JP2000229384A - Transparent coated molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain abrasion-resistant surface characteristics by a method in which the inner layer in transparent cured material layers is made a layer of a cured active energy ray-curable coating composition, and the outermost layer is made a silica layer of a cured coating composition containing a hydrolyzable silyl group-containing compound and polysilazane. SOLUTION: The inner layer contacting the outermost layer in transparent cured material layers A is a layer of a cured active energy ray-curable coating composition B containing a polyfuncitonal compound (a) having at least two active energy ray-curable polymerizable groups, and the outermost layer is a silica layer of a cured coating compound C containing a hydrolyzable silyl group-containing compound (b) and polysilazane (c). The active energy ray- curable polymerizable functional group of the compound (a) is preferably a (meth)acroyl group, and the compound (b) is preferably silazane. The polysilazane (c) is preferably perhydropolysilazane in view of its low baking temperature and the fineness of its cured coat after baking.

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 a transparent cured resin layer having excellent abrasion resistance, transparency, weather resistance, etc. on a transparent synthetic resin substrate. The inner layer in contact with the outermost layer of the material layer is a layer of a cured product derived from the active energy ray (especially ultraviolet) curable coating composition,
The present invention relates to a transparent coated molded article in which the outermost layer is a layer of silica derived from a coating composition that forms silica.

[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. Further, there is an example in which such a transparent synthetic resin material is used in place of glass (inorganic glass, hereinafter the same) for vehicles such as automobiles.

However, a transparent synthetic resin material has a disadvantage that the surface hardness is not sufficient to be used as a substitute for glass, and the surface is easily damaged or worn.

[0004] Therefore, there have been many attempts to improve the abrasion resistance and abrasion resistance of aromatic polycarbonate resins as described below. A polymer-curable compound having two or more polymerizable functional groups such as acryloyl groups in a molecule is applied to a substrate, and the polymer-curable compound is cured by active energy rays such as heat or ultraviolet rays, and the surface has scratch resistance. And ways to improve abrasion resistance (one of the most common methods). A method in which a metal alkoxide compound such as a silicon-based compound is applied to a substrate and cured by heat in order to impart higher surface hardness to the substrate. A method in which a mixture of a compound having an acryloyl group and colloidal silica is applied to a substrate and cured with an active energy ray such as ultraviolet rays to form a transparent cured layer having excellent scratch resistance (Japanese Patent Application Laid-Open No. 61-181809). Gazette).

A method using polysilazane instead of the silicon-based metal alkoxide compound, that is, a method in which polysilazane is applied to a substrate and cured by heat or the like (JP-A-8-143689). A method in which a protective film is formed on a plastic film and a polysilazane solution is applied on the surface to form a silica surface layer (Japanese Patent Application Laid-Open No. 9-39161). A method in which a silicone-based thermopolymerized cured product is applied 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). Form an underlayer containing an acrylic photopolymerization-curable paint and a polysiloxane composition having a silanol group, and an upper layer made of a silicon-based thermopolymerization-curable paint, cure the underlayer by irradiating ultraviolet rays, and cure the upper layer by heat treatment. (Japanese Unexamined Patent Publication No. Hei 7-118425).

According to the method (1), the composition for coating is relatively stable, and is particularly excellent in productivity because it can be cured by ultraviolet rays. Further, even when the molded product is subjected to bending, no crack is generated in the cured film. According to the method, a cured film having extremely excellent wear resistance can be formed.
In the method of (1), by using colloidal silica in combination with the polymerizable curable compound, it is possible to achieve both high surface hardness and high productivity.

In the method (1), polysilazane undergoes a condensation reaction or an oxidation reaction in the presence of oxygen to change into a higher-order crosslinked product of silicon dioxide, and a silica coating is formed. In the method (1), a silicone-based thermopolymerized cured product layer is formed on the cured product layer of the ultraviolet curable compound. In the above method, the silanol groups of the upper layer and the silanol groups of the base layer (polysiloxane composition) are siloxane-bonded by a dehydration bonding reaction during the polymerization of the upper layer (silicon-based thermopolymerization coating), and the upper layer and the base layer are firmly connected. To join.

It is known that the surface of a silica layer formed of the above-mentioned polysilazane or thermosetting silicone resin has abrasion resistance, and a silica coating derived from polysilazane has a high surface hardness. I have.

[0009]

However, in the above-mentioned method, since the cured film is made of only an organic substance, there is a limit in the expression level of the surface scratch resistance. The methods (1), (2), (3), (3), (3), (4), (5) have a drawback that the cured film tends to peel off or crack because of poor adhesion between the cured film and the substrate. In addition, the method described above was inferior to the method of applying the above-mentioned metal alkoxide compound to a base material and curing it by heat in terms of the surface scratch resistance level. And the method of
There is a problem that the outermost layer is inferior in abrasion resistance as compared with a cured layer made of polysilazane.

Accordingly, an object of the present invention is to provide a transparent coated molded article having a surface having a high abrasion resistance almost equivalent to that of inorganic glass and having excellent surface characteristics.

[0011]

In order to achieve the above object, the present inventors have determined that the outermost layer of the silica layer, such as abrasion resistance and abrasion resistance, has a different surface property between the silica layer and the inner layer. As a result of the study, it was found that the addition of a specific compound to the silica layer improved the adhesion between the silica layer and the inner layer in contact with the silica layer, and completed the present invention.

That is, the present invention provides a transparent synthetic resin base material and a transparent cured material layer (A) provided on at least a part of the surface of the transparent synthetic resin base material, the transparent hardened material layer comprising at least two layers, an outermost layer and an inner layer. In the coated molded article, the inner layer in contact with the outermost layer of the transparent cured product layer (A) has an active energy containing a polyfunctional compound (a) having two or more active energy ray-curable polymerizable functional groups. A silica layer which is a layer of a cured product of the line-curable coating composition (B), and whose outermost layer is a cured product of the coating composition (C) containing the hydrolyzable silyl group-containing compound (b) and polysilazane (c). The present invention provides a transparent coated molded article characterized by the following.

In the present invention, a hydrolyzable silyl group-containing compound (b) having a high affinity for the inner layer (hereinafter referred to as a silyl group-containing compound (b)) is added to the silica layer to form a silica layer (outermost layer). By forming a network between the inner layer and the inner layer, the adhesion between the two layers is improved, and the surface properties such as abrasion resistance and scratch resistance of the silica layer are improved.

Further, the transparent cured material layer (A) in the present invention
Consists of at least two layers, an outermost layer and an inner layer,
The outermost layer of silica coating is not directly laminated on a relatively soft transparent synthetic resin base material, but is laminated on a hard transparent hardened material having high abrasion resistance. Therefore, it is considered that the displacement of the outermost layer due to an external force applied to the transparent coated molded article due to scratching is reduced, and surface characteristics higher than those provided by a normal inorganic coating are obtained.

That is, according to the present invention, although the outermost layer is a coating mainly composed of an inorganic substance, it adheres sufficiently to the inner layer and consequently to the transparent synthetic resin substrate (hereinafter simply referred to as the substrate). In addition, it is possible to provide a transparent synthetic resin molded article having a transparent cured product layer having surface abrasion resistance equal to or close to that of glass.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, the transparent cured product layer (A) is in direct contact with the transparent cured product layer forming the outermost layer (hereinafter referred to as the transparent cured product outermost layer) and the transparent cured product outermost layer. It is composed of at least two layers of a transparent cured product layer (hereinafter, referred to as a transparent cured product inner layer).

The inner layer of the transparent cured product is formed of a polyfunctional compound (a) having two or more active energy ray-curable polymerizable functional groups (hereinafter referred to as a polyfunctional compound (a)). Line-curable coating composition (B) (hereinafter, referred to as
(Referred to as coating composition (B)).

In the present invention, a second inner layer made of a thermoplastic resin such as a thermoplastic acrylic resin or another synthetic resin such as an adhesive is present between the substrate and the inner layer of the transparent cured product. It may be. In this case, the second inner layer is preferably made of a composition having sufficient adhesion to both (the base material and the inner layer of the transparent cured product).

In the present invention, the transparent cured product inner layer comprises:
It has the effect of improving the adhesion between the substrate or the second inner layer on the substrate and the outermost layer, and improving the surface properties of the outermost layer by reducing the displacement of the outermost layer due to external force.

That is, the coating composition (B) contains a polyfunctional compound (a) for the purpose of increasing the adhesion to the substrate or the second inner layer and reducing the displacement of the outermost layer due to external force. Things.

In the present invention, in order to obtain an inner layer of a transparent cured product having higher abrasion resistance, the coating composition (B) is used.
May be mixed with colloidal silica having an average particle diameter of 200 nm or less to form a cured product containing colloidal silica.

That is, in the present invention, the inner layer of the transparent cured product has a haze value (the haze value after the abrasion test and the haze value before the abrasion test) after the abrasion resistance test (100 tests) according to JIS-R3212. Difference) is preferably 15% or less, more preferably 10% or less, and particularly preferably 5% or less.
The following is preferred.

A) Description of Polyfunctional Compound (a) Hereinafter, 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.

A-1) In the present invention, the polyfunctional compound (a) is a mixture of one or more polyfunctional compounds.

When a plurality of types of polyfunctional compounds are used, they may be different compounds in the same category or different categories. For example, a combination of different compounds each of which is acrylic urethane, or a combination of which one is acrylic urethane and the other is an acrylate compound having no urethane bond may be used.

Further, a monofunctional compound having one polymerizable functional group which can be polymerized by an active energy ray (hereinafter, referred to as a monofunctional compound) may be contained together with the polyfunctional compound.

When the above monofunctional compound is used in the coating composition (B), the ratio of the monofunctional compound to the total of the polyfunctional compound (a) and the monofunctional compound is not particularly limited, but may be 0. ~ 60% by weight is preferred, especially 0 ~
30% by weight is preferred.

If the proportion of the monofunctional compound is too large, the hardness of the cured coating film may decrease, and the abrasion resistance may be insufficient.

As the above monofunctional compound, a compound having a (meth) acryloyl group is preferable, and a compound having an acryloyl group is particularly preferable. Further, the 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.

Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate
Acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate and the like can be mentioned.

A-2) The active energy ray-curable polymerizable functional group of the polyfunctional compound (a) includes an unsaturated group such as a (meth) acryloyl group, a vinyl group and an allyl group and a group having the same. However, a (meth) acryloyl group is preferred. In addition, polyfunctionality means having two or more of these polymerizable functional groups. Among the above groups and compounds, those having an acryloyl group, such as an acryloyloxy group, acrylic acid and acrylate, are more preferable.

A-3) The number of the polymerizable functional groups in one molecule is 2 or more, and the upper limit is not particularly limited, but is usually preferably 2 to 50, and particularly preferably 3 to 30. The kind of the polymerizable functional group contained in one molecule is not particularly limited, and may be one kind or two or more kinds.

That is, the polyfunctional compound (a) is
Preferably, it is preferably selected from one or more polymerizable functional groups selected from (meth) acryloyl groups, among which compounds having two or more acryloyl groups which are more easily polymerized by ultraviolet rays. More preferably, (meth)
It is a polyester of a compound having two or more acryloyloxy groups, that is, a compound of a compound having two or more hydroxyl groups such as a polyhydric alcohol and (meth) acrylic acid.

In addition to the above polymerizable functional groups, for example,
Hydroxyl group, carboxyl group, halogen atom, urethane bond, ether bond, ester bond, thioether bond,
It may have various functional groups and bonds such as an amide bond and a diorganosiloxane bond. In such a case, the compound (meth) acryloyl group-containing compound having a urethane bond (so-called acryl urethane) has no urethane bond ( (Meth) acrylate compounds are preferred.

In the present invention, since the cured product of the coating composition (B) can exhibit sufficient abrasion resistance, the polyfunctional compound (a) contains a trifunctional or higher polyfunctional compound. , Is preferably contained at least in part (preferably at least 30% by weight), particularly preferably at least 50% by weight.

I) 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 compounds. A reaction product of a compound having an isocyanate group (hereinafter, referred to as a polyisocyanate), (2) the compound (X1)
A reaction product of a compound (X2) having at least two hydroxyl groups with a polyisocyanate, (3) a reaction product of a compound (X3) having a (meth) acryloyl group and an isocyanate group and the compound (X2), and the like. There is.

In each of the above reaction products, a hydroxyl group may be present, but preferably no isocyanate group is present. Therefore, in the production of the above reaction product, the total number of moles of hydroxyl groups of all reaction raw materials is preferably equal to or larger than the total number of moles of isocyanate groups. That is, the following compounds are mentioned as the compound (X1).

A compound having one (meth) acryloyl group and one hydroxyl group, a (meth) acryloyl group 2
Compounds having at least one and one hydroxyl group, compounds having one (meth) acryloyl group and two or more hydroxyl groups, (meth)
A compound having two or more acryloyl groups and two or more hydroxyl groups. Specifically, 2-hydroxyethyl (meth) acrylate, trimethylolpropanedi (meth)
Examples include 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.

Ring-opening reaction product of a compound having at least one epoxy group with (meth) acrylic acid. In this case, by the reaction between the epoxy group and (meth) acrylic acid, the epoxy group is opened to form an ester bond and a hydroxyl group to form a compound having a (meth) acryloyl group and a hydroxyl group. Alternatively, the epoxy group of the 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.

That is, polyepoxides, which are so-called epoxy resins, are preferred. For example, compounds having two or more glycidyl groups such as polyhydric phenols-polyglycidyl ether (specifically, bisphenol A-diglycidyl ether) And alicyclic epoxy compounds are preferred.

A reaction product of a (meth) acrylate having an epoxy group and a compound having a hydroxyl group or a carboxyl group. The (meth) acrylate having an epoxy group includes, for example, glycidyl (meth) acrylate.

The following are examples of the polyisocyanate. -Normal monomeric polyisocyanate. For example, 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 XDI, hydrogenated MD
And the like (abbreviations in []) are preferred, but non-yellowing polyisocyanates (polyisocyanates not having an isocyanate group directly bonded to an aromatic nucleus) are preferable, and specific examples thereof include aliphatic polyisocyanates such as hexamethylene diisocyanate. Examples include alicyclic polyisocyanates such as isocyanate and isophorone diisocyanate, and aromatic polyisocyanates such as xylylene diisocyanate. Also,
As described later, these multimers and denatured products are also preferable.

Prepolymer compounds such as multimers, modified polyisocyanates or isocyanate group-containing urethane prepolymers. Examples of the polymer include a trimer (isocyanurate-modified), dimer, and carbodiimide-modified. Examples of the modified include urethane-modified products obtained by denaturation with a polyhydric alcohol such as trimethylolpropane. There are a buret modified product, an allohanate modified product, a urea modified product and the like.

Examples of the prepolymer compound include isocyanate group-containing urethane prepolymers obtained by reacting polyols such as polyether polyols and polyester polyols described below with polyisocyanates. Two or more isocyanates may be used in combination.

Next, examples of the compound (X2) include the following. Polyhydric alcohol aliphatic polyhydric alcohol, or alicyclic polyhydric alcohol or polyhydric alcohol having an aromatic nucleus,
Polyhydric alcohols having 20 hydroxyl groups are preferable, and polyhydric alcohols having 2 to 15 hydroxyl groups are particularly preferable.

As the polyhydric alcohol having an aromatic nucleus,
For example, an alkylene oxide adduct of a polyhydric phenol or a ring-opened product of a polyepoxide having an aromatic nucleus such as a polyhydric phenol-polyglycidyl ether may be used.

That is, as the polyhydric alcohol,
For example, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexanediol, dimethylolcyclohexane, trimethylolpropane, glycerin, pentane Erythritol, 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.

Polyols higher in molecular weight than polyhydric alcohols Polyether polyols, polyester polyols, polyether ester polyols, polycarbonate polyols and the like can be mentioned. Also, a hydroxyl group-containing vinyl polymer can be used as the polyol.

Examples of the hydroxyl group-containing vinyl polymer include:
For example, there is 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.

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

The above-mentioned polyhydric alcohols and polyols may be used in combination of two or more. Then, the compound (X
Examples of 3) include 2-isocyanatoethyl (meth) acrylate and methacryloyl isocyanate.

Ii) As the (meth) acrylate compound having no urethane bond, a polyester of a compound having two or more hydroxyl groups and a (meth) acrylic acid similar to the compound (X2) is 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, commercially available epoxy resins such as glycidyl ether type polyepoxide and alicyclic type polyepoxide can be used. Specific examples of the polyfunctional compound containing no urethane bond include the following compounds.

A) The following (meth) acrylates of aliphatic polyhydric alcohols. 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-
Hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate.

B) (meth) acrylates of the following polyhydric alcohols or polyphenols 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.

(C) the following (meth) acrylates of hydroxyl group-containing compounds-alkylene oxide adducts, (meth) acrylates of hydroxyl group-containing compounds-caprolactone adducts,
(Meth) acrylate of polyoxyalkylene polyol. Here, EO represents ethylene oxide, and PO represents propylene oxide.

Trimethylolpropane-EO adduct tri (meth) acrylate, trimethylolpropane-P
O adduct tri (meth) acrylate, dipentaerythritol-caprolactone adduct hexa (meth) acrylate, tris (2-hydroxyethyl) isocyanurate-caprolactone adduct tri (meth) acrylate, tris (2-hydroxyethyl) ) Tri (meth) acrylate of isocyanurate-caprolactone adduct.

Thus, specific preferred polyfunctional compounds (a) are the following polyfunctional compounds having no urethane bond with acrylic urethane. Examples of the acrylic urethane include acrylic urethane which is a reaction product of pentaerythritol or polypentaerythritol which is a polymer thereof, polyisocyanate and hydroxyalkyl (meth) acrylate), or hydroxyl group-containing poly (meth) of pentaerythritol or polypentaerythritol Acrylic urethane, which is a reaction product of acrylate and polyisocyanate, having 3 or more functional groups (preferably 4 to 20 functional groups)
Compound.

Examples of the polyfunctional compound having no urethane bond include pentaerythritol poly (meth) acrylate and isocyanurate poly (meth) acrylate.
The pentaerythritol-based poly (meth) acrylate refers to pentaerythritol or a polyester of polypentaerythritol and (meth) acrylic acid (preferably having a functionality of 4 to 20).

The 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).

It is also preferable to use these preferable polyfunctional compounds in combination with other bifunctional or higher polyfunctional compounds (particularly poly (meth) acrylates of polyhydric alcohols).
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).

B) In order to cure the polyfunctional compound (a), the coating composition (B) usually contains a photopolymerization initiator. As the photopolymerization initiator, known ones can be used, and a plurality of photopolymerization initiators may be used in the transparent cured material layer. However, a commercially available photopolymerization initiator is particularly preferable.

Examples of the photopolymerization initiator include arylketone photopolymerization initiators (for example, 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, diacylphosphine oxide photopolymerization initiators, and other photopolymerization initiators Agents and the like. In particular, an acylphosphine oxide-based photopolymerization initiator and a diacylphosphine oxide-based photopolymerization initiator are preferably used. Further, the photopolymerization initiator may be used in combination with a photosensitizer such as an amine.

That is, 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,
-(4-isopropylphenyl) -2-hydroxy-2
-Methylpropan-1-one, 1- (4-dodecylphenyl) -2-methylpropan-1-one, 1- {4-
(2-hydroxyethoxy) phenyl} -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- {4-
(Methylthio) phenyl} -2-morpholinopropane-
1-on.

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'-diethylisophthalophenone, α-acyloxime ester, methyl phenylglyoxylate.

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 (B) depends on the amount of the curable component (the polyfunctional compound (a)).
And the total amount of monofunctional compound) is 0.0 with respect to 100 parts by weight.
The amount is preferably 1 to 20 parts by weight, particularly preferably 0.1 to 10 parts by weight.

The coating composition (B) may contain, if necessary, various compounding agents (for example, a light stabilizer, an ultraviolet absorber, an antioxidant, a thermal polymerization inhibitor, etc.) in addition to the above basic components. Agents, leveling agents, defoamers, thickeners, antisettling agents, pigments, dispersants, antistatic agents, surfactants such as antifoggants,
Curing catalyst selected from acids, alkalis and salts, etc.).

In the coating liquid containing the coating composition (B) for forming the layer of the coating composition (B), the solvent is usually an essential component, and the polyfunctional compound (a) is particularly low. Solvents are used unless they are viscous liquids. As the above-mentioned solvent, a solvent usually used for the coating composition (B) containing the polyfunctional compound (a) as a curing component can be used. Although a dispersion medium of the raw material colloidal silica described below 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.

That is, for example, solvents such as lower alcohols, ketones, ethers and cellosolves, n-butyl acetate and diethylene glycol monoacetate, which are mentioned as solvents used for hydrolysis for modifying the colloidal silica described later. Esters, halogenated hydrocarbons, hydrocarbons and the like, but for coating of an aromatic polycarbonate resin having low solvent resistance, lower alcohols, cellosolves, esters, mixtures thereof and the like are suitable. It is.

The amount of the solvent can be appropriately changed depending on the required viscosity of the composition, the desired thickness of the cured film, the conditions of the drying temperature, and the like, but is usually 100 times the curable component in the composition. It is used up to the weight, preferably 0.1 to 50 times the weight.

A-5) The active energy ray for curing the coating composition (B) is not particularly limited, but ultraviolet rays are preferred. 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 as the ultraviolet light source.

The thickness of the layer of the cured product formed using the coating composition (B) is preferably 1 to 50 μm, more preferably 2 to 3 μm.
0 μm is preferred. When the layer thickness is more than 50 μm, curing by active energy rays is insufficient, and the adhesion to the substrate is easily damaged. When the thickness is less than 1 μm, the abrasion resistance of this layer may be insufficient, and There is a possibility that the abrasion resistance and the abrasion resistance of the outermost layer formed on this layer may not be sufficiently exhibited.

In the present invention, colloidal silica having an average particle diameter of 200 nm or less may be added to the coating composition (B) in order to increase the abrasion resistance and hardness of the inner layer of the transparent cured product which is in direct contact with the outermost layer. . The colloidal silica preferably has an average particle size of 1 to 100 nm, particularly 1 to 5 nm.
0 nm is preferred.

The amount of the colloidal silica added is
It is preferably at least 5 parts by weight, particularly preferably at least 10 parts by weight, per 100 parts by weight of the curable component (the total of the polyfunctional compound (a) and the monofunctional compound) of the transparent cured material layer.

When the amount is small, it is difficult to obtain sufficient abrasion resistance. When the amount is too large, clouding (haze) tends to occur in the coating. When performing secondary processing such as, for example, cracks are likely to occur.

Therefore, the upper limit of the amount of colloidal silica in the curable component of the transparent cured product layer is determined by the curable component 100
300 parts by weight to the parts by weight are preferred. That is, the most preferred amount of colloidal silica is 100 curable components.
It is 50 to 250 parts by weight based on parts by weight.

As the colloidal silica, a surface-unmodified colloidal silica can be used, but a surface-modified colloidal silica (hereinafter referred to as a modified colloidal silica) is preferably used. By using the surface-modified colloidal silica, the dispersion stability of the colloidal silica in the coating composition (B) is improved, and the adhesion between the colloidal silica and the polyfunctional compound (a) is improved. .

The average particle size of the colloidal silica fine particles is considered to be substantially unchanged 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 medium of the colloidal silica, and the dispersion medium of the raw material colloidal silica is not particularly limited, and the modification can be performed by changing the dispersion medium if necessary. Although the dispersion medium can be changed after the modification, 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 material layer are, for reasons such as easiness of production, Preferably, they are all the same medium (solvent).

As such a medium, an ordinary solvent for a coating material, which is a solvent having a relatively low boiling point, is preferable from the viewpoint of drying properties and the like, and examples thereof include the following compounds.

Water, methanol, ethanol, isopropyl alcohol, n-butanol, t-butanol, 4-
Lower alcohols such as 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 the above-mentioned medium, organic solvents are preferable, and alcohols and cellosolves are particularly preferable. In addition, an integrated body of colloidal silica and a dispersion medium in which the colloidal silica is dispersed is hereinafter referred to as a colloidal silica dispersion.

The modification of the colloidal silica is preferably performed using a compound having a hydrolyzable silicon group or a silicon group having a hydroxyl group bonded thereto (hereinafter, referred to as a modifier).
That is, it is considered that silanol groups are generated by hydrolysis of hydrolyzable silicon groups, and these silanol groups react and bond with silanol groups that are considered to be present on the colloidal silica surface, and the modifier binds to the colloidal silica surface. Can be

The above-mentioned modifying agents may be used in combination of two or more kinds, and as described later, a reaction product obtained by preliminarily reacting two kinds of modifying agents having reactive functional groups reactive with each other is modified. It can also be used as an agent. That is, the modifying agent may have two or more hydrolyzable silicon groups or silanol groups, or 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 (a partial hydrolysis condensate may be generated in the modification process). More preferably, a compound having an organic group bonded to a silicon atom and at least one of the organic groups being an organic group having a reactive functional group is used.

Examples of the reactive functional group include an amino group, a mercapto group, an epoxy group and a (meth) acryloyloxy group. 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 (particularly, a polymethylene group). preferable. Therefore, specific examples of the modifying agent include the following compounds when classified according to the type of the reactive functional group.

(Silane) containing (meth) acryloyloxy group: 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, etc. .

Amino group-containing silanes: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane,
3-ureidopropyltriethoxysilane, N- (N-
Vinylbenzyl-2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and the like.

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

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

Isocyanate group-containing silanes: 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropylmethyldiethoxysilane and the like.

The reaction products 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 product of amino group-containing silanes and (meth) acryloyloxy group-containing silanes ・ Reaction product of epoxy group-containing silanes and mercapto group-containing silanes ・ Mercapto group-containing silanes 2 Reaction products of molecules, and the like.

In the modification of the colloidal silica, the amount of the modifier used is not particularly limited, but 100 parts by weight of the colloidal silica (solid content in the dispersion) and the modifier 1 are used.
-100 parts by weight are suitable. When the amount of the modifier is less than 1 part by weight, the effect of surface modification is hardly obtained, and when it exceeds 100 parts by weight, a hydrolyzate-condensate of an unreacted modifier or a modifier not supported on the surface of colloidal silica is used. When the transparent coating layer (cured composition) is cured, they act as a chain transfer agent or act as a plasticizer of the cured film, which may lower the hardness of the cured film.

The modification of the colloidal silica is usually carried out by bringing the above-mentioned modifier into contact with the colloidal silica in the presence of a catalyst and hydrolyzing it. Examples of the catalyst include acids and alkalis. Preferably, an acid selected from inorganic acids and organic acids is used.

Examples of the inorganic acids include hydrohalic acids such as hydrochloric acid, hydrofluoric acid and hydrobromic acid, and sulfuric acid, nitric acid and phosphoric acid. Examples of the organic acids include formic acid, acetic acid, oxalic acid and acrylic acid. And methacrylic acid.

The reaction temperature is preferably from room temperature to the boiling point of the solvent used, and the reaction time is preferably from 0.5 to 24 hours, depending on the temperature.

C) Description of Coating Composition (C) The coating composition (C) which usually forms the outermost silica layer
Contains a hydrolyzable silyl group-containing compound (b) and a polysilazane (c). Examples of the hydrolyzable silyl group-containing compound (b) forming the silica include a silane compound having four hydrolyzable groups bonded to a silicon atom, a partially hydrolyzed condensate thereof, a silicone-based thermosetting compound, and a silazane. No.

Examples of the silane compound in which four hydrolyzable groups are bonded to a silicon atom and its partially hydrolyzed condensate include tetraalkoxysilane and its partially hydrolyzed condensate, and preferably silazane is used.

The polysilazane (c) is composed of a polymer having a chain, cyclic or cross-linked structure, or a mixture of a plurality of the above structures in the molecule, and forms silica having a more dense structure. The outermost layer can be obtained.

Examples of the polysilazane include polysilazane (perhydropolysilazane) substantially free of an 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. Among them, perhydropolysilazane is particularly preferred in view 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 molecular weight of the polysilazane is preferably 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 baked, and if the number average molecular weight is more than 50,000, it becomes difficult to dissolve in a solvent, and the coating composition (C) may become viscous. It is not preferable because there is.

The coating liquid for forming the layer of the coating composition (C) usually contains a solvent that dissolves the hydrolyzable silyl group-containing compound (b) and the polysilazane (c). As the solvent for dissolving polysilazane, hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, halogenated hydrocarbon solvents, aliphatic ethers and ethers such as alicyclic ethers can be used. .

Specifically, hydrocarbons such as pentane, hexane, isohexane, methylpentane, heptane, isoheptane, octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, etc. Halogenated hydrocarbons such as methylene, chloroform, carbon tetrachloride, bromoform, 1,2-dichloroethane, 1,1-dichloroethane, trichloroethane, tetrachloroethane, ethyl ether, isopropyl ether, ethyl butyl ether, butyl ether, dioxane, dimethyl dioxane, tetrahydrofuran And ethers such as tetrahydropyran.

When the above-mentioned solvent is used, plural kinds of solvents may be mixed and used for adjusting the solubility of polysilazane and the evaporation rate of the solvent.

The amount of the solvent to be used can be appropriately selected depending on the coating method to be adopted, the structure of polysilazane, the average molecular weight, and the like. preferable.

In order to cure the polysilazane to silica, heating usually called calcination is required. However, in the present invention, the calcination temperature is limited because the base material is a synthetic resin.

In the present invention, the heat resistance of the cured product of the coating composition (B) is generally higher than that of the substrate. However, in some cases, the heat resistance of the cured product of the coating composition (B) may be lower than the heat resistance of the base material, in which case it is necessary to fire 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.

In the present invention, when the polysilazane is cured at a low temperature, it is preferable to use a catalyst, and curing at room temperature is possible depending on the type and amount of the catalyst. The atmosphere for curing is preferably an atmosphere in which oxygen is present, such as in air.

It is preferable to use a catalyst capable of curing polysilazane at a lower temperature.
As such a catalyst, known catalysts can be used. For example, fine particles of metals such as gold, silver, palladium, platinum, and nickel described in JP-A-7-196886, and JP-A-5-93275 Examples thereof include those carboxylic acid complexes described in the gazette.

When a catalyst is used, the catalyst is not added to the polysilazane solution, but is added to JP-A-9-3.
As described in JP-A No. 1333, a method of directly contacting the coated molded article with a catalyst solution, specifically, an aqueous amine solution or the like, or exposing the coated molded article to a vapor thereof for a certain period of time can be mentioned.

D) Hydrolyzable silyl group-containing compound (b)
In the present invention, a hydrolyzable silyl group-containing compound (b) is added to the coating composition (C) in order to increase the adhesion between the coating composition (B) and the coating composition (C). ing. As the hydrolyzable silyl group-containing compound (b),
There are a silane coupling agent represented by the following formula 1 and silazane.

ZR ¹ -Si (R ² ) _p (X) _{3 -p} Formula 1 wherein the symbols in the formula 1 have the following meanings. X: hydrolyzable group. R ¹ : divalent organic group (bonded to a silicon atom by a silicon-carbon bond). R ² : a monovalent organic group. Z: functional group. p: 1 or 2.

In the above formula 1, examples of X include an alkoxy group, an acyl group, an amino group, an isocyanate group and the like, and the most preferred is an alkoxy group having 1 to 4 carbon atoms. R ¹ is a hydrocarbon group having 2 to 8 carbon atoms, most preferably an alkylene group.
R ² is an alkyl group having 1 to 4 carbon atoms, Z is a (meth) acryloyl group, a mercapto group, an amino group,
Epoxy, vinyl and isocyanate groups are exemplified.

In the present invention, by adding the silane coupling agent, the functional group represented by Z and the functional group of the polyfunctional compound (a) in the inner layer are polymerized or reacted,
Further, it is considered that the inner layer and the outermost layer are more closely adhered to each other by the dehydration reaction between the functional group represented by X and the polysilazane in the outermost layer. In the case of silazane, it is considered that the organic group of silazane has an affinity for the cured inner layer and improves the adhesion. As the silyl group-containing compound (b),
One or more silazane or silane coupling agents may be used.

Examples of the silazane include 1,1,3,3-tetramethyldisilazane, hexamethyldisilazane, 1,3
-Bis (chloromethyl) -1,1,3,3-tetramethyldisilazane, heptamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, hexaphenylcyclodisilazane, 1,1,3,3,5,5
-Hexamethylcyclotrisilazane, 1,1,3,3
5,5,7,7-octamethylcyclotetrasilazane,
Perhydropolysilazane, methyl group-containing polysilazane and the like can be used.

As the silane coupling agent, for example,
(Meth) described as a modifier for the colloidal silica
Acryloyloxy group-containing silanes, amino group-containing silanes, mercapto group-containing silanes, epoxy group-containing silanes, or isocyanate group-containing silanes can be used.

Among the above, silanes containing a (meth) acryloyloxy group or silanes containing a mercapto group capable of reacting with a radical in the inner layer are particularly preferred.

The amount of the silyl group-containing compound (b) in the coating composition (C) is from 0.01 to 200 parts by weight, especially from 0.1 to 50 parts by weight, per 100 parts by weight of the polysilazane (c).
Parts by weight are preferred.

The coating composition (C) may further contain, if necessary, stabilizers such as an ultraviolet absorber, a light stabilizer and an antioxidant;
Surfactants such as a leveling agent, an antifoaming agent, a thickener, an antisettling agent, a pigment, a dispersant, an antistatic agent and an antifogging agent may be appropriately blended and used.

In the present invention, the thickness of the cured product layer formed using the coating composition (C) is 0.05 to 10 μm.
Is preferred, and particularly preferably 0.1 to 3 μm.

When the thickness of the outermost layer is more than 10 μm, improvement in surface properties such as scratch resistance cannot be expected any more, and the outermost layer becomes brittle due to a slight deformation of the coated molded article. Tends to occur, and 0.05 μm
If it is less than 3, the abrasion resistance and abrasion resistance of the outermost layer may not be sufficiently exhibited.

E) The two types of coating compositions (B) described above,
Method of forming two layers of transparent cured product (transparent cured product layer (A)) formed using (C) For example, first apply coating composition (B) on a substrate and cure Then, a usual coating technique such as coating the coating composition (C) on the surface of the cured product and curing the coating composition can be employed.

In the case of having a second inner layer, after coating, the coating composition is dried to remove the solvent (when the composition of the second inner layer contains a solvent), and then the coating composition (B) is added. The used layer is cured by irradiating ultraviolet rays or the like, and the coating composition (C)
Is cured by heating or left at room temperature or by exposure to the vapor of a curing catalyst solution.

The means for applying the coating composition is not particularly limited, and examples thereof include a dip method, a flow coat method, a spray method, a bar coat method, a gravure coat method, a roll coat method, a blade coat method, and an air knife coat method. Known methods such as a spin coating method, a spin coating method, a slit coating method, and a microgravure coating method can be employed.

The combination (timing) of the curing of the coating composition (B) and the coating and curing of the coating composition (C) includes the following methods. 1) A method of applying the coating composition (B) thereon, irradiating a sufficient amount of active energy rays after applying the coating composition, sufficiently completing the curing, and then coating the coating composition (C) thereon (described above). Method).

2) After coating the coating composition (B) to form an uncured layer of the coating composition (B), the coating composition (C) was coated on the uncured layer. Forming a layer of the uncured material of the coating composition (C), and then irradiating a sufficient amount of active energy rays to terminate the curing of the uncured material of the coating composition (B). In this case, the uncured product of the coating composition (C) is cured by leaving the uncured product of the coating composition (B) at room temperature or by being exposed to the vapor of a catalyst solution.

3) After applying the coating composition (B), a minimum active energy ray (usually about 3
(Irradiation amount of up to 00 mJ / cm ² ) to form a partially cured layer of the coating composition (B), and then apply the coating composition (C) on the partially cured layer to form a coating. A method of forming a layer of the uncured material of the composition (C) and thereafter irradiating a sufficient amount of active energy rays to terminate the curing of the uncured material of the coating composition (B). The method of curing the uncured material of the coating composition (C) is the same as in the case 2) above.

In the present invention, the method 2) or 3) described above is preferable in order to increase the interlayer adhesion between the two cured product layers. However, in the case of the method 2), when the dipping method is used as a method of applying the coating composition (C), the component of the uncured material of the coating composition (B) is changed to a dipping liquid of the coating composition (C). Therefore, there is a restriction that coating by such a dipping method is not suitable.

In the present invention, according to the method described above,
A transparent cured product layer (A) comprising at least two layers as described above is formed on both surfaces or one surface of the substrate.

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 at the same level as those of glass. It can be used for various purposes such as use as a material.

In the present invention, when manufacturing a bent molded product (such as a window material for a vehicle), the transparent cured product layer (A) can be formed by using a base material that has been bent in advance. On the partially cured layer of the coating composition (B),
It is preferable to bend the coating composition (C) in a state where a layer of an uncured product or a partially cured product is formed.

That is, when a base material that has been bent in advance is used, it may be difficult to form each layer by coating and curing, and a layer of a cured product of the coating composition (B) may be formed. The substrate can be bent by hot bending or the like. However, when a layer of a cured product of the coating composition (C) is formed, the cured product is hard, so that it becomes difficult to bend. .

After the bending, or almost simultaneously with the bending, the uncured or partially cured product of the coating composition (C) is cured, so that the desired bent molded article can be obtained.

Since the bending is performed in a heated state,
The uncured or partially cured product of the coating composition (C) is cured by heating during bending, but usually the uncured or partially cured product of the coating composition (C) is compared with the time required for bending. Since the time required for curing the cured product is long, the coating composition (C)
It is unlikely that the bending process will be difficult due to the hardening.

Accordingly, the bent molded article of the present invention comprises a layer of a partially cured product of the coating composition (B) on a substrate and an uncured product of the coating composition (C) on the surface of the layer. Alternatively, after forming layers of partially cured products, the substrate having these layers is bent, and then the uncured or partially cured product of the coating composition (C) and the partially cured product of the coating composition (B) are removed. It can be manufactured by curing.

Specifically, for example, after forming a layer of an uncured material or a partially cured material of the coating composition (C), it is heated to the heat softening temperature of the substrate for about 5 minutes, and then subjected to bending. . Thereafter, the bending process of the present invention is carried out by keeping the coating composition (C) at a temperature at which the uncured or partially cured product can be cured, or by leaving it at room temperature, or by exposing it to the vapor of a curing catalyst solution. A coated molded article can be obtained.

According to the above-described method, the base material is deformed before the coating composition (C) is sufficiently cured, and thereafter, a hard silica layer is formed. Therefore, problems such as cracks do not occur in the silica layer.

F) The material of the transparent synthetic resin substrate in the present invention is not particularly limited, and 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), and a polystyrene resin may be used, and a substrate made of an aromatic polycarbonate resin is particularly preferably used.

The transparent synthetic resin substrate may be a molded substrate, for example, a sheet substrate such as a flat plate or a corrugated plate, a film substrate, a substrate molded into various shapes, or at least a surface. Examples of the layer include a laminate made of various transparent synthetic resins, and a flat (unbent) flat base material is particularly preferably used.

The thickness of the base material can be appropriately selected depending on its use. For example, when used for applications such as window materials, the thickness of the sheet is preferably 1 to 100 mm.

[0142]

EXAMPLES Synthesis Examples (Examples 1-2) and Examples (Examples 3-1)
9) and Comparative Examples (Examples 20 to 22), but the present invention is not limited to these.

For Examples 3 to 20, the base material having a thickness of 3
mm transparent aromatic polycarbonate resin plate (150 m
mx 300 mm), and measurement and evaluation of various physical properties
The procedure was as follows, and the results are shown in Table 1.

[Initial haze value, abrasion resistance] JIS-R3212
According to the abrasion resistance test method described above, a haze value was measured with a haze meter when a 500 g weight was combined with each of two CS-10F abrasion wheels and rotated 500 times. The haze is measured at four points on the wear cycle orbit,
The average was calculated. The initial haze indicates the value (%) of the haze before the abrasion test, and the abrasion resistance indicates the value (%) of (haze after the abrasion test)-(haze before the abrasion test).

[Adhesion] The sample was cut with 11 blades at 1 mm intervals in the vertical and horizontal directions with a razor blade to make 100 grids. Then, after closely attaching a commercially available cellophane tape, the number (m) of the grids remaining without peeling the coating when peeled sharply in the forward direction by 90 degrees is m / 100.
Expressed by

[Abrasion resistance after moisture resistance test]
C. and a relative humidity of 95% for 2 weeks, and then, according to the abrasion resistance test method in JIS-R3212 described above,
The haze was measured in the same manner.

[Weather Resistance] Using a sunshine weather meter, exposure was performed for 3000 hours in a cycle of 12 minutes of rainfall and 48 minutes of drying at a black panel temperature of 63 ° C., and the appearance was evaluated.

[Bending] The sample was held in a hot air circulating oven at 170 ° C. for 5 minutes, and immediately after being taken out, pressed against a mold having a curvature of 180 mmR so that the coated surface of the transparent cured material layer was convex, and bent. Processed.

[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] Ethyl cellosolve dispersed colloidal silica (silica content: 30% by weight, average particle size: 11 nm)
To 100 parts by weight, 5 parts by weight of 3-acryloyloxypropyltrimethoxysilane and 3.0 parts by weight of 0.1N hydrochloric acid were added, and the mixture was heated and stirred at 100 ° C. for 6 hours and then aged at room temperature for 12 hours to obtain acrylsilane. A modified colloidal silica dispersion was obtained.

[Example 3] 10 equipped with a stirrer and a cooling pipe
In a 0 ml four-necked flask, add isopropyl alcohol 1
5 g, butyl acetate 15 g, ethyl cellosolve 7.5 g,
150 mg of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethyl Phenyl) -1,3,5-triazine and 2- [4-[(2-
Hydroxy-3-tridecyloxypropyl) oxy]
-2-hydroxyphenyl] -4,6-bis (2,4-
850 mg of a mixture of (dimethylphenyl) -1,3,5-triazine and 200 m of N-methyl-4-methacryloyloxy-2,2,6,6-tetramethylpiperidine
g was added and dissolved, and then 10.0 g of dipentaerythritol hexaacrylate was added, followed by stirring at room temperature for 1 hour to obtain a coating composition (hereinafter, referred to as coating liquid 1).

The coating solution 1 was applied to the substrate using a bar coater (wet thickness: 30 μm), and was kept in a hot air circulating oven at 80 ° C. for 5 minutes. This was put in an air atmosphere using a high-pressure mercury lamp at 2000 mJ / cm ² (wavelength 300 to
Ultraviolet light having a cumulative energy amount of 390 nm region (the same applies hereinafter) was applied to form a cured product of a 7 μm-thick transparent coating layer.

Next, a xylene solution of a perhydropolysilazane curable at a low temperature (solid content: 20% by weight,
A coating liquid (hereinafter referred to as coating liquid 2) obtained by adding 3 parts by weight of 3-acryloyloxypropyltrimethoxysilane to 100 parts by weight of perhydropolysilazane to Tonen Co., Ltd. product name "L110") was again coated with a bar coater. Coating (wet thickness: 3 μm) and holding in a hot air circulating oven at 80 ° C. for 10 minutes to remove the solvent, and then again in an air atmosphere using a high-pressure mercury lamp at 2000 mJ / cm ^2.
UV light was applied. Subsequently, the outermost layer was sufficiently hardened by holding in a hot air circulating oven at 100 ° C. for 120 minutes. Then, it was confirmed by IR analysis that the outermost layer was almost completely a 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 layer sufficiently cured by using the above-mentioned coating liquid 1, the abrasion resistance of the surface of the transparent cured layer was evaluated. 2.8% wear resistance after 100 revolutions
Met.

Example 4 The procedure was the same as in Example 3 except that the method of adjusting the sample was changed as follows. The coating solution 1 was applied and kept in a hot air circulating oven at 80 ° C. for 5 minutes. This is 150 mJ / c using a high pressure mercury lamp in an air atmosphere.
Irradiation with ultraviolet light of m ² was performed to form a cured product of a transparent coating layer having a thickness of 7 μm. A coating solution 2 was applied thereon and cured in the same manner as in Example 3. The measurement was performed using this sample.

Example 5 The procedure of Example 4 was repeated, except that the sample adjustment method was changed as follows. Finally, instead of holding in a hot air circulating oven at 100 ° C. for 120 minutes,
Cured for 1 day in an environment of 3 ° C. and 55% relative humidity. The measurement was performed using this sample.

Example 6 The procedure was the same as Example 3 except that the sample preparation method was changed as follows. The coating liquid 2 was added to a catalyst-free xylene solution of perhydropolysilazane (solid content 20% by weight, trade name "V110" manufactured by Tonen Co., Ltd.) with 3-acryloyloxypropyltrimethoxysilane per 100 parts by weight of perhydropolysilazane. To 3 parts by weight (hereinafter, referred to as coating liquid 3). The measurement was performed using this sample.

Example 7 The procedure was the same as in Example 6, except that the sample preparation method was changed as follows. The coating solution 1 was applied and kept in a hot air circulating oven at 80 ° C. for 5 minutes. This is 150 mJ / c using a high pressure mercury lamp in an air atmosphere.
Irradiation with ultraviolet light of m ² was performed to form a cured product of a transparent coating layer having a thickness of 7 μm. On this, coating liquid 3 was applied and cured in the same manner as in Example 3. The measurement was performed using this sample.

Example 8 The procedure was the same as in Example 7, except that the sample adjustment method was changed as follows. Finally, instead of holding in a hot air circulating oven at 100 ° C. for 120 minutes,
Cured for 1 day in an environment of 3 ° C. and 55% relative humidity. The measurement was performed using this sample.

Example 9 The procedure was the same as in Example 8, except that the sample adjustment method was changed as follows. Finally, instead of curing for 1 day in an environment of 23 ° C. and 55% relative humidity, 25 ° C.
Cured by holding on a bath of 3% aqueous triethylamine solution kept for 3 minutes. The measurement was performed using this sample.

Example 10 The procedure was the same as Example 3 except that the sample preparation method was changed as follows. The coating liquid 2 is a catalyst-free perhydropolysilazane xylene solution (solid content 20% by weight, trade name “V110” manufactured by Tonen Corporation)
To 3 parts by weight of 3-mercaptopropyltrimethoxysilane per 100 parts by weight of perhydropolysilazane (hereinafter referred to as coating liquid 4). The measurement was performed using this sample.

Example 11 The procedure was the same as in Example 10, except that the sample preparation method was changed as follows. The coating solution 1 was applied and kept in a hot air circulating oven at 80 ° C. for 5 minutes. It is 150m in an air atmosphere using a high pressure mercury lamp.
Irradiation with ultraviolet light of J / cm ² was performed to form a cured product of a transparent coating layer having a thickness of 7 μm. On top of this, coating liquid 4 was applied in the same manner as in Example 3.
Was applied and cured. The measurement was performed using this sample.

Example 12 The procedure was the same as in Example 11, except that the sample adjustment method was changed as follows. Finally 100
Instead of keeping in a hot air circulating oven at 120 ° C. for 120 minutes, it was cured for one day in an environment of 23 ° C. and 55% relative humidity.
The measurement was performed using this sample.

Example 13 The procedure was the same as Example 12 except that the sample adjustment method was changed as follows. Finally 23
Instead of curing for 1 day in an environment of ℃ and 55% relative humidity,
It was cured by holding it on a 3% aqueous solution of triethylamine kept at 25 ° C. for 3 minutes. The measurement was performed using this sample.

Example 14 The procedure was the same as in Example 3, except that the sample preparation method was changed as follows. The coating liquid 2 was added to a polysilazane xylene solution (solid content: 20% by weight, trade name “NL710” manufactured by Tonen Co., Ltd.) in which a part of hydrogen on silicon atoms was substituted with a methyl group) for 3-acryloyloxypropyltrimethoxysilane. Was changed to a coating liquid (hereinafter referred to as coating liquid 5) obtained by adding 3 parts by weight to 100 parts by weight of perhydropolysilazane. The measurement was performed using this sample.

Example 15 The procedure was the same as Example 14 except that the sample adjustment method was changed as follows. The coating solution 1 was applied and kept in a hot air circulating oven at 80 ° C. for 5 minutes. It is 150m in an air atmosphere using a high pressure mercury lamp.
Irradiation with ultraviolet light of J / cm ² was performed to form a cured product of a transparent coating layer having a thickness of 7 μm. On top of this, a coating liquid 5 was prepared in the same manner as in Example 3.
Was applied and cured. The measurement was performed using this sample.

[Example 16] The procedure of Example 15 was repeated, except that the sample preparation method was changed as follows. Finally 100
Instead of keeping in a hot air circulating oven at 120 ° C. for 120 minutes, it was cured for one day in an environment of 23 ° C. and 55% relative humidity.
The measurement was performed using this sample.

[Example 17] 1 equipped with a stirrer and a cooling pipe
In a 00 ml four-necked flask, 15 g of isopropyl alcohol, 15 g of butyl acetate and 7.5 of ethyl cellosolve were added.
g, 2,4,6-trimethylbenzoyldiphenylphosphine oxide 150 mg, 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4 -Dimethylphenyl) -1,3,5-triazine and 2- [4-
[(2-hydroxy-3-tridecyloxypropyl)
Oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine (850 mg) and N-methyl-4-methacryloyloxy-2,2,6, 200 mg of 6-tetramethylpiperidine was added and dissolved, and then 10.0 g of dipentaerythritol hexaacrylate was added, followed by stirring at room temperature for 1 hour to obtain a coating composition. Subsequently, the mercaptosilane-modified colloidal silica dispersion synthesized in Example 1 was added to 3
0.3 g was further added and the mixture was further stirred at room temperature for 15 minutes to obtain a coating composition (hereinafter, referred to as coating liquid 6).

Example 5 Using Coating Liquid 6 Instead of Coating Liquid 1
A sample was prepared in the same manner as described above. 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 coating liquid 6, the abrasion resistance of the surface of the transparent cured material layer was evaluated. 1.5% wear resistance after 100 revolutions
Met.

[Example 18] 1 equipped with a stirrer and a cooling pipe
In a 00 ml four-necked flask, 15 g of isopropyl alcohol, 15 g of butyl acetate and 7.5 of ethyl cellosolve were added.
g, 2,4,6-trimethylbenzoyldiphenylphosphine oxide 150 mg, 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4 -Dimethylphenyl) -1,3,5-triazine and 2- [4-
[(2-hydroxy-3-tridecyloxypropyl)
Oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 850 mg, and N-methyl-4-methacryloyloxy-2,2,6, 200 mg of 6-tetramethylpiperidine was added and dissolved, and then 10.0 g of dipentaerythritol hexaacrylate was added, followed by stirring at room temperature for 1 hour to obtain a coating composition. Subsequently, the acrylsilane-modified colloidal silica dispersion liquid synthesized in Example 2 was used for 30.
3 g 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 7).

Example 5 A coating liquid 7 was used in place of the coating liquid 1.
A sample was prepared in the same manner as described above. The measurement was performed using this sample.

On the other hand, another sample of an aromatic polycarbonate resin plate having a transparent cured product layer sufficiently cured using the above-mentioned coating liquid 6 was evaluated for abrasion resistance on the surface of the transparent cured product layer. Abrasion resistance after 100 rotations is 1.4%
Met.

Example 19 The procedure of Example 5 was repeated, except that the sample preparation method was changed as follows. The coating liquid 1 was coated (wet thickness 30 μm) using a bar coater,
It was kept in a hot air circulating oven at 0 ° C. for 5 minutes. This was irradiated with 150 mJ / cm ² ultraviolet rays using a high-pressure mercury lamp in an air atmosphere to form a 7 μm-thick partially cured product layer. Then, the coating liquid 2 was again coated thereon (wet thickness: 6 μm) using a bar coater, and kept in a hot air circulating oven at 80 ° C. for 5 minutes to remove the solvent. 2000mJ / c using a mercury lamp
It irradiated with ultraviolet rays of m ^2, and held 5 minutes at subsequent 170 ° C. hot air circulating oven, as transparent cured layer coated surface immediately after extraction is convex side, pressed against a mold having a curvature of 64MmR, bending Processed. And at room temperature
As a result of observing the appearance of the sun-cured sample, it was found that the sample had a good cured layer without cracks and wrinkles.

On the other hand, the sample finally obtained in Example 5 having two fully cured cured layers was held in a hot air circulating oven at 170 ° C. for 5 minutes. 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 20 The procedure of Example 3 was repeated, except that the sample preparation method was changed as follows. The coating liquid 2 is a low temperature curable xylene solution of perhydropolysilazane (solid content: 20% by weight, trade name “L110” manufactured by Tonen Co., Ltd.)
(Hereinafter referred to as coating liquid 8). The measurement was performed using this sample.

Example 21 Coating liquid 1 was coated using a bar coater (wet thickness: 30 μm) and kept in a hot air circulating oven at 80 ° C. for 5 minutes. In an air atmosphere,
Ultraviolet rays of 2000 mJ / cm ² were irradiated using a high-pressure mercury lamp to cure the transparent cured product layer having a thickness of 7 μm. The measurement was performed using this sample.

Example 22 A low-temperature curable perhydropolysilazane dibutyl ether solution (solid content: 20% by weight, trade name “L120” manufactured by Tonen Co., Ltd.) was applied using a bar coater (wet thickness: 3 μm). After holding in a hot air circulating oven at 80 ° C. for 10 minutes to remove the solvent, the sample was again 2,000 mJ / c in an air atmosphere using a high-pressure mercury lamp.
Irradiated with m ² ultraviolet rays. Subsequently, the outermost layer was sufficiently hardened by holding in a hot air circulating oven at 100 ° C. for 120 minutes. The measurement was performed using this sample.

[0179]

[Table 1]

From Table 1, the samples of Examples 3 to 18 containing the silyl group-containing compound (b) in the coating composition (C) are the samples containing no silyl group-containing compound (b) (Example 20). ), The abrasion resistance after the moisture resistance test, the abrasion resistance after the moisture resistance test and the abrasion resistance after the moisture resistance test and the weather resistance as compared with the sample having the coating layer of only the polyfunctional compound (a) (Example 21). Excellent in abrasion resistance, abrasion resistance after moisture resistance test, adhesion and weather resistance as compared with a sample having a coating layer containing only coating composition (C) containing polysilazane (c) (Example 22) I understood. And the result of Example 20 seems to be due to a decrease in the adhesion between the outermost layer and the inner layer in the moisture resistance test because the coating composition (C) does not contain the silyl group-containing compound (b). It is.

[0181]

According to the present invention, the transparent cured product layer (A)
Has at least a two-layer configuration of an outermost layer and an inner layer,
Since the outermost layer of silica is not laminated directly on the relatively soft transparent synthetic resin base material, it is laminated on the inner layer of the hard transparent cured product with high abrasion resistance. The displacement of the outermost layer due to an external force applied to damage the product is reduced, and surface characteristics higher than those provided by a normal inorganic coating can be obtained. Further, by adding the silyl group-containing compound (b) to the coating composition (C) to improve the adhesion between the outermost silica layer and the inner layer, the silica layer has an improved abrasion resistance and abrasion resistance. Surface properties can be improved.

According to the present invention, a transparent coated molded article having a surface having a high abrasion resistance almost equivalent to that of inorganic glass and having excellent surface characteristics can be obtained.

Continued on the front page F-term (reference) 4F100 AA20B AH03C AH03H AH06C AH06H AK01A AK01B AK25 AK45 AK79C AL05B AL05C BA03 BA07 BA10A BA10C BA32 DC21 EJ54 GB90 JB12C JB14B JK09 JK01 JN01JN01 FA1 JC30 JC35 KA03 KA06 KA14 NA01 NA03 NA11 PA17 PB08 PC08

Claims (4)

[Claims] 1. A transparent coated molded article having a transparent synthetic resin base material and a transparent cured product layer (A) provided on at least a part of the surface of the transparent synthetic resin base material and comprising at least an outermost layer and an inner layer. An active energy ray-curable coating in which the inner layer in contact with the outermost layer of the transparent cured material layer (A) contains a polyfunctional compound (a) having two or more active energy ray-curable polymerizable functional groups. A layer of a cured product of the composition (B), wherein the outermost layer is a silica layer which is a cured product of the coating composition (C) containing the hydrolyzable silyl group-containing compound (b) and the polysilazane (c). Characterized transparent coated molded products. 2. The coating composition (B) having an average particle size of 200
2. The transparent coated molded article according to claim 1, which contains colloidal silica having a diameter of not more than nm. 3. The cured product of the coating composition (B) is JIS
-Number of tests 10 by abrasion resistance test in R3212
The transparent coated molded article according to claim 1 or 2, which is a cured product having an abrasion resistance having a haze value of 10% or less after 0 times. 4. The method according to claim 1, wherein at least a part of said polysilazane (c) is perhydropolysilazane.
4. The transparent coated molded article according to 1.