JP2002248703A - Coated molding and its production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coated molding having a cured substance layer which has high scratch resistance and is excellent in surface lubricity and a method for producing the coated molding. SOLUTION: The cured substance layer composed of an inner layer of a cured coating composition (A) containing a compound having at least one polymerizable functional group which can be cured by active energy rays and the outermost layer of a cured coating composition (B) containing polysilazane and a lubricating agent is formed at least in a part of the surface of a base material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a method of adding a cured material layer derived from an active energy ray (especially ultraviolet) curable coating composition and a lubricity-imparting agent to a surface of a substrate from the substrate side. The present invention relates to a coated molded article having a cured layer on which a silica layer derived from polysilazane is formed and which has excellent scratch resistance, surface lubricity, transparency and the like, and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, as a transparent material replacing glass,
A transparent synthetic resin material is used. The present inventors have heretofore included a polyfunctional compound having two or more active energy ray-curable polymerizable functional groups and polysilazane for the purpose of improving the abrasion resistance of the surface of a resin substrate to the level of glass. A coated molded article having a cured product layer of a coating composition has been proposed.

[0003]

The above coated molded article is
Sliding parts that have high abrasion resistance but keep rubbing with other objects at all times, such as discs that are supposed to slide with the ascending / descending parts of the resin window for automobiles or the read head that cannot avoid friction with the surrounding molding When used, the surface lubricity was not sufficiently satisfactory such that abnormal noise was not generated when rubbed and frictional resistance was hardly generated when rubbed.

[0004] An object of the present invention is to provide a coated molded article having a cured layer having high scratch resistance and excellent surface lubricity, and a method for producing the same.

[0005]

In order to achieve the above object, a coated molded article of the present invention is a coated molded article having two or more cured product layers formed on at least a part of the surface of a substrate. The inner layer in contact with the outermost layer of the cured product layer,
A cured product layer of a coating composition (A) containing a compound having one or more active energy ray-curable polymerizable functional groups, wherein the outermost layer contains polysilazane and a lubricity-imparting agent (B). Characterized in that it is a cured layer.

According to the above invention, a coating composition (A) having high adhesiveness to a substrate is provided via an inner layer made of a cured product,
Since the outermost layer made of the cured product of the coating composition (B) having excellent scratch resistance is formed, the bonding strength of the outermost layer to the substrate can be increased. Further, since the inner layer is harder than the base material and softer than the outermost layer, the inner layer has an effect of receiving the external force applied to the outermost layer and reducing the displacement of the outermost layer, thereby preventing the outermost layer from cracking. Furthermore, since the outermost layer is made of a cured product of the coating composition (B) containing polysilazane and a lubricity-imparting agent, it has excellent scratch resistance and surface lubricity. Therefore, it is possible to provide a coated molded article having a cured product layer having excellent scratch resistance, surface lubricity, transparency, and the like.

[0007] One of the methods for producing a coated molded article of the present invention is a method for producing a coated molded article having two or more cured product layers formed on at least a part of the surface of a substrate.
Forming an uncured material layer, a partially cured material layer, or a cured material layer of the coating composition (A) containing a compound having one or more active energy ray-curable polymerizable functional groups on at least a part of the surface of the base material When an uncured or partially cured layer of the coating composition (B) containing polysilazane and a lubricity-imparting agent is formed on the surface thereof, and the layer of the coating composition (A) is a cured layer, The layer of the coating composition (B) is cured, and when the layer of the coating composition (A) is an uncured layer or a partially cured layer, the layers of the coating composition (A) and the coating composition (B) are removed. It is characterized by being cured in any order or simultaneously.

According to the above invention, an inner layer made of a cured product of the coating composition (A) containing a compound having at least one active energy ray-curable polymerizable functional group is formed on at least a part of the surface of the substrate. By forming an outermost layer made of a cured product of the coating composition (B) containing polysilazane and a lubricity-imparting agent, the adhesion of the outermost layer to the substrate surface is improved by the inner layer, and The displacement of the outermost layer with respect to the external force applied to the
Improves scratch resistance. Therefore, a coated molded article having a cured product layer having excellent scratch resistance, surface lubricity, transparency and the like can be produced.

Another method for producing a coated molded article according to the present invention is a method for producing a coated molded article on at least a part of the surface of a substrate.
In the method for producing a coated molded article having at least one cured product layer, a coating composition (A) comprising a compound having at least one active energy ray-curable polymerizable functional group on at least a part of the surface of the substrate. Is formed, and a layer of a coating composition (B) containing polysilazane and a lubricity-imparting agent is formed on the surface of the layer. Then, after bending, the coating composition (A) and the coating composition ( The curing of B) is performed in any order or simultaneously.

[0010] According to the above invention, the base material is deformed before the polysilazane contained in the coating composition (B) is sufficiently cured, and then the polysilazane is cured to form hard silica. A bent molded article without cracks or the like in the outermost layer made of the cured product of the product (B) is obtained.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The coated molded article of the present invention comprises a coating composition (A) containing a compound having at least one active energy ray-curable polymerizable functional group on the surface of a substrate from the substrate side. It has an inner layer made of a cured product and an outermost layer made of a cured product of the coating composition (B) containing polysilazane and a lubricity-imparting agent. Note that a third layer made 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, a cured product layer composed of an inner layer and an outermost layer is preferred.

Next, each of the above layers will be described in more detail. First, a coating composition (A) for forming an inner layer
Will be described. In the following description, an acryloyl group and a methacryloyl group are collectively referred to as a (meth) acryloyl group, and a (meth) acryloyloxy group,
The same applies to expressions such as (meth) acrylic acid and (meth) acrylate.

[0013] Among the compounds having one or more active energy ray-curable polymerizable functional groups contained in the coating composition (A) (hereinafter, referred to as active energy ray-curable components), those polymerizable by active energy rays. As a compound having one functional functional group (hereinafter, simply referred to as a monofunctional compound),
A compound having a (meth) acryloyl group is preferable, and a compound having an acryloyl group is particularly preferable. In addition, it may have a functional group such as a hydroxyl group and an epoxy group. Examples of the monofunctional compound include the following.

Alkyl (meth) acrylate (alkyl group has 1 to 13 carbon atoms), allyl (meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate, butanediol (meth) acrylate, butoxytriethylene glycol Things (meta)
Acrylate, t-butylaminoethyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth)
Acrylate, 2-cyanoethyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2,3-dibromopropyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl ( Meth) acrylates,

N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2 (2-ethoxyethoxy) ethyl (meth) acrylate, Ethylhexyl (meth) acrylate, glycerol (meth) acrylate, glycidyl (meth)
Acrylate, heptadecafluorodecyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyltrimethylammonium chloride, 2-hydroxypropyl (meth) acrylate, isobornyl (meth) acrylate , 3- (meth) acryloyloxypropyltrimethoxysilane, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, methoxydipropylene Glycol (meth) acrylate, methoxylated cyclodecatriene (meth) acrylate,

Morpholine (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, octafluoropentyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, phenoxyethyl (meth) acrylate,
Phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxy (meth) acrylate,
Polypropylene glycol (meth) acrylate, sodium sulfonic acid (meth) acrylate, tetrafluoropropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, trifluoroethyl (meth) acrylate, vinyl acetate, N-vinylcaprolactam, N- Vinylpyrrolidone, N-vinylformamide, morpholino (meth) acrylate, 2-morpholinoethyl (meth) acrylate.

Examples of the compound having two or more active energy ray-curable polymerizable functional groups (hereinafter, simply referred to as a polyfunctional compound) include, for example, JP-A-11-240103.
No. 0016-0020, 0023-00
47. Preferred polyfunctional compounds include compounds having two or more (preferably 2 to 50, more preferably 3 to 30) one or more polymerizable functional groups selected from (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 a polyhydric alcohol and (meth) acrylic acid is preferable. Further, compounds having various functional groups and bonds other than the above-mentioned polymerizable functional groups may be used. In particular, a (meth) acryloyl group-containing compound having a urethane bond (hereinafter, referred to as acrylic urethane) and a (meth) acrylate compound having no urethane bond are preferable.

The acryl urethane is acryl uretne, which is a reaction product of pentaerythritol or its polymer, polypentaerythritol, polyisocyanate and hydroxyalkyl (meth) acrylate, and is an active energy ray-curable polymer. Which is a reaction product of a polyfunctional compound having two or more (more preferably 4 to 20) functional functional groups or a hydroxyl group-containing poly (meth) acrylate of pentaerythritol or polypentaerythritol with polyisocyanate A polyfunctional compound which is urethane and has two or more (more preferably 4 to 20) active energy ray-curable polymerizable functional groups is exemplified.

Examples of the (meth) acrylate compound having no urethane bond include pentaerythritol poly (meth) acrylate and isocyanurate poly (meth) acrylate. The pentaerythritol-based poly (meth) acrylate is pentaerythritol or a polyester of polypentaerythritol and (meth) acrylic acid (preferably having 4 to 20 active energy ray-curable polymerizable functional groups). Say. Also, isocyanurate-based poly (meth)
Acrylate is a polyester obtained by adding 1 to 6 mol of caprolactone or alkylene oxide to 1 mol of tris (hydroxyalkyl) isocyanurate or tris (hydroxyalkyl) isocyanurate, and a polyester of (meth) acrylic acid. (Preferably having two or three active energy ray-curable polymerizable functional groups).

In the present invention, the above-mentioned preferred polyfunctional compound and another polyfunctional compound having two or more active energy ray-curable polymerizable functional groups (particularly poly (meth) acrylate of polyhydric alcohol) May be used in combination.

The proportion of the monofunctional compound or the polyfunctional compound in the active energy ray-curable component contained in the coating composition (A) is not particularly limited. Since the hardness of the cured product layer itself of the composition (A) is reduced and the scratch resistance of the entire cured product layer is reduced, the mass ratio of the polyfunctional compound and the monofunctional compound (polyfunctional compound / monofunctional compound) Compound) is preferably one or more.

The coating composition (A) may contain the following solvents and various functional additives in addition to the above basic components.

As the solvent, a solvent usually used for a coating composition containing a polyfunctional compound as a curable component can be used.
For example, hydrocarbons, halogenated hydrocarbons, ketones, ethers, esters and the like can be mentioned. In addition,
It is preferable to use an appropriate solvent according to the type of the resin to be the base material, and when a low solvent-resistant resin is used for the base material, lower alcohols, cellosolves, esters, or a mixture thereof are used. preferable. Specifically, a solvent described in paragraph No. 0074 of JP-A-11-268196 can be used. In the present invention, esters, cellosolves and lower alcohols are particularly preferred.

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, drying conditions, and the like. In the present invention, the solvent is preferably used in an amount of 100 times or less, more preferably 5 times or less, by mass based on the active energy ray-curable component in the coating composition (A).

Further, the coating composition (A) preferably contains a photopolymerization initiator in order to efficiently cure the active energy ray-curable component. As the photopolymerization initiator, known ones can be used, and particularly, commercially available ones that are easily available are preferable.

Examples of the photopolymerization initiator include arylketone photopolymerization initiators (for example, acetophenones, benzophenones, alkylaminobenzophenones, benzyls, benzoins, benzoin ethers, benzyldimethyl ketals, benzoyl benzoates, α -Acyloxime esters), sulfur-containing photopolymerization initiators (eg, sulfides, thioxanthones, etc.), acylphosphine oxide photopolymerization initiators, diacylphosphine oxide photopolymerization initiators, and other photopolymerization initiators. No. Specifically, Japanese Unexamined Patent Application Publication No. 11-268196
Compounds described in Paragraph Nos. 0063 to 0065 of Japanese Patent Application Laid-Open Publication No. H10-163, 1988 are exemplified. In the present invention, an acylphosphine oxide-based photopolymerization initiator is particularly preferred. A plurality of photopolymerization initiators may be used in combination, or may be used in combination with a photosensitizer such as an amine.

The amount of the photopolymerization initiator used in the coating composition (A) is preferably from 0.01 to 20 parts by mass, more preferably from 0.1 to 1 part by mass, per 100 parts by mass of the active energy ray-curable component.
0 parts by mass is preferred.

Functional compounding agents other than the above-mentioned photopolymerization initiators include ultraviolet absorbers, light stabilizers, antioxidants, thermal polymerization inhibitors, leveling agents, defoamers, thickeners, antisettling 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 One or more types selected from the group consisting of curing catalysts are included.

As the ultraviolet absorber, benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, salicylic acid-based ultraviolet absorbers, phenyltriazine-based ultraviolet absorbers and the like, which are used as synthetic resin ultraviolet absorbers, are preferred. Specifically, Japanese Unexamined Patent Application Publication No. 11-268196
And the compounds described in paragraph No. 0078 of the publication. In the present invention, 2- {2-hydroxy-5-
Polymerizable functional groups in the molecule such as (2-acryloyloxyethyl) phenyl} benzotriazole, 2-hydroxy-3-methacryloyloxypropyl-3- (3-benzotriazole-4-hydroxy-5-t-butylphenyl) propionate Is particularly preferable.

As the light stabilizer, a hindered amine light stabilizer used as a light stabilizer for a synthetic resin is preferable. Specifically, the compounds described in paragraph No. 0080 of JP-A-11-268196 can be mentioned. In the present invention, those having a polymerizable functional group in the molecule such as N-methyl-4-methacryloyloxy-2,2,6,6-tetramethylpiperidine are particularly preferable.

Examples of the antioxidant include hindered phenolic antioxidants such as 2,6-di-t-butyl-p-cresol and phosphorus-based 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 which do not correspond to the lubricity imparting agent in the present invention. Examples of the thickener include polymethyl methacrylate-based polymers, hydrogenated castor oil-based compounds, and fatty acid amide-based compounds.

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

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 fluorescent whitening agent and an oxazole fluorescent whitening agent such as 2,5-bis {5′-t-butylbenzooxazolyl- (2 ′)} thiophene.

Examples of the antifouling additive include silicone resin antifouling additives and fluororesin antifouling additives which do not correspond to the lubricity imparting agent in the present invention. As rust inhibitors, silica, polyphosphoric acid, phosphate, molybdate,
Examples include 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 antistatic agents,
Examples include a nonionic antistatic agent, a cationic antistatic agent, and an anionic antistatic agent.

Examples of the antifogging agent include nonionic surfactants. Examples of the coupling agent include a silane coupling agent and a titanate coupling agent. Examples of the curing catalyst include curing catalysts selected from acids, alkalis, and salts.

The thickness of the inner layer made of the cured product of the coating composition (A) is preferably 1 to 50 μm, particularly preferably 2 to 30 μm. If the thickness of the inner layer 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 of the inner layer is more than 50 μm, the curing by the active energy ray becomes insufficient, and the adhesion to the base material is liable to be deteriorated.

Next, the coating composition (B) for forming the outermost layer
Will be described. As the polysilazane contained in the coating composition (B), polysilazane described in paragraphs 0097 to 0104 of JP-A-11-240103 is preferably exemplified.

In the present invention, perhydropolysilazane is preferable, and the number average molecular weight is preferably 200 to 50,000. If the number average molecular weight is less than 200, it is difficult to obtain a uniform cured product even when firing, and if it exceeds 50,000, it is difficult to dissolve in a solvent, which is not preferable.

The lubricating agent in the present invention is
A compound capable of reducing the dynamic friction coefficient of the surface of the cured product of the coating composition (B) by 10% or more by adding the imparting agent. Examples of such a lubricity imparting agent include the following compounds.

Generally used silicon compounds (eg, polydimethylsiloxane, polydimethylsiloxane / polyether block copolymer, alkyl group-modified polydimethylsiloxane), fluorine compounds, fatty acid esters which are esterified products of polyol compounds and fatty acids Wax and the like (hereinafter, these are collectively referred to as non-reactive lubricants).

Although the above-mentioned non-reactive lubricant can sufficiently achieve the expected performance under ordinary use conditions, it does not react with the matrix formed by the coating composition (B).
When used for a long time, these non-reactive lubricants gradually disappear from the surface of the cured product layer and disappear, resulting in a higher friction coefficient of the surface of the cured product layer and lower surface lubricity. And may cause injury.

A compound in which a reactive functional group capable of forming a covalent bond with a matrix formed by the coating composition (B) is introduced into the above-mentioned non-reactive lubricant (hereinafter, these are collectively referred to as a reactive lubricant). ).

Specific examples of the reactive functional group include a silanol group, an alkoxysilyl group, and a radical reactive functional group. The radical-reactive functional group referred to herein may be any group that has reactivity with a (meth) acryl group or an active radical derived from silazane. For example, a (meth) acryl group, an allyl group, a vinyl group, a vinyl ether Groups, halogen substituents, mercapto groups and the like.

In the present invention, polydimethylsiloxane having a methacryloyl group, amino group or silanol group in the molecule is particularly preferred.

The reactive lubricant forms a covalent bond with the silica matrix formed by the polysilazane upon irradiation with active energy rays (in this case, radicals derived from the photoinitiator are converted from the coating composition (A) constituting the inner layer). It is considered that the cured product layer is supplied for a long period of time.

The ratio of the lubricity imparting agent in the coating composition (B) is 0.01 to 100 parts by mass of polysilazane.
-10 parts by mass is preferred. The ratio of the lubricity imparting agent is 0.0
If the amount is less than 1 part by mass, sufficient surface lubricity cannot be exhibited and 10
When the amount is more than the mass part, the outermost layer itself is plasticized and the scratch resistance is reduced.

The coating composition (B) can contain the following solvents and various functional additives in addition to the above basic components.

As the solvent, hydrocarbons, halogenated hydrocarbons, ethers, esters and ketones can be used. Specifically, a solvent described in paragraph No. 0106 of JP-A-11-240103 is preferably exemplified. In the present invention, xylene or dibutyl ether is particularly preferred.

In order to adjust the solubility of polysilazane and the evaporation rate of the solvent, a plurality of kinds of solvents may be mixed and used.

The amount of the solvent used depends on the coating method to be employed, the structure of polysilazane, the average molecular weight, and the like, but is preferably adjusted so that the solid content concentration is 0.5 to 80% by mass.

As the functional compounding agent, the functional compounding agent described in the above coating composition (A) is preferably exemplified.

The thickness of the outermost layer made of the cured product of the coating composition (B) is preferably from 0.05 to 10 μm, particularly preferably from 0.1 to 10 μm.
３3 μm is preferred. If the thickness of the outermost layer exceeds 10 μm,
Improvements in surface properties such as scratch resistance cannot be expected, and the layer becomes brittle, and even the slightest deformation of the coated molded article tends to cause cracks and the like in the outermost layer. Also, 0.05μ
If it is less than m, the abrasion resistance and the abrasion resistance of the outermost layer may not be sufficiently exhibited.

Next, the base material will be described. As a material of the base material, various synthetic resins, various metals, glass, and the like can be used. Of these, synthetic resins are preferred, and transparent synthetic resins are particularly preferred. As a transparent synthetic resin, for example,
Aromatic polycarbonate resins, polymethyl methacrylate resins (acrylic resins), polystyrene resins, and the like are preferable, and aromatic polycarbonate resins are particularly preferable. This base material is a molded one, for example, a sheet-like base material such as a flat plate or a corrugated plate, a film-like base material, a base material formed into various shapes, a laminate in which at least a surface layer is made of various transparent synthetic resins, and the like. Is preferred. In the present invention, a flat base material that is not particularly bent is preferable. The thickness of the substrate is not particularly limited,
For applications such as window materials, 0.1 to 100 mm is preferable.

The coated molded article of the present invention is suitably used for applications such as protection of the signal reading surface of a blue laser disk (registered trademark).

Next, a method for producing a coated molded product of the present invention will be described. One of the methods for producing a coated molded article of the present invention is to prepare a coating composition (A) containing a compound having at least one active energy ray-curable polymerizable functional group on at least a part of the surface of a substrate. Forming a cured product layer, a partially cured product layer or a cured product layer, and forming an uncured or partially cured product layer of the coating composition (B) containing polysilazane and a lubricity-imparting agent on the surface thereof; When the layer of the product (A) is a cured product layer, the layer of the coating composition (B) is cured, and when the layer of the coating composition (A) is an uncured product layer or a partially cured product layer, the coating composition This is a method of curing the layers of the product (A) and the coating composition (B) in any order or simultaneously.

The method for applying the coating compositions (A) and (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. Various methods can be adopted.

The active energy ray for curing the coating composition (A) is not particularly limited, and examples thereof include ultraviolet rays, electron beams and other active energy rays, and ultraviolet rays are preferred. As the ultraviolet light source, a xenon lamp, a pulse xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, a tungsten lamp, and the like can be used.

The curing of the coating composition (B) can be carried out by irradiating with the above-mentioned active energy ray, leaving it at room temperature, or
Paragraph Nos. 0111 to 0115 of JP-A-1-240104
Can be adopted.

In the present invention, low temperature (below 180 ° C.)
To cure the polysilazane.
In order to cure polysilazane at a low temperature, it is preferable to add a catalyst to the coating composition (A), and it is preferable to use a catalyst that can be cured at a lower temperature. Examples of such a catalyst include fine particles of metals such as gold, silver, palladium, platinum and nickel described in JP-A-7-196886, amines described in JP-A-9-31333, and the like. Acids.

The particle size of the metal fine particles is preferably smaller than 0.1 μm, and more preferably smaller than 0.05 μm in order to ensure transparency of the cured product. Further, since the specific surface area increases as the particle diameter decreases, the catalytic ability also increases. Therefore, it is preferable to use a catalyst having a smaller particle diameter from the viewpoint of improving the catalytic performance.

The above amines include, for example, monoalkylamine, dialkylamine, trialkylamine,
Monoarylamine, diarylamine, cyclic amine and the like can be mentioned. Examples of the acids include organic acids such as acetic acid and inorganic acids such as hydrochloric acid.

When the metal fine particles are previously added to the coating composition (B) as a catalyst, the amount is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, per 100 parts by mass of polysilazane. Parts by weight are preferred. 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, which may impair the transparency.

The above amines and acids are used in the coating composition (B)
To the surface coated with the coating composition (B), a solution of amines or acids (including an aqueous solution),
It may be in contact with those vapors (including vapors from aqueous solutions).

The timing of the curing of the coating composition (A) and the application to curing of the coating composition (B) can be exemplified by the following four methods.

(1) After coating the coating composition (A), a sufficient amount of active energy rays are applied to completely cure the coating composition (A), and then the coating composition is applied to the surface. A layer of the object (B) is formed.

(2) The coating composition (A) is applied to form an uncured layer of the coating composition (A), and then the coating composition (B) is applied to the surface thereof to form the coating composition. The uncured material layer of (B) is formed, and thereafter, a sufficient amount of active energy rays is irradiated to complete the curing of the coating composition (A). In this case, the coating composition (B) is cured almost simultaneously with the coating composition (A), or is cured by heating after the curing of the coating composition (A).

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

(4) An uncured or partially cured layer of the coating composition (A) and an uncured layer of the coating composition (B) were formed as described in (2) or (3) above. Thereafter, the uncured material of the coating composition (B) is partially cured or completely cured first, and then the uncured material layer or the partially cured material layer of the coating composition (A) is completely cured. In this case, at the time of curing the uncured material layer 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 addition, according to the method (4), when the coating composition (A) is completely cured, the coating composition (B) is partially cured or completely cured when oxygen is likely to be a curing inhibition factor. Can act as a barrier layer to prevent the cured product of the coating composition (A) from being insufficiently cured. When the coating composition contains a solvent, it is preferable that after coating, the composition is dried to remove the solvent and then cured.

The coated molded article obtained as described above is
Surface properties such as scratch resistance and abrasion resistance have almost the same level as glass, and have excellent surface lubrication,
It can be used for various applications where conventional glass was used.

Another method of producing a coated molded article according to the present invention is a coating composition comprising a compound having at least one active energy ray-curable polymerizable functional group on at least a part of the surface of a substrate. After forming a layer of the product (A), further forming a layer of a coating composition (B) containing polysilazane and a lubricity-imparting agent on the surface thereof, and then bending the coating composition, the coating composition (A) and the This is a method of curing the coating composition (B) in any order or simultaneously.

Normally, when manufacturing a bent coated product, a base material that has been bent in advance is used.
When such a base material is used, it may be difficult to form each layer by applying and curing each coating composition.

On the other hand, when bending is performed after forming a layer of each coating composition on the surface of a flat base material, only a cured product layer of the coating composition (A) is formed on the surface of the base material. Can be bent by hot bending or the like, but when the cured product layer of the coating composition (B) is formed, the cured product (silica) of the coating composition (B) is hard. When it is performed, cracks are likely to occur.

Therefore, in the present invention, the substrate is bent in a state where the coating composition (B) is in an uncured or partially cured product, and thereafter, the uncured or partially cured product of the coating composition (B) is obtained. Is completely cured, without causing cracks in the cured product layer of the coating composition (B), and a coated molded product that is easily bent can be produced.

Usually, since the bending is performed in a heated state, the curing of the uncured or partially cured product of the coating composition (B) proceeds by this heating. Since it takes a long time to cure the uncured product or partially cured product (B), it can be easily bent.

Specifically, for example, as in the timing of the above (2) or (3), a layer of an uncured or partially cured product of the coating composition (A) is formed on the surface of the substrate, and then After forming a layer of the uncured material or partially cured material of the coating composition (B) on the surface of the layer, the substrate is heated at the heat softening temperature of the substrate for about 5 minutes, and then bent. Thereafter, the coating composition (A) and the coating composition (B) are completely cured.
The curing of the uncured material or the partially cured material of the coating composition (A) may be performed by irradiating an active energy ray, and the curing of the uncured material or the partially cured material of the coating composition (B) is performed using the coating composition Curing may be performed by maintaining the temperature at which the uncured or partially cured material (B) can be cured. The order of the curing of the coating composition (A) after the bending and the curing of the coating composition (B) are not particularly limited, and either one may be performed first.

According to the above production method, the coating composition (B)
Since the base material is deformed before is sufficiently cured, and a cured product (silica) of the hard coating composition (B) is formed thereafter, problems such as cracks do not occur. For this reason, for example, a bent coated product used as a window material for a vehicle can be obtained.

[0080]

The present invention will now be described with reference to Examples (Examples 1 to 8 and 10),
A description will be given based on a comparative example (Example 9), but the present invention is not limited thereto. Measurement and evaluation of various physical properties of Examples 1 to 9 were performed by the following methods, and the results are shown in Table 1. A transparent aromatic polycarbonate resin plate (150 mm × 150 mm, thickness 3 mm) was used as a substrate, and a disk-shaped substrate (thickness 1. 2 mm, 12 cm diameter disc) was used.

[Initial haze value, abrasion resistance] JIS-R321
According to the abrasion resistance test method in No. 2, a haze was measured with a haze meter when 500 g weights were combined with each of the two CS-10F wear wheels and rotated 500 times. The haze was measured at four points on the wear cycle track, and the average value was calculated. The initial haze value indicates the value (%) of the haze value before the abrasion test, and the abrasion resistance indicates the value (%) of (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 into eleven vertical and horizontal lines at 1 mm intervals with a razor blade to make 100 grids. Then, the number (m) of the grids left without peeling off the coating when the cellophane tape on the market was closely adhered and then peeled sharply in the forward direction by 90 degrees was represented by m / 100.

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

[Sliding resistance (dynamic friction coefficient)]
The dynamic friction coefficient was measured using "ester HEIDON-14" (trade name, manufactured by HEIDON). As an accelerated test, a temperature of 23 ± 2
Under an environmental condition of 50 ° C. and a relative humidity of 50 ± 5%, a magnetic head “RF320-74G” (trade name, manufactured by Sony Corporation) was brought into contact with the disk so that the load became 2 gf, and the disk was rotated at 600 rpm. 5 million revolutions were continuously run, and before and after that (in Table 1, "initial",
The coefficient of kinetic friction was measured after "endurance".

[Example 1] 2 equipped with a stirrer and a cooling pipe
In a 00 mL four-necked flask, isopropyl alcohol 20.5 g, butyl acetate 20.5 g, 1-methoxy-2
-Propanol 10.3 g, 2,4,6-trimethylbenzoyldiphenylphosphine oxide 0.33 g, 2
-[4- (2-hydroxy-3-dodecyloxypropyloxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) 1,3,5-triazine 0.66 g, PMMA resin 2 0.0 g and N-methyl-
0.44 g of 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine was added and dissolved.

Subsequently, 10.0 g of urethane acrylate (containing an average of 15 acryloyl groups per molecule), which is a reaction product of dipentaerythritol polyacrylate having a hydroxyl group and partially nullated hexamethylene diisocyanate, and caprolactone-modified tris ( 10.0 g of (acryloyloxyethyl) isocyanurate (trade name “Alonix M-325” manufactured by Toagosei Co., Ltd.) was added, and the mixture was stirred at room temperature for 1 hour to obtain a coating liquid 1.

Further, a xylene solution of perhydropolysilazane (solid content: 20% by mass, manufactured by Clariant Japan Co., Ltd.)
To 100 g of a brand name "N-V110"), 60 mg of a silicone oil (trade name "X-22-164C" manufactured by Shin-Etsu Chemical Co., Ltd.) in which both ends of polydimethylsiloxane are modified with a methacryl group is added as a lubricity imparting agent. At room temperature
After stirring for an hour, a coating liquid 2 was obtained.

Then, the coating liquid 1 was applied to the base material by a spin coating method (wet thickness: 20 μm) and kept in a hot air circulating oven at 80 ° C. for 5 minutes to remove the solvent. 150mJ / c using medium and high pressure mercury lamp
Ultraviolet rays of m ² (integrated ultraviolet energy in the wavelength range of 300 to 390 nm, the same applies hereinafter) were applied to form a 6 μm-thick partially cured product layer.

Then, the coating liquid 2 was applied to the surface by a spin coating method (wet thickness: 6 μm), and was kept in a hot air circulating oven at 80 ° C. for 10 minutes to remove the solvent. 1500 mJ / using a high pressure mercury lamp
Irradiated with ultraviolet light of cm ² . Then, a sample in which a cured product layer having a film thickness of 7.6 μm was formed by holding for 24 hours in an environment of 23 ° C. and 50% relative humidity was produced.

[Example 2] Polydimethylsiloxane modified with silanol groups at both ends instead of the lubricating agent "X-22-164C" (trade name "DMS", manufactured by Shin-Etsu Chemical Co., Ltd.) A sample was prepared in exactly the same procedure as in Example 1, except that -S27 ") was used.

[Example 3] Polydimethylsiloxane modified at both ends with a mercapto group (Shin-Etsu Chemical Co., Ltd .; trade name: "X-22-164C") instead of the lubricity-imparting agent "X-22-164C" -22-167B "), and a sample was prepared in exactly the same procedure as in Example 1.

[Example 4] In the above coating liquid 2, instead of the lubricity imparting agent "X-22-164C", unmodified polydimethylsiloxane (trade name "L" manufactured by Nippon Unicar Co., Ltd.)
A sample was prepared in exactly the same procedure as in Example 1, except that -45 ") was used.

[Example 5] Silicone oil modified with a fluoroalkyl group in place of the lubricity-imparting agent "X-22-164C" in the above coating liquid 2 (model number "FLS-525" manufactured by Asahi Glass Co., Ltd.) A sample was prepared in exactly the same procedure as in Example 1 except that the sample was used.

[Example 6] In Example 1, coating solution 1 was applied
After drying, the coating solution 2 was applied without irradiating the sample with ultraviolet rays, and the subsequent steps were performed in exactly the same manner as in Example 1 to prepare a sample.

Example 7 In Example 1, a sample was prepared by irradiating ultraviolet rays at the end, and further curing for 3 minutes in a bath of a 3% by volume aqueous solution of triethylamine kept at 25 ° C. to prepare a sample.

Example 8 In Example 1, a xylene solution of a low-temperature curable perhydropolysilazane (solid content: 20% by mass,
Clariant Japan, product name "NL110")
To 100 g, 60 mg of the terminally unmodified polydimethylsiloxane (trade name "L-45" manufactured by Nippon Unicar Co., Ltd.) used in Example 4 as a lubricity imparting agent was added, and the mixture was stirred at room temperature for 1 hour to give a coating liquid 3. I got

Coating liquid 1 on the substrate (wet thickness 20
μm) and kept in a hot-air circulating oven at 80 ° C. for 5 minutes to remove the solvent, and then, in an air atmosphere, using a high-pressure mercury lamp, irradiating ultraviolet rays of 1500 mJ / cm ² to form a film having a thickness of 6 μm.
m of the cured product layer was formed.

Then, the coating liquid 3 was applied to the surface by a spin coating method (wet thickness: 6 μm), and was kept in a hot air circulating oven at 80 ° C. for 10 minutes to remove the solvent. Was held in a hot air circulating oven for 2 hours to form a sample having a cured product layer having a thickness of 7.6 μm.

[Example 9] In Example 1, instead of the coating liquid 2, a xylene solution of perhydropolysilazane (solid content 2
0 mass%, manufactured by Clariant Japan Co., Ltd., trade name "N-V
A sample was prepared in exactly the same procedure as in Example 1, except that 110 ") was used.

Example 10 Only in this example, a coating liquid 1 was applied by a bar coating method (wet thickness: 30 μm) using a polycarbonate plate (150 mm × 300 mm, thickness: 3 mm) as a base material. The solvent was removed by holding in a hot air circulating oven for 5 minutes to remove the solvent, and then irradiated with 150 mJ / cm ² ultraviolet light using a high-pressure mercury lamp in an air atmosphere to obtain a film thickness of 6 μm.
A partially cured layer of μm was formed.

Next, the coating liquid 2 was coated on the surface by a bar coating method (wet thickness: 6 μm), and was kept in a hot air circulating oven at 80 ° C. for 10 minutes to remove the solvent.
This was 1500 mJ in an air atmosphere using a high-pressure mercury lamp.
/ Cm ² was applied to form a cured layer having a total thickness of 7.2 μm.

Subsequently, 5 minutes in a hot air circulating oven at 170 ° C.
After being held for one minute and immediately after being taken out, it was pressed against a mold having a curvature of 64 mmR so that the surface on which the cured product layer was formed became convex, subjected to bending, and then cured at room temperature for one day. This sample had a good appearance without cracks or wrinkles.

[0104]

[Table 1]

[0105]

According to the present invention, a cured product of a coating composition (A) containing a compound having at least one active energy ray-curable polymerizable functional group on at least a part of the surface of the substrate is provided. By forming an inner layer and forming an outer layer made of a cured product of the coating composition (B) containing polysilazane and a lubricity-imparting agent on the surface of the inner layer, it has excellent scratch resistance, surface lubricity, transparency, etc. A coated molded article having a cured product layer can be provided.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F100 AK25 AK79C AT00A BA03 BA07 BA10A BA10C CA24C EH46 GB41 JB14B JK12 JK16 YY00B YY00C

Claims (8)

[Claims] 1. A coated molded article having two or more cured product layers formed on at least a part of the surface of a substrate, wherein an inner layer in contact with the outermost layer of the cured product layer is activated energy ray cured. A cured product layer of a coating composition (A) containing a compound having at least one hydrophilic polymerizable functional group, wherein the outermost layer is a cured product layer of a coating composition (B) containing polysilazane and a lubricity-imparting agent A coated molded article characterized by the following. 2. The coated molded article according to claim 1, wherein the cured product layer of the coating composition (A) has a thickness of 1 to 50 μm. 3. The coated molded article according to claim 1, wherein the cured product layer of the coating composition (B) has a thickness of 0.05 to 10 μm. 4. The coated molded article according to claim 1, wherein said polysilazane is perhydropolysilazane. 5. The coated molded article according to claim 1, wherein the lubricity imparting agent is a compound having a radical polymerizable functional group in a molecule. 6. The coated molded article according to claim 1, wherein the lubricity imparting agent is a compound having a silanol group or an alkoxysilyl group in a molecule. 7. A method for producing a coated molded article having two or more cured product layers formed on at least a part of the surface of a substrate, wherein at least a part of the surface of the substrate has an active energy ray-curable An uncured material layer, a partially cured material layer, or a cured material layer of a coating composition (A) containing a compound having one or more polymerizable functional groups, and a coating composition containing polysilazane and a lubricity-imparting agent on the surface thereof An uncured material layer or a partially cured material layer of the product (B) is formed, and when the coating composition (A) is a cured product layer, the coating composition (B) is cured, and the coating composition (B) is cured. When the layer (A) is an uncured material layer or a partially cured material layer, the coated composition (A) and the coating composition (B) are cured in any order or at the same time. Manufacturing method. 8. A method for producing a coated molded article having two or more cured product layers formed on at least a part of the surface of a substrate, wherein at least a part of the surface of the substrate has an active energy ray-curable Forming a layer of a coating composition (A) containing a compound having one or more polymerizable functional groups, further forming a layer of a coating composition (B) containing polysilazane and a lubricity-imparting agent on the surface thereof, A method for producing a coated molded product, comprising, after bending, curing the coating composition (A) and the coating composition (B) in any order or simultaneously.