it is large, a phenyl group-containing organic polymer and a relatively large amount of water will coexist in the solvent, making uniform dispersion difficult.

Further, the phenyl group-containing organic polymer may be previously dissolved in a solvent, and then a sol-gel reaction may be carried out with a polysiloxane oligomer and an alkoxysilane having an organic functional group containing a phenyl group. in this case,
Since not enough water has been consumed for the sol-gel reaction yet,
The organic polymer and a relatively large amount of water coexist in the solvent. Therefore, it is necessary to suppress the amount of added water to a small amount, which is generally disadvantageous for increasing the density of siloxane bonds and uniformly dispersing the organic polymer. The liquid obtained by the above method is called a coating liquid.

Weight composition of each component Polysiloxane oligomer weight: The ratio of the total weight of the alkoxysilane having an organic functional group containing π electrons (including the phenyl group-containing alkoxysilane and the silane coupling agent) depends on the required physical properties. However, it is preferably 95: 5 to 20:80, more preferably 90:10.
~ 25: 75. If the amount of the polysiloxane oligomer used is too small, the surface hardness will be insufficient and the material properties will deteriorate. Also, if the amount of polysiloxane oligomer used is too large, cracks easily occur, making it difficult to uniformly disperse the phenyl group-containing organic polymer, and also to improve the adhesion.
It becomes difficult to give characteristics such as flexibility.

There is no particular limitation on the weight ratio of the phenyl group-containing alkoxysilane to the silane coupling agent, which also changes depending on the required physical properties. In consideration of imparting properties to the material, the content ratio of the phenyl group-containing alkoxysilane component is 5 with respect to the total weight of the alkoxysilane having an organic functional group containing a π electron added during the synthesis of the siloxane polymer by the sol-gel method. % Or more is desirable.

The addition amount of the phenyl group-containing organic polymer is not particularly limited, and the most preferable range varies depending on the concentration, amount of added water, etc. It is preferably less than 10%. Further, the addition of the organic polymer is effective even in a relatively small amount, but in consideration of imparting characteristics to the material,
It is preferably at least 1%.

Cured coating film There is no particular limitation on the method of applying the hard coating liquid in the present invention to the substrate, and a good film can be formed by a method generally used by those skilled in the art. Exemplary techniques include spray coating, dip coating, roller coating, flow coating and the like. If you want to further promote the condensation reaction and make the crosslinking stronger,
It can be cured in various ways. For example, thermal curing or curing utilizing infrared or microwave energy. Taking heat curing as an example, it is preferable to perform heat treatment at 80 to 200 ° C. for about 10 minutes to 4 hours. During the heat curing stage, polymerization, condensation and crosslinking of the partial condensate occur to form a coating. The thickness of the coating depends largely on the end use of the article. The thickness after curing is usually in the range of about 1 μm to about 15 μm, preferably about 2 μm to about 10 μm. The substrate can be applied to various materials and forms, but considering that the cured coating film is transparent, it is suitable as a plastic substrate, especially a transparent plastic substrate.
Specifically, a plastic laminate in which a cured coating is formed on the surface of a polycarbonate resin sheet, a poly (meth) acrylic resin sheet or a composite sheet in which a (meth) acrylic resin layer is provided on one or both sides of a polycarbonate resin layer Suitable for

In all steps up to coating in the present invention, the cured coating film is improved or newly provided with functions such as strength, surface hardness, weather resistance, chemical resistance, flame retardancy and antistatic property. For the purpose, UV absorbers such as hydroxybenzophenones, benzotriazoles, cyanoacrylates, benzylidene malonates and triazines, and Si, Ti to adjust the inorganic content and the crosslink density between polymers are used. , Zr, Fe, Cu, Sn, B, Al,
A metal such as Ge, Ce, Ta, W, a metal oxide, a metal complex, an inorganic salt, a silazane, or the like may coexist. Also,
Gelamide, drying, in order to suppress cracks that may occur during heat treatment, formamide, dimethylformamide, dioxane, oxalic acid and the like may be added as a drying inhibitor, or by adding acetylacetone or the like as an additive. Good.

The organic-inorganic hybrid hard coat (cured coating film) of the present invention has surface hardness, water resistance, mechanical strength, heat resistance, weather resistance, rigidity, chemical resistance, and the like which inorganic materials have.
While maintaining the properties such as stain resistance and flame retardancy, the properties of the organic polymer such as flexibility and impact resistance are satisfactorily imparted, and hardness and flexibility can be changed by changing the ratio of the constituent components. The balance of can be adjusted in a relatively wide range.

The organic-inorganic hybrid hard coat (cured coating film) thus obtained contains a reaction process such as polyaddition / polycondensation as compared with the one in which the organic polymer is covalently bonded to the surface of the silica matrix. Since it does not contain phenyl group, it is difficult to control by radical reaction and the reproducibility of various physical properties is poor, and the volume change due to condensation of organic components causes residual stress and cracking. The organic polymer becomes a high-performance and highly-functional material in which a siloxane polymer in which organic functional groups containing π electrons are uniformly dispersed is uniformly dispersed by π-π electron interaction.

Further, the use of π-π electron interaction can solve the lack of water resistance, which is a problem in a system using hydrogen bonds, and is therefore suitable for use as a hard coat paint.

[0049]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

[Coating Substrate] A polycarbonate plate is a commercially available product having a thickness of 0.5 mm (made by Mitsubishi Engineering Plastics, Iupilon sheet NF-200).
0) was used. Regarding the polycarbonate / acrylic coextruded sheet, PMMA (manufactured by Atofina, Atgras V-020) and polycarbonate (manufactured by Mitsubishi Engineering Plastics, Iupilon E-2000U) are used as a coextruded sheet using a feed block die. What was done was used. The surface acrylic thickness of the substrate was about 20 μm, and the total thickness was about 0.5 mm. Also,
All co-extruded plates are painted on the acrylic surface.

[Composition Design of Paint] In the present specification, only the paint to be applied to the polycarbonate / acrylic coextruded plate is changed in composition to a high hardness type (Synthesis Examples 2 and 3) and a flexible type (all other types). Two types are illustrated. However,
The physical properties such as hardness and flexibility are not the highest limit, and the composition is designed in a balanced manner in consideration of coating on a transparent plastic substrate. Therefore, it is possible to make the physical properties more extremely hard or soft by changing the composition. The same applies to the coating liquid applied to the polycarbonate plate.

[Preparation of Test Pieces for Evaluation of Physical Properties] Both the polycarbonate plate and the polycarbonate / acrylic coextruded plate were cut into a size of 50 × 40 mm, the masking film was peeled off only on one side to impregnate the coating material, and the pulling speed was 5 m.
The coating was performed by pulling up at m / s. Then 1
A coating film was prepared by heating and curing at 30 ° C. for 2 hours, and this was used as a test piece. The film thickness of the coating film was measured by a scanning electron microscope photograph of a cross section cut out perpendicularly to the coated surface by polishing.

[Cross-cut peeling test] The cross-cut peeling test for evaluating the adhesion was conducted before and after the boiling test with reference to JIS K5400. First, using a cutter knife, six vertical and horizontal parallel lines were drawn on the test piece at intervals of 2 mm to prepare 25 grids in a grid pattern. Next, an adhesive tape (“Cellophane tape” manufactured by Nichiban Co., Ltd.) was adhered and adhered onto these squares, and then the adhesive tape was instantly peeled off, and the peeled state of the coat layer of the test piece was observed. The result was displayed by the number of squares remaining without peeling.

[Boiling test] The boiling test is conducted according to JIS K 54.
Boiled for 2 hours at 95 ° C. with No. 00, a thermal shock test was performed under the above-mentioned conditions, and a change in appearance was confirmed. After that, the cross-cut peeling test was performed again, and the peeling state of the coat layer of the test piece was observed.

[Pencil Hardness Test] The pencil hardness was measured with reference to the pencil scratch test JIS K 5400. The apparatus was a Clemens scratch hardness tester manufactured by Tester Sangyo and the pencil was a uni pencil manufactured by Mitsubishi Pencil. The measurement conditions were a moving speed of the sample table of 30 mm / min and a load of 1.00 kg.

[Optical Properties] With respect to the optical properties, the total light transmittance (hereinafter T) of the test piece with the coat layer was measured by using a color difference / turbidity measuring device (COH-300A manufactured by Nippon Denshoku Industries Co., Ltd.). Turbidity (henceforth H) and yellowing degree (henceforth YI) were measured.

[Flexural Flexibility] Flexural flexibility is SUS30.
It was shown as the minimum radius of a round bar that was not bent when it was bent 180 ° with four round bars.

[Polycarbonate / acrylic coextrusion plate-
Examples] Synthesis example 1 Polysiloxane oligomer (MKC oligomer MS56S manufactured by Mitsubishi Chemical Co., Ltd.) 15 g, phenyltrimethoxysilane
(Shin-Etsu Chemical, product number LS-2750) 5 g, 3-methacryloxypropyltrimethoxysilane (Chisso, Sila Ace S710) 28 g, tetrahydrofuran 44 g
Then, 8.11 g of water and 0.39 g of 60% nitric acid are added, and the mixture is reacted for 1 day while heating at 60 ° C. afterwards,
An organic-inorganic hybrid hard coat paint was obtained by adding 0.5 g of polystyrene (manufactured by Sanyo Kasei Co., Ltd., Hymer SB75: weight average molecular weight of about 2000) and stirring for 1 day. The coating solution was a colorless and transparent uniform solution having a good appearance.

Example 1 A coating film was obtained from the above-mentioned polycarbonate / acrylic co-extruded plate using the coating material obtained in Synthesis Example 1. Its film thickness is 3.4
μm, optical characteristics (T = 91.3%, H = 0.1%, YI
= 2.1), adhesion 25, pencil hardness H, bending flexibility 10
It was R. Furthermore, even when immersed in hot water of 95 ° C. for 2 hours, the adhesion and appearance were good.

Synthesis Example 2 25 g of polysiloxane oligomer (MKC oligomer MS56S manufactured by Mitsubishi Chemical), 7 g of phenethyltrimethoxysilane (manufactured by Chisso, product number SIP6722.6), 3-methacryloxypropyltrimethoxysilane (manufactured by Chisso, Sila Ace S710). 15 g of 1,4-dioxane 4
After dissolving in 4g, water 8.11g, 60% nitric acid 0.39
g, and react for 1 day while heating to 60 ° C. Then, 0.5 g of polystyrene (manufactured by Sanyo Kasei Co., Ltd., Hymer SB75: weight average molecular weight of about 2000) was added and stirred for 1 day to obtain an organic-inorganic hybrid hard coat paint. The coating solution was a colorless and transparent uniform solution having a good appearance.

Example 2 A coating film was obtained from the coating material obtained in Synthesis Example 2 on the above-mentioned polycarbonate / acrylic coextrusion plate. Its film thickness is 3.8
μm, optical characteristics (T = 91.0%, H = 0.2%, YI
= 2.3), adhesion 25, pencil hardness 2H, bending flexibility 1
It was 2.5R. Furthermore, even when immersed in hot water of 95 ° C. for 2 hours, the adhesion and appearance were good.

Synthetic Example 3 Synthetic Example 1 except that the same amount of poly2,6-dimethylpolyphenylene ether (prototype manufactured by Mitsubishi Gas Chemical Co., Ltd .: weight average molecular weight of about 2600) was used in place of the polystyrene used in Synthetic Example 1. When the coating solution was synthesized under exactly the same conditions as above, a colorless and transparent solution having a good appearance and uniformly dispersed was obtained. The polyphenylene ether is synthesized by the usual oxidative coupling reaction of 2,6-xylenol.

Example 3 A coating film was obtained from the coating material obtained in Synthesis Example 3 on the above polycarbonate / acrylic coextrusion plate. The film thickness is 3.5
μm, optical characteristics (T = 89.9%, H = 0.9%, YI
= 2.9), adhesion 25, pencil hardness H, bending flexibility 10
It was R. Furthermore, even when immersed in hot water of 95 ° C. for 2 hours, the adhesion and appearance were good. That is, Example 1
Although a slight decrease in transparency was confirmed to the extent that it could not be visually recognized in comparison with, no difference was observed in all other evaluation physical properties, and a good coating film was obtained.

[Polycarbonate / acrylic coextrusion plate-
Comparative Example] Synthetic Example 4 A coating solution was synthesized under exactly the same conditions as in Synthetic Example 1 except that the polystyrene used in Synthetic Example 1 was not added. As a result, a colorless, transparent and well-dispersed solution having a uniform appearance was obtained. Was given.

Comparative Example 1 Synthesis example 4 was applied to the above polycarbonate / acrylic coextrusion plate.
A coating film was obtained from the coating material obtained in. The film thickness is 3.2μ
m, optical characteristics (T = 91.1%, H = 0.2%, YI =
2.3), adhesion 25, pencil hardness H, bending flexibility 15R
Met. Furthermore, even when immersed in hot water of 95 ° C. for 2 hours, the adhesion and appearance were good. That is, it was confirmed that the bending flexibility was lower than that in Example 1.

Synthesis Example 5 Instead of the phenyltrimethoxysilane used in Synthesis Example 1, the same amount of methyltrimethoxysilane (D03 manufactured by Chisso Corporation) was used.
The coating liquid was synthesized under exactly the same conditions as in Synthesis Example 1 except that 1A) was added. In this case as well, a colorless and transparent solution having a good appearance and uniformly dispersed was obtained.

Comparative Example 2 Polycarbonate / acrylic coextruded sheet (Mitsubishi Engineering Plastics, Iupilon sheet, thickness: 0.
5 mm), a coating film was obtained from the coating material obtained in Synthesis Example 5. The film thickness is 3.3 μm, and the optical characteristics (T = 89.9)
%, H = 0.6%, YI = 2.4), adhesiveness 25, pencil hardness H, and bending flexibility 15R. Furthermore, even when immersed in hot water of 95 ° C. for 2 hours, the adhesion and appearance were good. That is, although a decrease in flexibility was confirmed as compared with Example 1, no difference was observed with Comparative Example 1. This result shows that the coexistence of the alkoxysilane substituted with the organic functional group having a π electron and the phenyl group-containing organic polymer causes the effect of imparting flexibility due to uniform dispersion.

Synthesis Example 6 A coating solution was synthesized under exactly the same conditions as in Synthesis Example 2 except that the polystyrene used in Synthesis Example 2 was not added. As a result, a colorless and transparent solution having a good appearance and uniformly dispersed was obtained. Was given.

Comparative Example 3 A coating film was obtained from the above-mentioned polycarbonate / acrylic coextruded plate using the coating material obtained in Synthesis Example 6. Its film thickness is 3.6
μm, optical characteristics (T = 91.2%, H = 0.2%, YI
= 2.2), adhesion 25, pencil hardness 2H, bending flexibility 2
It was 0R. Furthermore, even when immersed in hot water of 95 ° C. for 2 hours, the adhesion and appearance were good. That is, it was confirmed that the bending flexibility was lower than that in Example 2.

[Polycarbonate Plate-Example] Synthesis Example 7 19 g of polysiloxane oligomer (MKC oligomer MS56S manufactured by Mitsubishi Chemical), 7 g of N-phenylaminotrimethoxysilane (manufactured by Chisso, product number SIP6724.0),
21 g of 3-glycidoxypropyltrimethoxysilane (manufactured by Chisso, Sila Ace S510) was dissolved in 44 g of tetrahydrofuran, and then 7.78 g of water and 0.
39g is put and it is made to react for 1 day, heating at 60 degreeC.
After that, polystyrene (manufactured by Sanyo Kasei, Hymer SB7
5: Weight average molecular weight of about 2000) 0.5 g was added and stirred for 1 day to obtain an organic-inorganic hybrid hard coat paint. The coating solution was a colorless and transparent uniform solution having a good appearance.

Example 4 A coating film was obtained from the above polycarbonate plate by using the coating material obtained in Synthesis Example 7. The film thickness was 3.4 μm, optical characteristics (T = 90.5%, H = 0.3%, YI = 2.1), adhesiveness 25, pencil hardness H, and bending flexibility 12.5R. Furthermore, even when immersed in hot water of 95 ° C. for 2 hours, the adhesiveness,
The appearance was good.

Synthetic Example 8 A coating solution was synthesized under exactly the same conditions as in Synthetic Example 7 except that the polystyrene used in Synthetic Example 7 was a higher molecular weight polystyrene (manufactured by Sanyo Kasei, Hymer ST95: weight average molecular weight of about 4000). As a result, a colorless and transparent solution having a good appearance and uniformly dispersed was obtained.

Example 5 A coating film was obtained from the above-mentioned polycarbonate plate using the coating material obtained in Synthesis Example 8. The film thickness was 3.6 μm, optical characteristics (T = 90.3%, H = 0.2%, YI = 2.5), adhesiveness 25, pencil hardness H, and bending flexibility 12.5R. Furthermore, even when immersed in hot water of 95 ° C. for 2 hours, the adhesiveness,
The appearance was good. That is, no difference was found in physical properties for evaluation from Example 4.

[Polycarbonate Plate-Comparative Example] Synthesis Example 9 Synthesis Example 7 except that the polystyrene used in Synthesis Example 7 was changed to a polystyrene having a significantly high molecular weight (Nacalai Tesque, Inc., standard reagent for GPC: weight average molecular weight of about 170000). The coating liquid was synthesized under exactly the same conditions as described above. However, the resin had low solubility and dispersibility, and a uniformly dispersed solution could not be obtained.

Comparative Example 4 A coating film was obtained from the above polycarbonate plate using the coating material obtained in Synthesis Example 9. The coating film was not uniform, and a small amount of polystyrene was present separately. No further evaluation was performed due to poor appearance due to phase separation. For reference, the optical characteristics were measured (T = 88.3%,
H = 1.2% and YI = 2.8).

Synthesis Example 10 A coating solution was synthesized under exactly the same conditions as in Synthesis Example 7 except that the same polystyrene addition amount as in Synthesis Example 7 was changed to 10 g. However, the resin had low solubility and dispersibility, and a uniformly dispersed solution could not be obtained.

Comparative Example 5 A coating film was obtained by coating the above polycarbonate plate with the coating material obtained in Synthesis Example 10. The coating film was not uniform and whitening was observed. No further evaluation was made due to poor appearance. The optical characteristics were measured for reference (T = 82.
2%, H = 44.5%, and YI = 3.3).

Synthesis Example 11 The coating liquid was synthesized under the same conditions as in Synthesis Example 7 except that polyethylene glycol (manufactured by Junsei Chemical Co., Ltd .: molecular weight 4000) was used in place of the polystyrene used in Synthesis Example 7, and it was colorless and transparent. A uniformly dispersed solution having a good appearance was obtained.

Comparative Example 6 A coating film was obtained from the above polycarbonate plate by using the coating material obtained in Synthesis Example 11. The film thickness was 3.5 μm, optical characteristics (T = 90.2%, H = 0.1%, YI = 2.0), adhesiveness 25, pencil hardness H, and bending flexibility 12.5R. However, as a result of being immersed in hot water at 95 ° C. for 2 hours, it was naturally peeled off and the appearance was whitened. It is considered that the coating film was poor in water resistance due to the water absorption of the hydrophilic polymer.

Synthesis Example 12 A coating solution was synthesized under the same conditions as in Synthesis Example 7 except that styrene (manufactured by Junsei Chemical Co., Ltd.) was used in place of the polystyrene used in Synthesis Example 7, and it was colorless and transparent and had a good appearance. A uniformly dispersed solution was obtained.

Comparative Example 7 A coating film was obtained from the above polycarbonate plate by using the coating material obtained in Synthesis Example 12. The film thickness was 3.4 μm, optical characteristics (T = 88.6%, H = 0.2%, YI = 2.0), adhesiveness 25, pencil hardness H, and bending flexibility 15R. This decrease in flexibility is considered to be due to the loss of styrene due to bleed-out and volatilization during heat curing. further,
Adhesion was not impaired even when immersed in hot water of 95 ° C. for 2 hours, but the appearance was white. This phenomenon is considered to be due to the fact that water entered the fine pores from which styrene had escaped. Thus, if the molecular weight is too small, the stability of the phenyl group-containing polymer component decreases.

Synthetic Example 13 Synthetic Example 7 except that methyltrimethoxysilane (manufactured by Chisso, D031A) was added in place of 3-glycidoxypropyltrimethoxysilane (manufactured by Chisso, Sila Ace S510) used in Synthetic Example 7. The coating liquid was synthesized under exactly the same conditions. In this case as well, a colorless and transparent solution having a good appearance and uniformly dispersed was obtained.

Comparative Example 8 A coating film was obtained from the above polycarbonate plate by using the coating material obtained in Synthesis Example 13. The film thickness was 3.4 μm, the optical characteristics (T = 90.3%, H = 0.3%, YI = 2.2), and the adhesion was 0. Since the adhesion was insufficient, the pencil hardness and bending flexibility were not evaluated. This decrease in adhesion indicates that there was not enough adhesion between the coating film and the polycarbonate to withstand tape peeling because there was not enough silane coupling agent in the coating solution.

To facilitate understanding, Table 1 shows the coating composition applied on the acrylic surface of the polycarbonate / acrylic coextruded plate described above, and Table 2 shows the examples and comparative examples where the acrylic surface of the polycarbonate / acrylic coextruded plate is applied. It was shown to.

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[Table 1]

[0086]

[Table 2]

Further, Table 3 shows the coating composition applied on the surface of the polycarbonate plate described above, and Table 4 shows Examples and Comparative Examples when the surface of the polycarbonate was applied.

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[Table 3]

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[Table 4]

[0090]

EFFECT OF THE INVENTION The organic-inorganic hybrid hard coat coating composition of the present invention is made to coexist with an alkoxysilane having an organic functional group containing a π electron, thereby impairing the appearance and hardness by the addition of a small amount of a phenyl group-containing organic polymer. Without
It is possible to add flexibility and water resistance.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 125/06 C09D 125/06 171/12 171/12 201/02 201/02 // C08L 33:10 C08L 33:10 (72) Inventor Koji Shiraoka 1-83-1 Midorigaoka, Ikeda-shi, Osaka Independent administrative agency National Institute of Advanced Industrial Science and Technology Kansai Center (72) Inventor Toshizumi Hirota 5-6, Higashihachiman, Hiratsuka-shi, Kanagawa No. 2 Sanritsu Gas Chemical Co., Ltd. Hiratsuka Laboratory (72) Inventor Tetsuo Yazawa 1-831 Midorigaoka, Ikeda-shi, Osaka Independent Administrative Institution AIST Kansai Center F-term (reference) 4D075 BB26Z CA02 CA03 CA13 CA38 DA06 DB43 DB48 DC01 DC13 DC24 EB14 EB22 EB32 EB33 EB35 EB39 EB43 EB44 EB52 EB56 EC45 EC54 4F006 AA22 AA36 AB39 BA02 CA00 DA04 4F100 AK12A AK25B AK45C AK52A AK54A BA03 BA07 BA10A BA10C CA30A EH46A EJ05A GB07 GB32 JB07 JK12 JK17 JM01A JM10A JN01 YY00A 4J038 CC032 DF062 DL031 DL032 EA012 GA05 GA09 GA15 JC32 JC34 JC35 JC36 KA03 KA09 MA08 NA04 NA11

Claims (9)

[Claims] 1. A sol comprising a polysiloxane oligomer and an alkoxysilane having an organic functional group containing a phenyl group.
An organic-inorganic hybrid hard coat paint comprising a siloxane polymer synthesized by a gel method and a phenyl group-containing organic polymer uniformly dispersed in its matrix. 2. The organic-inorganic hybrid hard coat paint according to claim 1, wherein the alkoxysilane having an organic functional group containing a phenyl group is a phenyl group-containing alkoxysilane. 3. The primerless organic-inorganic hybrid hard coat according to claim 2, wherein the alkoxysilane having an organic functional group containing a phenyl group is a phenyl group-containing alkoxysilane and a silane coupling agent. paint. 4. The phenyl group-containing organic functional group contained in the alkoxysilane is selected from a phenyl group, a phenethyl group, a phenoxy group, a phenoxyalkyl group, and an N-phenylaminoalkyl group.
The organic-inorganic hybrid hard coat paint according to any one of 3 above. 5. The organic-inorganic hybrid hard coat coating composition according to claim 1, wherein the main skeleton of the phenyl group-containing organic polymer is polystyrene or polyphenylene ether. 6. The addition amount of the phenyl group-containing organic polymer is in the range of 0.1% or more and less than 10% with respect to the total weight of the coating liquid.
The organic-inorganic hybrid hard coat paint according to the item. 7. The organic-inorganic hybrid hard coat coating composition according to claim 1, wherein the phenyl group-containing organic polymer has a weight average molecular weight of 1,000 to 100,000. 8. A plastic laminate obtained by applying the organic-inorganic hybrid hard coat coating composition according to any one of claims 1 to 7 on the surface of a plastic substrate and curing the coating. 9. The plastic substrate is a polycarbonate resin sheet, a poly (meth) acrylic resin sheet, or a composite sheet in which a (meth) acrylic resin layer is provided on one or both sides of a polycarbonate resin layer. 8. The plastic laminate according to item 8.