JP2000296579A - Coated molding and manufacture thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form two or more coating layers markedly showing non-coloring properties and anti-marring properties by forming the coating layer containing an ultraviolet absorber with a triazine skeleton in a molecule as an inner layer in contact with the outermost layer of the two or more coating layers and a cured product layer of a coating composition containing a polysilazane as the outermost layer. SOLUTION: This coated molding comprises two or more coating layers including at least an inner layer consisting of a coating layer in contact with the outermost layer on the surface of a base material and the outermost layer consisting of a cured product of a coating composition containing a polysilazane. In addition, a third layer comprising a thermoplastic resin layer such as a thermoplastic acrylic resin which is another synthetic resin and an adhesive layer, is present between the base material and the inner layer. When resistance to thermal impulse and the like are considered, two coating layers such as the outermost layer and the inner layer in contact with the former are desirably present. The coating layers contain an ultraviolet absorber having a triazine skeleton in a molecule as an essential component. This specific ultraviolet absorber is almost free from the possibilities that a coloring phenomenon might occur.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a non-colored, especially non-colored, film having, on the surface of a substrate, an outermost layer of silica derived from polysilazane and an inner layer containing a specific ultraviolet absorber in contact with the outermost layer. TECHNICAL FIELD The present invention relates to a coated molded article having two or more coating layers having excellent properties, transparency and scratch resistance, and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, a transparent synthetic resin material has been used as a transparent material instead of glass. Above all, aromatic polycarbonate resins are excellent in crush resistance, transparency, light weight, ease of processing and the like, and are utilized in various fields as transparent members having a large area such as outer walls and arcades by utilizing their features. Further, there is an example in which a transparent synthetic resin material is used instead of glass (inorganic glass; the same applies hereinafter) for a part of a vehicle such as an automobile. However, there is a disadvantage that the hardness of the surface is not sufficient to be used in place of glass, and the surface is easily damaged and worn, so that the transparency is easily lost.

As an aromatic polycarbonate resin member having improved scratch resistance and abrasion resistance, there is known a curing method of a coating composition containing a polyfunctional compound having two or more active energy ray-curable polymerizable functional groups. Some have two coating layers, an inner layer of the product and an outermost layer containing silica.

[0004]

The above-mentioned transparent coated molded article has a problem (coloring phenomenon) in which the coating layer, which is a cured product, exhibits a slight yellow color depending on the production method. As a result of examining the cause of the coloring phenomenon, it was found that at the interface between the inner layer and the outermost layer, the cured product of the coating composition containing the polyfunctional compound was mixed with silica to form an intermediate layer. Therefore, as a result of examining a composition that does not exhibit yellow in the intermediate layer, it was found that the coloring phenomenon could be avoided by using an ultraviolet absorber having a specific structure.
An object of the present invention is to provide a coated molded article on which two or more coating layers having excellent non-coloring property, transparency and scratch resistance are formed, and a method for producing the same.

[0005]

SUMMARY OF THE INVENTION The present invention provides the following coated molded article and a method for producing the same. In a coated molded article having two or more coating layers formed on at least a part of the surface of a base material, an ultraviolet absorber having a triazine skeleton in a molecule as an inner layer in contact with the outermost layer among the two or more coating layers A coated molded article, which is a coating layer (Q) containing (b), and the outermost layer is a layer of a cured product of a coating composition (B) containing polysilazane (c).

In a method for producing a coated molded article having two or more coating layers formed on at least a part of the surface of a substrate, a coating layer containing an ultraviolet absorber (b) having a triazine skeleton in a molecule ( Forming a coating (W) of the composition capable of forming Q) as an inner layer in contact with the outermost layer of the two or more coating layers, and forming a coating containing polysilazane (c) on the surface of the coating (W); Film (Z) of composition (B)
Is formed as the outermost layer, and the formation of the coating layer (Q) and the curing of the coating composition (B) are performed sequentially or simultaneously.

In a method for producing a coated molded article having two or more coating layers formed on at least a part of the surface of a substrate, a coating layer containing an ultraviolet absorber (b) having a triazine skeleton in a molecule ( Forming a coating (W) of the composition capable of forming Q) as an inner layer in contact with the outermost layer of the two or more coating layers, and forming a coating containing polysilazane (c) on the surface of the coating (W); Film (Z) of composition (B)
Is formed as the outermost layer, and then the substrate having these coatings (W) and (Z) is subjected to post-processing involving deformation of the surface of the substrate, and then formation and coating of the coating layer (Q) A method for producing a coated molded article in which the composition (B) is cured sequentially or simultaneously.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The coated molded article of the present invention is a cured product of an inner layer comprising a coating layer (Q) in contact with the outermost layer on the surface of a substrate and a coating composition (B) containing polysilazane (c). And at least two coating layers including at least an outermost layer made of A third layer composed of another synthetic resin, for example, a thermoplastic resin layer such as a thermoplastic acrylic resin or an adhesive layer may be present between the base material and the inner layer. But,
In consideration of thermal shock resistance and the like, two coating layers, an inner layer and an outermost layer that are in contact with the outermost layer, are preferable.

The coating layer (Q) contains, as an essential component, an ultraviolet absorber (b) having a triazine skeleton in the molecule. The present inventor has found that the cause of the coloring phenomenon is a benzophenone-based ultraviolet absorber or a benzotriazole-based ultraviolet absorber that is widely used as an ultraviolet absorber. This coloring phenomenon is considered to be due to the interaction of a basic substance such as ammonia, which is generated when the polysilazane in the outermost layer is cured, with the benzophenone-based UV absorber or the benzotriazole-based UV absorber in the inner layer. . The specific ultraviolet absorbent (b) in the present invention is less likely to cause such a coloring phenomenon.

The ultraviolet absorbent (b) in the present invention is a compound having a triazine skeleton in the molecule and having an ultraviolet absorbing ability. As this compound, a 1,3,5-triazine-based compound having an aromatic nucleus-containing substituent such as an aryl group or an aralkyl group at the 2,4,6-position is preferable. In particular, a compound in which at least one of the aromatic nucleus-containing substituents is a hydroxyphenyl group (which may have a substituent other than a hydroxyl group) is preferable. Examples of the other aromatic nucleus-containing substituent include a phenyl group which may have a substituent other than a hydroxyl group such as an alkyl group. The most preferred compound has one hydroxyphenyl group (which may have a substituent other than a hydroxyl group) and two phenyl groups (which may be substituted with an alkyl group) at the 2, 4, and 6 positions. Have one
3,5-triazine compound.

Preferred specific examples of the ultraviolet absorber (b) include the following compounds. 2- [4- (2-hydroxy-3-dodecyloxypropyloxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4 -(2-hydroxy-3-tridecyloxypropyloxy) -2-
[Hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (4-hexyloxy-2-hydroxyphenyl) -4,6-diphenyl-1,3,3 5-triazine.

As an easily available ultraviolet absorber (b), "Tinuvin 400" (2- [4- (2-hydroxy-3-dodecyloxypropyloxy) -2-hydroxyphenyl) manufactured by Ciba Specialty Chemicals, Inc. ] -4,6-bis (2,4-dimethylphenyl)-
1,3,5-triazine and 2- [4- (2-hydroxy-3-tridecyloxypropyloxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3 , 5-triazine).

The amount of the ultraviolet absorber (b) having a triazine skeleton in the molecule in the coating layer (Q) depends on the amount of the synthetic resin material (for example, the curable component (the total of the polyfunctional compound (a) and the monofunctional compound)). ) 0.01 to 100 parts by mass
The amount is preferably 50 parts by mass, particularly preferably 0.1 to 20 parts by mass.

Examples of the resin material forming the coating layer (Q) include a thermoplastic resin material and a curable resin material, and a curable resin material is preferable. As the curable resin material, a thermosetting resin material or a polyfunctional compound (a) having two or more active energy ray-curable polymerizable functional groups
A curable resin material containing a polyfunctional compound (a) is particularly preferable from the viewpoint of productivity and abrasion resistance that is developed.

As the thermoplastic resin material, polyethylene, chlorinated polyethylene, ethylene / vinyl acetate copolymer, polypropylene, polyisobutylene, acrylic resin, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetate, polystyrene , Polyamide, polyacetal, polybutylene terephthalate,
Examples include polyethylene terephthalate, polyphenylene oxide, polyphenylene sulfide, polyetheretherketone, polyarylate, polysulfone, polyetherimide, polyamideimide and the like.

Examples of the thermosetting resin material include epoxy resin, phenoxy resin, urethane resin, silicone resin, urea resin, melamine resin, diallyl phthalate resin, and unsaturated polyester resin.

In the present invention, a particularly preferred coating layer (Q) is a polyfunctional compound (a) having an ultraviolet absorber (b) and two or more active energy ray-curable polymerizable functional groups.
And a layer of a cured product of the coating composition (A). Hereinafter, this will be described. 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. Among these groups and compounds, more preferred are those having an acryloyl group, such as an acryloyloxy group, acrylic acid, and acrylate.

As the polyfunctional compound (a) in the coating composition (A), one compound may be used, or a plurality of compounds may be used. In the case of a plurality of types, 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.

Examples of the active energy ray-curable polymerizable functional group include unsaturated groups such as a (meth) acryloyl group, a vinyl group and an allyl group and groups having the same, and a (meth) acryloyl group is preferred. That is, as the polyfunctional compound (a), a compound having two or more polymerizable functional groups selected from (meth) acryloyl groups is preferable. More preferably, a compound having two or more (meth) acryloyloxy groups, that is, a polyester of a compound having two or more hydroxyl groups such as a polyhydric alcohol and (meth) acrylic acid is preferable.

The polyfunctional compound (a) may be a compound having two or more polymerizable functional groups in one molecule. The number of polymerizable functional groups in one molecule of the polyfunctional compound (a) is two or more, and the upper limit is not particularly limited. Usually, 2 to 50 pieces are suitable, and 3 to 30 pieces are particularly preferable. Further, “polyfunctional” in the polyfunctional compound (a) means having two or more polymerizable functional groups, and a monofunctional compound described later means a compound having one polymerizable functional group. I do.

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), a monofunctional compound having one polymerizable functional group that can be polymerized by an active energy ray may be contained. 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 particularly limited. However, the content is preferably 60% by mass or less, particularly preferably 30% by mass or less. If the proportion of the monofunctional compound exceeds 60% by mass, the hardness of the layer of the cured product may be reduced and the abrasion resistance may be insufficient.

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, the above-mentioned two types of polyfunctional compounds (a) will be described.

(1) A (meth) acryloyl group-containing compound having a urethane bond (hereinafter referred to as acryl urethane)
Examples thereof include the following compounds shown below. Compounds having a (meth) acryloyl group and a hydroxyl group (X
A reaction product of 1) and a compound having two or more isocyanate groups (hereinafter, referred to as polyisocyanate). A reaction product of compound (X1), compound (X2) having two or more hydroxyl groups, and polyisocyanate. A reaction product of the compound (X3) having a (meth) acryloyl group and an isocyanate group with the compound (X2).

In these reaction products, it is preferable that no isocyanate group is present, but a hydroxyl group may be present. Therefore, in the production of these reaction products, it is 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) may be a compound having one (meth) acryloyl group and one hydroxyl group, a compound having two or more (meth) acryloyl groups and one hydroxyl group, and a compound having one or more hydroxyl group. It may be a compound having one 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,
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.

Further, the compound (X1) may be a ring-opening reaction product of a compound having at least one epoxy group with (meth) acrylic acid. The reaction between the epoxy group and the (meth) acrylic acid causes the ring opening of the epoxy group to form an ester bond and a hydroxyl group, resulting in a compound having a (meth) acryloyl group and a hydroxyl group. Alternatively, the epoxy group of a compound having one or more epoxy groups may be opened to form a hydroxyl group-containing compound, which may be converted to a (meth) acrylate.

As the compound having one or more epoxy groups, a polyepoxide called an epoxy resin is preferable. 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 described above and above may be an ordinary monomeric polyisocyanate, a multipolymer or modified polyisocyanate, or a prepolymer compound such as an isocyanate group-containing urethane prepolymer.

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

Examples of the multimer include trimers (modified isocyanurates), dimers, and modified carbodiimides. Modified products include urethane obtained by denaturation with a polyhydric alcohol such as trimethylolpropane. Modified, buret modified, allohanate modified, urea modified and the like. As an example of the prepolymer, there is an isocyanate group-containing urethane prepolymer obtained by reacting a polyol such as a polyether polyol or a polyester polyol described below with a polyisocyanate. Two or more of these polyisocyanates can be used in combination.

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.

The compound (X2) includes 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.

Specific examples of the above-mentioned polyhydric alcohol are shown below. Ethylene glycol, propylene glycol,
1,4-butanediol, 1,6-hexanediol,
Diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexanediol, dimethylolcyclohexane, trimethylolpropane, glycerin, pentaerythritol, ditrimethylolpropane, dipentaerythritol, tris (2-hydroxyethyl) isocyanurate, tris (2-hydroxypropyl ) Ring-opened products of isocyanurate, bisphenol A-diglycidyl ether, and ring-opened products of vinylcyclohexene dioxide.

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

Specific examples of the above polyol include the following polyols. Polyethylene glycol,
Polyether polyols such as 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. . Compound (X3)
Examples thereof include 2-isocyanatoethyl (meth) acrylate and methacryloyl isocyanate.

(2) As the (meth) acrylate compound having no urethane bond, which is a preferable compound as a polyfunctional compound, a compound having two or more hydroxyl groups similar to the compound (X2) may be used. Polyesters with acrylic acid are preferred. As the compound having two or more hydroxyl groups, the above-mentioned polyhydric alcohols and polyols are preferable. Further, a (meth) acrylate compound which is a reaction product of a compound having two or more epoxy groups and (meth) acrylic acid is also preferable. Specific examples of the polyfunctional compound containing no urethane bond include, for example, the following compounds shown below.

(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.

(Meth) acrylates of polyhydric alcohols and 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, tris (2- (meth) acryloyloxyethyl),
Bisphenol A dimethacrylate.

(Meth) acrylate of hydroxyl group-containing compound-alkylene oxide adduct, (meth) acrylate of hydroxyl group-containing compound-caprolactone adduct, and (meth) acrylate of polyoxyalkylene polyol. In the following description, 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.

In the polyfunctional compound (a), since the cured product of the coating composition (A) can exhibit sufficient abrasion resistance, it has three or more active energy ray-curable polymerizable functional groups. The proportion of the polyfunctional compound is preferably 30% by mass or more, and more preferably 50% by mass, based on the total amount of the polyfunctional compound (a).
% By mass or more is preferred. Specific preferred polyfunctional compounds (a) are the following polyfunctional compounds having no urethane bond with acrylic urethane.

In the case of acrylic urethane, acrylic urethane which is a reaction product of pentaerythritol or its multimer, polypentaerythritol, polyisocyanate and hydroxyalkyl (meth) acrylate, or hydroxyl group-containing poly (pentaerythritol or polypentaerythritol) Acrylic urethane, which is a reaction product of meth) acrylate and polyisocyanate, is preferably a compound having three or more (preferably 4 to 20) active energy ray-curable polymerizable functional groups.

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 is a polyester of pentaerythritol or polypentaerythritol with (meth) acrylic acid (preferably having an active energy ray-curable polymerizable functional group of 4 to 20).
Individual thing). The isocyanurate-based poly (meth) acrylate is a polyester of (meth) acrylic acid with tris (hydroxyalkyl) isocyanurate or an adduct obtained by adding 1 to 6 mol of caprolactone or alkylene oxide to 1 mol of tris (hydroxyalkyl) isocyanurate. Active energy ray-curable polymerizable functional groups having 2 to 3). It is also preferable to use these preferable polyfunctional compounds in combination with other polyfunctional compounds having two or more active energy ray-curable polymerizable functional groups (particularly poly (meth) acrylate of polyhydric alcohol). The ratio of these preferable polyfunctional compounds is preferably 30% by mass or more, and particularly preferably 50% by mass or more, based on all the polyfunctional compounds (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, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (Meth) acrylate, glycidyl (meth) acrylate.

The coating composition (A) has an average particle diameter of 200 to increase the abrasion resistance and hardness of the inner layer comprising the coating layer (Q).
It is preferable to further include colloidal silica having a diameter of not more than nm. The average particle size of the colloidal silica is 1 to 100 nm.
Is more preferable, and 1 to 50 nm is particularly preferable. If the average particle size of the colloidal silica is more than 200 nm, clouding (haze) tends to occur.

When colloidal silica is used,
In order to sufficiently exhibit the effect, the amount of the colloidal silica is suitably from 5 to 300 parts by mass with respect to 100 parts by mass of the curable component (the total of the polyfunctional compound (a) and the monofunctional compound). Yes, 10 to 250 parts by mass is more preferable, 50
~ 250 parts by mass is more preferred. If the amount of the colloidal silica is less than 5% by mass, it is difficult to obtain sufficient wear resistance. When the amount of the colloidal silica exceeds 300 parts by mass, haze is easily generated in the coating film, and cracks are easily generated when the obtained coated molded product is subjected to secondary processing such as hot bending.

As the colloidal silica, a surface-unmodified colloidal silica can be used, but a surface-modified colloidal silica is preferably used. The surface-modified colloidal silica improves the dispersion stability of the colloidal silica in the composition. It is considered that the average particle size of the colloidal silica fine particles is not substantially changed or slightly increased by the modification, but the average particle size of the obtained modified colloidal silica is considered to be in the above range. Hereinafter, the surface-modified colloidal silica (hereinafter, simply referred to as modified colloidal silica) will be described.

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

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

As described above, the dispersion medium is particularly preferably an organic medium, and among the above-mentioned organic mediums, alcohols and cellosolves are particularly preferable. 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 the colloidal silica is preferably performed using a compound having a hydrolyzable silicon group or a silicon group to which a hydroxyl group is bonded (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, the modifier preferably has an organic group bonded to a silicon atom, and at least one 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 binds 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).

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

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, 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 products of amino 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, the modification can be performed by adding a modifier and a catalyst to the colloidal silica dispersion and hydrolyzing the modifier in the colloidal silica dispersion. Catalysts include 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. Further, as the organic acid, formic acid, acetic acid, oxalic acid, (meth) acrylic acid and the like 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 mass 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 mass, it is difficult to obtain the effect of surface modification. If the amount exceeds 100 parts by mass, a large amount of hydrolyzate to condensate of the unreacted modifier and the modifier not supported on the surface of the colloidal silica is generated, and these are chained when the curable component of the coating layer is cured. 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) preferably contains a photopolymerization initiator. Known photopolymerization initiators can be used.
Particularly, commercially available products that are easily available are preferable. A plurality of photopolymerization initiators may be used in the cured product layer.

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, etc.), sulfur-containing photopolymerization initiators (eg, sulfides, thioxanthones, etc.),
There are acylphosphine oxide-based photopolymerization initiators, diacylphosphine oxide-based photopolymerization initiators, and other photopolymerization initiators. In particular, the use of an acylphosphine oxide-based photopolymerization initiator and a diacylphosphine 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. 2,2-dichloro-4'-phenoxyacetophenone, 4'-t-butyl-2,2-
Dichloroacetophenone, 4'-t-butyl-2,2,
2-trichloroacetophenone, 2,2-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1- On, 1- (4-dodecylphenyl) -2-methylpropan-1-one, 1- {4- (2-hydroxyethoxy)
Phenyl} -2-hydroxy-2-methylpropane-1
-One, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- {4- (methylthio) phenyl}
-2-morpholinopropan-1-one.

Benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, 4-hydroxybenzophenone, acrylate Benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 3,3 ′, 4,4′-tetrakis (t-butylperoxycarbonyl) benzophenone,
9,10-phenanthrenequinone, camphorquinone,
Dibenzosuberone, 2-ethylanthraquinone, 1,3
-Phenylenebis (4-ethylbenzoyl), α-acyloxime esters (eg, 2-propionyloxyimino-1-phenylpropan-1-one), 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 (A) is 0.01 to 20 parts by mass based on 100 parts by mass of the curable component (the total of the polyfunctional compound (a) and the monofunctional compound). Is preferable, and 0.1 to 10 parts by mass is particularly preferable.

The coating composition (A) can contain a solvent and various functional additives in addition to the above basic components. The solvent is usually an essential component, and the coating composition (A) is preferably dissolved in a solvent and used for coating. The solvent is removed from the coating composition (A) before curing the coating composition (A). As the solvent, a solvent usually used for a coating composition containing the polyfunctional compound (a) as a curing component can be used. Further, a dispersion medium of raw material colloidal silica may 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 product layer, 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 by mass, based on 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 solvents 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.

Examples of the functional compounding agent include ultraviolet absorbers, light stabilizers, antioxidants, thermal polymerization inhibitors, leveling agents, defoamers, thickeners, anti-settling agents other than the above (b). Pigment (organic coloring pigment, inorganic pigment), coloring dye, infrared absorber, fluorescent brightener, dispersant, antifouling agent, rust inhibitor, conductive fine particles, antistatic agent, antifogging agent, coupling agent , And one or more functional compounding agents selected from the group consisting of curing catalysts.

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

The layer thickness of the cured product of the coating composition (A) is 1
To 50 μm, and particularly preferably 2 to 30 μm.
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 may not be sufficiently exhibited. If the thickness exceeds 50 μm,
The curing by the active energy ray becomes insufficient, and the adhesion to the substrate is easily deteriorated, which is not preferable.

The coating composition (B) forming the outermost layer contains polysilazane (c). Polysilazane (c)
It is a polymer having two or more repeating units of (—Si—N—), and the remaining two bonds of a silicon atom (tetravalent) or the remaining one bond of a nitrogen atom (trivalent) are respectively A hydrogen atom or an organic group (such as an alkyl group) is bonded. The polysilazane (c) may have a linear structure composed of only the above repeating units, or may have a cyclic structure in which one or both of the remaining two bonds of the silicon atom and the bond of the nitrogen atom are bonded. .

The polysilazane (c) is decomposed in the presence of oxygen, and becomes a silica by replacing nitrogen atoms with oxygen atoms. Silica formed from polysilazane forms denser silica than silica formed from a hydrolyzable silane compound. For example, silica formed from perhydropolysilazane is denser and has better surface properties such as abrasion resistance than silica formed from tetraalkoxysilane.

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

In the case of polysilazane in which an organic group such as an alkyl group or a trimethylsilyl group is bonded to a silicon atom, the silica containing an organic group formed has a higher resistance than silica formed from perhydropolysilazane. Although the surface properties such as abrasion may be inferior, a tougher cured film can be obtained and the film can be made thicker, so that it may be preferable to perhydropolysilazane for some purposes.

The polysilazane (c) includes those having a chain, cyclic or cross-linked structure, and those having a plurality of these structures in the molecule at the same time. Two or more kinds may be used as a mixture. Further, the molecular weight of 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, and if the number average molecular weight exceeds 50,000, it is difficult to dissolve in a solvent, which is not preferable.

In the case of polysilazane having an organic group bonded to a silicon atom, the organic group is preferably a hydrocarbon group or a halogenated hydrocarbon group, particularly preferably a hydrocarbon group such as an alkyl group. The carbon number of these organic groups is not particularly limited, and may be, for example, 20 or less, but is preferably small, and particularly preferably 4 or less.

The coating composition (B) may further contain an ultraviolet absorber (b) having a triazine skeleton in the molecule. As described above, the ultraviolet absorbent (b) having a triazine skeleton in the molecule hardly interacts with a basic substance such as ammonia generated when the polysilazane is cured.
By blending the ultraviolet absorbent (b) with the coating composition (B), the cured product layer has an ultraviolet absorbing ability, whereby the ultraviolet shielding ability as a transparent coated molded article is improved and the durability is improved. I do. When blending the ultraviolet absorbent (b) with the coating composition (B), the amount is preferably 0.01 to 50 parts by mass, particularly preferably 0.1 to 20 parts by mass, per 100 parts by mass of the curable component.

Further, as the solvent for dissolving the polysilazane, hydrocarbons, halogenated hydrocarbons, ketones, ethers, and esters can be used, and specific examples thereof include the following.

Pentane, hexane, isohexane, heptane, isoheptane, octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene,
Hydrocarbons such as ethylbenzene, methylene chloride, chloroform, carbon tetrachloride, bromoform, 1,2-dichloroethane, 1,1-dichloroethane, trichloroethane,
Halogenated hydrocarbons such as tetrachloroethane; ethers such as ethyl ether, isopropyl ether, ethyl butyl ether, butyl ether, dioxane, dimethyl dioxane, tetrahydrofuran, and tetrahydropyran; esters such as n-butyl acetate and diethylene glycol monoacetate;

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 to be employed, the structure of polysilazane, the average molecular weight, and the like, but is preferably adjusted to a solid content concentration of 0.5 to 80% by mass.

In order to cure the polysilazane into silica, heating which is usually called baking is performed. However, when the substrate is a synthetic resin, the firing temperature is limited. 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 base material. In such a case, it may be necessary to cure the polysilazane at a temperature lower than the heat resistance temperature of the cured product. Therefore, in the present invention, the firing temperature of polysilazane is preferably 180 ° C. or lower when a 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, it is preferable that the atmosphere in which the firing is performed is an atmosphere in which oxygen is present, such as in air. By firing polysilazane, its nitrogen atoms are replaced by oxygen atoms to produce silica. By firing in an atmosphere in which sufficient oxygen exists, a dense silica layer is formed. Further, treatment with water or steam is also useful for curing at a low temperature (Japanese Patent Laid-Open No. 7-22 / 1995).
3867).

As the catalyst, a catalyst capable of curing polysilazane at a lower temperature is preferable. For example, a metal catalyst comprising fine particles of a metal such as gold, silver, palladium, platinum and nickel (Japanese Patent Application Laid-Open No. 7-1996986) Carboxylic acid complexes (JP-A-5-93275).

Also, instead of adding the catalyst to the polysilazane solution, the coated molded article is directly contacted with a catalyst solution, specifically, an aqueous amine solution, as proposed in JP-A-9-31333. Alternatively, it is also preferable to adopt a method of exposing to the vapor for a certain time.

When a catalyst is blended with polysilazane, the amount of the catalyst blended is 0.01 with respect to 100 parts by mass of polysilazane.
It is preferably from 10 to 10 parts by mass, particularly preferably from 0.05 to 5 parts by mass. If the amount is less than 0.01 part by mass, a sufficient catalytic effect cannot be expected. If the amount exceeds 10 parts by mass, aggregation of the catalysts tends to occur, and the transparency may be impaired. Further, the coating composition (B) may include the above-mentioned functional compounding agent, if necessary.

The thickness of the layer of the cured product formed using the coating composition (B) is preferably from 0.05 to 10 μm, particularly preferably from 0.1 to 3 μm. The thickness of the outermost layer is 1
If it exceeds 0 μm, improvement in surface properties such as scratch resistance cannot be expected, and the layer becomes brittle, and cracks and the like are likely to occur in this layer even by slight deformation of the coated molded product. On the other hand, if the thickness is less than 0.05 μm, the outermost layer may not sufficiently exhibit wear resistance and scratch resistance.

As a method of forming two layers formed using the two kinds of coating compositions (A) and (B) as described above, a usual coating method can be adopted. For example, first, the coating composition (A) is applied to the surface of the base material and cured, and then the coating composition (B) is applied and cured on the surface of the cured product to form the desired coating. Goods are obtained.

When the resin material forming the coating layer (Q) is a thermoplastic resin material, it is dissolved in a solvent to form a film on the surface of the substrate, or is cast in a hot melt state on the surface of the substrate. It is preferable to form a coating film. When the resin material is a thermosetting resin material, it is preferable to form the coating on the surface of the base material by directly or by dissolving the precursor before curing in a solvent.

The means for applying the coating composition (A) or (B) is not particularly limited, and a known method can be employed. For example, dip coating, flow coating, spray coating, bar coating, gravure coating, roll coating, blade coating, air knife coating, spin coating, slit coating, micro gravure coating, die coating, etc. Method can be adopted. After coating, if the coating composition contains a solvent, it is dried to remove the solvent, and then, in the case of a layer using the coating composition (A), for example, by cooling, heating, or irradiation with ultraviolet light or the like. A layer is formed, and in the case of a layer using the coating composition (B), it is cured by irradiating with ultraviolet rays or the like, heating or standing at room temperature. Curing can also be accelerated by contact with an aqueous solution or vapor of amines or acids.

The following four methods can be used for the combination (timing) of the curing of the coating composition (A) and the coating and curing of the coating composition (B). Hereinafter, examples in which the coating composition (A) and the coating composition (B) are used will be described.
In other cases, it can be performed according to the following method. 1) A method of applying the coating composition (A), irradiating a sufficient amount of active energy rays after the coating to sufficiently complete the curing, and then coating the coating composition (B) on the surface (described above). Method).

2) After coating the coating composition (A) to form an uncured layer of the coating composition (A), the coating composition (B) is coated on the surface of the uncured layer. Coating composition (B)
A method of forming a layer of the uncured material, and irradiating a sufficient amount of active energy rays thereafter to complete the curing of the uncured material of the coating composition (A). In this case, the uncured material of the coating composition (B) cures almost simultaneously with the uncured material of the coating composition (A), or is cured by heating or the like after curing of the uncured material of the coating composition (A). .

3) The minimum amount of active energy rays (usually about 300
mJ / cm ² ) to form a partially cured layer of the coating composition (A), and then coat the coating composition (B) on the surface of the partially cured layer. Forming a layer of the uncured material of the coating composition (B) by irradiating a sufficient amount of active energy rays to terminate the curing of the uncured material of the coating composition (A). The curing of the uncured material of the coating composition (B) is the same as in the above 2).

4) After forming an uncured or partially cured layer of the coating composition (A) and an uncured layer of the coating composition (B) as in 2) or 3) above, The uncured material of the composition (B) is partially or completely cured first, and then the uncured or partially cured material of the coating composition (A) is completely cured. In this case, at the time of curing the uncured material of the coating composition (B), the coating composition (A) is preferably a partially cured material rather than an uncured material.

In order to increase the adhesion between the two cured product layers, the above method 2) or 3) is more preferable. In the method 4), the layer of the partially cured product or the completely cured product of the coating composition (B) is a barrier against penetration of oxygen, which is likely to be a curing inhibition factor when the coating composition (A) is completely cured. It acts as a layer and prevents the cured product of the coating composition (A) from becoming insufficiently cured.

The coated molded article obtained as described above is
Since its surface properties such as abrasion resistance and abrasion resistance are almost at the same level as glass, it can be used in various applications where glass has been conventionally used. However, in the case of an application as a window material for a vehicle among various uses, a bent molded product is often required, and in such a case, it is usually manufactured using a bent base material. However, when a bent substrate is used, it is often difficult to form each layer by coating and curing.

Therefore, as a result of intensive studies by the present inventors,
The substrate on which the layer of the cured product of the coating composition (A) is formed can be bent by hot bending or the like, but when the layer of the cured product of the coating composition (B) is formed, the cured product is not cured. It has been found that bending processing is difficult because the coating composition (B) is uncured or partially cured, because it is hard. The reason for this is that the bending process is usually performed in a heated state, and this heating cures the uncured or partially cured product of the coating composition (B). This is probably due to the long time required for curing the uncured or partially cured material.

The present invention relates to a method for producing a coated molded article having two or more coating layers formed on at least a part of the surface of a substrate, comprising an ultraviolet absorbent (b) having a triazine skeleton in the molecule. A coating (W) of a composition capable of forming a coating layer (Q) to be formed as an inner layer in contact with the outermost layer of the two or more coating layers;
A coating (Z) of the coating composition (B) containing the polysilazane (c) is formed as an outermost layer, and then the substrate having these coatings (W) and (Z) is deformed. And a method for producing a coated molded product in which formation of the coating layer (Q) and curing of the coating composition (B) are performed sequentially or simultaneously.

As post-processing involving deformation of the surface of the substrate,
In addition to the above-mentioned bending, there are inflation molding, blow molding and the like, but in the present invention, bending is preferable. Hereinafter, bending, which is a preferable post-processing, will be described.

As in the method 2) or 3), the surface of the uncured or partially cured product of the coating composition (A) is applied to the surface of the uncured or partially cured product of the coating composition (B). It is preferable to perform the bending process in a state where the layer is formed, and by curing the uncured or partially cured product of the coating composition (B) after or almost simultaneously with the bending process, the desired bent coating is obtained. A molded article is obtained.

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

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. Curing of the coating composition (A) may be performed before or after sufficient curing of the coating composition (B). 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 substrate in the present invention, various synthetic resins, various metals, inorganic glass and the like can be used. Of these, transparent synthetic resins are preferred. As the transparent synthetic resin, 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 a base material. Materials are preferred. The base material is a molded one, such as a sheet-like base material such as a flat plate or a corrugated sheet, a film-like base material, a base material formed into various shapes, and a laminate in which at least a surface layer is formed of various transparent synthetic resins. There is. Particularly, a flat substrate (not bent) is preferable. The thickness of the substrate is not particularly limited, but is 0.1 to 0.1 for applications such as window materials.
100 mm is preferred.

[0108]

EXAMPLES The present invention will be described below with reference to Synthesis Examples (Example 1), Examples (Examples 2 to 10, 12, and 13), and Comparative Examples (Example 11), but the present invention is not limited thereto. Examples 2 to 9,
The measurement and evaluation of various physical properties of Examples 11 to 13 were performed by the following methods, and the results are shown in Table 1. In addition,
As a base material, a transparent aromatic polycarbonate resin plate (150 mm × 300 mm) having a thickness of 3 mm was used. Also,
For reference, Table 1 also shows the results of measurement and evaluation of the physical properties of ordinary building glass sheets.

[Initial haze value, abrasion resistance] JIS-R321
According to the abrasion resistance test method in No. 2, a haze was measured using a haze meter when 500 g of weight was combined with each of two CS-10F abrasion wheels and rotated 500 times. The haze value was measured at four points of the wear cycle orbit, and the average value was calculated. The initial haze value indicates the haze value (%) before the abrasion test, and the abrasion resistance indicates (haze value after the abrasion test)-(haze value before the abrasion test) (%).

[Initial Yellowness] The yellowness (YI) values of two points of the sample were measured with a color meter manufactured by Suga Test Instruments Co., Ltd., and the average value was shown.

[Adhesion] The sample is cut with eleven vertical and horizontal lines at 1 mm intervals with a razor blade to make 100 grids. Then, when a commercially available cellophane tape is closely adhered and then rapidly peeled in the forward direction by 90 degrees, the number (m) of the grids remaining without peeling off the coating is represented by m / 100.

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

[Example 1] Ethyl cellosolve dispersed colloidal silica (silica content: 30% by mass, average particle size: 11 nm)
To 100 parts by mass, 5 parts by mass of 3-mercaptopropyltrimethoxysilane and 3.0 parts by mass of 0.1 mol / L 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. A mercaptosilane-modified colloidal silica dispersion was obtained.

[Example 2] 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-dodecyloxypropyloxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethyl Phenyl) -1,3,5-triazine 1000 mg and N-methyl-4-methacryloyloxy-2,2,6
200 mg of 6-tetramethylpiperidine was added and dissolved, followed by urethane acrylate (1) which was a reaction product of hydroxyl-containing dipentaerythritol polyacrylate and partially nullated hexamethylene diisocyanate.
9. Contains an average of 15 acryloyl groups per molecule)
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.

The coating liquid 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 3000 mJ / cm ² (wavelength 300 to
Ultraviolet light having a cumulative energy amount of ultraviolet light in a 390 nm region (hereinafter the same) was applied to form a transparent cured product layer having a thickness of 7 μm.

Next, a xylene solution of perhydropolysilazane (solid content: 20% by mass, trade name “L110” manufactured by Tonen Co., Ltd.) (hereinafter referred to as coating liquid 2) (which is hereinafter referred to as “coating liquid 2”) was further applied to the surface with a bar coater. Coating (wet thickness: 6 μm) using a hot air circulating oven at 80 ° C. for 10 minutes to remove the solvent, and then holding in a hot air circulating oven at 100 ° C. for 120 minutes to form the outermost layer. Fully cured. And it was confirmed by IR analysis that the outermost layer was a complete silica coating. Thus, a transparent cured product layer having a total film thickness of 8.2 μm was formed on the surface of the base material. The measurement was performed using this sample.

[Example 3] The sample preparation method in Example 2 was changed as follows. After coating the coating liquid 1, the coating liquid was kept in a hot air circulating oven at 80 ° C. for 5 minutes, and irradiated with ultraviolet rays of 150 mJ / cm ² using a high-pressure mercury lamp in an air atmosphere to obtain a 7 μm-thick partially cured product. A layer was formed. Then, instead of the coating liquid 2, a non-catalyst xylene solution of perhydropolysilazane (solid content: 20% by mass, trade name “V110” manufactured by Tonen Co., Ltd.) (hereinafter referred to as “coating liquid 3”) was applied again to the surface with the bar coater. Is applied (wet thickness: 6 μm) and kept in a hot air circulating oven at 80 ° C. for 10 minutes to remove the solvent. Then, the resultant is irradiated with ultraviolet rays of 3000 mJ / cm ^{2 in} an air atmosphere using a high-pressure mercury lamp. Irradiated. Further, it was kept in a hot air circulating oven at 100 ° C. for 120 minutes. The measurement was performed using this sample.

[Example 4] The sample preparation method in Example 3 was changed as follows. Lastly, instead of keeping in a hot air circulating oven at 100 ° 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 5 The sample preparation method in Example 3 was changed as follows. After the coating solution 1 was applied, the coating solution 1 was kept in a hot air circulating oven at 80 ° C. for 5 minutes, and then the coating solution 3 was again applied to the surface using a bar coater (wet thickness 6 μm). 10 ℃ in a hot air circulating oven at 10 ℃
After holding the solvent for 1 minute to remove the solvent, the mixture was irradiated with ultraviolet rays of 3000 mJ / cm ^{2 in} an air atmosphere using a high-pressure mercury lamp. Further, it was kept in a hot air circulating oven at 100 ° C. for 120 minutes. The measurement was performed using this sample.

Example 6 The sample preparation method in Example 4 was changed as follows. Finally 23 ° C, 55% relative humidity
Instead of being left for one day in an environment of
3% aqueous solution of triethylamine. The measurement was performed using this sample.

Example 7 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, 150 mg of 2,4,6-trimethylbenzoyldiphenylphosphine oxide,
-[4- (2-hydroxy-3-tridecyloxypropyloxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine 1000 mg, and N- 200 mg of methyl-4-methacryloyloxy-2,2,6,6-tetramethylpiperidine was added and dissolved, followed by 10.0 g of tris (2-acryloyloxyethyl) isocyanurate, and the mixture was stirred at room temperature for 1 hour. Subsequently, 30.3 of the mercaptosilane-modified colloidal silica dispersion synthesized in Example 1 was added.
g and further stirred at room temperature for 15 minutes to obtain a coating composition (hereinafter, referred to as coating liquid 4).

The coating liquid 4 was applied to the base material using a bar coater (wet thickness: 30 μm) and kept in a hot air circulating oven at 80 ° C. for 5 minutes. This was irradiated with 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 3 was again coated on this surface using a bar coater (wet thickness: 6 μm), kept in a hot air circulating oven at 80 ° C. for 10 minutes to remove the solvent, and then placed in an air atmosphere. Ultraviolet light of 3000 mJ / cm ² was irradiated using a high-pressure mercury lamp. Further, 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. Instead of holding in a hot air circulating oven at 100 ° C. for 120 minutes, 23 ° C. and a relative humidity of 55
% For 1 day. The measurement was performed using this sample.

[Example 9] The sample preparation method in Example 3 was changed as follows. Instead of the coating liquid 3, a xylene solution of polysilazane in which a part of hydrogen atoms bonded to silicon atoms is substituted with a methyl group (solid content: 20% by mass, trade name “NL710” manufactured by Tonen Corporation) (hereinafter referred to as coating Working liquid 5) was used. The measurement was performed using this sample.

[Example 10] The sample preparation method in Example 8 was changed as follows. 3000 using a high-pressure mercury lamp
After irradiating with ultraviolet rays of mJ / cm ^2, the mold was kept in a hot air circulating oven at 170 ° C. for 5 minutes, and immediately after being taken out, a mold having a curvature of 64 mmR was formed so that the coated surface of the transparent cured material layer was convex. Pressed and bent. And it was cured at room temperature for one day. As a result of observing the appearance of this sample, it was found that the sample had a good cured layer without cracks and wrinkles.

On the other hand, the sample having two fully cured layers finally obtained in Example 8 was held in a hot air circulating oven at 170 ° C. for 5 minutes, and immediately after being taken out, the coated surface of the transparent cured layer was obtained. Was pressed against a mold having a curvature of 64 mmR so as to be bent, and 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 11] The sample preparation method in Example 3 was changed as follows. Instead of 2- [4- (2-hydroxy-3-dodecyloxypropyloxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (5-methyl-2-) which is a triazole ultraviolet absorber
Same as Example 3 except that (hydroxyphenyl) benzotriazole was used. The measurement was performed using this sample.

Example 12 A coating liquid 6 was obtained by adding 5 g of Tinuvin 400 to 100 g of a thermoplastic acrylic resin solution (solid content: 30% by mass, trade name "Dianal LR269" manufactured by Mitsubishi Rayon Co., Ltd.). The coating liquid 6 was applied to the substrate using a bar coater (wet thickness: 20 μm), and kept in a hot air circulating oven at 80 ° C. for 5 minutes to form a transparent cured product layer having a thickness of 6 μm.

Next, the coating liquid 2 was further applied to the surface using a bar coater (wet thickness: 6 μm) and kept in a hot air circulating oven at 80 ° C. for 10 minutes to remove the solvent. 120 ° C. in a hot air circulating oven at 120 ° C.
The outermost layer was sufficiently cured by holding for about 1 minute. And it was confirmed by IR analysis that the outermost layer was a complete silica coating. Thus, a total film thickness of 7.2 is formed on the substrate surface.
A transparent cured product layer having a thickness of μm was formed. The measurement was performed using this sample.

Example 13 100 g of water and urea 8 were placed in a 1000 mL four-necked flask equipped with a stirrer and a reflux tube.
9 g (1.48 mol) was added and heated to 90 ° C. to dissolve the urea, then adjusted to pH 8 with ammonia, kept at 60 ° C., and 133 g of paraformaldehyde (4.
44 mol) and stirred until clear. afterwards,
500 g of butanol was added, and the pH was adjusted to 5 with oxalic acid.
Then, water was fractionated under reflux. Fractionation was continued until almost no water remained, and finally xylene was added to obtain a butanol-modified urea resin precursor whose nonvolatile content was adjusted to 30%.

30 g of this butanol-modified urea resin precursor
2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole (hereinafter referred to as AHB) 27
0 mg and 1.5 g of Tinuvin 400 were added to obtain a coating liquid 7. The coating liquid 7 was applied to the base material using a bar coater (wet thickness: 10 μm) and was kept in a hot air circulating oven at 80 ° C. for 5 minutes. Subsequently, it was kept in a hot air circulation oven at 100 ° C. for 30 minutes to form a transparent coating layer.

Next, the coating liquid 2 was further coated (wet thickness: 6 μm) using a bar coater again on this surface, and kept in a hot air circulating oven at 80 ° C. for 10 minutes. The outermost layer was sufficiently cured by holding in a circulation oven for 120 minutes. And it was confirmed by IR analysis that the outermost layer was a complete silica coating. Thus, a transparent coating layer having a total thickness of 4.2 μm was formed on the surface of the base material. The measurement was performed using this sample.

[0133]

[Table 1]

[0134]

The coated molded article of the present invention is excellent in yellowness as compared with those using an ultraviolet absorber other than the ultraviolet absorber (b).

Claims (11)

[Claims] 1. A coated molded article having two or more coating layers formed on at least a part of the surface of a substrate, wherein the inner layer in contact with the outermost layer of the two or more coating layers has a triazine skeleton in the molecule. A coating layer (Q) containing an ultraviolet absorbent (b) having the following formula: wherein the outermost layer is a layer of a cured product of the coating composition (B) containing polysilazane (c). . 2. A coating layer (Q) comprising the ultraviolet absorbent (b)
The coated molded article according to claim 1, which is a layer of a cured product of a composition containing the composition and a curable resin material. 3. The method according to claim 1, wherein the coating layer (Q) comprises the ultraviolet absorbent (b).
Coating composition (A) containing a polyfunctional compound (a) having two or more active energy ray-curable polymerizable functional groups
The coated molded article according to claim 1 or 2, which is a layer of a cured product of the above. 4. The coating composition (A) has an average particle size of 200 nm.
The coated molded article according to claim 3, further comprising the following colloidal silica. 5. The coated molded article according to claim 1, wherein the substrate is a transparent synthetic resin substrate. 6. The coated molded article according to claim 1, wherein the coating composition (B) further contains an ultraviolet absorber (b) having a triazine skeleton in a molecule. 7. The coated molded article according to claim 1, wherein the polysilazane (c) is perhydropolysilazane. 8. A method for producing a coated molded article having two or more coating layers formed on at least a part of the surface of a substrate, wherein the coating contains an ultraviolet absorber (b) having a triazine skeleton in the molecule. A coating (W) of the composition capable of forming the layer (Q) is formed as an inner layer in contact with the outermost layer of the two or more coating layers, and the surface of the coating (W) contains polysilazane (c). (Z) of the coating composition (B) to be applied
Is formed as the outermost layer, and the formation of the coating layer (Q) and the curing of the coating composition (B) are performed sequentially or simultaneously. 9. A method for producing a coated molded article having two or more coating layers formed on at least a part of the surface of a substrate, wherein the coating contains an ultraviolet absorber (b) having a triazine skeleton in the molecule. A coating (W) of the composition capable of forming the layer (Q) is formed as an inner layer in contact with the outermost layer of the two or more coating layers, and the surface of the coating (W) contains polysilazane (c). (Z) of the coating composition (B) to be applied
Is formed as the outermost layer, and then the substrate having these coatings (W) and (Z) is subjected to post-processing involving deformation of the surface of the substrate, and then formation and coating of the coating layer (Q) A method for producing a coated molded article in which the composition (B) is cured sequentially or simultaneously. 10. The method according to claim 8, wherein the substrate is a transparent synthetic resin substrate. 11. The method according to claim 9, wherein the post-processing is bending.