JP2001064542A - Coated molding and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a molding having a cured layer excellent in functional properties and resistant to cracking even when it is relatively thick by forming a cured layer of a coating composition containing a polyfunctional compound having active energy ray-curable polymerizable functional groups and a polysilazane on the surface of a substrate. SOLUTION: The cured layer is formed on the surface of a substrate such as an inorganic glass, a metal, or an opaque synthetic resin. The polyfunctional compound used is desirably a compound having at least two (meth)acryloyl groups, more desirably, a compound having at least two (meth)acryloyloxy groups, i.e., a polyester of a compound having at least two hydroxyl groups, such as a polyhydric alcohol, with (meth)acrylic acid. The polysilazane used is desirably one having a number-average molecular weight of 200-50,000, particularly, desirably, a perhydropolysilazane. The amount of the polysilazane used is desirably 10-1,000 pts.wt. per 100 pts.wt. polyfunctional compound. The thickness of the cured layer is desirably 0.1-100 μm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyfunctional compound having two or more active energy ray (particularly ultraviolet) curable polymerizable functional groups on a substrate made of inorganic glass, metal or opaque synthetic resin. A layer of a cured product of the coating composition (A) containing polysilazane is formed, and has scratch resistance, weather resistance,
The present invention relates to a coated molded article having a cured product layer having excellent chemical resistance, gas barrier properties, smoothness, and the like, and a method for producing the coated molded article.

[0002]

2. Description of the Related Art In order to impart a new function to the surface of a substrate made of inorganic glass, metal or opaque synthetic resin, a scratch-resistant film, a gas barrier film, an alkali barrier film, an ultraviolet absorbing film, an antistatic film, an antistatic film, etc. In some cases, functional films such as a cloudy film, a smoothness imparting film, a conductive film, an antifouling film, and a rustproofing film are laminated.

However, when the functional film is an organic film, the scratch resistance, chemical resistance, smoothness, etc. are insufficient, and when the inorganic film is an inorganic film, the scratch resistance, Although some degree of chemical resistance, smoothness, etc. can be imparted, there is a problem that the solubility of the functional compound imparting the functionality is insufficient, and cracks easily occur depending on the film thickness.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a scratch resistance,
Excellent weather resistance, chemical resistance, gas barrier properties, smoothness, etc.
It is an object of the present invention to provide a coated molded product having a cured product layer in which cracks are less likely to occur even when the film thickness is relatively large, and a method for producing the same.

[0005]

Means for Solving the Problems As a result of intensive studies to solve these problems, the present inventors have found that a polysilazane and a polyfunctional compound having two or more active energy ray-curable polymerizable functional groups are contained. The cured product of the coating composition (A)
It has been found that, by forming on a substrate surface, a coated molded article having excellent functionality and having a cured product layer in which cracks are hardly generated even when the film thickness is relatively thick can be obtained. Since the coating composition (A) is excellent in solubility of various functional compounding agents, a function can be easily imparted to the cured product layer.

That is, the present invention relates to a coated molded article having the following base material and a hardened material layer formed on at least a part of the following base material surface, wherein the hardened material layer has an active energy ray-curable property. A coated molded article characterized by being a cured product of a coating composition (A) containing a polyfunctional compound having two or more polymerizable functional groups and polysilazane. Substrate: inorganic glass, metal or opaque synthetic resin.

Further, in the method for producing a coated molded article having the following base material and a cured product layer formed on at least a part of the following base material surface, at least a part of the base material surface is
A coating composition (A) containing a polyfunctional compound having two or more active energy ray-curable polymerizable functional groups and polysilazane is applied, and then the polyfunctional compound is irradiated with active energy rays to form the polyfunctional compound. Curing and curing of the polysilazane are performed in any order or simultaneously to form a cured product layer of the coating composition (A). Substrate: inorganic glass, metal, and opaque synthetic resin.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION A coated molded article of the present invention comprises a substrate made of an inorganic glass, a metal or an opaque synthetic resin (hereinafter simply referred to as a substrate) having an active energy ray-curable polymerizable functional group on a surface thereof. Is formed by forming a cured layer of a coating composition (A) containing a polyfunctional compound having two or more polysilazane and polysilazane. A primer layer may be present to improve the properties. For example, a layer of a thermoplastic resin such as a thermoplastic acrylic resin or an adhesive layer may be present.

The cured product layer is composed of a cured product of a curable coating composition (A) containing a polyfunctional compound having two or more active energy ray-curable polymerizable functional groups and polysilazane.

In order to obtain a cured layer having high scratch resistance, a polyfunctional compound is used as the active energy ray-curable coating composition (A). Similarly, in order to form a cured product having high abrasion resistance, the coating composition (A) has an average particle diameter of 200 n.
It is also preferable to form a cured product containing colloidal silica by blending colloidal silica of m or less. In order to efficiently cure the polyfunctional compound with active energy rays (especially ultraviolet rays), the coating composition (A) preferably contains a photopolymerization initiator.

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

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

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

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

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

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

When the monofunctional compound is used in the coating composition (A), the ratio of the monofunctional compound to the total of the polyfunctional compound and the monofunctional compound is not particularly limited, but may be 60% by weight. The following is preferable, especially 30
% By weight or less is preferred. If the proportion of the monofunctional compound is too large, the hardness of the cured product layer may decrease and the abrasion resistance may be insufficient.

The polyfunctional compound may be a compound having various functional groups or bonds other than the polymerizable functional 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 two kinds of polyfunctional compounds will be described. A (meth) acryloyl group-containing compound having a urethane bond (hereinafter referred to as acrylic urethane)
For example, the following can be mentioned. (1) A reaction product of a compound (X1) having a (meth) acryloyl group and a hydroxyl group and a compound having two or more isocyanate groups (hereinafter, referred to as polyisocyanate). (2) A reaction product of the compound (X1), the compound (X2) having two or more hydroxyl groups, and a polyisocyanate. (3) A reaction product of the compound (X3) having a (meth) acryloyl group and an isocyanate group with the compound (X2).

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

The compound (X1) having a (meth) acryloyl group and a hydroxyl group may be a compound having one (meth) acryloyl group and one hydroxyl group, and two or more (meth) acryloyl groups and a hydroxyl group. It may be a compound having one, a compound having one (meth) acryloyl group and two or more hydroxyl groups, or a compound having two or more (meth) acryloyl groups and two or more hydroxyl groups.

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

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 compound having one or more epoxy groups may be ring-opened to form a hydroxyl group-containing compound, which may be converted to a (meth) acrylate.

As the compound having one or more epoxy groups, a polyepoxide which is a so-called epoxy resin is preferable. As the polyepoxide, for example, a compound having two or more glycidyl groups such as a polyhydric phenol-polyglycidyl ether (for example, bisphenol A-diglycidyl ether) or an alicyclic epoxy compound is preferable. Further, a reaction product of a (meth) acrylate having an epoxy group and a compound having a hydroxyl group or a carboxyl group can also be used as the compound (X1). Examples of the (meth) acrylate having an epoxy group include glycidyl (meth) acrylate.

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

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

Specific examples of the monomeric polyisocyanate include, 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.

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

Compound (X2) having two or more hydroxyl groups
Examples include polyhydric alcohols and polyols having a higher molecular weight than polyhydric alcohols. As the polyhydric alcohol, a polyhydric alcohol having 2 to 20 hydroxyl groups is preferable, and a polyhydric alcohol having 2 to 15 hydroxyl groups is particularly preferable. The polyhydric alcohol may be an aliphatic polyhydric alcohol, an alicyclic polyhydric alcohol or a polyhydric alcohol having an aromatic nucleus. Examples of the polyhydric alcohol having an aromatic nucleus include an alkylene oxide adduct of a polyhydric phenol and a ring-opened product of a polyepoxide having an aromatic nucleus such as polyhydric phenol-polyglycidyl ether.

Examples of 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 polyhydric alcohol include the following polyhydric alcohols. Ethylene glycol, propylene glycol, 1,4-butanediol, 1,6
-Hexanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexanediol, dimethylolcyclohexane, trimethylolpropane, glycerin, pentaerythritol,
Ditrimethylolpropane, dipentaerythritol,
Tris (2-hydroxyethyl) isocyanurate, tris (2-hydroxypropyl) isocyanurate, ring-opened product of bisphenol A-diglycidyl ether, and ring-opened product of vinylcyclohexene dioxide.

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

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. .

Examples of the compound (X3) having a (meth) acryloyl group and an isocyanate group include 2-isocyanatoethyl (meth) acrylate and methacryloyl isocyanate.

Next, the (meth) acrylate compound having no urethane bond will be described. As the (meth) acrylic acid ester compound having no urethane bond, which is a preferable compound in the polyfunctional compound, a polyester of a compound having two or more hydroxyl groups similar to the compound (X2) and a (meth) acrylic acid Is preferred. As the compound having two or more hydroxyl groups, the above-mentioned polyhydric alcohols and polyols are preferable. Further, a (meth) acrylate compound which is a reaction product of a compound having two or more epoxy groups and (meth) acrylic acid is also preferable. As a compound having two or more epoxy groups, there is a polyepoxide called an epoxy resin. For example, glycidyl ether type polyepoxide,
A commercially available epoxy resin such as an alicyclic polyepoxide can be used.

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

The following (meth) acrylates of the following polyhydric alcohols or 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, tris (2- (meth) acryloyloxyethyl) isocyanurate, bisphenol A dimethacrylate.

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

As the polyfunctional compound, a cured product of the coating composition (A) can exhibit sufficient abrasion resistance.
The amount of the polyfunctional compound having three or more active energy ray-curable polymerizable functional groups is preferably 30% by weight or more, more preferably 50% by weight or more of the polyfunctional compound. Preferred specific examples of the polyfunctional compound include:
It is a polyfunctional compound having no urethane bond with the following 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-containing poly (pentaerythritol or polypentaerythritol) Acrylic urethane, which is a reaction product of a meth) acrylate and a polyisocyanate, is preferably a polyfunctional compound having three or more active energy ray-curable polymerizable functional groups, particularly an active energy ray-curable polymerizable compound. Polyfunctional compounds having 4 to 20 functional groups are preferred. As the polyfunctional compound having no urethane bond, pentaerythritol-based poly (meth) acrylate and isocyanurate-based poly (meth) acrylate are preferable.

The above pentaerythritol-based poly (meth)
Acrylate is a polyester of pentaerythritol or polypentaerythritol with (meth) acrylic acid (preferably an active energy ray-curable polymerizable functional group having 4
~ 20). Isocyanurate-based poly (meth) acrylate is tris (hydroxyalkyl)
Polyester of isocyanurate or an adduct obtained by adding 1 to 6 mol of caprolactone or alkylene oxide to 1 mol of the same and (meth) acrylic acid (having two to three active energy ray-curable polymerizable functional groups) Thing). It is also preferable to use a combination of these preferable polyfunctional compounds and other polyfunctional compounds having two or more polymerizable functional groups (particularly poly (meth) acrylate of polyhydric alcohol). In addition, these preferable polyfunctional compounds are preferably 30% by weight or more based on the total polyfunctional compounds, and more preferably 5% by weight.
0% by weight or more is preferred.

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

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

In order to cure the polyfunctional compound, the coating composition (A) usually contains a photopolymerization initiator. Known photopolymerization initiators can be used. Particularly, commercially available products that are easily available are preferable. A plurality of photopolymerization initiators may be used in the 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.),
Acylphosphine oxide-based photopolymerization initiators, diacylphosphine oxide-based photopolymerization initiators, and other photopolymerization initiators can be used. 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-dichlorobenzene Ethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2
-Hydroxy-2-methylpropan-1-one, 1-
(4-dodecylphenyl) -2-methylpropane-1-
On, 1- {4- (2-hydroxyethoxy) phenyl} -2-hydroxy-2-methyl-propan-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 (for example, 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 addition amount of the photopolymerization initiator in the coating composition (A) is preferably 0.01 to 20 parts by weight based on 100 parts by weight of the curable component (the total of the polyfunctional compound and the monofunctional compound). And particularly preferably 0.1 to 10 parts by weight. As the active energy ray for curing the coating composition (A), ultraviolet rays are particularly preferable. However, it is not limited to ultraviolet rays, and an electron beam or other active energy rays can be used. Xenon lamps, pulsed xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, carbon arc lamps, tungsten lamps, and the like can be used as the ultraviolet light source.

On the other hand, the coating composition (A) of the present invention
Contains polysilazane as an essential component. Examples of the polysilazane include polysilazane (perhydropolysilazane) substantially containing no organic group, an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, or
Polysilazane in which a group in which some or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with a substituent is bonded to a silicon atom, polysilazane in which a hydrolyzable group such as an alkoxy group is bonded to a silicon atom, Examples include polysilazane to which an organic group such as an alkyl group is bonded. In particular, perhydropolysilazane is preferred from the viewpoint of low firing temperature and denseness of a cured film after firing. In addition, a cured product in which polysilazane is sufficiently cured becomes silica containing almost no nitrogen atoms.

These polysilazanes are composed of a polymer having a chain, cyclic or crosslinked structure, or a mixture having a plurality of these structures in the molecule. 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 even when firing. On the other hand, if the number average molecular weight is more than 50,000, it becomes difficult to dissolve in a solvent, and the coating composition (A) may become viscous.

In order to cure the polysilazane into silica, it is generally necessary to perform heating called calcination. However, in the present invention, when an opaque synthetic resin substrate is used as the substrate, the firing temperature of polysilazane is preferably set to 180 ° C. or lower.

A catalyst is usually used to lower the firing temperature of polysilazane. Depending on the type and amount of the catalyst, it can be fired at a low temperature, and in some cases, can be cured at room temperature. The atmosphere for curing is preferably 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.

As the catalyst, it is preferable to use a catalyst which cures polysilazane at a lower temperature. Examples of such a catalyst include fine particles of a metal such as gold, silver, palladium, platinum and nickel proposed in JP-A-7-196886, and a carboxylic acid of the metal proposed in JP-A-5-93275. Use of complexes.
Further, instead of adding the catalyst to the coating composition (A), the coating composition (A) is directly added to a catalyst solution, specifically an aqueous amine solution, as proposed in JP-A-9-31333. , Or a method of exposing it to the vapor for a certain period of time.

JP-A-11-181290 describes that the curing of polysilazane is promoted by irradiation with an active energy ray in the presence of a photoradical generator. By optimizing, it is possible to cure with an active energy ray even when the catalyst is not contained.

The ratio of the polysilazane to the polyfunctional compound in the coating composition (A) can be appropriately selected depending on the scratch resistance, the crack resistance and the compatibility. In particular, when the balance between the scratch resistance and the crack resistance is taken into consideration. Have a polysilazane content of 10 to 10 with respect to 100 parts by weight of the polyfunctional compound.
00 parts by weight is preferred. If the ratio of the polysilazane to the polyfunctional compound is less than the above, the scratch resistance is insufficient, and if it is more than the above, the film easily cracks,
It is not preferable because the adhesion to the substrate is also insufficient.

The coating composition (A) may contain a solvent and various functional additives in addition to the above basic components. The solvent is usually an essential component, and the solvent is used unless the polyfunctional compound is a liquid having a particularly low viscosity. As the solvent, a solvent that is soluble in both the polyfunctional compound and the polysilazane is used. Further, it is preferable to select and use an appropriate solvent depending on the type of the base material. Among these, a solvent containing no hydroxyl group in the molecule is particularly preferable in consideration of the storage stability of polysilazane.

Specific examples include hydrocarbons, halogenated hydrocarbons, ketones, ethers, esters and the like.
More specifically, the following are mentioned. 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, Halogenated hydrocarbons such as 2-dichloroethane, 1,1-dichloroethane, trichloroethane and tetrachloroethane, ethyl ether, isopropyl ether, ethyl butyl ether, butyl ether, dioxane, dimethyldioxane, tetrahydrofuran,
Ethers such as tetrahydropyran, n-butyl acetate,
Esters such as diethylene glycol monoacetate.

The amount of the solvent can be appropriately changed depending on the required viscosity of the composition, the desired thickness of the cured layer, the drying temperature conditions, and the like. Usually, the weight is preferably 100 times or less, more preferably 0.1 to 50 times the weight of the curable component (the total of the active energy ray-curable component and the polysilazane) in the composition.

The functional compounding agents include ultraviolet absorbers, light stabilizers, antioxidants, thermal polymerization inhibitors, leveling agents, defoamers, thickeners, anti-settling agents, pigments (organic color pigments, inorganic pigments) ), Coloring dyes, infrared absorbers, fluorescent brighteners, dispersants, antifouling agents, rust inhibitors, conductive fine particles, antistatic agents, antifogging agents, coupling agents, and curing catalysts. One or more functional ingredients selected.
By appropriately blending these functional compounding agents, various functions can be imparted, durability can be improved, and adhesion to a substrate can be improved. In particular, when the coated molded article is used outdoors, it is particularly preferable to add an ultraviolet absorber or a light stabilizer in order to prevent deterioration of the cured product layer.

As the ultraviolet absorber, a known ultraviolet absorber can be used. Examples of such an ultraviolet absorber include a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a salicylic acid-based ultraviolet absorber, and a phenyltriazine-based ultraviolet absorber. Specific compounds include, for example, the following compounds.

Octyl 3- {3- (2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenyl} propionate, 2- (3,5-di-t-
Pentyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-
t-butylphenyl) benzotriazole, 2- (2-
Hydroxy-3-tert-butyl-5-methylphenyl)-
5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) -5-chlorobenzotriazole, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone,
2,2′-dihydroxy-4-methoxybenzophenone, pt-butylphenyl salicylate, 2- {2
-Hydroxy-5- (2-acryloyloxyethyl)
Phenyl @ benzotriazole, 2-hydroxy-3-
Methacryloyloxypropyl 3- (3- (benzotriazol-2-yl) -4-hydroxy-5-t-butylphenyl) propionate.

Since the coating composition (A) is a composition containing a polyfunctional compound having two or more active energy ray-curable polymerizable functional groups, of the specific compounds described above, -{2-hydroxy-5- (2-acryloyloxyethyl) phenyl} benzotriazole, 2
-Hydroxy-3-methacryloyloxypropyl 3-
Those having a photopolymerizable functional group in the molecule, such as (3- (benzotriazol-2-yl) -4-hydroxy-5-t-butylphenyl) propionate, are particularly preferable.

As the light stabilizer, a hindered amine light stabilizer which is also commonly used as a light stabilizer for a synthetic resin is preferable. Examples of the hindered amine light stabilizer include the following.

2,2,6,6-tetramethyl-4-piperidyl benzoate, N- (2,2,6,6-tetramethyl-4-piperidyl) dodecylsuccinimide, 1
-[(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] -2,2,6,6-tetramethyl-4-piperidyl (3,5-di-t-butyl-4- Hydroxyphenyl) propionate, bis (2,2,6,6-tetramethyl-4-piperidyl)
Sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,2)
6,6-pentamethyl-4-piperidyl) 2-butyl-2- (3,5-di-t-butyl-4-hydroxybenzyl) malonate, N, N'-bis (2,2,6,6-
Tetramethyl-4-piperidyl) hexamethylenediamine, tetrakis (2,2,6,6-tetramethyl-4-
Piperidyl) butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) butanetetracarboxylate, bis (2
2,6,6-tetramethyl-4-piperidyl) di (tridecyl) butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) di (tridecyl) butanetetracarboxylate, 3 , 9-Bis [1,1-dimethyl-2- {tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyl) butylcarbonyloxy} ethyl]-
2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2-ditris (1,2,2,6,6-pentamethyl-4-piperidyl) Oxycarbonyl) butylcarbonyloxydiethyl] -2,4,8,10-tetraoxaspiro [5.
5] undecane, 1,5,8,12-tetrakis [4
6-bis {N- (2,2,6,6-tetramethyl-4-
Piperidyl) butylamino {-1,3,5-triazin-2-yl] -1,5,8,12-tetraazadodecane, 1- (2-hydroxyethyl) -2,2,6,6-
Tetramethyl-4-piperidinol / dimethyl succinate condensate, 2-t-octylamino-4,6-dichloro-
s-Triazine / N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine condensate, N, N'-bis (2,2,6,6-tetramethyl- 4-piperidyl) hexamethylenediamine / dibromoethane condensate and the like.

Examples of the antioxidant include hindered phenol antioxidants such as 2,6-di-t-butyl-p-cresol, and phosphorus antioxidants such as triphenylphosphite. Examples of the leveling agent include a silicone resin-based leveling agent and an acrylic resin-based leveling agent.

Examples of the antifoaming agent include silicone resin antifoaming agents such as polydimethylsiloxane. Examples of the thickener include polymethyl methacrylate-based polymers, hydrogenated castor oil-based compounds, and fatty acid amide-based compounds.

Examples of the coloring dye include an organic solvent-soluble azo metal complex dye and an organic solvent-soluble phthalocyanine dye. Examples of the organic color pigment include a condensed polycyclic organic pigment and a phthalocyanine organic pigment. Examples of the inorganic pigment include titanium dioxide, cobalt oxide, molybdenum red, and titanium black.

Examples of the infrared absorber include polymethine, phthalocyanine, metal complex, aminium, diimonium, anthraquinone, dithiol metal complex, naphthoquinone, indolephenol, azo, and triarylmethane compounds. Is mentioned. Examples of the fluorescent whitening agent include a coumarin-based fluorescent whitening agent and 2,5-bis (5 ′
And oxazole-based fluorescent whitening agents such as -t-butylbenzoxazolyl- (2 ')) thiophene.

Examples of the antifouling agent include silicone resin antifouling additives and fluororesin antifouling additives. Examples of the rust inhibitor include silica, polyphosphate, phosphate, molybdate, phosphomolybdate, phytic acid, phytate, phosphonic acid, phosphonate and the like.

Examples of the conductive fine particles include metal powders such as zinc, aluminum, and nickel, iron phosphide, and antimony-doped tin oxide. As a coupling agent,
Examples include a silane coupling agent and a titanate coupling agent.

Examples of the antistatic agent include a nonionic antistatic agent, a cationic antistatic agent, and an anionic antistatic agent. Examples of the curing catalyst include curing catalysts selected from acids, alkalis, and salts.

The thickness of the layer of the cured product formed using the coating composition (A) is preferably from 0.1 to 100 μm, particularly preferably from 1 to 50 μm. This layer thickness is 100μ
If it exceeds m, curing by active energy rays becomes insufficient,
It is not preferable because the adhesion to the substrate is easily damaged. On the other hand, if the thickness is less than 0.1 μm, the abrasion resistance may be insufficient, and it is difficult to ensure the amount of the functional compounding agent to be added.

As a method for forming a layer of a cured product formed using the coating composition (A), a usual coating method can be employed. Means for applying the coating composition (A) is not particularly limited, and a known method can be employed. For example, dip method, flow coat method, spray method, bar coat method, gravure coat method, roll coat method, blade coat method,
Methods such as an air knife coating method, a spin coating method, a slit coating method, and a microgravure coating method can be employed.

When the coating composition (A) contains a solvent, it is dried after application to remove the solvent, and then the polyfunctional compound is cured by irradiation with ultraviolet light or the like, and the polysilazane is irradiated with ultraviolet light or heated. The mixture is cured by leaving it at room temperature or by exposing it to the vapor of a curing catalyst solution of a polysilazane compound.

In the present invention, the following three methods can be used to cure the coating composition (A) containing the polyfunctional compound and the polysilazane. 1) After applying the coating composition (A) and irradiating a sufficient amount of active energy rays to sufficiently cure the polyfunctional compound, the partially cured or uncured polysilazane is heated. Or curing at room temperature or by exposing to the vapor of a curing catalyst solution of polysilazane. 2) After applying the coating composition (A), the uncured polysilazane is cured by heating, leaving it at room temperature, or exposing it to the vapor of a curing catalyst solution of polysilazane, and then curing it. And curing the polyfunctional compound by irradiating the active energy ray. 3) A method in which the curing of the polyfunctional compound and the curing of the polysilazane by irradiation of the active energy ray are performed almost simultaneously. 3)
In the method (1), the curing of the polysilazane is usually slower than the curing of the polyfunctional compound. Therefore, it is considered that the curing is actually performed by the same process as 1).

The inorganic glass of the present invention has a surface coated with a primer such as a silane coupling agent,
Also includes those having a surface coated with a functional thin film such as a conductive thin film or a colored thin film. Examples of the metal in the present invention include a zinc-plated steel sheet, an aluminum-plated steel sheet, a stainless steel sheet, and an aluminum sheet. In addition, those in which a conductive film or a corrosion-resistant film is coated on the surface of these metals are also included. The opaque synthetic resin in the present invention includes:
It also includes those in which a coloring pigment, an inorganic pigment or a coloring dye is added to a transparent synthetic resin, and those in which a coloring paint is applied to the surface of a transparent synthetic resin.

The coated molded article of the present invention may be a bent molded article according to the application. In the case of a bent molded product, a coating composition comprising an uncured, partially cured, or completely cured polyfunctional compound and an uncured or partially cured polysilazane on a substrate (A )) After forming an uncured or partially cured layer
Preferably, bending is performed.

[0080]

The present invention will be described below with reference to Examples (Examples 1 to 11) and Comparative Examples (Example 12). Measurement and evaluation of various physical properties of Examples 1 to 12 were performed by the following methods, and the results are shown in Table 1.

[Initial Scratch Resistance] The state of surface scratches when a 500 g weight is combined with each of two CS-10F abrasion wheels and rotated 500 times according to the abrasion resistance test method in JIS-R3212 is shown below. The evaluation was performed in three stages. ：: scarcely scarred Δ: Some scratches are partially formed. ×: The entire surface is clearly scratched.

[Adhesion] The sample was cut 11 times in the vertical and horizontal directions at intervals of 1 mm with a razor blade to make 100 grids. Then, when a commercially available cellophane tape is closely adhered and then rapidly peeled in the forward direction by 90 degrees, the number (m) of the grids remaining without peeling off the coating is represented by m / 100. Initial adhesion after sample preparation was measured.

[Example 1] 1 equipped with a stirrer and a cooling pipe
In a 00 mL four-necked flask, dibutyl ether 20 was added.
g, xylene 30 g, 2- [4- (2-hydroxy-3)
-Dodecyloxypropyl) oxy-2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl)
-1,3,5-triazine 2 g, 2,4,6-trimethylbenzoyldiphenylphosphine oxide 0.15
g, and 0.2 g of 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate were added and dissolved, followed by 10 g of tris (2-acryloyloxyethyl) isocyanurate and a xylene solution of perhydropolysilazane (solid content). 20% by weight, manufactured by Tonen Corporation, trade name "V11
0 ") and stirred at room temperature for 1 hour under a nitrogen atmosphere to obtain a coating composition (hereinafter, referred to as coating liquid 1).

On a surface of a transparent glass plate having a thickness of 3 mm, N
After applying a 5% isopropyl alcohol solution of-(2-aminoethyl) -3-aminopropyltrimethoxysilane, the mixture was heated and dried at 80 ° C for 5 minutes. Next, the coating liquid 1 was applied thereon (wet thickness: 16 μm) using a bar coater and kept in a hot air circulating oven at 80 ° C. for 5 minutes. Then, in an air atmosphere, using a high-pressure mercury lamp,
After irradiating ultraviolet rays of 500 mJ / cm ² (the integrated energy amount of ultraviolet rays in a wavelength range of 300 to 390 nm, the same applies hereinafter), the cured product layer having a thickness of 3.2 μm is kept in a hot air circulating oven at 100 ° C. for 120 minutes. Was formed. This sample had an ultraviolet absorbing function and also had excellent scratch resistance. The measurement was performed using this sample.

Example 2 The sample preparation method in Example 1 was changed as follows. Finally, instead of keeping in a hot-air circulating oven at 100 ° C. for 120 minutes, it was cured for 7 days in an environment of 23 ° C. and 55% relative humidity. The measurement was performed using this sample.

Example 3 The sample preparation method in Example 1 was changed as follows. "UV irradiation" and "100 ℃
The procedure of “holding in a hot-air circulation oven for 120 minutes” was reversed to form a 3.2 μm-thick cured layer. The measurement was performed using this sample.

Example 4 The sample preparation method in Example 1 was changed as follows. The coating liquid 1 was coated (wet thickness: 16 μm) and kept in a hot air circulating oven at 80 ° C. for 5 minutes. This is placed in an air atmosphere using a high-pressure mercury lamp.
Irradiation of ultraviolet rays of 2,000 mJ / cm ² , the thickness of 3.2 μm
m of the cured product layer was formed. The measurement was performed using this sample.

Example 5 The sample preparation method in Example 4 was changed as follows. Instead of 50 g of a xylene solution of perhydropolysilazane (solid content: 20% by weight, trade name “V110” manufactured by Tonen Corporation) in the coating liquid 1, a xylene solution of organic polysilazane modified with a terminal methyl group (solid content: 20%)
50% by weight (trade name “L710”, manufactured by Tonen Co., Ltd.). The measurement was performed using this sample.

Example 6 The sample preparation method in Example 1 was changed as follows. "Tris (2
-Acryloyloxyethyl) isocyanurate 10
Instead of "g", "10 g of dipentaerythritol hexaacrylate" was used. The measurement was performed using this sample.

[Example 7] The sample preparation method in Example 1 was changed as follows. "2- [4-
(2-hydroxy-3-dodecyloxypropyl) oxy-2-hydroxyphenyl] -4,6-bis (2,4
-Dimethylphenyl) -1,3,5-triazine 2 g "
Instead of “Sb ₂ O ₅ sol (Sb ₂ O _{5 having} an average particle size of 20
nm, dispersion medium isopropanol, solid content concentration 30% by weight) 30 g ". This sample had an antistatic function and also had excellent scratch resistance performance. The measurement was performed using this sample.

[Example 8] The sample preparation method in Example 1 was changed as follows. "2- [4-
(2-hydroxy-3-dodecyloxypropyl) oxy-2-hydroxyphenyl] -4,6-bis (2,4
-Dimethylphenyl) -1,3,5-triazine 2 g "
In place of the above, 0.02 g of "metal complex-based near-infrared absorber (trade name" SIR-159 "manufactured by Mitsui Toatsu Dye Co., Ltd.)" was used. This sample had a near-infrared absorption function and was excellent in scratch resistance. The measurement was performed using this sample.

[Example 9] [2- [4-
(2-hydroxy-3-dodecyloxypropyl) oxy-2-hydroxyphenyl] -4,6-bis (2,4
-Dimethylphenyl) -1,3,5-triazine 2 g "
Was used instead of "1 g of aluminum polyphosphate" to obtain a coating composition (hereinafter, referred to as coating liquid 2).

The surface of the aluminum-plated steel sheet is
After degreasing, wash and dry, then apply Coating Liquid 2 (C
Hot air circulation oven at 80 ℃
For 5 minutes. And in an air atmosphere, a high-pressure mercury lamp
3000 mJ / cm using ^TwoIrradiation of ultraviolet light, film thickness
A cured product layer of 3.2 μm was formed. This sample is rustproof
It had a function and also had excellent scratch resistance performance. This sample
The measurement was performed using

Example 10 The sample preparation method in Example 9 was changed as follows. Instead of “1 g of aluminum polyphosphate” in the coating liquid 2, “Sb ₂ O ₅ sol (S
an average particle size of b ₂ O ₅ of 20 nm, a dispersion medium of isopropanol,
30 g of solid content concentration). This sample had an antistatic function and also had excellent scratch resistance performance.
The measurement was performed using this sample.

[Example 11] A milky white colored polycarbonate resin plate containing titanium oxide as an inorganic pigment (thickness: 3 m)
m) with coating liquid 1 (wet thickness 16 μm)
It was kept in a hot air circulating oven at 80 ° C. for 5 minutes. 3000 mJ / cm using a high-pressure mercury lamp in an air atmosphere
Irradiation of ultraviolet light of No. ² was performed to form a cured product layer having a thickness of 3.2 μm. This sample was excellent in weather resistance and scratch resistance. The measurement was performed using this sample.

Example 12 Dibutyl ether 10 was added to a 100 mL four-necked flask equipped with a stirrer and a condenser.
g, xylene 40 g, 2- [4- (2-hydroxy-3)
-Dodecyloxypropyl) oxy-2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl)
−1,3,5-triazine 1 g, 2,4,6-trimethylbenzoyldiphenylphosphine oxide 0.08
g, and 0.1 g of 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate are added and dissolved. Subsequently, 10 g of tris (2-acryloyloxyethyl) isocyanurate is added, and the mixture is added at room temperature under a nitrogen atmosphere for 1 hour. The mixture was stirred to obtain a coating composition (hereinafter, referred to as coating liquid 3).

[0097] The surface of a transparent glass plate having a thickness of 3 mm was N-
After a 5% isopropyl alcohol solution of (2-aminoethyl) -3-aminopropyltrimethoxysilane was applied, it was dried by heating at 80 ° C. for 5 minutes. Then on top of this,
Coating the coating liquid 3 using a bar coater (wet thickness 16
μm) and kept in a hot air circulating oven at 80 ° C. for 5 minutes. Then, in an air atmosphere, using a high-pressure mercury lamp,
After irradiating with ultraviolet rays of 0 mJ / cm ² , it was kept in a hot air circulating oven at 100 ° C. for 120 minutes to form a cured product layer having a thickness of 3.2 μm. Although this sample had an ultraviolet absorbing function, the scratch resistance was insufficient. The measurement was performed using this sample.

[0098]

[Table 1]

[0099]

The coated molded article of the present invention is an excellent coated molded article having various functions and high scratch resistance.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 183/16 C09D 183/16 (72) Inventor Hiroshi Shimoda 1150 Hazawacho, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture Asahi Glass Co., Ltd. In-house F-term (reference) 4F100 AA01A AB01A AG00A AK01A AK25 AK45 AK51 AK52B AT00A BA02 DC21 DC21B EH46 EH462 EJ52 EJ52B EJ522 EJ54 JB01 JB12B JD02 JK15 JK16 JL09 JN02A PCY01PC034

Claims (3)

[Claims] 1. A coated molded article having a substrate described below and a cured layer formed on at least a part of the surface of the substrate, wherein the cured layer is an active energy ray-curable polymerizable functional group. A coated molded article, which is a cured product of a coating composition (A) containing a polyfunctional compound having two or more groups and polysilazane. Substrate: inorganic glass, metal or opaque synthetic resin. 2. The cured product layer has a thickness of 0.1 to 100 μm.
The coated molded article according to claim 1, which is: 3. A method for producing a coated molded article having the following substrate and a cured product layer formed on at least a part of the surface of the substrate, wherein at least a part of the surface of the substrate is cured with active energy rays. Composition (A) containing a polyfunctional compound having two or more hydrophilic polymerizable functional groups and polysilazane
And then curing the polyfunctional compound by irradiation with active energy rays and curing the polysilazane in any order or simultaneously to form a cured layer of the coating composition (A). A method for producing a coated molded article, characterized in that: Substrate: inorganic glass, metal, and opaque synthetic resin.