JPH11129406A - Infrared absorption transparent coated molding and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve a scuff resistance by selecting as an inner layer a layer of a hardened material of an activation energy beam curable coated composition as a transparent hardened material layer containing an infrared absorbent, and laminating thereon a layer of a hardened material for forming a silica by a curing reaction at a room temperature or by heating. SOLUTION: The infrared absorption transparent coated molding comprises a transparent synthetic resin base material, and two or more layers of transparent hardened material layer having an outermost layer provided on a surface of the base material and one or more inner layers. Here, the one or more layer of the inner layers are each a layer of a hardened material of an activation energy beam curable coated composition containing a multifunctional compound having two or more activation energy beam curable polymerizable functional groups and an infrared absorber. And, the outermost layer is a layer of a hardened material of a curable coated composition for forming a silica. Accordingly, since a displacement of the outermost layer due to an external force applied to the molding to damage it becomes short, surface characteristics equivalent to or better than those to be given by a normal inorganic coating.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent coated molded article having excellent infrared absorbing properties, and a transparent cured product layer having excellent abrasion resistance and scratch resistance while maintaining excellent infrared absorbing properties. The present invention relates to an infrared-absorbing transparent coated molded article having the following, and a method for producing the infrared-absorbed transparent coated molded article.

[0002]

2. Description of the Related Art In recent years, transparent synthetic resin base materials such as glass, polycarbonate resin, and acrylic resin have been used in order to provide heat insulation and heat insulation performance by blocking infrared rays as heat rays, and to be used as a noise prevention filter for electronic equipment. There is a strong demand for providing infrared absorption to the glass.

Conventionally, methods for imparting infrared absorption to a transparent synthetic resin substrate include (1) a method in which an infrared absorber is mixed and mixed with the transparent synthetic resin substrate itself, and (2) gas-layer film formation such as sputtering. A method of directly forming an infrared absorbing thin film on the surface of a transparent synthetic resin substrate by a method has been proposed. But,
The method (1) requires a high processing temperature at the time of mixing, and thus has a problem that the usable infrared absorbers are significantly limited. The method (2) requires a large capital investment and is not suitable for multi-product production. Further, depending on the type of the thin film, the moisture resistance, chemical resistance, durability and the like are not sufficient.

[0004]

SUMMARY OF THE INVENTION In order to solve such problems, (3) a method of forming a thin film of a resin containing an infrared absorbent (Japanese Patent Laid-Open Nos. 4-160037 and 5-42)
622) has been proposed. However, when a large amount of an infrared absorber is added, the resin layer is plasticized and the scratch resistance is reduced.

[0005] In order to improve the scratch resistance of the surface, a method of forming a polysilazane-based film on the surface after coating a silicone-based primer to which an infrared absorbing agent is added (Japanese Patent Laid-Open No. 8-165146) has been proposed. ,
The formation of a silicone-based primer requires high-temperature heating for a relatively long time, which is unsuitable for a transparent substrate such as a plastic, and the productivity is poor.

[0006]

Means for Solving the Problems The present inventor studied a method for improving abrasion resistance without lowering productivity, and as a result, as a transparent cured material layer containing an infrared absorbing agent, an active energy ray-curable coating was obtained. The above-mentioned problems can be solved by selecting a layer of a cured product of the composition as an inner layer and laminating a layer of a cured product of the composition capable of forming silica by a curing reaction at room temperature or under heating thereon. I found something.
The present invention is the following invention relating to an infrared-absorbing transparent coated article excellent in productivity and abrasion resistance.

The transparent synthetic resin substrate comprises an outermost layer provided on the surface of the transparent synthetic resin substrate and one or more inner layers.
In the infrared-absorbing transparent coated molded article having at least one transparent cured product layer, at least one of the inner layers has the following coating composition (A)
Wherein the outermost layer is a layer of a cured product of the following coating composition (B). Coating composition (A): An active energy ray-curable coating composition containing a polyfunctional compound (a) having two or more active energy ray-curable polymerizable functional groups and an infrared absorber. Coating composition (B): a curable coating composition capable of forming silica.

After forming a layer of a cured product of the coating composition (A), an uncured layer of the coating composition (B) is formed on the surface of the layer of the cured product, and curing is performed. And a method for producing the infrared-absorbing transparent coated molded article.

After forming an uncured or partially cured layer of the coating composition (A), an uncured layer of the coating composition (B) is formed on the surface of the uncured or partially cured layer. And thereafter curing the uncured or partially cured product of the coating composition (A) and the uncured product of the coating composition (B).

After forming a layer of the uncured or partially cured product of the coating composition (A) and a layer of the uncured or partially cured product of the coating composition (B) on the surface of the layer, The substrate having the layer is bent, 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), if present, A method for producing the bent infrared-absorbing transparent coated molded article, characterized by curing.

In the present invention, the transparent cured layer is composed of the outermost layer and the outermost layer.
It consists of two or more layers consisting of two or more inner layers, and the outermost layer, which is a silica coating, is not directly laminated on a relatively soft transparent synthetic resin base material, but a hard transparent hardening with high abrasion resistance It is laminated on the object inner layer. For this reason, infrared-absorbing transparent coated molded products (hereinafter also referred to as transparent coated molded products)
It is considered that the displacement of the outermost layer due to an external force applied to the surface of the substrate reduces the displacement of the outermost layer, so that surface characteristics equivalent to or better than those of a normal inorganic coating can be obtained.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The transparent cured product layer in the present invention comprises:
It is composed of two or more layers of an inner layer made of a transparent cured product directly in contact with the outermost layer and an outermost layer made of a transparent cured product. A third layer made of another synthetic resin may be present between the transparent synthetic resin base (hereinafter simply referred to as the base) and the transparent cured product layer. For example, a layer of a thermoplastic resin such as a thermoplastic acrylic resin or an adhesive layer may be present. Usually, the transparent cured material layer is composed of two layers, an inner layer and an outermost layer. The inner layer may be composed of two or more different types of transparent cured products.

In order to obtain an inner layer having high abrasion resistance, a polyfunctional compound (a) is used as the active energy ray-curable coating composition (A). Similarly, in order to form a cured product having high abrasion resistance, the coating composition (A) has an average particle diameter of 20%.
It is also preferable to mix a colloidal silica of 0 nm or less to form a cured product containing the colloidal silica. In addition, the polyfunctional compound (a) is converted into an active energy ray (especially, an ultraviolet ray).
The coating composition (A) usually contains a photopolymerization initiator in order to efficiently cure the composition.

The polyfunctional compound (a) having two or more active energy ray-curable polymerizable functional groups in the coating composition (A) may be a single compound or a mixture of a plurality of compounds. You may. 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 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 having two or more active energy ray-curable polymerizable functional groups includes α, such as a (meth) acryloyl group, a vinyl group and an allyl group. A β-unsaturated group or a group having the same is preferred, and a (meth) acryloyl group is particularly preferred. That is, as the polyfunctional compound, a compound having two or more polymerizable functional groups selected from (meth) acryloyl groups is preferable. Among them, an acryloyl group which is more easily polymerized by ultraviolet rays is preferable.

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 kinds of the 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. Usually, 2 to 50 is appropriate, and especially 2 to 30.
Is preferred.

In this 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. As described above, more preferred of these groups and compounds are those having an acryloyl group, such as an acryloyloxy group, acrylic acid, and acrylate.

Preferred compounds as the polyfunctional compound (a) 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 preferable.

In the coating composition (A), two or more polyfunctional compounds may be contained as the polyfunctional compound (a). 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 combination in the coating composition (A), the ratio of the monofunctional compound to the total of the polyfunctional compound (a) and the monofunctional compound is not particularly limited, but is not particularly limited. 0-60% by weight is suitable.
If the proportion of the monofunctional compound is too large, the hardness of the cured film is reduced, and the abrasion resistance may be insufficient. A more preferable ratio of the monofunctional compound to the total of the polyfunctional compound (a) and the monofunctional compound is 0 to 30% by weight of the composition.
It is.

The polyfunctional compound (a) 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, these two polyfunctional compounds will be described.

The (meth) acryloyl group-containing compound having a urethane bond (hereinafter referred to as acrylic urethane) includes, for example, (1) a compound (X1) having a (meth) acryloyl group and a hydroxyl group and two or more isocyanate groups. (2) reaction product of compound (X1) and compound (X2) having two or more hydroxyl groups with polyisocyanate, (3) (meth) acryloyl group And a reaction product of the compound (X3) having an isocyanate group with the compound (X3). In these reaction products,
Preferably, no isocyanate groups are present, but hydroxyl groups may be present. Therefore, in the production of these reaction products, it is 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.

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 (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 to form a compound having a (meth) acryloyl group and a hydroxyl group. Alternatively, the compound having one or more epoxy groups may be ring-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 (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 a trimer (isocyanurate-modified), a dimer, and a carbodiimide-modified.
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. Two or more of these polyisocyanates can be used in combination.

Specific examples of the monomeric polyisocyanate include, for example, the following polyisocyanates (abbreviations in []). 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 (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.

Examples of the polyhydric alcohol having an aromatic nucleus include an alkylene oxide adduct of a polyhydric phenol and a ring-opened product of a polyepoxide having an aromatic nucleus such as polyhydric phenol-polyglycidyl ether.

The high molecular weight polyol includes polyether polyol, polyester polyol, polyether ester polyol, polycarbonate polyol and the like. Further, a hydroxyl group-containing vinyl polymer can also 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, 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.

Examples of the hydroxyl group-containing vinyl polymer include a copolymer of a hydroxyl group-containing monomer such as allyl alcohol, vinyl alcohol, hydroxyalkyl vinyl ether and hydroxyalkyl (meth) acrylate and a hydroxyl group-free monomer such as olefin. .

The compound (X3) having a (meth) acryloyl group and an isocyanate group includes 2-isocyanatoethyl (meth) acrylate.

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 preferable as the polyfunctional compound (a), a polyester of a compound having two or more hydroxyl groups and a polyester of (meth) acrylic acid similar to the compound (X2) can be used. preferable. 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.

As a compound having two or more epoxy groups, there is a polyepoxide called an epoxy resin. For example, glycidyl ether type polyepoxide,
A commercially available epoxy resin such as an alicyclic polyepoxide can be used.

Specific examples of the polyfunctional compound containing no urethane bond include the following compounds. (Meth) acrylates of the following 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, triglycerol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropanetetra (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate.

The following (meth) acrylates of the following polyhydric alcohols or phenols having an aromatic nucleus or a 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.

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

As the polyfunctional compound (a), at least a part thereof (preferably 30% by weight or more) is used because the cured product of the coating composition (A) can exhibit sufficient abrasion resistance.
Preferably comprises a trifunctional or higher polyfunctional compound. Preferably, 50% by weight or more thereof is composed of a trifunctional or more polyfunctional compound. Further, specific preferred polyfunctional compounds (a) are the following polyfunctional compounds having no urethane bond with acrylic urethane.

In the case of acrylurethane, acrylurethane which is a reaction product of pentaerythritol or its multimer polypentaerythritol with polyisocyanate and hydroxyalkyl (meth) acrylate, or hydroxyl-containing poly (pentaerythritol or polypentaerythritol) Acrylic urethane, which is a reaction product of (meth) acrylate and polyisocyanate, is preferably a trifunctional or more (preferably 4 to 20) compound.

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 polyester of polypentaerythritol and (meth) acrylic acid (preferably having a functionality of 4 to 20). Isocyanurate-based poly (meth) acrylate refers to tris (hydroxyalkyl) isocyanurate or 1 to 6 per mole thereof.
It refers to a polyester (2- to 2-functional) of (meth) acrylic acid with an adduct obtained by adding mol of caprolactone or alkylene oxide.

It is also preferable to use these preferred polyfunctional compounds in combination with other polyfunctional compounds having two or more functional groups (particularly polyhydric alcohol poly (meth) acrylate).
These preferable polyfunctional compounds are preferably at least 30% by weight, particularly preferably at least 50% by weight, based on the total polyfunctional compound (a).

As the monofunctional compound which can be used together with the polyfunctional compound (a), 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) may contain an effective amount of colloidal silica having an average particle diameter of 200 nm or less in order to enhance the abrasion resistance of the transparent cured product layer directly in contact with the outermost layer. The average particle size of the colloidal silica is preferably from 1 to 100 nm, particularly preferably from 1 to 50 nm. 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 using these colloidal silicas,
In order to sufficiently exert the effect to be used, the amount of the colloidal silica is 5 parts by weight with respect to 100 parts by weight of the curable component (the total of the polyfunctional compound and the monofunctional compound) of the coating composition (A). Parts or more is suitable, and 10 parts by weight or more is preferable.

When the amount is small, it is difficult to obtain sufficient abrasion resistance. On the other hand, if the amount is too large, clouding (haze) is likely to occur in the coating, and when the obtained transparent coated molded product is subjected to secondary processing such as hot bending, cracks are likely to occur. . Therefore, the amount of colloidal silica in the coating composition (A) is preferably 300 parts by weight or less based on 100 parts by weight of the curable component. A more preferred amount of the colloidal silica is 50 to 250 parts by weight based on 100 parts by weight of the curable component.

As the colloidal silica, a surface-unmodified colloidal silica can be used. Preferably, a surface-modified colloidal silica (hereinafter simply referred to as a modified colloidal silica) is used. The use of 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. Hereinafter, the modified colloidal silica will be described.

Various dispersion media are known as the dispersion media of colloidal silica, and the dispersion media of the 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 it is as the medium (solvent) of the coating composition (A).

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 colloidal silica, the dispersion medium of the modified colloidal silica, and the medium of the coating composition (A) 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. Lower alcohols such as water, methanol, ethanol, isopropanol, n-butanol, 2-methylpropanol, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol; cellosolves such as methyl cellosolve, ethyl cellosolve, 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 product 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 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 hydrolysis of the hydrolyzable silicon groups, and these silanol groups react with and bind to silanol groups that 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 reaction product obtained by previously reacting two types of modifiers having reactive functional groups that are reactive with each other can be used as the modifier.

The modifying agent may have two or more hydrolyzable silicon groups or silanol groups, a partial hydrolysis condensate of a compound having a hydrolyzable silicon group or a partial condensation of a compound having a silanol group. It may be a thing. 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. The organic group to which the reactive functional group is bonded is preferably an alkylene group having 8 or less carbon atoms or a phenylene group, excluding the reactive functional group, and particularly preferably an alkylene group having 2 to 4 carbon atoms (among them, a polymethylene group). Specific modifiers are classified according to the type of reactive functional group.
For example, there are the following compounds. (Meth) acryloyloxy group-containing silanes; γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane and the like.

Amino group-containing silanes; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane,
γ-ureidopropyltriethoxysilane, N- (N-
Vinylbenzyl-β-aminoethyl) -γ-aminopropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and the like.

Mercapto group-containing silanes; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane and the like.

Epoxy group-containing silanes; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane and the like.

Isocyanate group-containing silanes; γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane and the like.

Examples of the reaction product obtained by preliminarily reacting two types of modifiers having reactive functional groups reactive with each other include, for example, a reaction product of an amino group-containing silane and an epoxy group-containing silane, Reaction products of group-containing silanes and (meth) acryloyloxy group-containing silanes, reaction products of epoxy group-containing silanes and mercapto group-containing silanes, mercapto group-containing silanes 2
There are reaction products of molecules.

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

As the catalyst, there are acids and alkalis. 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 and hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid and the like can be used. 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 suitable. If the amount of the modifier is less than 1 part by weight, it is difficult to obtain the effect of surface modification. If the amount exceeds 100 parts by weight, a large amount of unreacted modifier or hydrolyzate to condensate of the modifier not supported on the surface of the colloidal silica is generated, and these are chained during curing of the cured composition of the transparent coating layer. It may act as a transfer agent or as a plasticizer for the cured film, reducing the hardness of the cured film.

In order to cure the polyfunctional compound (a), the coating composition (A) usually contains a photopolymerization initiator. Known to 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, etc.), sulfur-containing photopolymerization initiators (eg, sulfides, thioxanthones, etc.),
There are acylphosphine oxide-based photopolymerization initiators, bisacylphosphine oxide-based photopolymerization initiators, and other photopolymerization initiators.

In particular, the use of an acylphosphine oxide-based photopolymerization initiator and a bisacylphosphine 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-methylpropane-1
-One, 4- (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 amount of the photopolymerization initiator in the coating composition (A) is 0.01 to 20 parts by weight based on 100 parts by weight of the curable component (total of the polyfunctional compound (a) and the monofunctional compound). Particularly preferred is 0.1 to 10 parts by weight.

The coating composition (A) contains an infrared absorber as an essential component. Examples of the infrared absorbent include polymethine, phthalocyanine, metal complex, aminium, diimonium, anthraquinone, dithiol metal complex, naphthoquinone, indolephenol, azo, and triarylmethane compounds. Although not limited to these compounds, the maximum absorption wavelength is 750 to 1100 nm especially for heat ray absorption and noise prevention of electronic equipment.
Is preferred, and a metal complex-based or diimmonium-based compound is particularly preferred.

The content of the infrared absorbing agent varies depending on the thickness of the cured product of the coating composition (A) and the required infrared absorbing ability. Usually, however, the curable component (polyfunctional) in the coating composition (A) is used. The range is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the total of the functional compound and the monofunctional compound).

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 the polyfunctional compound (a) as a curing component can be used. 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 drying temperature conditions, and the like. Usually, it is used in an amount of 100 times or less, preferably 0.1 to 50 times the weight of the curable component in the composition. Examples of the solvent include solvents such as lower alcohols, ketones, ethers, and cellosolves, which are mentioned as the solvent used for the 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 of an aromatic polycarbonate resin having low solvent resistance, lower alcohols, cellosolves, esters, a mixture thereof and the like are suitable.

The coating composition (A) may contain, if necessary, stabilizers such as an ultraviolet absorber, a light stabilizer, an antioxidant and a thermal polymerization inhibitor, a leveling agent, an antifoaming agent, a thickener, and an antisettling agent. , Pigments, dispersants, antistatic agents, surfactants such as antifoggants,
A curing catalyst selected from acids, alkalis, salts, and the like may be appropriately contained.

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-based 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 electron beams and 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 hydro lamps, carbon arc lamps, tungsten lamps, fusion lamps and the like can be used.

The thickness of the layer of the cured product formed from the coating composition (A) is preferably 1 to 50 μm. If the thickness is more than 50 μm, curing by active energy rays becomes insufficient, and the adhesion to the substrate is easily impaired, which is not preferable. If the thickness 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 on this layer may not be sufficiently exhibited. A more preferred layer thickness is 2 to 30 μm.

Next, the curable coating composition (B) capable of forming the outermost layer of silica contains a soluble compound capable of forming silica and usually a solvent. Examples of the soluble compound capable of forming silica include a tetrafunctional hydrolyzable silane compound, a partially hydrolyzed condensate thereof, and polysilazane.
Examples of tetrahydrolyzable silane compounds and their partially hydrolyzed condensates include tetraalkoxysilanes and their partially hydrolyzed condensates. 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.

As the polysilazane, a hydrolyzable group such as polysilazane (perhydropolysilazane) or an alkoxy group substantially containing no organic group is bonded to a silicon atom, and an organic group such as an alkyl group is bonded to the polysilazane or silicon atom. And polysilazane. As such a polysilazane, a silica which substantially does not contain an organic group is preferably formed by a hydrolysis reaction at the time of curing even if it has an organic group. 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.

The polysilazane is composed of a polymer having a chain, cyclic or cross-linked structure, or a mixture having a plurality of these 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 is more than 50,000, it is difficult to dissolve in a solvent, and the coating composition (B) may become viscous.

Solvents for dissolving polysilazane include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, halogenated hydrocarbon solvents, aliphatic ethers, and the like.
Ethers such as alicyclic ethers can be used. Specifically, the following can be exemplified.

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,
Halogenated hydrocarbons such as 1,2-dichloroethane, 1,1-dichloroethane, trichloroethane, tetrachloroethane and the like. 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 to adjust the solubility of polysilazane and the evaporation rate of the solvent. The amount of the solvent to be used varies depending on the coating method employed, the structure of polysilazane, the average molecular weight, and the like, but is preferably adjusted in the range of 0.5 to 80% by weight in terms of solid concentration.

In order to cure the polysilazane into silica, heating which is usually called calcination is required. But,
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 that of the substrate.
However, in some cases, the heat resistance of the cured product may be lower than the heat resistance of the substrate, and 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 general synthetic resin such as an aromatic polycarbonate resin 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, the atmosphere in which oxygen is present, such as air, is preferably used as the atmosphere in which the firing is performed. 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 capable of curing polysilazane at a lower temperature. Such catalysts include, for example, gold, silver, palladium, platinum,
There is a metal catalyst composed of fine particles of a metal such as nickel.
The particle size of these metal fine particles is preferably smaller than 0.1 μm, and further preferably smaller than 0.05 μm in order to ensure transparency of the cured product. In addition, since the specific surface area increases as the particle size decreases and the catalytic ability increases, it is preferable to use a catalyst having a smaller particle size in terms of improving the catalytic performance.

The amount of the catalyst was as follows: polysilazane 100
The amount is 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight based on parts by weight. If the amount is less than 0.01 part by weight, a sufficient catalytic effect cannot be expected. If the amount is more than 10 parts by weight, aggregation of the catalysts tends to occur, and the transparency may be impaired.

The coating composition (B) may contain, if necessary, stabilizers such as an ultraviolet absorber, a light stabilizer and an antioxidant, a leveling agent, an antifoaming agent, a thickener, an antisettling 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 refers to perhydropolysilazane unless otherwise specified.

The thickness of the cured product layer formed using the coating composition (B) is preferably 0.05 to 10 μm. If the thickness of the outermost layer 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 easily generated 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 scratch resistance. More preferred layer thickness is 0.1 to 3 μm
m.

The two kinds of coating compositions (A) as described above,
As a method of forming two transparent cured layers formed using (B), a usual coating method can be employed. For example, first, the coating composition (A) is applied and cured on a base material, 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 any known or well-known method can be employed. For example, dipping, flow coating, spraying,
Methods such as bar coating, gravure coating, roll coating, blade coating, air knife coating, spin coating, slit coating, and microgravure coating can be used.

After coating, if the coating composition contains a solvent, the coating composition is dried to remove the solvent, and then, in the case of a layer using the coating composition (A), the coating composition is cured by irradiating ultraviolet rays or the like. In the case of the layer using (B), the layer is cured by heating or left at room temperature. As the combination (timing) of the curing of the coating composition (A) and the application to the curing of the coating composition (B), the following three methods are exemplified.

1) After the coating composition (A) is applied, a sufficient amount of active energy rays are irradiated to substantially complete the curing, and then the coating composition (B) is applied thereon. Method (method described above).

2) 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 a layer of the uncured material 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 is cured by heating after curing the uncured material of the coating composition (A).

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

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 dipping method is used as a method of applying the coating composition (B), the coating composition (A)
However, there is a possibility that the uncured component may contaminate the dipping solution of the coating composition (B), and thus there is a restriction that the coating by such a dipping method is not suitable.

Further, the transparent coated molded article of the present invention is characterized in that its surface properties such as abrasion resistance and scratch resistance are almost equal to those of glass. Can be used. Among these uses, there are uses as window materials for vehicles.

However, in such applications, a bent molded product is often required. In the case of manufacturing such a bent transparent coated molded article of the present invention, the transparent coated molded article of the present invention can be formed using the bent base material.
However, when a bent substrate is used, it is often difficult to form each layer by coating and curing. On the other hand, according to conventional studies by the present inventors, a substrate on which a layer of a cured product of the coating composition (A) is formed can be bent by hot bending or the like. However, when a layer of the cured product of the coating composition (B) is formed, the cured product is hard, so that bending is difficult.

The inventor of the present invention has proposed a base material having such a layer (a layer of a cured product of the coating composition (A)) if the layer is an uncured or partially cured product of the coating composition (B). ) Can be bent. Further, as in the methods 2) and 3), an uncured or partially cured layer of the coating composition (B) is formed on the uncured or partially cured layer of the coating composition (A). It can also be bent in a state where it has been bent. 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 usually performed in a heated state.

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

Therefore, the bent molded article of the present invention can be obtained by coating an uncured, partially cured or cured layer of the coating composition (A) on a substrate and forming the coating composition (A) on the surface of the layer. After forming the layer of the uncured or partially cured product of B), the substrate having these layers is bent, and then the uncured or partially cured product of the coating composition (B) and the coating composition ( When the uncured product or partially cured product of A) is present, it can be produced by curing it.

Specifically, for example, the coating composition (B)
After forming a layer of an uncured material or a partially cured material, the substrate is heated to a thermal softening temperature of the substrate for about 5 minutes, and then subjected to bending. Thereafter, the temperature is lower than the thermal softening temperature of the substrate and the coating composition (B)
By performing the curing while maintaining the temperature at which the uncured or partially cured product can be cured, the bent molded article of the present invention can be obtained. According to such a method, the base material is deformed before the coating composition (B) is sufficiently cured, and a hard silica layer is formed thereafter, so that problems such as cracks do not occur in the silica layer.

As the material of the transparent synthetic resin substrate in the present invention, various transparent synthetic resins can be used. For example, a transparent synthetic resin such as an aromatic polycarbonate resin, a polymethyl methacrylate resin (acrylic resin), or a polystyrene resin can be used as the material of the base material. In particular, a substrate made of an aromatic polycarbonate resin is preferable. 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. Particularly, a flat substrate (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. The two or more transparent cured material layers described above are formed on both surfaces or one surface of the sheet.

By utilizing the excellent scratch resistance, these infrared-absorbing transparent coated molded articles can be used as window materials for buildings and vehicles, and protective plates for various displays such as Braun tube and plasma displays.

[0112]

EXAMPLES The present invention will be described below with reference to Synthesis Examples (Examples 1 to 5), Examples (Examples 6 to 16), and Comparative Examples (Examples 17 to 19), but the present invention is not limited thereto. Examples 6 to 15,
Various physical properties of Examples 17 to 19 were measured by the following methods, and the results are shown in Table 1.

[Abrasion Resistance] According to the abrasion resistance test method according to JIS-R3212, a haze meter was measured with a haze meter when 500 g weights were combined with each of two CS-10F abrasion wheels and rotated 500 times. The haze was measured at four points on the wear cycle orbit, and the average value was calculated. The value (%) of (haze after abrasion test)-(haze before abrasion test) was shown.

[Infrared absorption] The absorption spectrum was measured with a spectrophotometer, and the maximum absorption wavelength (nm) in the infrared region of 800 nm or more and its transmittance (%) were measured.

[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 0.1 N hydrochloric acid were added to 100 parts by weight,
The mixture was heated and stirred at 00 ° C. for 6 hours, and then aged at room temperature for 12 hours to obtain a mercaptosilane-modified colloidal silica dispersion.

[Example 2] An acrylic silane-modified colloidal silica dispersion was prepared in the same manner as in Example 1 except that 5 parts by weight of γ-acryloyloxypropyltrimethoxysilane was used instead of 5 parts by weight of 3-mercaptopropyltrimethoxysilane. A liquid 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
A mercaptosilane-modified colloidal silica dispersion was obtained in the same manner as in Example 1 except that 00 parts by weight and the reaction temperature was 83 ° C.

[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-t-amyl-2-hydroxyphenyl) benzotriazole 200
mg, and bis (1-octyloxy-2,2,6,6
-Tetramethyl-4-piperidinyl) sebacate 100
mg, diimonium-based near infrared absorber (Nippon Kayaku Co., Ltd.)
(Trade name: IRG-002) (10 mg), followed by dissolution. Then, urethane acrylate (1
Containing an average of 15 acryloyl groups per molecule) 10.
0 g, and stirred at room temperature for 1 hour to form a coating composition (hereinafter, referred to as “coating composition”).
Coating solution 1) was obtained.

This coating liquid 1 was applied (wet thickness 16 μm) to a transparent aromatic polycarbonate resin plate (150 mm × 300 mm) having a thickness of 3 mm using a bar coater, and the coating solution was placed 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 /
The transparent cured material layer having a thickness of 5 μm was cured by irradiating ultraviolet rays of cm ² (integrated energy of ultraviolet rays in a wavelength range of 300 to 390 nm).

Next, a xylene solution of perhydropolysilazane of low temperature curability (solids 20% by weight, trade name: HERVIC.
LT) (hereinafter, referred to as coating liquid 2) is again coated (wet thickness: 6 μm) using a bar coater, kept in a hot air circulating oven at 80 ° C. for 10 minutes, and then in a hot air circulating oven at 100 ° C. For 120 minutes to sufficiently cure the outermost layer. And it was confirmed by IR analysis that the outermost layer was a complete silica coating. Thus, a total film thickness of 6.2 μm was formed on the aromatic polycarbonate resin plate.
Was formed. The measurement was performed using this sample.

[Example 7] The sample adjustment method in Example 6 was changed as follows. That is, after applying the coating liquid 1,
It was kept in a hot air circulating oven at 80 ° C. for 5 minutes, and was kept in an air atmosphere using a high-pressure mercury lamp at 150 mJ / cm ^2.
Ultraviolet rays (integrated energy of ultraviolet rays in a wavelength region of 300 to 390 nm) were irradiated to form a transparent cured product layer having a thickness of 5 μm. Then, the coating liquid 2 was applied thereon again using a bar coater (wet thickness: 6 μm) and kept in a hot air circulating oven at 80 ° C. for 10 minutes. 3000 mJ / cm ²
(Integrated energy of ultraviolet light in a wavelength range of 300 to 390 nm). Then, it was kept in a hot air circulating oven at 100 ° C. for 120 minutes. The measurement was performed using this sample.

[Example 8] The sample preparation method in Example 7 was changed as follows. That is, instead of holding in a hot air circulating oven at 100 ° C. for 120 minutes, curing was performed at room temperature for one day. The measurement was performed using this sample.

[Example 9] The sample preparation method in Example 6 was changed as follows. That is, after applying the coating liquid 1,
Hold in a hot air circulating oven at 80 ° C. for 5 minutes, then
The coating solution 2 was applied thereon again using a bar coater (wet thickness: 6 μm), kept in a hot air circulating oven at 80 ° C. for 10 minutes, and then 3,000 mJ in an air atmosphere using a high-pressure mercury lamp. / Cm ² (wavelength 300-3
Ultraviolet rays (integrated energy of ultraviolet rays in a region of 90 nm) were irradiated and kept in a hot air circulating oven at 100 ° C. for 120 minutes. The measurement was performed using this sample.

Example 10 Isopropanol 15 was added to 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-
(3,5-di-t-amyl-2-hydroxyphenyl)
200 mg of benzotriazole, 200 mg of bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate and a metal complex-based near infrared absorber (trade name: SIR- manufactured by Mitsui Toatsu Dye Co., Ltd.) 159)
20 mg was added and dissolved, and then 10.0 g of tris (acryloxyethyl) isocyanurate was added, and the mixture was added at room temperature for 1 hour.
Stirred for hours. Subsequently, 30.3 g of the mercaptosilane-modified colloidal silica dispersion synthesized in Example 1 was added, and the mixture was further stirred at room temperature for 15 minutes to obtain a coating composition (hereinafter, referred to as coating liquid 3).

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 16 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.
Ultraviolet rays of J / cm ² (integrated amount of ultraviolet energy in a wavelength region of 300 to 390 nm) were irradiated to form a partially cured layer having a thickness of 5 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. 3000
Ultraviolet rays of mJ / cm ² (integrated energy of ultraviolet rays in a wavelength range of 300 to 390 nm) were irradiated and kept in a hot air circulating oven at 100 ° C. for 120 minutes. The measurement was performed using this sample.

[Example 11] The sample preparation method in Example 10 was changed as follows. That is, 100 ° C at the end
Instead of holding for 120 minutes in a hot air circulating oven,
Cured at room temperature for one day. The measurement was performed using this sample.

Example 12 The same conditions were used except that the modified colloidal silica dispersion used in Example 10 was changed to the same amount of the acrylsilane-modified colloidal silica dispersion synthesized in Example 2. The measurement was performed using this sample.

Example 13 The same conditions were used except that the modified colloidal silica dispersion used in Example 10 was changed to the same amount of the aminosilane-modified colloidal silica dispersion synthesized in Example 3. The measurement was performed using this sample.

Example 14 The same conditions were used except that the modified colloidal silica dispersion used in Example 10 was changed to the same amount of the epoxysilane-modified colloidal silica dispersion synthesized in Example 4. The measurement was performed using this sample.

Example 15 The same conditions were used except that the modified colloidal silica dispersion used in Example 10 was replaced with the same amount of the isopropanol-dispersed mercaptosilane-modified colloidal silica dispersion synthesized in Example 5. The measurement was performed using this sample.

[Example 16] The sample preparation method in Example 10 was changed as follows. That is, the coating liquid 3 is coated with a transparent aromatic polycarbonate resin plate (150 mm thick) having a thickness of 3 mm.
(mm × 300 mm) using a bar coater (wet thickness: 16 μm) and kept in a hot air circulating oven at 80 ° C. for 5 minutes. This was irradiated with 150 mJ / cm ² (ultraviolet integrated energy in a wavelength range of 300 to 390 nm) using a high-pressure mercury lamp in an air atmosphere.
A partially cured layer of μm was formed.

Then, the coating liquid 2 was again coated (wet thickness: 6 μm) using a bar coater, and
After holding ℃ in a hot-air circulating oven for five minutes, which in air atmosphere, using a high pressure mercury lamp 3000 mJ / cm ²
(UV integrated energy in the wavelength range of 300 to 390 nm), followed by holding 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. And at room temperature
As a result of observing the appearance of the cured product, 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 the two fully cured cured layers was held in a hot air circulating oven at 170 ° C. for 5 minutes, and immediately after the sample was 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 17 A coating liquid 1 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 is 3,000 in an air atmosphere using a high-pressure mercury lamp.
Ultraviolet rays of mJ / cm ² (integrated energy of ultraviolet rays in a wavelength range of 300 to 390 nm) were irradiated to form a 6 μm-thick transparent cured material layer. The measurement was performed using this sample.

[Example 18] A coating liquid 3 was coated with a transparent aromatic polycarbonate resin plate having a thickness of 3 mm (150 mm x 300 m).
m) using a bar coater (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.
Ultraviolet rays of mJ / cm ² (integrated energy of ultraviolet rays in a wavelength range of 300 to 390 nm) were irradiated to form a 6 μm-thick transparent cured material layer. The measurement was performed using this sample.

Example 19 The conditions were the same as in Example 6, except that no infrared absorber was added. The measurement was performed using this sample.

[0139]

[Table 1]

[0140]

The infrared-absorbing transparent coated molded article of the present invention is
This is an infrared-absorbing transparent coated molded article having a surface with high abrasion resistance almost equivalent to that of inorganic glass and excellent in surface properties. Further, in the present invention, it is possible to produce an infrared-absorbing transparent coated molded article excellent in such surface properties, which is bent by using a flat substrate.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09D 183/16 C09D 183/16 (72) Inventor Hiroshi Yamamoto 1150 Hazawacho, Kanagawa-ku, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture Asahi Glass Co., Ltd.

Claims (6)

[Claims] 1. A transparent synthetic resin substrate, comprising an outermost layer provided on the surface of the transparent synthetic resin substrate and one or more inner layers.
In the infrared-absorbing transparent coated molded article having at least one transparent cured product layer, at least one of the inner layers has the following coating composition (A)
Wherein the outermost layer is a layer of a cured product of the following coating composition (B). Coating composition (A): An active energy ray-curable coating composition containing a polyfunctional compound (a) having two or more active energy ray-curable polymerizable functional groups and an infrared absorber. Coating composition (B): a curable coating composition capable of forming silica. 2. The coating composition (A) further comprises an average particle size of 20
The infrared-absorbing transparent coated molded article according to claim 1, comprising colloidal silica having a diameter of 0 nm or less. 3. The molded article according to claim 1, wherein the coating composition (B) is a coating composition containing polysilazane. 4. A method comprising forming a layer of a cured product of the coating composition (A), forming an uncured layer of the coating composition (B) on the surface of the layer of the cured product, and curing the layer. The method for producing an infrared-absorbing transparent coated molded product according to claim 1, 2 or 3. 5. An uncured material or a partially cured material layer of the coating composition (A) is formed, and the uncured material layer of the coating composition (B) is formed on the surface of the uncured or partially cured material layer. The infrared ray according to claim 1, 2 or 3, wherein the infrared ray is formed, and then the uncured or partially cured product of the coating composition (A) and the uncured product of the coating composition (B) are cured. A method for producing an absorbent transparent coated molded article. 6. An uncured, partially cured or cured layer of the coating composition (A) and a layer of the uncured or partially cured product of the coating composition (B) formed on the surface of the layer. The substrate having these layers is bent, and then the uncured or partially cured product of the coating composition (B) and, if any, the uncured or partially cured product of the coating composition (A). 4. The method for producing an infrared-absorbing transparent coated molded product according to claim 1, 2 or 3, wherein the molded product is cured.