JPH11309805A - Transparent coated molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a transparent coated molding, wherein a curable substance layer developing extremely high weatherability is formed on a transparent synthetic resin base. SOLUTION: An inner layer, which is composed of a curable substance formed from an active energy beam-curable coated composition containing an ultraviolet light absorber, and an outermost layer, which is composed of a silica derived from a polysilazane and contacted with the inner layer, are formed on a transparent synthetic resin base. The outermost layer is a silica coating, which is not directly laminated on the comparatively soft transparent synthetic resin base, but is laminated on the inner layer, wherein adhesion and wear resistance are improved by adding a multifunctional compound, thereby, a transparent coated molding having surface characteristics higher than those imparted by ordinary inorganic coating can be obtained. The inner layer contacting with the outermost layer contains the ultraviolet light absorber, thereby the transparent coated molding, wherein weatherability is considerably improved, can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a cured product layer derived from an active energy ray-curable coating composition containing an ultraviolet absorber on a transparent synthetic resin substrate, and a coating material capable of forming silica. The present invention relates to a transparent coated molded article having at least two silica layers.

[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 hardness of the surface is not sufficient to be used as a substitute for glass, and the surface is apt to be damaged and easily worn, 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 an active energy ray such as heat or ultraviolet light, and to obtain scratch resistance. There is a method of obtaining a molded article having a transparent cured product layer having excellent properties. According to this method, the composition for coating is relatively stable, and particularly excellent in productivity because it can be cured by ultraviolet rays. Even when a molded product is subjected to bending, cracks do not occur in the cured coating and the surface has scratch resistance. 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 layer 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.

A method of forming a protective film on a plastic film and applying a polysilazane solution to the surface to form a silica surface layer has also been proposed (JP-A-9-39).
161). The protective coating is provided to prevent the plastic film from being attacked by the solvent of the polysilazane solution. Further, a method has been proposed 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 (Japanese Patent Application Laid-Open No. 6-212004). However, these also have insufficient weather resistance depending on the composition, and further improvement is required.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and has as its object to improve the weather resistance among the surface characteristics such as abrasion resistance, abrasion resistance and weather resistance. An object of the present invention is to provide a transparent coated molded article having excellent properties.

[0009]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, the surface characteristics of a silica layer formed of polysilazane, a thermosetting silicone resin, etc., have been changed so that the inner layer in contact with the silica layer has The inventors have found that the material has an influence on the material, and found that the addition of an ultraviolet absorber to the inner layer improves the weather resistance, thereby completing the present invention.

That is, the transparent coated molded article of the present invention comprises a transparent synthetic resin substrate and two or more transparent cured product layers formed on at least a part of the surface of the transparent synthetic resin substrate. Wherein the inner layer in contact with the outermost layer of the transparent cured material layer contains a polyfunctional compound (a1) having two or more active energy ray-curable polymerizable functional groups and an ultraviolet absorber (a2). It is a first cured product layer of the product (A), and the outermost layer is a second cured product layer of the coating material (B) capable of forming silica.

According to the present invention, the transparent cured product layer is composed of two or more layers, and the outermost layer, which is a silica coating, is not directly laminated on a relatively soft transparent synthetic resin base material, but is formed by multi-layering. Since the coating composition (A) containing the functional compound (a1) is laminated on the inner layer having high adhesion and abrasion resistance, which is the first transparent cured product layer of the coating composition (A), the transparent coating molded article is damaged. By reducing the displacement of the outermost layer due to the external force applied as described above, surface characteristics higher than those provided by a normal inorganic coating can be obtained.

Further, by adding an ultraviolet absorber to the coating composition (A), not only the coloring and the deterioration of the substrate itself can be reduced, but also the occurrence of cracks due to the deterioration of the transparent cured material layer itself and the like can be prevented. Is also significantly suppressed. By adding an ultraviolet absorber to the lower layer and reducing the amount of transmitted ultraviolet light, the chemical bond formed near the interface between the outermost layer and the lower layer and the covalent bond formed between the layers are stabilized, and as a result, The lowering of the interlayer adhesion of the lower layer is suppressed, and the occurrence of cracks and the like is suppressed.

In the present invention, the coating composition (A)
Preferably contain colloidal silica having an average particle size of 200 nm or less. Thereby, a cured product having higher wear resistance and hardness can be formed. Further, the coating agent (B) preferably contains polysilazane. Since polysilazane forms denser silica, an outermost layer having more excellent surface properties can be obtained.

Further, after the uncured material layer or the partially cured material layer of the coating agent (B) is formed on the transparent synthetic resin substrate, and the uncured material layer or the partially cured material layer is cured. A transparent coated molded product that has been previously bent can be used as a transparent member in more fields. It is necessary that the coating agent (B) is not completely cured at the stage of the bending process, and the layer in contact with the coating agent (B) may be any of the uncured, partially cured, or cured product of the coating composition (A). It may consist of.

[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 inner layer in contact with the outermost layer of the transparent hardened material layer has a high adhesion to the outermost layer when the hardened material layer of the active energy ray-curable coating composition (A) is used. 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. Also the third
Examples of the 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 (a1) is used as the active energy ray-curable coating composition (A). Similarly, in order to form a cured product having high abrasion resistance, it is also preferable to mix colloidal silica having an average particle diameter of 200 nm or less with the coating composition (A) to form a cured product containing colloidal silica. . In order to efficiently cure the polyfunctional compound (a1) with active energy rays (especially ultraviolet rays), a photopolymerization initiator is usually added to the coating composition (A).

The polyfunctional compound (a1) having two or more active energy ray-curable polymerizable functional groups in the coating composition (A) may be one kind of polyfunctional compound.
Further, a plurality of types of compounds may be used. If more than one,
The compounds 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 may be used, or one of which may be acrylic urethane and the other may be an acrylic ester compound having no urethane bond.

The active energy ray-curable polymerizable functional group in the polyfunctional compound (a1) is preferably a polymerizable unsaturated group such as a (meth) acryloyl group, a vinyl group or an allyl group, or a group having the same. More preferably, it is a (meth) acryloyl group. That is, as the polyfunctional compound, a compound having two or more polymerizable functional groups selected from an acryloyl group and a methacryloyl group is preferable, and among them, a compound having two or more acryloyl groups which are more easily polymerized by ultraviolet rays. Is more preferable. Further, polyfunctionality means having two or more polymerizable functional groups, and a monofunctional compound described later means a compound having one polymerizable functional group.

The polyfunctional compound (a1) may be a compound having a total of two or more polymerizable functional groups in one molecule, or a compound having two or more polymerizable functional groups in total. May be a compound having the same. Polyfunctional compound (a
1) The number of polymerizable functional groups in one molecule is 2 or more, and the upper limit is not particularly limited, but is preferably 2 to 50, and more preferably 3 to 30.

In the present specification, an acryloyl group and a methacryloyl group are collectively referred to as a (meth) acryloyl group. The same applies to expressions such as (meth) acryloyloxy group, (meth) acrylic acid, and (meth) acrylate. 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.

Preferred compounds as the polyfunctional compound (a1) 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 kinds of polyfunctional compounds may be contained as the polyfunctional compound (a1). Further, together with the polyfunctional compound, a monofunctional compound having one polymerizable functional group that can be 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 (a1) and the monofunctional compound is not particularly limited, 0-60% by weight is preferred,
0-30% 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 (a1) may be a compound having various functional groups or bonds other than the polymerizable functional group. For example, it may have a hydroxyl group, a carboxyl group, a halogen atom, a urethane bond, an ether bond, an ester bond, a thioether bond, an amide bond, a diorganosiloxane bond, and 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. (1) A reaction product of a compound (X1) having a (meth) acryloyl group and a hydroxyl group and a compound having two or more isocyanate groups (hereinafter, referred to as polyisocyanate). (2) A reaction product of the compound (X1), the compound (X2) having two or more hydroxyl groups, and a polyisocyanate. (3) A reaction product of the compound (X3) having a (meth) acryloyl group and an isocyanate and the compound (X2).

In these reaction products, it is preferable that no isocyanate group is present, but a hydroxyl group 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 (X1) 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.

Specific examples include, in the above order, 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol di (meth) acrylate, and the like. 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 (X1) 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. Examples of the polyepoxide include a glycidyl ether type polyepoxide and an alicyclic type polyepoxide. Specifically, there is a glycidyl ether type polyepoxide having two or more glycidyl ether groups such as polyglycidyl ether of polyhydric phenols (for example, bisphenol A diglycidyl ether). Preferably, a polyepoxide commercially available as an epoxy resin is used. 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 (X1). 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, trans-cyclohexane-1,4-diisocyanate, xylylene diisocyanate [XDI] , Hydrogenated X
DI, 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 (X2) having two or more hydroxyl groups
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.

The polyhydric alcohol having an aromatic nucleus includes
Examples thereof 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. Examples of the high molecular weight polyol include a polyether polyol, a polyester polyol, a polyether ester polyol, and a polycarbonate polyol. 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, 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 (X3) having a (meth) acryloyl group and an isocyanate 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 (a1), a compound having two or more hydroxyl groups similar to the compound (X2) and a (meth) acrylic acid Are preferred. As a compound having two or more hydroxyl groups,
The above-mentioned polyhydric alcohols and polyols are preferred. (Meth) acrylic acid ester compounds which are reaction products of a compound having two or more epoxy groups with (meth) acrylic acid are also preferred. As the compound having two or more epoxy groups, there is a polyepoxide called an epoxy resin as described above.

Specific examples of the polyfunctional compound containing no urethane bond include the following compounds. (1) 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.

(2) (meth) acrylates of polyhydric alcohols and polyphenols having the following aromatic nuclei or triazine rings: 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, tris (2- (meth) acryloyloxyethyl) Isocyanurate, bisphenol A dimethacrylate.

(3) 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 (a1), 30% by weight or more of the polyfunctional compound (a1) is 3% because the cured product of the coating composition (A) can exhibit sufficient abrasion resistance. It is preferably composed of a polyfunctional compound having a functionality of at least 50.
More preferably, the weight% or more is composed of a trifunctional or more polyfunctional compound. Further, preferred specific examples of the polyfunctional compound (a1) 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-based poly (meth) acrylate and isocyanurate-based poly (meth) acrylate are preferable.

The above pentaerythritol-based poly (meth)
The acrylate refers to a polyester of pentaerythritol or polypentaerythritol with (meth) acrylic acid (preferably having a functionality of 4 to 20).

The above-mentioned 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 thereof and (meth) acrylic acid. Polyester with acid (2- or 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 30% by weight or more, and particularly preferably 50% by weight or more, based on all the polyfunctional compounds (a1).

As the monofunctional compound that can be used together with the polyfunctional compound (a1), 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) acrylic acid ester, that is, (meth) acrylate.

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 size of 200 nm or less in order to increase the abrasion resistance and hardness of the first transparent cured product layer directly in contact with the outermost layer. The average particle size of the colloidal silica is 1 to 10
It is preferably 0 nm, particularly preferably 1 to 50 nm. Further, the colloidal silica is preferably the following surface-modified colloidal silica from the viewpoint of improving the dispersion stability of the colloidal silica and the adhesion between the colloidal silica and the polyfunctional compound.

When such colloidal silica is used, the amount of the colloidal silica is determined by the amount of the curable component (a polyfunctional compound and a monofunctional polyfunctional compound) of the transparent cured material layer in order to sufficiently exhibit the effect of the use. The total amount is preferably 5 to 300 parts by weight, more preferably 10 to 250 parts by weight, even more preferably 10 to 50 parts by weight, per 100 parts by weight of the compound.
If the amount of the colloidal silica is less than 5 parts by weight, it is difficult to obtain sufficient wear resistance. Further, when the amount of colloidal silica is 30
If the amount is more than 0 parts by weight, the coating is liable to be clouded (haze), and when the obtained transparent coated molded article is subjected to secondary processing such as hot bending described later, cracks are easily generated. Problem easily occurs.

As the colloidal silica, a surface-unmodified colloidal silica can be used, but a surface-modified colloidal silica is preferably used. 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 first 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, a usual 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, 2-methylpropanol, 4-hydroxy-4-methyl-2-pentanone and ethylene glycol. Cellosolves such as methyl cellosolve, 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. (1) (meth) acryloyloxy group-containing silanes: 3
-(Meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane and the like.

(2) Amino group-containing silanes: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrisilane Methoxysilane, N- (2-aminoethyl) -3
-Aminopropylmethyldimethoxysilane, N- (2-
Aminoethyl) -3-aminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, N-
(N-vinylbenzyl-2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-anilinopropyltrimethoxysilane and the like.

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

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

(5) Isocyanate group-containing silanes: 3
-Isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropylmethyldiethoxysilane and the like.

The above two types of modifiers having a reactive functional group 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 (a1), 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 first transparent cured product layer.

Examples of the photopolymerization initiator include arylketone photopolymerization initiators (eg, acetophenones, benzophenones, alkylaminobenzophenones, benzyls, benzoins, benzoin ethers, benzyldimethyl ketals, benzoyl benzoates, 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, -(4- (2-hydroxyethoxy) phenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 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 0.01 to 2 parts by weight per 100 parts by weight of the curable component (the total of the polyfunctional compound (a1) and the monofunctional compound).
0 parts by weight is preferable, and 0.1 to 10 parts by weight is particularly preferable.

The coating composition (A) may contain various additives in addition to the above basic components. As a coating liquid for forming a layer of the coating composition (A), a solvent is usually an essential component, and a 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 the polyfunctional compound (a1) 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. 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 coating solution, the desired thickness of the cured film, the drying temperature conditions, etc., and is 100 times or less the weight of the curable component in the coating solution. Is preferred, and the weight is more preferably 0.1 to 50 times.
After coating the coating liquid, the solvent is removed by heating or the like (usually called drying) to form a layer of the coating composition (A). 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 with an aromatic polycarbonate resin having low solvent resistance, lower alcohols, cellosolves, esters, mixtures thereof and the like are suitable.

The coating composition (A) comprises an ultraviolet absorbent (a
2) is contained as an essential component. UV absorber (a2)
Plays a role in suppressing coloring and deterioration of the base material itself due to ultraviolet rays, and also plays an important role in preventing the polymer chains in the coating composition from being cut by ultraviolet rays. In particular, in the present invention, the addition of the ultraviolet absorber (a2) is effective for preventing the chemical bond near the interface between the outermost layer and the lower layer and the deterioration of the covalent bond formed between the outermost layer and the lower layer. Adhesion is secured, and the occurrence of weather-resistant cracks and the like is significantly suppressed.

In the present invention, the ultraviolet absorber (a2) is not particularly limited as long as there is no problem in solubility in the composition, and various ultraviolet absorbers can be used. In addition, two or more ultraviolet absorbers can be used in combination. As the ultraviolet absorber (a2), a known ultraviolet absorber such as a commercially available one can be used. Examples of such an ultraviolet absorber include a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a salicylic acid-based ultraviolet absorber, and a phenyltriazine-based ultraviolet absorber. Specific compounds include, for example, the following compounds.

Octyl 3- {3- (2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenyl} propionate, 2- (3,5-di-t-
Pentyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-
t-butylphenyl) benzotriazole, 2- (2-
Hydroxy-3-tert-butyl-5-methylphenyl)-
5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) -5-chlorobenzotriazole, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone,
2,2'-dihydroxy-4-methoxybenzophenone, pt-butylphenyl salicylate.

The amount of the ultraviolet absorber (a2) in the coating composition (A) depends on the amount of the curable component (the polyfunctional compound (a1)).
And a monofunctional compound) in an amount of 0.
The amount is preferably from 0.1 to 50 parts by weight, particularly preferably from 0.1 to 20 parts by weight.

The coating composition (A) may contain, if necessary, stabilizers such as a light stabilizer, an antioxidant and a thermal polymerization inhibitor, a leveling agent, an antifoaming agent, a thickener, an antisettling agent, and a pigment. A surfactant such as a dispersant, an antistatic agent and an antifogging agent, and a curing catalyst selected from acids, alkalis and salts may be appropriately blended and used.

As the active energy ray for curing the coating composition (A), ultraviolet rays are particularly preferable. 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. 50 μm thick
If it is more than that, the curing by the active energy ray becomes insufficient, and the adhesion to the base material is easily deteriorated, which is not preferable. 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 coating agent (B) for forming a silica layer on the second transparent cured material layer, which is the outermost layer, is a coating agent containing a compound capable of forming silica. It may be. Preferred is a coating composition containing a compound capable of forming silica, a catalyst, a curing agent and the like. Further, in order to form a coating film of the coating agent (B), a coating liquid containing a compound capable of forming silica and a solvent capable of dissolving the same is usually used.

As the compound forming silica, 3-4
Functional hydrolyzable silane compounds and partial hydrolyzed condensates thereof, silicone-based thermosetting compounds, polysilazanes, and the like are available. Examples of the tetrafunctional hydrolyzable silane compound and its partially hydrolyzed condensate include tetraalkoxysilane and its partially hydrolyzed condensate, and as the trifunctional hydrolyzable silane compound and its partially hydrolyzed condensate, Are, for example, organotrialkoxysilanes and partially hydrolyzed condensates thereof. In addition, 3-4 functionality in this hydrolysable silane compound means that the number of hydrolysable groups couple | bonded with the silicon atom is 3-4. However, polysilazane is preferably used. Since polysilazane forms silica having a more dense structure, an outermost layer having more excellent surface characteristics 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 preferred from the viewpoint of low firing temperature and denseness of a cured film after firing. In addition, a cured product in which polysilazane is sufficiently cured becomes silica containing almost no nitrogen atoms.

The polysilazane is composed of a polymer having a chain, cyclic or crosslinked structure, or a mixture of these structures in the molecule. The molecular weight of polysilazane is preferably from 200 to 50,000 in number average molecular weight. 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 is not preferable because it becomes difficult to dissolve in a solvent and the coating agent (B) may become viscous.

Usually, a solvent capable of dissolving polysilazane is used as a coating solution for forming a layer of polysilazane or a coating composition containing polysilazane. As the solvent, aliphatic hydrocarbons, alicyclic hydrocarbons, hydrocarbon solvents such as aromatic hydrocarbons, halogenated hydrocarbon solvents, aliphatic ethers, ethers such as alicyclic ethers can be used,
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 chloride, bromoform,
Halogenated hydrocarbons such as 1,2-dichloroethane, 1,1-dichloroethane, trichloroethane, and tetrachloroethane; ethers such as ethyl ether, isopropyl ether, ethyl butyl ether, butyl ether, dioxane, dimethyldioxane, 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 prepare within the range.

In order to cure 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 set to 180 ° C. or lower when a synthetic resin such as an aromatic polycarbonate resin is used as a base material.

For curing polysilazane at a low temperature, a catalyst is used, and curing can be performed at room temperature depending on the type and amount of the catalyst. As the atmosphere for curing, an atmosphere in which oxygen is present, such as air, is preferable.

As the catalyst, it is preferable to use a catalyst which cures polysilazane at a lower temperature. Examples of such a catalyst include fine particles of a metal such as gold, silver, palladium, platinum and nickel proposed in JP-A-7-196886, and a carboxylic acid of the above metal proposed in JP-A-5-93275. Use of complexes. Further, instead of adding the catalyst to the polysilazane solution, as proposed in JP-A-9-31333, a catalyst solution,
Specifically, there is a method of directly contacting the coated molded article with an amine aqueous solution or the like, or exposing the coated molded article to the vapor for a certain time.

The coating agent (B) may contain, if necessary, stabilizers such as an ultraviolet absorber, a light stabilizer, an antioxidant, a leveling agent, an antifoaming agent, a thickener, an anti-settling agent, and a pigment. Surfactants such as a dispersant, an antistatic agent and an antifogging agent may be appropriately blended and used.

In the following, polysilazane means perhydropolysilazane unless otherwise specified. The perhydropolysilazane and the acrylic monomer were mixed and cured by irradiation with active energy rays in the presence of a photoinitiator, and the cured product was analyzed by solid-state NMR of silicon and carbon.
It has been confirmed by the present inventors that a peak derived from the binding of is observed. For this reason, it is considered that the interface between the coating composition (A) and the coating agent (B) in the present invention is bonded not only by physical mixing of both layers but also by a covalent bond.

The thickness of the second transparent cured product layer formed using the coating agent (B) is preferably from 0.05 to 10 μm, more preferably from 0.1 to 3 μm. If the thickness is more than 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 likely to occur in this layer even by slight deformation of the coated molded product. If the thickness is less than 0.05 μm, the outermost layer may not be able to sufficiently exhibit abrasion resistance and abrasion resistance.

In the present invention, as a method of forming two transparent cured material layers formed by using the above two kinds of coating composition (A) and coating agent (B), a usual coating method is used. Can be adopted. For example, first, a coating composition (A) is applied and cured on a base material, and then a coating agent (B) is applied and cured on the surface of the cured product to obtain a desired transparent coated molded article. Is 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 agent (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 agent (B).

Curing of the coating composition (A) and the coating agent (B)
The following four methods can be cited as combinations (timing) from coating to curing of the composition. (1) 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 coating agent (B) thereon (as described above). Method).

(2) After coating the coating composition (A) to form an uncured material layer of the coating composition (A), the coating agent (B) is applied on the uncured material layer. To form an uncured material layer of the coating agent (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 agent (B) cures 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 coated. The composition is cured by exposing it to the vapor of the curing catalyst solution of the agent (B).

(3) The minimum active energy ray (usually about 30) which becomes dry to the touch after coating the coating composition (A).
Irradiation amount up to 0 mJ / cm ² ) to form a partially cured product layer of the coating composition (A), and then coat the coating material (B) on the partially cured product layer to form a coating material ( A method in which the uncured material of the coating composition (A) is terminated by irradiating an active energy ray in an amount sufficient to completely cure the uncured material layer of B). The curing of the uncured material of the coating agent (B) is the same as in the above (2).

(4) As described in (2) and (3) above, the uncured or partially hardened layer of the coating composition (A) and the coating agent (B)
After the uncured material layer is formed, the uncured material of the coating agent (B) is first partially cured or completely cured, and then the uncured or partially cured material of the coating composition (A) is completely cured. How to let. In this case, the coating composition (A) is preferably a partially cured product rather than an uncured product when the uncured product of the coating agent (B) is cured.

In order to increase the adhesion between the two cured product layers, the above method (2) or (3) is more preferable.
However, in the case of the method (2), when the dip method is used as a method of applying the coating agent (B), the coating composition (A)
There is a possibility that the uncured material component may contaminate the dip solution of the coating agent (B), so that there is a restriction that coating by such a dipping method is not suitable. In the method (4), the partially cured product or the completely cured product layer of the coating agent (B) is exposed to oxygen which is likely to be a curing inhibition factor when the coating composition (A) is completely cured. It 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 product of the present invention, the surface properties such as abrasion resistance and scratch resistance are almost at the same level as those of glass, so that it can be used in various applications where glass has been conventionally used. 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 product so as 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 a conventional study 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 agent (B) is formed, the cured product is hard, so that bending is difficult.

The present inventor has found that a substrate having the first transparent cured product layer of the coating composition (A) can be bent as long as the layer is an uncured or partially cured product of the coating agent (B). Was. Further, as in the methods (2) to (4), the uncured material and the partially cured material layer of the coating agent (B) are formed on the uncured material and the partially cured material layer of the coating composition (A). Bending can also be performed in the formed state. By curing the uncured or partially cured product of the coating agent (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 material of the coating agent (B) is cured by heating for bending,
Usually, the time required for curing the uncured or partially cured product of the coating agent (B) is longer than the time required for the bending process, so that the bending process becomes difficult due to the curing of the coating agent (B). It is few. Further, the curing of the coating agent (B) after bending is a condition advantageous for adopting the method (4).

Therefore, the layer of the uncured, partially cured or cured product of the coating composition (A) on the substrate and the uncured or partially cured product layer of the coating agent (B) are formed on the surface of the layer. After forming, bending and then curing the uncured or partially cured material of the coating agent (B) and the uncured or partially cured material of the coating composition (A), if any Thus, the bent coated article of the present invention can be produced.

Specifically, for example, after a layer of a partially cured product or a cured product of the coating agent (B) is formed, the coating is heated at a thermal softening temperature of the substrate for about 5 minutes, and then subjected to bending. Thereafter, the coating agent (B) is left at a temperature at which the uncured or 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 agent (B). A bent molded article can be obtained. According to such a method, a hard silica layer is formed after bending before the coating agent (B) is sufficiently cured, so that there is no problem such as cracks 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, or a polyarylate resin can be used, and a substrate made of an aromatic polycarbonate resin is particularly preferable. This transparent synthetic resin substrate is a molded one, for example, a sheet-like substrate such as a flat plate or a corrugated plate, a film-like substrate,
There are a base material formed into various shapes, a laminate having at least a surface layer made of various transparent synthetic resins, and the like. In particular, a flat base material that is not bent is preferable.

In the present invention, a flat sheet made of an aromatic polycarbonate resin is particularly preferred as the substrate. The thickness of this sheet is preferably 1 to 100 mm for applications such as window materials. At least two transparent cured material layers as described above are formed on both surfaces or one surface of the sheet.

[0116]

EXAMPLES The present invention will be described below with reference to Synthesis Examples (Examples 1 to 5), Examples (Examples 6 to 17), and Comparative Examples (Examples 18 to 22), but the present invention is not limited thereto. Examples 6 to 17,
The measurement and evaluation of various physical properties of Examples 19 to 22 were performed by the following methods, and the results are shown in Table 1. In addition,
Table 1 shows the results of measurement and evaluation of the physical properties of ordinary building glass sheets.

[Initial haze value, abrasion resistance] JIS-R321
According to the abrasion resistance test method described in No. 2, a haze meter was used to measure the haze value when 500 g weights were combined with each of the two CS-10F abrasion wheels and 500 and 1000 rotations were performed. Measurement of haze is based on the 4th cycle of the wear cycle.
The average was calculated at several locations. The initial haze value is the haze value (%) before the abrasion test, and the abrasion resistance is (haze value after the abrasion test).
-The value (%) of (the haze value before the abrasion test) is shown. In addition, the abrasion resistance test of the inner layer before forming the outermost layer is performed in the same manner as described above using a sample obtained by applying the curable coating composition (A) to the base material and sufficiently curing. The abrasion resistance was evaluated by measuring the pre-haze value and the haze value after 100 rotations.

[Adhesion] The sample is cut with eleven slits in the vertical and horizontal directions at intervals of 1 mm 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] The appearance was evaluated after exposure for 3000 hours at a black panel temperature of 63 ° C. in a cycle of rainfall of 12 minutes and drying of 48 minutes using a sunshine weather meter.

[Example 1] 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 2 Example 1 was repeated except that 5 parts by weight of γ-acryloyloxypropyltrimethoxysilane was used instead of 5 parts by weight of 3-mercaptopropyltrimethoxysilane.
In the same manner as described above, an acrylsilane-modified colloidal silica dispersion was obtained.

Example 3 An aminosilane-modified colloid was prepared in the same manner as in Example 1 except that 5 parts by weight of N-phenyl-3-aminopropyltrimethoxysilane was used instead of 5 parts by weight of 3-mercaptopropyltrimethoxysilane. A silica dispersion was obtained.

EXAMPLE 4 Epoxysilane-modified colloidal silica was prepared in the same manner as in Example 1 except that 5 parts by weight of 3-glycidoxypropyltrimethoxysilane was used instead of 5 parts by weight of 3-mercaptopropyltrimethoxysilane. A dispersion was obtained.

[Example 5] Instead of ethylcellosolve-dispersed colloidal silica, isopropanol-dispersed colloidal silica (silica content: 30% by weight, average particle size: 11 nm) 1
Example 1 except that the reaction temperature was 83 ° C. using 00 parts by weight.
In the same manner as described above, a mercaptosilane-modified colloidal silica dispersion was obtained.

Example 6 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-tert-pentyl-2-hydroxyphenyl) benzotriazole 50
0 mg, and 200 mg of N-methyl-4-methacryloyloxy-2,2,6,6-tetramethylpiperidine
And then dissolved, and 10.0 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, is added at room temperature. The mixture was stirred for 1 hour to obtain a coating composition (hereinafter, referred to as coating liquid 1).

This coating solution 1 was applied to a transparent aromatic polycarbonate resin plate (150 mm × 300 mm) having a thickness of 3 mm using a bar coater (wet thickness: 30 μm), and dried in a hot air circulating 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 (integrated ultraviolet energy in a wavelength range of 300 to 390 nm, hereinafter simply referred to as integrated energy) were irradiated to form a transparent cured product layer having a thickness of 7 μm.

Next, a xylene solution of perhydropolysilazane, which is curable at a low temperature (solid content: 10% by weight,
Tonen Co., Ltd., trade name "L110") (hereinafter referred to as coating liquid 2) was again 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. After the removal, the outermost layer was sufficiently cured by holding in a hot air circulating oven at 100 ° C. for 120 minutes. And it was confirmed by IR analysis that the outermost layer was a complete silica coating. Thus, a transparent cured product layer having a total film thickness of 7.6 μm was formed on the aromatic polycarbonate resin plate. The measurement was performed using this sample.

On the other hand, with respect to another sample of the aromatic polycarbonate resin plate having a transparent cured material layer sufficiently cured by using the above-mentioned coating liquid 1, the abrasion resistance of the surface of the transparent cured material layer was evaluated. 2.8% wear resistance after 100 revolutions
Met.

[Example 7] The sample preparation method in Example 6 was changed as follows. After the coating liquid 1 was applied, the coating liquid was kept in a hot air circulating oven at 80 ° C. for 5 minutes, and the accumulated energy was 150 mJ / c using a high-pressure mercury lamp in an air atmosphere.
Irradiation with ultraviolet rays of m ² was performed to form a partially cured layer having a thickness of 7 μm. Then, the coating liquid 2 was again 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. Ultraviolet rays having an integrated energy of 3000 mJ / cm ² were irradiated using a high-pressure mercury lamp. Finally, the sample is placed in a hot air circulating oven at 100 ° C. for 120 minutes.
After holding for a minute, the measurement was performed using this sample.

[Example 8] The sample preparation method in Example 7 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 9 The sample preparation method in Example 6 was changed as follows. After the coating solution 1 was coated, the coating solution 1 was kept in a hot air circulating oven at 80 ° C. for 5 minutes, and then the coating solution 2 was again coated thereon (wet thickness 6 μm) using a bar coater. After holding the solvent in a hot air circulating oven at 10 ° C. for 10 minutes to remove the solvent, this was irradiated with ultraviolet rays having an integrated energy of 3000 mJ / cm ^{2 in} an air atmosphere using a high-pressure mercury lamp. 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 8 was changed as follows. The coating liquid 2 is a catalyst-free perhydropolysilazane xylene solution (solid content 10% by weight, trade name “V110” manufactured by Tonen Corporation) (hereinafter referred to as coating liquid 3).
Finally, instead of leaving it in an environment of 23 ° C. and 55% relative humidity for 1 day, it is cured by keeping it on a bath of a 3% aqueous solution of triethylamine kept at 25 ° C. for 3 minutes, The measurement was performed using this sample.

Example 11 Isopropanol 15 was placed in a 100 mL four-necked flask equipped with a stirrer and a condenser.
g, butyl acetate 15 g, 2,4,6-trimethylbenzoyldiphenylphosphine oxide 150 mg, 2-
500 mg of (3,5-di-tert-pentyl-2-hydroxyphenyl) benzotriazole and 200 mg of N-methyl-4-methacryloyloxy-2,2,6,6-tetramethylpiperidine were added and dissolved, followed by tris 10.0 g of (2-acryloyloxyethyl) isocyanurate was added and stirred at room temperature for 1 hour. continue,
30.3 g of the mercaptosilane-modified colloidal silica dispersion synthesized in Example 1 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 3 was applied to a transparent aromatic polycarbonate resin 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. This was irradiated with ultraviolet rays having an integrated energy amount of 150 mJ / cm ² using a high-pressure mercury lamp in an air atmosphere.
m was formed. Then, the coating liquid 2 is again coated thereon by using a bar coater (wet thickness 6).
μm) 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 having an integrated energy of 3000 mJ / cm ^{2 in} an air atmosphere using a high-pressure mercury lamp. 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.

On the other hand, with respect to a sample of an aromatic polycarbonate resin plate on which a transparent cured product layer sufficiently cured by using the above coating liquid 4 was formed, the abrasion resistance of the surface of the transparent cured product layer was evaluated. The abrasion resistance after 100 rotations was 0.9%.

[Example 12] The sample preparation method in Example 11 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 13 This sample was used under the same conditions except that the modified colloidal silica dispersion used in Example 11 was changed to the same amount of the acrylsilane-modified colloidal silica dispersion synthesized in Example 2. The above measurement was carried out. In addition, the abrasion resistance after 100 rotations of the transparent cured material layer sufficiently cured using the coating liquid using the acrylic silane-modified colloidal silica dispersion was 1.1%.

Example 14 This sample was used under the same conditions except that the modified colloidal silica dispersion used in Example 11 was changed to the same amount of the aminosilane-modified colloidal silica dispersion synthesized in Example 3. The measurement was performed.
In addition, the abrasion resistance after 100 rotations of the transparent cured material layer sufficiently cured by using the coating liquid using the aminosilane-modified colloidal silica dispersion was 1.3%.

Example 15 This sample was used under the same conditions except that the modified colloidal silica dispersion used in Example 11 was changed to the same amount of the epoxysilane-modified colloidal silica dispersion synthesized in Example 4. The above measurement was carried out. The abrasion resistance after 100 rotations of the transparent cured product layer sufficiently cured using the coating liquid using the epoxysilane-modified colloidal silica dispersion was 1.2%.

[Example 16] Under the same conditions, except that the modified colloidal silica dispersion used in Example 11 was changed to the same amount of the isopropanol-dispersed mercaptosilane-modified colloidal silica dispersion synthesized in Example 5, The measurement was performed using a sample. In addition, the abrasion resistance after 100 rotations of the transparent cured material layer sufficiently cured by using the coating liquid using the mercaptosilane-modified colloidal silica dispersion was 1.4%.

[Example 17] The sample preparation method in Example 8 was changed as follows. The coating liquid 2 was prepared by dissolving a xylene solution of polysilazane in which hydrogen on silicon atoms was partially substituted with a methyl group (solid content: 10% by weight, manufactured by Tonen Co., Ltd., trade name “NL7
10 ") (hereinafter referred to as coating liquid 6) and finally 2
Instead of being left for 1 day in an environment of 3 ° C. and 55% relative humidity, the sample was cured by holding it on a bath of a 3% aqueous solution of triethylamine kept at 25 ° C. for 3 minutes, and the measurement was performed using this sample. went.

[Example 18] The sample preparation method in Example 11 was changed as follows. The coating liquid 4 is applied to a transparent aromatic polycarbonate resin plate (150 mm × 30 mm) having a thickness of 3 mm.
0 mm) using a bar coater (wet thickness 30)
μm) and kept in a hot air circulating oven at 80 ° C. for 5 minutes. This was irradiated with ultraviolet rays of 150 mJ / cm ^{2 in} an air atmosphere using a high-pressure mercury lamp to obtain a film thickness of 7 m.
A partially cured layer of μm was formed. Then, the coating liquid 2 was applied thereon again using a bar coater (wet thickness: 6 μm), kept in a hot air circulating oven at 80 ° C. for 5 minutes to remove the solvent, and then put in an air atmosphere. Using a high-pressure mercury lamp, irradiate ultraviolet rays with an integrated energy amount of 3000 mJ / cm ² , and subsequently hold in a hot air circulating oven at 170 ° C. for 5 minutes so that the coated surface of the transparent cured material layer becomes convex immediately after being taken out. It was pressed against a mold having a curvature of 64 mmR 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 11 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 19] A coating liquid having the same composition as that of Example 6 except that 500 mg of 2- (3,5-di-tert-pentyl-2-hydroxyphenyl) benzotriazole was not added (hereinafter referred to as coating liquid 5). ) Was prepared, and the coating liquid 5 and the coating liquid 2 were used to prepare 2 under the same conditions and method as in Example 6.
A sample having a two-layer cured product layer was produced. The measurement was performed using this sample. Further, with respect to the sample of the aromatic polycarbonate resin plate on which the transparent cured product layer of the coating liquid 5 was formed, the abrasion resistance of the surface of the transparent cured product layer was evaluated. The abrasion resistance after 100 rotations was 2.8%.

[Example 20] A coating liquid 1 was coated on a transparent aromatic polycarbonate resin plate (150 mm x 300 m) having a thickness of 3 mm.
m) using a bar coater (wet thickness 20μ)
m) and kept in a hot air circulating oven at 80 ° C. for 5 minutes. This was irradiated with ultraviolet rays of 3000 mJ / cm ^{2 in} an air atmosphere using a high-pressure mercury lamp to obtain a
The μm transparent cured material layer was cured, and the measurement was performed using this sample.

[Example 21] A coating liquid 2 was coated with a transparent aromatic polycarbonate resin plate (150 mm x 300 m) having a thickness of 3 mm.
m) 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 22 A coating liquid 4 was coated with a transparent aromatic polycarbonate resin plate (150 mm × 300 m) having a thickness of 3 mm.
m) using a bar coater (wet thickness 20μ)
m) and kept in a hot air circulating oven at 80 ° C. for 5 minutes. This was irradiated with ultraviolet rays having an integrated energy amount of 3000 mJ / cm ² using a high-pressure mercury lamp in an air atmosphere.
The μm transparent cured material layer was cured, and the measurement was performed using this sample.

[0148]

[Table 1]

[0149]

As described above, according to the present invention, the outermost layer is a silica film, and this layer is not directly laminated on a relatively soft transparent synthetic resin substrate.
Since it is laminated on the inner layer with improved adhesion and abrasion resistance by adding a polyfunctional compound, it is possible to obtain a transparent coated molded article having surface properties that are higher than those provided by a normal inorganic coating. . Further, since the inner layer in contact with the outermost layer also contains an ultraviolet absorbent, a transparent coated molded article having significantly improved weather resistance can be obtained.

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

Claims (4)

[Claims] 1. A transparent coated molded article having a transparent synthetic resin base material and two or more transparent cured product layers formed on at least a part of the surface of the transparent synthetic resin base material. An inner layer in contact with the outermost layer is a polyfunctional compound having two or more active energy ray-curable polymerizable functional groups (a
1) a first cured product layer of the coating composition (A) containing the ultraviolet absorbent (a2), and the outermost layer is a second cured product layer of the coating material (B) capable of forming silica. A transparent coated molded article characterized by the following. 2. The coating composition (A) has an average particle size of 200 n.
2. The transparent coated molded article according to claim 1, which contains m or less of colloidal silica. 3. The transparent coated molded article according to claim 1, wherein said coating agent (B) is a coating composition containing polysilazane. 4. An uncured material layer or a partially cured material layer of the coating agent (B) is formed on the transparent synthetic resin substrate, and the uncured material layer or the partially cured material layer is cured. 4. The transparent coated molded product according to claim 1, which is bent before.