JPH11277684A - Transparent coated molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain both high scratch resistance and high surface water repellency by adding a fluorosilicon compound having a certain molecular weight in a transparent coated molding having a transparent synthetic resin material and at least two transparent curable material layers formed at least on a part of the base surface. SOLUTION: When a transparent coated molding excellent in scratch resistance and water repellency of a surface is formed, a transparent synthetic resin base and at least two transparent curable material layers, which are formed at least on a part of the base surface, are provided. An inner layer contacting with an outermost layer of the transparent curable layers is composed of an active energy beam-curable layer containing a polyfunctional compound having at least two active energy beam-curable polymerizable functional groups. The outermost layer is a curable material layer containing a curable compound forming a silica, and a fluorosilicon compound containing organosiloxane units, wherein a fluorine-containing organic group is combined with a silicon atom. And a colloidal silica having an average particle diameter of 200 nm or lower is contained in the inner layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a layer of a cured product derived from an active energy ray-curable coating composition, a curable compound forming silica and a silica derived from a fluorosilicone compound on a transparent synthetic resin substrate. The present invention relates to a transparent coated molded article having a two-layered transparent cured product layer having excellent scratch resistance and water repellency, and a method for producing a bent transparent coated molded article.

[0002]

2. Description of the Related Art In recent years, as a transparent material replacing glass,
Transparent synthetic resin materials have been used. Above all, aromatic polycarbonate resin is excellent in crush resistance, transparency, light weight, easy processability, etc.
It is used in various areas as a large-area transparent member such as an arcade. Also, there is an example in which such a transparent synthetic resin material is used instead of glass (inorganic glass, the same applies hereinafter) for some vehicles such as automobiles. However, there is a problem that the surface hardness is not sufficient to be used as a substitute for glass, and the surface is easily damaged and abraded, so that the transparency is easily impaired.

Therefore, many attempts have conventionally been made to improve the scratch resistance and abrasion resistance of aromatic polycarbonate resins. One of the most common methods is to apply a polymer curable compound having two or more polymerizable functional groups such as an acryloyl group in a molecule to a base material, and to cure it with active energy rays such as heat or ultraviolet rays, and to scratch it. There is a method of obtaining a molded article having a transparent cured coating film having excellent properties. This method
The composition for coating is also relatively stable, and is particularly excellent in productivity because it can be cured by ultraviolet rays.Even when a bending process is applied to a molded product, cracks do not occur in the cured film and scratch resistance on the surface and Abrasion resistance can be improved. However, since the cured film is made of only an organic substance, there is a limit to the level of expression of scratch resistance on the surface.

On the other hand, as a method for imparting a higher surface hardness to a transparent synthetic resin substrate (hereinafter simply referred to as a substrate), there is a method in which a metal alkoxide compound is applied to a substrate and cured by heat. Silicon-based compounds are widely used as metal alkoxides, and can form cured films having extremely excellent wear resistance. However, since the adhesion between the cured film and the substrate is poor, there have been problems such as easy peeling and cracking of the cured film.

As a method for solving the problems of these techniques, as disclosed in Japanese Patent Application Laid-Open No. 61-181809, a mixture of a compound having an acryloyl group and colloidal silica is applied to a substrate, and the active energy such as ultraviolet rays is applied. There is a method of curing with a wire to form a transparent cured material having excellent scratch resistance. By using colloidal silica in combination with a polymerizable curable compound, it is possible to achieve both high surface hardness and high productivity. However, the method of applying the above-mentioned metal alkoxide compound to a substrate and curing it by heat is still inferior in the level of expression of the surface scratch resistance.

A method is also known in which polysilazane is applied to a substrate and cured by heat or the like instead of the silicon-based metal alkoxide compound (Japanese Patent Application Laid-Open No. H8-14368).
9). It is believed that polysilazane undergoes condensation and oxidation reactions in the presence of oxygen and changes to silica (higher cross-linked silicon dioxide), which may contain nitrogen atoms. A silica coating free of silica is formed. The silica coating derived from polysilazane has a high surface hardness. However, this film has poor adhesion between the film and the substrate as in the case of the metal alkoxide compound, and thus has problems such as easy peeling and cracking of the film.

Japanese Patent Application Laid-Open No. 9-39161 describes a method in which a protective film is formed on a plastic film, and a polysilazane solution is applied on the surface to form a silica surface layer. The protective coating is provided to prevent the plastic film from being attacked by the solvent of the polysilazane solution. Japanese Patent Application Laid-Open No. 6-212004 proposes a method in which a silicone-based thermopolymerized cured product is coated on an uncured product and a partially cured product of an ultraviolet-curable compound, irradiated with ultraviolet rays, and further subjected to heat polymerization. However, these also have insufficient weather resistance depending on the composition, and further improvement is required.

On the other hand, in the field of automotive glass, attempts have been made to make the surface water-repellent by applying various coatings to the surface of the inorganic glass. The method of improving the surface scratch resistance in order to use a transparent organic material in the field of replacing inorganic glass has been described above. Naturally, the transparent organic material is also required to have such a function of making the surface water-repellent. However, at present, a technique for achieving both high scratch resistance and sufficient surface water repellency has not been established.

[0009]

SUMMARY OF THE INVENTION Accordingly, the present invention has been made in view of the above-mentioned problems of the prior art, and an object of the present invention is to provide a transparent coating having both high scratch resistance and sufficient surface water repellency. An object of the present invention is to provide a molded article and a method for producing a bent transparent coated molded article.

[0010]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, the silica layer is not a low molecular weight so-called fluorine-containing silane coupling agent,
It has been found that by adding a fluorosilicone compound having a certain molecular weight, both high scratch resistance and high surface water repellency can be achieved, and the present invention has been completed.

That is, the first invention of the present invention is:
In a transparent coated molded article having a transparent synthetic resin substrate and at least two transparent cured product layers formed on at least a part of the surface of the substrate, an inner layer in contact with an outermost layer of the transparent cured product layers, The cured product layer of the active energy ray-curable coating composition (A) containing a polyfunctional compound having two or more active energy ray-curable polymerizable functional groups, wherein the outermost layer forms silica. A transparent coating molding comprising a cured product layer of a coating composition (B) containing a curable compound (b) and a fluorosilicone compound containing an organosiloxane unit having a fluorine-containing organic group bonded to a silicon atom. Offer goods.

According to the first aspect of the invention, the transparent cured material layer has at least two layers, and the outermost layer, which is a silica coating, is directly laminated on a relatively soft transparent synthetic resin substrate. And is laminated on the inner layer which is a hard transparent cured product having high abrasion resistance. For this reason, it is considered that the displacement of the outermost layer due to an external force applied to scratch the transparent coated molded product is reduced, so that surface characteristics higher than those provided by a normal inorganic coating can be obtained. Further, since the outermost layer is a cured product of the coating composition (B) containing a fluorosilicone compound having a certain molecular weight, high scratch resistance and high surface water repellency are exhibited.

[0013] Further, a second invention according to the present invention is characterized in that it has a transparent synthetic resin base material and at least two transparent cured material layers formed on at least a part of the surface of the base material, and is formed by bending. In a method for producing a transparent coated molded article,
An active energy ray-curable coating composition (A) containing a polyfunctional compound having two or more active energy ray-curable polymerizable functional groups on at least a part of the substrate surface, A layer of an uncured product, a partially cured product or a cured product of the coating composition (A) is formed, and on the surface of this layer, a curable compound (b) forming silica and a fluorine-containing organic group are converted to silicon atoms. A coating composition (B) containing a fluorosilicone compound containing bound organosiloxane units is applied, and then the substrate having the coating composition (A) and the layer of the coating composition (B) is bent. Processing, then curing the coating composition (B), and curing the uncured or partially cured product of the coating composition (A), if any, if present. Characterized bent To provide a method of manufacturing a light coating moldings.

According to the second aspect, a curable compound is applied to a transparent synthetic resin base material, and before the curable compound is cured, a process of bending the transparent synthetic resin base material is performed. Thus, the cured product layer formed on the surface of the transparent synthetic resin substrate can be easily formed into a curved surface without cracks or the like.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The transparent cured product layer in the present invention comprises:
It comprises at least two layers: a transparent cured product layer directly in contact with the outermost layer and a transparent cured product layer forming the outermost layer. The layer of the cured product of the active energy ray-curable coating composition (A) among the transparent cured product layers has high adhesion to the outermost layer. In addition, it has high adhesion to the transparent synthetic resin substrate. A third layer made of another synthetic resin may exist between the substrate and the transparent cured product layer. In this case, the third layer preferably has sufficient adhesion to both the transparent cured product layer and the outermost layer which are in direct contact with the outermost layer. Further, examples of the third layer include a layer of a thermoplastic resin such as a thermoplastic acrylic resin, an adhesive layer, and the like.

In order to obtain an inner layer having high adhesion and abrasion resistance, a polyfunctional compound is used as the active energy ray-curable coating composition (A). Similarly, in order to form a cured product having high wear resistance, the coating composition (A) has an average particle size of 2%.
It is also preferable to form a cured product containing colloidal silica by blending colloidal silica having a size of 00 nm or less. In addition,
In order to efficiently cure the polyfunctional compound with active energy rays (particularly ultraviolet rays), a photopolymerization initiator is usually added to the coating composition (A).

The polyfunctional compound having two or more active energy ray-curable polymerizable functional groups in the coating composition (A) may be one kind of polyfunctional compound, or a plurality of kinds of compounds. May be used. In the case of a plurality of compounds, they may be different compounds in the same category, or may be compounds in different categories. For example, a combination of different compounds, each of which is acrylic urethane described below,
A combination in which one is acrylic urethane and the other is an acrylic ester compound having no urethane bond may be used.

Here, in the present specification, an acryloyl group and a methacryloyl group are collectively referred to as a (meth) acryloyl group. The same applies to (meth) acryloyloxy group, (meth) acrylic acid, (meth) acrylate and the like.
In the present invention, among these groups and compounds, those having an acryloyl group are more preferable, such as an acryloyloxy group, acrylic acid, and acrylate.

The active energy ray-curable polymerizable functional group in the polyfunctional compound is an α, β-unsaturated group such as a (meth) acryloyl group, a vinyl group, an allyl group or a group having the same. It is preferably a (meth) acryloyl group. That is, the polyfunctional compound is preferably a compound having two or more polymerizable functional groups selected from (meth) acryloyl groups, and among them, two acryloyl groups which are more easily polymerized by ultraviolet light are preferred. More preferably, the compound has the above.

The polyfunctional compound has 2 per molecule.
It may be a compound having two or more kinds of polymerizable functional groups in total, or a compound having two or more same polymerizable functional groups in total. The number of polymerizable functional groups in one molecule of the polyfunctional compound is 2 or more, and the upper limit is not particularly limited, but is preferably 2 to 50, and more preferably 3 to 30.

Preferred compounds as polyfunctional compounds are compounds having two or more (meth) acryloyl groups. Among them, a compound having two or more (meth) acryloyloxy groups, that is, a polyester of a compound having two or more hydroxyl groups such as polyhydric alcohol and (meth) acrylic acid is more preferable.

In the coating composition (A), two or more polyfunctional compounds may be contained as the polyfunctional compound. Further, together with the polyfunctional compound, a monofunctional compound having one polymerizable functional group polymerized by an active energy ray may be included. As the monofunctional compound, a compound having a (meth) acryloyl group is preferable, and a compound having an acryloyl group is particularly preferable.

When the monofunctional compound is used in the coating composition (A), the ratio of the monofunctional compound to the total of the polyfunctional compound and the monofunctional compound is not particularly limited, but may be from 0 to 60. % By weight, preferably from 0 to 30% by weight.
% Is more preferred. If the proportion of the monofunctional compound exceeds 60% by weight, the hardness of the cured coating film is reduced, and the abrasion resistance may be insufficient.

The polyfunctional compound may be a compound having various functional groups or bonds other than the polymerizable functional groups. For example, hydroxyl group, carboxyl group, halogen atom,
It may have a urethane bond, an ether bond, an ester bond, a thioether bond, an amide bond, a diorganosiloxane bond, or the like. In particular, a (meth) acryloyl group-containing compound having a urethane bond (so-called acryl urethane) and a (meth) acrylate compound having no urethane bond are preferable.

Hereinafter, the above-mentioned two types of polyfunctional compounds will be described. Examples of the (meth) acryloyl group-containing compound having a urethane bond (hereinafter referred to as acrylic urethane) include the following. Compound having a (meth) acryloyl group and a hydroxyl group (M
A reaction product of 1) with a compound having two or more isocyanate groups (hereinafter referred to as polyisocyanate). A reaction product of the compound (M1), the compound (M2) having two or more hydroxyl groups, and a polyisocyanate. A reaction product of the compound (M3) having a (meth) acryloyl group and an isocyanate group and the compound (M2).

It is preferable that these reaction products have no isocyanate group. However, hydroxyl groups may be present. Therefore, in the production of these reaction products, it is more preferable that the total number of moles of hydroxyl groups of all reaction raw materials is equal to or larger than the total number of moles of isocyanate groups.

The compound (M1) having a (meth) acryloyl group and a hydroxyl group may be a compound having one (meth) acryloyl group and one hydroxyl group, and two or more (meth) acryloyl groups and a hydroxyl group. It may be a compound having one, a compound having one (meth) acryloyl group and two or more hydroxyl groups, or a compound having two or more (meth) acryloyl groups and two or more hydroxyl groups.

As a specific example, for example, 2-
Examples include hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane mono (meth) acrylate, and pentaerythritol di (meth) acrylate. These are monoesters of a compound having two or more hydroxyl groups and (meth) acrylic acid or polyesters having one or more hydroxyl groups.

The compound (M1) may be a ring-opening reaction product of a compound having at least one epoxy group with (meth) acrylic acid. The reaction between the epoxy group and the (meth) acrylic acid causes the ring opening of the epoxy group to form an ester bond and a hydroxyl group, resulting in a compound having a (meth) acryloyl group and a hydroxyl group. Alternatively, the epoxy group of a compound having one or more epoxy groups may be opened to form a hydroxyl group-containing compound, which may be converted to a (meth) acrylate.

As the compound having one or more epoxy groups, a polyepoxide called an epoxy resin is preferable. As the polyepoxide, for example, a compound having two or more glycidyl groups such as a polyhydric phenol-polyglycidyl ether (for example, bisphenol A-diglycidyl ether) or an alicyclic epoxy compound is preferable. Further, a reaction product of a (meth) acrylate having an epoxy group and a compound having a hydroxyl group or a carboxyl group can also be used as the compound (M1). Examples of the (meth) acrylate having an epoxy group include glycidyl (meth) acrylate.

The polyisocyanate may be an ordinary monomeric polyisocyanate, a multipolymer or modified polyisocyanate, or a prepolymer compound such as an isocyanate group-containing urethane prepolymer.

Examples of the multimer include trimer (isocyanurate-modified), dimer, carbodiimide-modified and the like.
Examples of the modified form include a urethane modified form, a buret modified form, an allonate modified form, and a urea modified form obtained by modification with a polyhydric alcohol such as trimethylolpropane.
Examples of prepolymers include isocyanate group-containing urethane prepolymers obtained by reacting polyols such as polyether polyols and polyester polyols described below with polyisocyanates. These polyisocyanates can be used in combination of two or more.

Specific examples of the monomeric polyisocyanate include the following polyisocyanates (the names in [] are abbreviated). 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, methylene bis (4-phenyl isocyanate) [MDI], hexamethylene diisocyanate, isophorone diisocyanate, transcyclohexane-1,4-diisocyanate, xylylene diisocyanate [XDI], Hydrogenated XD
I, hydrogenated MDI.

As the polyisocyanate, a non-yellowing polyisocyanate (polyisocyanate having no isocyanate group directly bonded to an aromatic nucleus) is particularly preferable.
Specific examples include aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as isophorone diisocyanate, and aromatic polyisocyanates such as xylylene diisocyanate. As described above, polymers and modified products of these polyisocyanates are also preferable.

Compound having two or more hydroxyl groups (M2)
Examples include polyhydric alcohols and polyols having a higher molecular weight than polyhydric alcohols. As the polyhydric alcohol, a polyhydric alcohol having 2 to 20 hydroxyl groups is preferable, and a polyhydric alcohol having 2 to 15 hydroxyl groups is particularly preferable. The polyhydric alcohol may be an aliphatic polyhydric alcohol, an alicyclic polyhydric alcohol or a polyhydric alcohol having an aromatic nucleus. Examples of the polyhydric alcohol having an aromatic nucleus include an alkylene oxide adduct of a polyhydric phenol and a ring-opened polyepoxide having an aromatic nucleus such as a polyhydric phenol-polyglycidyl ether.

The high molecular weight polyol includes polyether polyol, polyester polyol, polyether ester polyol, polycarbonate polyol and the like. Also, a hydroxyl group-containing vinyl polymer can be used as the polyol. These polyhydric alcohols and polyols can be used in combination of two or more.

Specific examples of the polyhydric alcohol include, for example, the following polyhydric alcohols. ethylene glycol,
1,2-propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexanediol, dimethylolcyclohexane, trimethylolpropane, glycerin, pentaerythritol, ditrimethylolpropane , Dipentaerythritol, tris (2-hydroxyethyl) isocyanurate, tris (2-hydroxypropyl) isocyanurate, ring-opened product of bisphenol A-diglycidyl ether, and ring-opened product of vinylcyclohexene dioxide.

Specific examples of the polyol include the following polyols. Polyether polyols such as polyethylene glycol, polypropylene glycol, bisphenol A-alkylene oxide adduct, and polytetramethylene glycol. A polyester polyol obtained by ring-opening polymerization of a cyclic ester such as poly-ε-caprolactone polyol. Polyester polyols obtained by the reaction of polybasic acids such as adipic acid, sebacic acid, phthalic acid, maleic acid, fumaric acid, azelaic acid, glutaric acid and the above-mentioned polyhydric alcohols. A polycarbonate diol obtained by reacting 1,6-hexanediol with phosgene.

As the hydroxyl group-containing vinyl polymer, for example, a copolymer of a hydroxyl group-containing monomer such as allyl alcohol, vinyl alcohol, hydroxyalkyl vinyl ether, hydroxyalkyl (meth) acrylate and a hydroxyl group-free monomer such as olefin can be used. is there. Examples of the compound (M3) having a (meth) acryloyl group and an isocyanate group include 2-isocyanatoethyl (meth) acrylate and methacryloyl isocyanate.

Next, the (meth) acrylate compound having no urethane bond will be described. As the (meth) acrylic acid ester compound having no urethane bond, which is a preferable compound in the polyfunctional compound, a polyester of (meth) acrylic acid with a compound having two or more hydroxyl groups similar to the compound (M2) Is preferred. As the compound having two or more hydroxyl groups, the above-mentioned polyhydric alcohols and polyols are preferable. Further, a (meth) acrylate compound which is a reaction product of a compound having two or more epoxy groups and (meth) acrylic acid is also preferable.

Specific examples of the polyfunctional compound containing no urethane bond include the following compounds. (A) The following (meth) acrylates of aliphatic polyhydric alcohols. 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate.

(B) (meth) acrylates of polyhydric alcohols and phenols having the following aromatic nucleus or triazine ring: Tris (2- (meth) acryloyloxyethyl) isocyanurate, bis (2- (meth) acryloyloxyethyl) -2-hydroxyethyl isocyanurate, tris (2- (meth) acryloyloxypropyl) isocyanurate, bis (2 -(Meth) acryloyloxyethyl) bisphenol A, bis (2- (meth) acryloyloxyethyl) bisphenol S, bis (2- (meth) acryloyloxyethyl) bisphenol F, bisphenol A dimethacrylate.

(C) The following (meth) acrylates of hydroxyl-containing compounds-alkylene oxide adducts, (meth) acrylates of hydroxyl-containing compounds-caprolactone adducts, and (meth) acrylates of polyoxyalkylene polyols. Here, EO represents ethylene oxide, and PO represents propylene oxide. Trimethylolpropane-EO
Tri (meth) acrylate of adduct, tri (meth) acrylate of trimethylolpropane-PO adduct, hexa (meth) acrylate of dipentaerythritol-caprolactone adduct, tris (2-hydroxyethyl) isocyanurate-caprolactone adduct Tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate-caprolactone adduct tri (meth) acrylate.

As the polyfunctional compound, a cured product of the coating composition (A) can exhibit sufficient abrasion resistance.
It is preferable that 30% by weight or more of the polyfunctional compound is composed of a trifunctional or more polyfunctional compound, and it is more preferable that 50% or more of the polyfunctional compound is composed of a trifunctional or more polyfunctional compound. Further, preferred specific examples of the polyfunctional compound are the following acrylic urethane and a polyfunctional compound having no urethane bond.

In the case of acrylic urethane, acrylic urethane which is a reaction product of pentaerythritol or its multimer, polypentaerythritol, polyisocyanate and hydroxyalkyl (meth) acrylate), or hydroxyl group-containing poly (pentaerythritol or polypentaerythritol) Acrylic urethane which is a reaction product of a (meth) acrylate and a polyisocyanate,
Compounds having more than one functionality are preferred, and compounds having 4 to 20 functionality are more preferred.

As the polyfunctional compound having no urethane bond, pentaerythritol poly (meth) acrylate and isocyanurate poly (meth) acrylate are preferable. The pentaerythritol-based poly (meth) acrylate refers to pentaerythritol or a polyester of polypentaerythritol and (meth) acrylic acid (preferably having a functionality of 4 to 20). The isocyanurate-based poly (meth) acrylate refers to tris (hydroxyalkyl) isocyanurate or an adduct obtained by adding 1 to 6 mol of caprolactone or alkylene oxide to 1 mol of the same and (meth) acrylic acid. Polyester (2 to 3 functional).

These preferred polyfunctional compounds and the other two
It is also preferable to use a polyfunctional compound having a functionality higher than or equal to that (particularly, a polyhydric alcohol poly (meth) acrylate).
In addition, these preferable polyfunctional compounds are preferably at least 30% by weight, more preferably at least 50% by weight, based on all the polyfunctional compounds.

As the monofunctional compound that can be used together with the polyfunctional compound, for example, a compound having one (meth) acryloyl group in the molecule is preferable. Such a monofunctional compound may have a functional group such as a hydroxyl group and an epoxy group. Preferred monofunctional compounds are (meth) acrylates, ie (meth) acrylates.

Specific examples of the monofunctional compound include the following compounds. Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) Acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate.

The coating composition (A) can contain an effective amount of colloidal silica having an average particle diameter of 200 nm or less in order to increase the abrasion resistance and hardness of the cured product layer directly in contact with the outermost layer. The average particle size of the colloidal silica is preferably 1 to 100 nm, particularly preferably 1 to 50 nm. If the average particle size of the colloidal silica exceeds 200 nm, fogging (haze) tends to occur, which is not preferable.

When using colloidal silica,
In order to sufficiently exhibit the effect to be used, the amount of colloidal silica is 5 to 100 parts by weight of the curable component (the total of the polyfunctional compound and the monofunctional compound) of the transparent cured material layer. Preferably 300 parts by weight, more preferably 10 to 250 parts by weight, even more preferably 10 to 50 parts by weight. If the amount of the colloidal silica is less than 5 parts by weight, it is difficult to obtain sufficient abrasion resistance. On the other hand, when the amount of the colloidal silica exceeds 300 parts by weight, fogging (haze) tends to occur in the coating, and the obtained transparent coated molded product is subjected to secondary processing such as hot bending described later. Problems tend to occur, such as cracks.

Further, as the colloidal silica, unmodified colloidal silica can be used. However, the surface-modified colloidal silica is modified to improve the dispersion stability of the colloidal silica and the adhesion between the colloidal silica and the polyfunctional compound. It is preferred to use colloidal silica. The use of surface-modified colloidal silica improves the dispersion stability of the colloidal silica in the composition. It is considered that the average particle size of the colloidal silica fine particles is not substantially changed or slightly increased by the modification, but the average particle size of the obtained modified colloidal silica is considered to be in the above range.

The surface modified colloidal silica (hereinafter simply referred to as modified colloidal silica) will be described below. Various dispersion media are known as dispersion media of colloidal silica, and the dispersion media of raw material colloidal silica are not particularly limited. If necessary, the modification can be performed by changing the dispersion medium, and the dispersion medium can be changed after the modification.
The dispersion medium of the modified colloidal silica is preferably used as a medium (solvent) of the cured composition of the transparent cured product layer directly in contact with the substrate.

The medium of the coating composition (A) is preferably a solvent having a relatively low boiling point, that is, an ordinary solvent for coatings, from the viewpoint of drying properties and the like. For reasons such as ease of production, it is preferable that the dispersion medium of the raw material colloidal silica, the dispersion medium of the modified colloidal silica and the medium of the cured composition of the transparent cured layer are all the same medium (solvent).
As such a medium, an organic medium widely used as a solvent for paint is preferable.

As the dispersion medium, for example, the following dispersion medium can be used. water. Lower alcohols such as methanol, ethanol, isopropanol, n-butanol, t-butanol, 4-hydroxy-4-methyl-2-pentanone and ethylene glycol. Methyl cellosolve,
Cellosolves such as ethyl cellosolve and butyl cellosolve. Dimethylacetamide, toluene, xylene, methyl acetate, ethyl acetate, butyl acetate, acetone and the like.

As described above, the dispersion medium is particularly preferably an organic dispersion medium, and among the above-mentioned organic dispersion mediums, alcohols and cellosolves are more preferred. Note that an integrated body of colloidal silica and a dispersion medium in which the colloidal silica is dispersed is referred to as a colloidal silica dispersion.

The modification of the colloidal silica is preferably carried out using a compound having a hydrolyzable silicon group or a silicon group having a hydroxyl group bonded thereto (hereinafter, these are referred to as modifiers). It is considered that silanol groups are generated by the hydrolysis of the hydrolyzable silicon groups, and these silanol groups react with and bind to silanol groups which are considered to be present on the colloidal silica surface, and the modifier binds to the colloidal silica surface. Two or more modifiers may be used in combination. Further, as described later, a modifying agent 2 having a reactive functional group
The reaction product obtained by pre-reacting the species can also be used as a modifying agent.

The modifier may have two or more hydrolyzable silicon groups or silanol groups, and may be a partially hydrolyzed condensate of a compound having a hydrolyzable silicon group or a compound having a silanol group. It may be a partial condensate. Preferably, a compound having one hydrolyzable silicon group is used as a modifying agent (a partially hydrolyzed condensate may be generated during the modification treatment). Further, it is preferable that the modifier has an organic group bonded to a silicon atom, and one or more of the organic groups is an organic group having a reactive functional group.

Preferred reactive functional groups are amino, mercapto, epoxy and (meth) acryloyloxy. As the organic group to which the reactive functional group is bonded,
An alkylene group having 8 or less carbon atoms or a phenylene group excluding a reactive functional group is preferable, and an alkylene group having 2 to 4 carbon atoms (particularly, a polymethylene group) is particularly preferable.

Specific examples of the modifying agent include the following compounds when classified according to the type of the reactive functional group. (A) (Meth) acryloyloxy group-containing silanes 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane and the like.

(B) Amino group-containing silanes 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane,
N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, N- (N-vinylbenzyl-2-aminoethyl)-
3-aminopropyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and the like.

(C) Mercapto group-containing silanes 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane and the like.

(D) Epoxy group-containing silanes 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane and the like.

(E) Isocyanate group-containing silanes 3-isocyanatopropyltrimethoxysilane, 3-
Isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropylmethyldiethoxysilane and the like.

The two types of modifying agents having the reactive functional groups are
Examples of the reaction product obtained by preliminarily reacting include a reaction product of an amino group-containing silane and an epoxy group-containing silane, and a reaction product of an amino group-containing silane and a (meth) acryloyloxy group-containing silane. Products, reaction products of epoxy group-containing silanes and mercapto group-containing silanes, and reaction products of two molecules of mercapto group-containing silanes.

The modification of colloidal silica is usually carried out by bringing a modifier having a hydrolyzable group into contact with colloidal silica in the presence of a catalyst and hydrolyzing it. For example, it can be modified by adding a modifier and a catalyst to a colloidal silica dispersion and hydrolyzing the modifier in the colloidal silica dispersion.

The catalyst includes an acid and an alkali. Preferably, an acid selected from inorganic acids and organic acids is used.
As the inorganic acid, for example, hydrohalic acid such as hydrochloric acid, hydrofluoric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid and the like can be used. The organic acids include formic acid, acetic acid, oxalic acid,
(Meth) acrylic acid can be used. The reaction temperature is preferably from room temperature to the boiling point of the solvent used, and the reaction time is preferably in the range of 0.5 to 24 hours, depending on the temperature.

In the modification of the colloidal silica, the amount of the modifier used is not particularly limited, but the modifiers 1 to 10 are added to 100 parts by weight of the colloidal silica (solid content in the dispersion).
0 parts by weight is preferred. If the amount of the modifier is less than 1 part by weight,
It is difficult to obtain the effect of surface modification. On the other hand, when the amount exceeds 100 parts by weight, a large amount of hydrolyzate, condensate and the like of the unreacted modifier and the modifier not supported on the surface of the colloidal silica is generated. They may act as a chain transfer agent or act as a plasticizer of the cured film to lower the hardness of the cured film.

In order to cure the polyfunctional compound, the coating composition (A) usually contains a photopolymerization initiator. Known photopolymerization initiators can be used. Particularly, commercially available products that are easily available are preferable. A plurality of photopolymerization initiators may be used in the transparent cured product layer.

Examples of the photopolymerization initiator include arylketone photopolymerization initiators (for example, acetophenones, benzophenones, alkylaminobenzophenones, benzyls, benzoins, benzoin ethers, benzyldimethyl ketals, benzoylbenzoates, α-Acyloxime esters), sulfur-containing photopolymerization initiators (eg, sulfides, thioxanthones, etc.), acylphosphine oxide photopolymerization initiators, and other photopolymerization initiators can be used. In particular, the use of an acylphosphine oxide-based photopolymerization initiator is preferred. Further, the photopolymerization initiator can be used in combination with a photosensitizer such as an amine. Specific examples of the photopolymerization initiator include the following compounds. 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-
1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-methylpropan-1-one, -(2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 2
-Methyl-1- {4- (methylthio) phenyl} -2-
Morpholinopropan-1-one.

Benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 3,3 ', 4,4'-tetrakis (t-
Butylperoxycarbonyl) benzophenone, 9.1
0-phenanthrenequinone, camphorquinone, dibenzosuberone, 2-ethylanthraquinone, 4 ', 4 "-
Diethyl isophthalophenone, α-acyloxime ester, methylphenylglyoxylate.

4-benzoyl-4'-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone. 2,4
6-trimethylbenzoyldiphenylphosphine oxide, benzoyldiphenylphosphine oxide, 2,6
-Dimethylbenzoyldiphenylphosphine oxide,
Bis (2,6-dimethoxybenzoyl) -2,4,4-
Trimethylpentylphosphine oxide, bis (2,
4,6-trimethylbenzoyl) phenylphosphine oxide.

The addition amount of the photopolymerization initiator in the coating composition (A) is preferably 0.01 to 20 parts by weight based on 100 parts by weight of the curable component (the total of the polyfunctional compound and the monofunctional compound). And particularly preferably 0.1 to 10 parts by weight.

The coating composition (A) may contain a solvent and various additives in addition to the above basic components. The solvent is usually an essential component, and the solvent is used unless the polyfunctional compound is a liquid having a particularly low viscosity. As the solvent, a solvent usually used for a coating composition containing a polyfunctional compound as a curing component can be used. Further, the dispersion medium of the raw material colloidal silica can be used as a solvent as it is. Further, it is preferable to select and use an appropriate solvent depending on the type of the base material.

The amount of the solvent can be appropriately changed depending on the required viscosity of the composition, the desired thickness of the cured film, the conditions of the drying temperature, etc., and is preferably 100 times or less by weight of the curable component in the composition. , More preferably 0.1 to 50 times the weight.
Examples of the solvent include solvents such as lower alcohols, ketones, ethers, and cellosolves, which are mentioned as solvents used for hydrolysis for modifying the colloidal silica. Other examples include esters such as n-butyl acetate and diethylene glycol monoacetate, halogenated hydrocarbons, hydrocarbons, and the like. For coating an aromatic polycarbonate resin base material having low solvent resistance, lower alcohols, cellosolves, esters, mixtures thereof and the like are suitable.

The coating composition (A) may contain a stabilizer such as an ultraviolet absorber, an antioxidant and a thermal polymerization inhibitor, if necessary.
Leveling agents, defoamers, thickeners, anti-settling agents, pigments, dispersants, antistatic agents, surfactants such as anti-fogging agents, acids,
A curing catalyst selected from alkalis and salts may be appropriately blended and used.

The coating composition (A) preferably contains an ultraviolet absorber or a light stabilizer. As the ultraviolet absorber, a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a salicylic acid-based ultraviolet absorber, and the like which are generally used as an ultraviolet absorber for a synthetic resin are preferable. As the light stabilizer, a hindered amine light stabilizer (such as a 2,2,4,4-tetraalkylpiperidine derivative) which is also commonly used as a light stabilizer for a synthetic resin is also preferable.

Ultraviolet rays are particularly preferred as the active energy ray for curing such a coating composition (A). However, it is not limited to ultraviolet rays, and an electron beam or other active energy rays can be used. Xenon lamps, pulsed xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps,
Ultra-high pressure mercury lamps, metal halide lamps, carbon arc lamps, tungsten lamps and the like can be used.

The thickness of the cured product layer formed using the coating composition (A) is preferably 1 to 50 μm,
More preferably, it is 30 μm. When the thickness exceeds 50 μm, curing by active energy rays becomes insufficient,
It is not preferable because the adhesion to the substrate is easily damaged. Also,
If it is less than 1 μm, the abrasion resistance of this layer may be insufficient, and the abrasion resistance and abrasion resistance of the outermost layer may not be sufficiently exhibited.

Next, the curable coating composition (B) of the outermost layer is
The curable compound (b) forming silica and a fluorosilicone compound containing an organosiloxane unit in which a fluorine-containing organic group is directly bonded to a silicon atom are contained as essential components.

Examples of the curable compound (b) forming silica include a tri- or tetra-functional hydrolyzable silane compound, a partially hydrolyzed condensate thereof, a silicone-based thermosetting compound and polysilazane. Examples of the tri- to tetra-functional hydrolyzable silane compound and its partially hydrolyzed condensate include tetraalkoxysilane and its partially hydrolyzed condensate. However, polysilazane is preferably used. 3
Polysilazane forms a silica having a more dense structure as compared with a tetrafunctional hydrolyzable silane compound or the like, so that an outermost layer having more excellent surface properties can be obtained.

Examples of the polysilazane include polysilazane (perhydropolysilazane) having substantially no organic group, polysilazane in which a hydrolyzable group such as an alkoxy group is bonded to a silicon atom, and an organic group such as an alkyl group bonded to a silicon atom. And polysilazane. In particular, perhydropolysilazane is preferable from the viewpoint of low firing temperature and denseness of a cured film after firing. The cured product obtained by sufficiently curing the polysilazane becomes silica containing almost no nitrogen atoms.

These polysilazanes are composed of a polymer having a chain, cyclic or crosslinked structure, or a mixture of these plural structures in the molecule. The polysilazane preferably has a number average molecular weight of 200 to 50,000. If the number average molecular weight is less than 200, it is difficult to obtain a uniform cured film even when firing. When the number average molecular weight exceeds 50,000, it becomes difficult to dissolve in a solvent,
Further, the coating composition (B) is not preferable because it may become viscous.

Examples of the solvent for dissolving polysilazane include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, halogenated hydrocarbon solvents, ethers such as aliphatic ethers and alicyclic ethers. Can be used, and specifically, the following can be used. Hydrocarbons such as pentane, hexane, isohexane, methylpentane, heptane, isoheptane, octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene and ethylbenzene. Methylene chloride, chloroform, carbon tetrachloride, bromoform, 1,2-dichloroethane, 1,1-
Halogenated hydrocarbons such as dichloroethane, trichloroethane and tetrachloroethane. Ethers such as ethyl ether, isopropyl ether, ethyl butyl ether, butyl ether, dioxane, dimethyl dioxane, tetrahydrofuran and tetrahydropyran;

When these solvents are used, a plurality of types of solvents may be mixed in order to adjust the solubility of polysilazane and the evaporation rate of the solvent. The amount of the solvent used depends on the coating method employed, the structure of polysilazane, the average molecular weight, and the like, but the solid content is 0.5 to 80% by weight.
It is preferable to adjust within the range.

In order to cure the polysilazane into silica, it is generally necessary to perform heating called calcination. However, in the present invention, the firing temperature is limited because the base material is a synthetic resin. That is, it is difficult to cure the substrate by heating it to a temperature higher than the heat resistant temperature of the substrate. Generally, the heat resistance of the cured product of the coating composition (A) is higher than the heat resistance of the substrate. However, in some cases, the heat resistance of the cured product may be lower than the heat resistance of the base material. In such a case, it may be necessary to cure the polysilazane at a temperature lower than the heat resistance temperature of the cured product. Therefore, in the present invention, the firing temperature of polysilazane is preferably 180 ° C. or lower when a synthetic resin such as aromatic polycarbonate is used as a base material.

A catalyst is usually used to lower the firing temperature of polysilazane. Depending on the type and amount of the catalyst, it can be calcined at a low temperature, and in some cases, can be cured at room temperature. Further, it is preferable that the atmosphere in which the firing is performed is an atmosphere in which oxygen is present, such as in air. By firing polysilazane, its nitrogen atoms are replaced by oxygen atoms to produce silica. By firing in an atmosphere in which sufficient oxygen exists, a dense silica layer is formed.

It is preferable to use a catalyst which cures polysilazane at a lower temperature. Examples of such a catalyst include the use of fine particles of a metal such as gold, silver, palladium, platinum and nickel described in JP-A-7-196986, and the use of a carboxylic acid complex of the metal described in JP-A-5-93275. . Also, instead of adding the catalyst to the polysilazane solution,
As described in 33, a method of directly contacting the coated molded product with a catalyst solution, specifically, an aqueous amine solution or the like, or exposing the coated molded product to a vapor thereof for a certain period of time can be mentioned.

Next, the coating composition (B) contains, as an essential component, a fluorosilicone compound containing an organosiloxane unit having a fluorine-containing organic group bonded to a silicon atom. The silicone compound described here is a compound containing one or more siloxane bonds (Si-O-Si). A siloxane unit forms a siloxane bond [Si-O]
Unit (here, two bonds of a silicon atom of the [Si-O] unit are bonded with a hydrogen atom, a hydroxyl group, an organic group, and the like). The organosiloxane unit refers to a siloxane unit in which an organic group is bonded to a silicon atom of the siloxane unit by a silicon-carbon bond. In the organosiloxane unit, the organic group bonded to the silicon atom through a silicon-carbon bond may be bonded to only one of the two bonding hands of the silicon atom (the other is a hydrogen atom, etc.), or is bonded to both. May be.

In the present invention, the fluorine-containing organic group directly bonded to a silicon atom is preferably a fluorine-containing organic group represented by R ^f -Y-. In this R ^f —Y—, Y is a divalent hydrocarbon group having 1 to 20 carbon atoms in which an etheric oxygen atom may be inserted between carbon-carbon bonds, and R ^f is an etheric oxygen atom. Carbon number 1 which can be included
Represents 30 monovalent polyfluorohydrocarbon groups.

[0091] The proportion of fluorine atoms in ^the R ^f group is preferably ^at the R ^f
It is preferably at least 60% when expressed as [number of fluorine atoms in group] / [number of hydrogen atoms in hydrocarbon group having the same number of carbon atoms corresponding to the R ^f group] × 100 (%), particularly Is preferably 80% or more, and more preferably substantially 100%, that is, a perfluorohydrocarbon group in which substantially all of the hydrogen atoms of the hydrocarbon group are substituted with fluorine atoms. The perfluorohydrocarbon group may also contain an etheric oxygen atom.

Further, the R ^f group may have a linear or branched structure, and a linear structure is particularly preferable. In the case of a branched structure, the branched portion is preferably a short chain having about 1 to 3 carbon atoms, and a structure in which the branched portion is present at the terminal of the ^Rf group is preferred. The carbon number of the R ^f group is preferably from 1 to 18, and particularly preferably from 4 to 12. Particularly preferred R ^f groups are perfluoroalkyl groups having 1 to 18 (particularly 4 to 12) carbon atoms. The perfluoroalkyl group may contain an etheric oxygen atom.

Specific examples of the R ^f group include the following. In the following specific examples, groups corresponding to the groups having the respective structural isomers shall be included. First,
Specific examples of the R ^f group containing no etheric oxygen atom include the following.

[0094] C ₄ F ₉ - [However, CF ₃ (CF _{2) 3}
−, (CF ₃ ) ₂ CFCF ₂ −, (CF ₃ ) ₃ C—, C
Including structurally isomer groups such as F ₃ CF ₂ CF (CF ₃ ) —], C ₅ F ₁₁ —, provided that CF ₃ (CF ₂ ) ₄ —,
_{(CF 3) 2 CF (CF} 2) 2 -, (CF 3) 3 CCF 2
-, CF ₃ (CF ₂ ) ₂ CF (CF ₃ )-and the like, including groups of structural isomerism], C ₆ F _13- [where CF ₃ (CF
_{2) 2 C (CF 3)} 2 - including structural isomers groups such], C
_{8 F 17 -, C 10 F} 21 -, C 12 F 25 -, C 14 F 29 -, C 16
_{F 33 -, C 18 F 37} -, C 20 F 41 -, (CF 3) 2 CF
(CF ₂ ) _s-wherein s is 0 or an integer of 1 or more;
H (CF ₂ ) _t-wherein t is an integer of 1 or more.

[0095] Further, the R ^f is a group containing an etheric oxygen atom, the carbon in the above ^the R ^f group - carbon-carbon bond, or an etheric oxygen atom between above ^the R ^f group and Y It refers to an inserted group, and is preferably a group in which an etheric oxygen atom is inserted between carbon-carbon bonds in the R ^f group.

The R ^f group containing an etheric oxygen atom is preferably a group containing a polyfluorooxyalkylene moiety, and more preferably a group containing a perfluorooxyalkylene moiety. In particular, a group containing a perfluorooxyalkylene moiety and having a terminal perfluoroalkyl group is preferred. Examples of the perfluorooxyalkylene include perfluorooxymethylene, perfluorooxyethylene, perfluorooxypropylene, and perfluorooxybutylene.

Specific examples of the R ^f group containing an etheric oxygen atom include groups selected from the group consisting of those represented by the following chemical formulas. In addition, the above-mentioned specific examples also include groups corresponding to the groups having the respective structural isomers. However, in the formula, u, y, v, and w each represent an integer of 1 or more, and preferably an integer of 1 to 5.

[0098]

Embedded image CF ₃ (CF ₂ ) ₄ OCF (CF ₃ ) —, F
[CF (CF ₃ ) CF ₂ O] _u CF (CF ₃ ) CF ₂ C
F ₂ −, F [CF (CF ₃ ) CF ₂ O] _y CF (CF
_{3) -, F (CF 2} CF 2 CF 2 O) v CF 2 CF 2
_{-, F (CF 2 CF 2} O) w CF 2 CF 2 -.

Y is a C 2-20 carbon atom which may have an etheric oxygen atom inserted between carbon-carbon bonds.
When a hydrocarbon group is a monovalent hydrocarbon group and contains an etheric oxygen atom, there is no etheric oxygen atom at either end, and the ether is present between two adjacent carbon atoms in the hydrocarbon group. It contains an oxygen atom.

As Y not containing an etheric oxygen atom, an alkylene group is preferable, and any of a straight-chain or branched structure may be used. Y is preferably - (CH _{2) i} -
[Wherein, i is an integer of 1 to 20, preferably 2 to 8. ] It is a linear alkylene group represented by these. In the case of a branched structure, the number of carbon atoms in the branched portion is 1 to 3.
Those having a short chain of a degree are preferred. As Y in which an etheric oxygen atom is inserted between carbon-carbon bonds, a group in which an etheric oxygen atom is inserted at one position between the carbon-carbon bonds of the above-described alkylene group is preferable.

The fluorinated organic group represented by R ^f -Y- is preferably a fluorinated organic group represented by the following formula [IV], [V] or [VI]. ^{R f1 -Y 1 - [IV]} R f2 -Y 2 -O-Y 3 - [V] R f3 -Y 4 -O-Y 5 - [VI]

In the formula, R ^f1 and R ^f2 each independently represent an R ^f group, R ^f3 represents an R ^f group containing an etheric oxygen atom, and R ^f1 , R ^f2 and R ^f3 each represent And R ^f groups are preferred. Also,
Y ¹ , Y ² , Y ³ , Y ⁴ , and Y ⁵ are each independently a divalent hydrocarbon group containing no etheric oxygen atom, and are each independently — (CH ₂ ) _h — h is 2 to 10
, Preferably an integer of 2 to 4. The linear alkylene group represented by these is preferable.

Further, as the above R ^f1 , R ^f2 , R ^f3 ,
It is preferably an R ^f group represented by the following formula [VII] or [VIII]. However, in the formula, d represents an integer of 1 to 18, preferably 4 to 12, and e represents an integer of 1 to 10, preferably an integer of 1 to 5.

[0104]

^{Embedded image} R ^f1 , R ^f2 ; C _d F _{2d + 1-} [VII] R ^f3 ; F [CF (CF ₃ ) CF ₂ O] _e CF (CF ₃ )-[VIII]

Specific examples of the R ^f group represented by the above formula [IV] having the R ^f1 group of the above formula [VII] include those selected from the group consisting of the following chemical formulas. The structure of the perfluoroalkyl group in the formula shows a linear structure or a branched structure, and preferably has a linear structure. _{C 4 F 9 - (CH 2} ) 2 -, C 4 F 9 - (CH 2)
_{3 -, C 4 F 9 -} (CH 2) 4 -, C 5 F 11 - (CH
_{2) 2 -, C 5 F} 11 - (CH 2) 3 -, C 6 F 13 - (C
_{H 2) 2 -, C 8} F 17 - (CH 2) 2 -, C 8 F 17 -
_{(CH 2) 3 -, C} 8 F 17 - (CH 2) 4 -, C 9 F 19
— (CH ₂ ) ₂ —, C ₉ F ₁₉ — (CH ₂ ) ₃ —, C ₁₀ F
_{21 - (CH 2) 2 -} .

Specific examples of the R ^f group represented by the above formula [V] having the R ^f2 group of the above formula [VII] include those selected from the group consisting of the following chemical formulas. The structure of the perfluoroalkyl group in the formula shows a linear structure or a branched structure, and preferably has a linear structure. _{C 4 F 9 - (CH 2} ) 2 -O- (CH 2) 3 -, C
_{6 F 13 - (CH 2)} 2 -O- (CH 2) 3 -, C 8 F 17
— (CH ₂ ) ₂ —O— (CH ₂ ) ₃ —, C ₈ F ₁₇ — (C
_{H 2) 3 -O- (CH 2} ) 3 -.

Specific examples of the R ^f group represented by the above formula [VI] having the R ^f3 group of the above formula [VIII] include those selected from the group consisting of the following chemical formulas.

[0108]

Embedded image F [CF (CF ₃ ) CF ₂ O] ₂ CF (CF
_{3) CH 2 O (CH 2} ) 3 -, F [CF (CF 3) CF
₂ O] ₃ CF (CF ₃ ) CH ₂ O (CH ₂ ) ₃ —, F
[CF (CF ₃ ) CF ₂ O] ₄ CF (CF ₃ ) CH ₂ O
(CH ₂ ) ₃ —, F (CF ₂ CF ₂ CF ₂ O) ₂ CF _{2
CF 2 CH 2 O (CH 2} ) 3 -.

As the siloxane unit in which the fluorine-containing organic group represented by R ^f —Y— is directly bonded to a silicon atom, both of the two bonds of the silicon atom in the siloxane unit have R
siloxane ^{units f} -Y- is bonded, two one to R ^f -Y- is bonded to a hydrogen atom on the other bond, a hydroxyl group, hydrolyzable group, a monovalent organic group other than R ^f -Y- There is a siloxane unit to which is bonded. The preferred siloxane unit is a siloxane unit in which one of two bonds is bonded to R ^f -Y- and the other is bonded to a monovalent hydrocarbon group (hereinafter, represented by R ¹⁰ ) (that is, [Si (-Y −R ^f ) (R ¹⁰ )
O]). This siloxane unit is
For example, a hydrosiloxane unit ([SiH (R ¹⁰ )
O]) to CH ₂ ＣＨCH—
It can be produced by adding an unsaturated compound of Y'- ^Rf (Y 'is a group or a bond excluding two carbon atoms on the silicon terminal side of Y).

The fluorosilicone compound of the present invention may have another siloxane unit in addition to the siloxane unit having a fluorine-containing organic group. In particular, [Si
(-R ¹⁰⁾ preferably has a diorganosiloxane unit represented by ₂ O]. In addition, the above [SiH (R
¹⁰ ) A hydrosiloxane unit represented by O], a siloxane unit having a hydroxyl group directly bonded to a silicon atom, a siloxane unit having a hydrolyzable group, and an organic group having a hydrolyzable group-bonded silyl group are bonded to a silicon atom. There are siloxane units and the like. Hereinafter, a hydrogen atom, represented by A ¹ are collectively organic group having hydroxyl group, a hydrolyzable group and a hydrolyzable group bonded silyl groups. The siloxane unit having A ¹ is [S
i (A ¹ ) (R ¹⁰ ) O].

[0111] preferably an alkyl group and a phenyl group having 4 or less carbon atoms as a monovalent hydrocarbon group represented by R ^10, especially a methyl group. The hydrolyzable group refers to a group or an atom which is bonded to a silicon atom and can be hydrolyzed in the presence of water to form a hydroxyl group bonded to the silicon atom. Preferred hydrolyzable groups are a monovalent organic group having a terminal bonded to a silicon atom such as an alkoxy group or an acyl group being an oxygen atom, and a monovalent organic group having a terminal bonded to a silicon atom such as an alkylamino group being a nitrogen atom. And a chlorine atom. Hereinafter, such a monovalent hydrolyzable group is represented by Z.

The organic group having a hydrolyzable group-bonded silyl group in A ¹ is preferably an organic group represented by the following formula [II]. Here, R represents a monovalent hydrocarbon group, a represents an integer of 2 or more, and b represents 0, 1 or 2. Preferably, R is an alkyl group having 4 or less carbon atoms, particularly a methyl group, a is an integer of 2 to 8, and b is 0 or 1. Z is particularly preferably a methoxy group, an ethoxy group or a chlorine atom (however, in the case of a chlorine atom, b is 0). — (CH ₂ ) _a —Si (R) _b Z _3-b [II]

[0113] siloxane units A ¹ is represented by an organic group represented by the formula ^{[II] [Si (A 1} ) (R 10) O] , for example, hydro siloxane unit ([SiH (R
¹⁰ ) CH ₂ ＣＨCH—
(CH ₂₎ can be prepared by adding _{a-2 -Si (R) b} Z 3-b becomes unsaturated compound.

The fluorosilicone compound having a siloxane unit as described above is preferably a linear polymer. Further, three R ¹⁰ are bonded to the silicon atom at the terminal of the polymer, or two R ¹⁰ and A ¹ or R ^f -Y- are 1
It is preferable that they are individually bonded.

The fluorosilicone compound preferred in the present invention is a fluorosilicone compound represented by the following formula [I]. Note that the formula [I] does not indicate that each siloxane unit is polymerized in the form of a block in the fluorosilicone compound, nor does it indicate that each siloxane unit bonds in the order represented by the formula. Absent. The preferred fluorosilicone compound in the present invention is a random polymer in which each siloxane unit is randomly present, and k added to each siloxane unit in the formula,
m and n simply represent the number of each siloxane unit present in one molecule.

[0116]

Embedded image R ¹¹ —Si (R ¹⁰ ) ₂ O · [Si (R ¹⁰ ) ₂ O] _k · [Si (A ¹ ) (R ¹⁰ ) O] _m · [Si (A ² ) (R ¹⁰ ) O] _n · Si (R ¹⁰ ) ₂ -R ¹² [I]

In the above formula [I], A ¹ is a hydrogen atom,
Represents a hydroxyl group, a monovalent hydrolyzable group or a monovalent organic group represented by the formula [II], and when k is 2 or more, each A ¹ may be different. A ² represents the above R ^f -Y-. Each R
¹⁰ represents a monovalent hydrocarbon group which may be the same or different. R ¹¹ and R ¹² are each independently R ¹⁰ , A ¹ ,
Or an A ^2. k represents an integer of 0 or more, m represents an integer of 0 or more, and n represents an integer of 1 or more.

In the formula [I], k is preferably 0 to 50, particularly preferably 2 to 30. m is preferably 0 to 20, more preferably 1 to 10, and particularly preferably 1 to 5. n is preferably from 1 to 100, particularly preferably from 5 to 80. k / m / n can be appropriately changed depending on the fluorine content, but is preferably 50/1/100 to 3/1/1,
Particularly, the ratio is preferably from 10/20 to 2/1/1. Furthermore, since the fluorosilicone compound represented by the formula [I] of the present invention preferably flows at room temperature, its molecular weight is preferably about 5 × 10 ² to 1 × 10 ⁵ , particularly 1 × 10 ^5.
It is preferably from 10 ³ to 1 × 10 ⁴ .

As the fluorosilicone compound in the present invention, a fluorosilicone compound having one or more siloxane units having A ¹ as described above is preferable.
In particular, A ¹ is an organic group represented by the formula [II] [Si
A fluorosilicone compound having a siloxane unit represented by (A ¹ ) (R ¹⁰ ) O] is preferred. Since this fluorosilicone compound has a hydrolyzable group-bonded silyl group, the fluorosilicone compound has a hydrolyzable group-bonded silyl group, so that the curable compound (b) is cured by the hydrolysis of the hydrolyzable group-bonded silyl group. Is considered to cause a co-curing reaction to form a siloxane bond. Thus, it is considered that the fluorosilicone compound is bonded to a silicon atom in silica, which is a cured product of the curable compound (b), and is fixed thereto. Therefore, it seems that the fluorosilicone compound can remain in the cured product layer of the coating composition (B) for a long period of time.

The amount of the fluorosilicone compound in the coating composition (B) is preferably 0.01 to 20 parts by weight, particularly preferably 0.05 to 10 parts by weight, per 100 parts by weight of the curable compound (b). The coating composition (B) may further contain a stabilizer such as an ultraviolet absorber, a light stabilizer, or an antioxidant, a leveling agent, an antifoaming agent, a thickener, an antisettling agent, a pigment, a dispersion, if necessary. Surfactants such as an agent, an antistatic agent and an antifogging agent may be appropriately blended and used.

The thickness of the transparent cured product layer formed using the coating composition (B) is preferably from 0.05 to 10 μm, more preferably from 0.1 to 3 μm. If the thickness exceeds 10 μm, further improvement in surface properties such as scratch resistance cannot be expected, and the layer becomes brittle, and cracks and the like are liable to occur in this layer even by slight deformation of the coated molded product. On the other hand, if the thickness is less than 0.05 μm, the outermost layer may not have sufficient abrasion resistance and abrasion resistance.

In the present invention, as a method for forming two transparent cured material layers formed using the two kinds of coating compositions (A) and (B) as described above, a usual coating method is employed. it can. For example, first, the coating composition (A) is applied and cured on a substrate, and then the coating composition (B) is applied and cured on the surface of the cured product to form the desired transparent coating. Goods are obtained.

The means for applying these coating compositions is not particularly limited, and known methods can be employed. For example, dip coating, flow coating, spray coating, bar coating, gravure coating, roll coating, blade coating, air knife coating, spin coating, slit coating, micro gravure coating, etc. are used. it can.

After coating, if the coating composition contains a solvent, it is dried to remove the solvent, and then, in the case of a layer composed of the coating composition (A), it is cured by irradiating ultraviolet rays or the like. In the case of a layer composed of the coating composition (B), the layer is cured by heating or left at room temperature or by exposing it to the vapor of a curing catalyst solution of the coating composition (B).

Combination (timing) of curing of coating composition (A) and application to curing of coating composition (B)
There are the following four methods. (A) A method of applying the coating composition (A), irradiating a sufficient amount of active energy rays after the coating to sufficiently complete the curing, and then coating the composition (B) thereon (as described above). Method).

(B) After coating the coating composition (A) to form an uncured layer of the coating composition (A), apply the coating composition (B) on the uncured layer. To form an uncured material layer of the coating composition (B), and then irradiate a sufficient amount of active energy rays to terminate the curing of the uncured material of the coating composition (A). In this case, the uncured material of the coating composition (B) is cured almost simultaneously with the uncured material of the coating composition (A), or after the uncured material of the coating composition (A) is cured, it is heated or left at room temperature or A method of curing by exposing the coating composition (B) to the vapor of a curing catalyst solution.

(C) The minimum active energy ray (usually about 30
(A cumulative energy amount up to 0 mJ / cm ² ) to form a partially cured layer of the coating composition (A), and then apply the coating composition (B) on the partially cured layer. A method of forming an uncured material layer of the coating composition (B) and thereafter irradiating a sufficient amount of active energy rays to terminate the curing of the uncured material of the coating composition (A). The curing of the uncured coating composition (B) is the same as in (b) above.

(D) After forming the uncured or partially hardened material layer of the coating composition (A) and the uncured material layer of the coating composition (B) as described in (b) to (c) above, Coating composition (B)
A method of first partially curing or completely curing the uncured material of Example 1, and thereafter completely curing the uncured material or partially cured material of the coating composition (A). In this case, at the time of curing the uncured material of the coating composition (B), the coating composition (A) is preferably a partially cured material rather than an uncured material.

In order to increase the interlayer adhesion between the two cured product layers, the above method (b) or (c) is preferable. However, in the case of the method (b), the coating composition (B)
When a dip method is used as a method of applying the coating composition, the components of the uncured material of the coating composition (A) may contaminate the dip solution of the coating composition (B). Is not suitable. In the method (d), the coating composition (B) is partially cured or completely cured when the coating composition (A) is completely cured. Acts as a barrier layer and reduces the possibility that the cured product of the coating composition (A) will be insufficiently cured.

Further, as a feature of the transparent coated molded article of the present invention, the surface properties such as abrasion resistance and scratch resistance are almost at the same level as those of glass. It can be used. However, among various uses, in the case of uses as window materials for vehicles,
In many cases, a bent molded product is required.

Therefore, in the present invention, it is preferable to perform bending on the transparent coated molded article so as to be able to cope with such uses. In the case of producing a bent transparent coated molded article, the transparent coated molded article of the present invention can be formed using a bent substrate. However, when a bent base material is used, it is often difficult to form each layer by applying and curing the coating composition.

On the other hand, according to the conventional studies by the present inventors, the substrate on which the cured product layer of the coating composition (A) is formed can be bent by hot bending or the like. However, when a cured product layer of the coating composition (B) is formed, the cured product is hard, so that bending is difficult.

The present inventor has found that a substrate having a transparent cured product layer of the coating composition (A) can be bent as long as it is a layer of the uncured or partially cured product of the coating composition (B). . Further, as in the above methods (b) to (d), the uncured or partially cured product layer of the coating composition (B) is placed on the uncured or partially cured product layer of the coating composition (A). Bending can be performed in a state in which is formed. By curing the uncured or partially cured product of the coating composition (B) after or almost simultaneously with the bending, the intended bent coated article can be obtained. The bending is performed in a heated state.

Therefore, the uncured or partially cured product of the coating composition (B) is cured by heating for bending, but usually, the uncured material of the coating composition (B) is shorter than the time required for bending. Since the time required for curing the cured product or the partially cured product is longer, there is little possibility that the bending of the coating composition (B) becomes difficult due to the curing of the coating composition (B).

Therefore, in the present invention, an uncured, partially cured, or cured layer of the coating composition (A) is formed on a substrate, and the coating composition (B) is coated on the surface of the layer. After forming a cured product or a partially cured product layer, bending is performed, and then the uncured or partially cured product of the coating composition (B), and the uncured or partially cured product of the coating composition (A) Is present, a cured molded article can be produced by curing it.

Specifically, for example, after forming an uncured or partially cured layer of the coating composition (B), the coating composition is heated at a heat softening temperature of the substrate for about 5 minutes, and then subjected to bending. afterwards,
The coating composition (B) is left at a temperature at which an uncured product or a partially cured product is cured, or at room temperature, or is cured by exposing it to the vapor of a curing catalyst solution of the coating composition (B). A bent molded article can be obtained. According to such a method, a hard silica layer is formed after bending before the coating composition (B) is sufficiently cured, so that a problem such as a crack does not occur in the silica layer.

In the present invention, various transparent synthetic resins can be used as the material of the transparent synthetic resin substrate. For example, a transparent synthetic resin such as an aromatic polycarbonate resin, a polymethyl methacrylate resin (acrylic resin), a polystyrene resin, an aromatic polyester resin, or a polyimide resin can be used. Further, in order to perform the above-described thermal bending, it is preferable that these transparent synthetic resins are thermoplastic resins. More preferred transparent synthetic resins are thermoplastic aromatic polycarbonate resins, polymethyl methacrylate resins (acrylic resins), and polystyrene resins.

In particular, as the material of the substrate in the present invention,
Aromatic polycarbonate resins are preferred. This transparent synthetic resin substrate is a molded one, for example, a sheet-like substrate such as a flat plate or a corrugated sheet, a film-like substrate, a substrate molded into various shapes, and at least a surface layer made of various transparent synthetic resins. There is a laminate and the like. In the present invention, the substrate is particularly preferably a flat sheet or film made of an aromatic polycarbonate resin. At least two transparent cured material layers as described above are formed on both surfaces or one surface of the sheet or film. In addition, it is preferable that the thickness of the sheet as the base material is 1 to 100 mm for uses such as window materials.

[0139]

The present invention will be described below with reference to Synthesis Examples (Examples 1 to 3), Examples (Examples 4 to 12), and Comparative Examples (Examples 13 to 16), but the present invention is not limited thereto. Measurements and evaluations of various physical properties of Examples 4 to 16 were performed by the following methods, and the results are shown in Table 1. Table 1 also shows the results of measurement and evaluation of similar physical properties using glass (ordinary inorganic glass sheet for construction).

[Contact Angle] The contact angle of the outermost layer surface with water was measured. [Initial haze value, abrasion resistance] According to the abrasion resistance test method according to JIS-R3212, a haze meter was measured with a haze meter when a 500 g weight was combined with each of two CS-10F abrasion wheels and rotated 1000 times. The haze was measured at four points of the wear cycle orbit, and the average value was calculated. The initial haze value indicates the value (%) of the haze value before the abrasion test, and the abrasion resistance indicates the value (%) of (haze value after the abrasion test)-(haze value before the abrasion test).

[Adhesion] The sample is cut into eleven vertical and horizontal lines at 1 mm intervals with a razor blade to make 100 grids. Then, when a commercially available cellophane tape is closely adhered and then rapidly peeled in the forward direction by 90 degrees, the number (m) of the grids remaining without peeling off the coating is represented by m / 100. [Weather resistance] Using a sunshine weather meter, the appearance was evaluated after exposure for 3000 hours in a cycle of 12 minutes of rainfall and 48 minutes of drying at a black panel temperature of 63 ° C.

[Example 1] 200c equipped with a stirrer and a thermometer
The four-necked flask (c) was sufficiently purged with nitrogen to obtain 100 g of oily hydrosilicone represented by the following formula [IX].
I put it.

[0143]

Embedded image (CH ₃ ) ₃ SiO. [SiH (CH ₃ ) O] _20. [Si (CH ₃ ) ₂ O] ₃₀ .Si (CH ₃ ) ₃ [IX]

After the temperature was raised to 90 ° C., CF ₃ (CF
₂ ) A solution of chloroplatinic acid dissolved in 230.8 g of ₇ CH ₂ CH = CH ₂ so as to be 2 ppm as platinum,
The solution was dropped from a dropping funnel. With the progress of the reaction, an increase in the internal temperature of about 10 ° C. was observed. After stirring for 1 hour, 10.0 g of CH ₂ ＣＨCHSi (OCH ₃ ) ₃ was further added dropwise. After confirming the disappearance of H-Si by IR spectrum, 4
After time the reaction was stopped. After adding 0.5 g of activated carbon and stirring at room temperature for 1 hour, the mixture was filtered to obtain a clear oil. The obtained product was analyzed by NMR and IR. As a result, it was confirmed that the product had a structure represented by the formula [X].

[0145]

Embedded image (CH ₃ ) ₃ SiO · ｛Si [(CH ₂ ) ₃ (CF ₂ ) ₇ CF ₃ ] (CH ₃ ) O｝ ₁₆ · ｛Si [(CH ₂ ) ₂ Si (OCH ₃ ) ₃ ] (CH ₃ ) O｝ _4. [Si (CH ₃ ) ₂ O] ₃₀ .Si (CH ₃ ) ₃ [X]

The identification data of the formula [X] is as follows. IR; peak of H-Si existing before the reaction (215
0 cm ^-1 ) disappeared. ¹ H NMR (CDCl ₃ , TMS) δ (ppm);
_{43~0.51 (m, Si-CH 2} -C-C-CF 2
−), 1.52 (tt, Si—C—CH ₂ —C—CF ₂
−), 2.19 to 2.46 (m, Si—C—C—CH ₂
—CF ₂ —) ¹⁹ FNMR (CDCl ₃ , CFCl ₃ ) δ (ppm);
−81.7 (CF ₃ ), −115.1 (CF ₂ CF
_{3), - 126.9 (CH 2} CF 2), - 122.5~
-124.1 (CF _2).

Example 2 In Example 1, CH ₂ ＣＨCHSi
By the same procedure except that (OCH ₃ ) ₃ was not added, a fluorosilicone compound in which Si—H remained as shown by the following formula [XI] was obtained.

[0148]

Embedded image (CH_Three )_Three SiO ・ ｛Si [(CH_Two )_Three (CF_Two )₇ CF_Three ] (CH_Three ) O｝₁₆・ [SiH (CH_Three ) O]_Four ・ [Si (CH_Three )_Two O]₃₀・ Si (CH_Three ) _Three [XI]

[Example 3] Ethyl cellosolve-dispersed colloidal silica (silica content: 30% by weight, average particle size: 11 nm)
5 parts by weight of 3-mercaptopropyltrimethoxysilane and 3.0 parts by weight of 0.1N hydrochloric acid were added to 100 parts by weight, and 10 parts by weight were added.
After heating and stirring at 0 ° C. for 6 hours, the mixture was aged at room temperature for 12 hours to obtain a mercaptosilane-modified colloidal silica dispersion.

[Example 4] 1 equipped with a stirrer and a cooling pipe
In a 00 mL four-necked flask, add isopropanol 15
g, butyl acetate 15 g, ethyl cellosolve 7.5 g,
2,4,6-trimethylbenzoyldiphenylphosphine oxide 150 mg, 2- (3,5-di-t-pentyl-2-hydroxyphenyl) benzotriazole 10
00 mg, and N-methyl-4-methacryloyloxy-2,2,6,6-tetramethylpiperidine 200 m
g of urethane acrylate (containing an average of 15 acryloyl groups per molecule) which is a reaction product of hydroxyl-containing dipentaerythritol polyacrylate and partially nullated hexamethylene diisocyanate. For 1 hour to obtain a coating composition (hereinafter referred to as coating liquid 1).

This coating solution 1 was applied (wet thickness 30 μm) to one side of a transparent aromatic polycarbonate plate (150 mm × 300 mm) having a thickness of 3 mm using a bar coater, and dried in a hot air circulation oven at 80 ° C. Hold for minutes. This was put in an air atmosphere using a high-pressure mercury lamp at 3000 mJ /
Ultraviolet rays of cm ² (the integrated energy amount of ultraviolet rays in a wavelength range of 300 to 390 nm, the same applies hereinafter) were applied to form a transparent cured product layer having a thickness of 7 μm.

Next, a xylene solution of perhydropolysilazane (solid content: 10
Weight percent, trade name “L110” manufactured by Tonensha Co., Ltd.) and 0.5% of the fluorosilicone compound [X] prepared in Example 1 added to polysilazane (hereinafter referred to as “coating solution 2”). Is applied (wet thickness: 6 μm) and kept in a hot air circulating oven at 80 ° C. for 10 minutes to remove the solvent, and then kept in a hot air circulating oven at 100 ° C. for 120 minutes to form the outermost layer. Fully cured. And it was confirmed by IR analysis that the polysilazane in the outermost layer was silica. Thus, a transparent cured product layer having a total film thickness of 7.6 μm was formed on the aromatic polycarbonate plate. The measurement was performed using this sample.

[Example 5] The sample preparation method in Example 4 was changed as follows. After applying the coating liquid 1, the coating liquid was kept in a hot air circulating oven at 80 ° C. for 5 minutes, and irradiated with ultraviolet rays of 150 mJ / cm ² using a high-pressure mercury lamp in an air atmosphere to obtain a 7 μm-thick partially cured product. A layer was formed. Then, the coating liquid 2 was coated on the partially cured product layer using a bar coater (wet thickness: 6 μm), and was kept in a hot air circulating oven at 80 ° C. for 10 minutes to remove the solvent. Medium, 3000 mJ / cm using high pressure mercury lamp
Irradiation of ultraviolet light of ² . Finally, the sample was held in a hot-air circulating oven at 100 ° C. for 120 minutes, and the measurement was performed using the sample.

Example 6 The sample preparation method in Example 5 was changed as follows. Finally, instead of holding in a hot air circulating oven at 100 ° C. for 120 minutes, the sample was cured for one day in an environment of 23 ° C. and a relative humidity of 55%, and the measurement was performed using this sample.

[Example 7] The sample preparation method in Example 4 was changed as follows. After applying the coating liquid 1, the coating liquid 1 was kept in a hot air circulating oven at 80 ° C. for 5 minutes, and then the coating liquid 2 was coated thereon using a bar coater (wet thickness 6 μm).
m) and kept in a hot-air circulating oven at 80 ° C. for 10 minutes to remove the solvent, and then this was irradiated with ultraviolet rays of 3000 mJ / cm ^{2 in} an air atmosphere using a high-pressure mercury lamp. Finally, the sample is placed in a hot air circulating oven at 100 ° C. for 12 minutes.
After holding for 0 minutes, the measurement was performed using this sample.

[Example 8] The sample adjustment method in Example 6 was changed as follows. The coating liquid 2 was mixed with a catalyst-free xylene solution of perhydropolysilazane (solid content 10% by weight,
Si-H prepared in Example 2 instead of the fluorosilicone compound [X] having a hydrolyzable silicon group in the side chain prepared in Example 1
What changed to a fluorosilicone compound [XI] with a bond and added 0.5% to polysilazane
Coating liquid 3) and finally 23 ° C, relative humidity 5
Instead of curing in a 5% environment for one day, the sample was cured by holding it on a bath of a 3% by weight aqueous solution of triethylamine kept at 25 ° C. for 3 minutes, and the measurement was performed using this sample.

Example 9 1 equipped with a stirrer and a cooling pipe
In a 00 mL four-necked flask, add isopropanol 15
g, butyl acetate 15 g, 2,4,6-trimethylbenzoyldiphenylphosphine oxide 150 mg, 2-
1000 mg of (3,5-di-t-pentyl-2-hydroxyphenyl) benzotriazole and 200 mg of N-methyl-4-methacryloyloxy-2,2,6,6-tetramethylpiperidine were added and dissolved, followed by dissolution. 10.0 g of tris (2-acryloyloxyethyl) isocyanurate was added, and the mixture was stirred at room temperature for 1 hour. continue,
30.3 g of the mercaptosilane-modified colloidal silica dispersion prepared in Example 3 was added and further stirred at room temperature for 15 minutes to obtain a coating composition (hereinafter, referred to as coating liquid 4).

Next, this coating liquid 4 was applied to one side of a transparent aromatic polycarbonate plate (150 mm × 300 mm) having a thickness of 3 mm using a bar coater (wet thickness 30 μm).
m) and kept in a hot air circulating oven at 80 ° C. for 5 minutes. It is 150m in an air atmosphere using a high pressure mercury lamp.
Irradiation with ultraviolet rays of J / cm ² was performed to form a partially cured layer having a thickness of 7 μm. Then, a coating liquid 2 is applied on the partially cured product layer.
Was coated (wet thickness: 6 μm) using a bar coater, and kept in a hot air circulating oven at 80 ° C. for 10 minutes to remove the solvent. Then, it was exposed to ultraviolet light of 3000 mJ / cm ^{2 in} an air atmosphere using a high-pressure mercury lamp. Was irradiated. Finally, the sample was held in a hot-air circulating oven at 100 ° C. for 120 minutes, and the measurement was performed using the sample.

[Example 10] The sample preparation method in Example 9 was changed as follows. Lastly, instead of holding in a hot air circulating oven at 100 ° C. for 120 minutes, the sample was left for 1 day in an environment of 23 ° C. and a relative humidity of 55%, and the measurement was performed using this sample.

[Example 11] The sample preparation method in Example 6 was changed as follows. The coating liquid 2 was treated with a partially methylated polysilazane (polysilazane in which part of hydrogen atoms bonded to silicon atoms were substituted with methyl groups) in a xylene solution (solid content: 10% by weight, manufactured by Tonen Corporation, trade name: “NL71”).
0 ") and 0.5% of the fluorosilicone compound [X] prepared in Example 1 with respect to polysilazane (hereinafter referred to as coating liquid 5). Instead of leaving it for 1 day in an environment of 25%
The sample was cured by holding it on a bath of a 3% by weight aqueous solution of triethylamine kept for 3 minutes, and the measurement was performed using this sample.

[Example 12] The sample preparation method in Example 10 was changed as follows. The coating liquid 4 is coated on a transparent aromatic polycarbonate plate having a thickness of 3 mm (150 mm × 300 m).
m) Coating on one side using a bar coater (wet thickness 30)
μm) and kept in a hot air circulating oven at 80 ° C. for 5 minutes. This was placed in an air atmosphere using a high-pressure mercury lamp for 150
Irradiation with ultraviolet rays of mJ / cm ² was performed to form a partially cured layer having a thickness of 7 μm. Then, the coating liquid 2 is coated on the partially cured material layer using a bar coater (wet thickness: 6 μm), and is kept in a hot air circulating oven at 80 ° C. for 5 minutes to remove the solvent. Medium and high-pressure mercury lamps were used to irradiate ultraviolet rays of 3000 mJ / cm ² . Subsequently, it was kept in a hot air circulating oven at 170 ° C. for 5 minutes, and immediately after being taken out, it was pressed against a mold having a curvature of 64 mmR so that the coated surface became convex, and subjected to bending. As a result of observing the appearance of the cured product at room temperature for one day, it was found that the cured product layer had no cracks or wrinkles.

On the other hand, the sample finally obtained in Example 10 having two fully cured cured layers was held in a hot air circulating oven at 170 ° C. for 5 minutes, and immediately after being taken out, the coated surface of the transparent cured layer was coated. It was pressed against a mold having a curvature of 64 mmR so as to be on the convex side, and was subjected to bending. As a result of observing the appearance of the obtained sample, cracks and wrinkles were found in the cured product layer.

Example 13 Instead of the coating liquid 2 in Example 4, a low-temperature curable xylene solution of perhydropolysilazane (solid content: 10% by weight, manufactured by Tonen Co., Ltd., trade name "L11
0 ") and a sample having two cured product layers was produced using the same conditions and method as in Example 4. The measurement was performed using this sample.

[Example 14] Transparent aromatic polycarbonate plate (150 mm x 300 mm) having a thickness of 3 mm was prepared by applying coating liquid 1.
Using a bar coater on one side (wet thickness 20μ)
m) and kept in a hot air circulating oven at 80 ° C. for 5 minutes. This is 3,000 in an air atmosphere using a high-pressure mercury lamp.
The transparent cured product layer having a thickness of 6 μm was cured by irradiating ultraviolet rays of mJ / cm ² , and the measurement was performed using this sample.

[Example 15] A coating solution 2 was coated with a transparent aromatic polycarbonate plate having a thickness of 3 mm (150 mm x 300 mm).
On one side using a bar coater (wet thickness 10μ)
m) and kept in a hot air circulating oven at 80 ° C. for 10 minutes. Subsequently, it was kept in a hot air circulating oven at 100 ° C. for 120 minutes to cure a transparent cured product layer having a thickness of 6 μm, and the measurement was performed using this sample.

Example 16 Coating liquid 4 was coated with a transparent aromatic polycarbonate plate having a thickness of 3 mm (150 mm × 300 mm)
Using a bar coater on one side (wet thickness 20μ)
m) and kept in a hot air circulating oven at 80 ° C. for 5 minutes. This is 3,000 in an air atmosphere using a high-pressure mercury lamp.
The transparent cured material layer having a thickness of 5 μm was cured by irradiating ultraviolet rays of mJ / cm ² , and the measurement was performed using this sample.

[0167]

[Table 1]

[0168]

According to the present invention, a cured product of a coating composition (B) containing a fluorosilicone compound and a curable compound (b) and an inner layer composed of a cured product of the coating composition (A) on the surface of a substrate is provided. The transparent coating having high scratch resistance derived from the two-layered transparent cured product layer and high water repellency derived from the fluorosilicone compound is formed by forming the transparent cured product layer composed of the two outermost layers. A molded article can be obtained.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takashi Shibuya 1150 Hazawa-cho, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture Inside Asahi Glass Co., Ltd. (72) Inventor Hiroshi Yamamoto 1150 Hazawa-cho, Kanagawa-ku, Yokohama-shi, Kanagawa Asahi Glass Co., Ltd.

Claims (5)

[Claims] 1. A transparent coated molded article having a transparent synthetic resin substrate and at least two transparent cured product layers formed on at least a part of the surface of the substrate, wherein an outermost layer of the transparent cured product layers is provided. Is a cured layer of the active energy ray-curable coating composition (A) containing a polyfunctional compound having two or more active energy ray-curable polymerizable functional groups, and the outermost layer is , A cured layer of a coating composition (B) containing a curable compound (b) forming silica and a fluorosilicone compound containing an organosiloxane unit having a fluorine-containing organic group bonded to a silicon atom. Transparent coated molded products. 2. The coating composition (A) further comprises a colloidal silica having an average particle size of 200 nm or less.
The transparent coated molded article according to the above. 3. The transparent coated molded article according to claim 1, wherein the fluorosilicone compound is a compound represented by the following general formula [I]. Embedded image R ¹¹ —Si (R ¹⁰ ) ₂ O · [Si (R ¹⁰ ) ₂ O] _k · [Si (A ¹ ) (R ¹⁰ ) O] _m · [Si (A ² ) (R ¹⁰ ) O] _n · Si (R ¹⁰ ) ₂ —R ¹² [I] In the formula [I], A ^{1 is a} hydrogen atom, a hydroxyl group, a monovalent hydrolyzable group or a monovalent group represented by the following formula [II]. A represents an organic group, and when k is 2 or more, each A ¹ may be different. A ² represents a monovalent fluorine-containing organic group represented by the following formula [III]. R ¹⁰ : represents a monovalent hydrocarbon group, and each R ¹⁰ may be the same or different. R ¹¹ and R ¹² each independently represent R ¹⁰ , A ¹ or A ² . k represents an integer of 0 or more, m represents an integer of 0 or more, and n represents an integer of 1 or more. However, in the formula [II], R represents a monovalent hydrocarbon group, a represents an integer of 2 or more, and b represents 0, 1 or 2. In the formula [III], Y may be a divalent hydrocarbon group in which an etheric oxygen atom may be inserted between carbon-carbon bonds, and R ^f may contain an etheric oxygen atom. Represents a certain monovalent polyfluorohydrocarbon group. -(CH ₂ ) _a -Si (R) _b Z _3-b [II] -Y-R ^f [III] 4. The transparent coated molded article according to claim 1, wherein said curable compound (b) is polysilazane. 5. A method for producing a bent transparent coated molded article having a transparent synthetic resin substrate and at least two transparent cured layers formed on at least a part of the surface of the substrate. An active energy ray-curable coating composition (A) containing a polyfunctional compound having two or more active energy ray-curable polymerizable functional groups on at least a part of the surface of the substrate. A layer of an uncured, partially cured or cured product of the coating composition (A), and a curable compound (b) forming silica and a fluorine-containing organic group formed on the surface of this layer by a silicon atom A coating composition (B) containing a fluorosilicone compound containing an organosiloxane unit bonded to a coating composition, and then coating the base material having the coating composition (A) and a layer of the coating composition (B). Bend, and then Curing is performed by curing the composition (B) and, if the uncured or partially cured product of the coating composition (A) is present, curing the uncured or partially cured product. For producing transparent coated molded articles.