JP2002234906A - Ultraviolet-curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ultraviolet-curable resin composition which forms a coating film excellent in abrasion resistance and slipperiness, is excellent in applicability with a spin coater, and is used as a hard coating agent for optical disks. SOLUTION: This composition contains (a) an organic-inorganic composite obtained by subjecting a silica sol and an acrylate having an alkoxysilyl group to hydrolysis and condensation, (b) a polyfunctional acrylate having at least three acryloyl groups in the molecule, (c) an acrylic resin having an organosiloxane backbone, (d) propylene glycol monomethyl ether and/or propylene glycol monomethyl ether acetate, and (e) photopolymerization initiator.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet curable resin composition for forming a coating film having high abrasion resistance and excellent slip properties, and more particularly, to an optical disk and a liquid crystal having excellent spin coater coating properties. The present invention relates to an ultraviolet curable resin composition useful as an overcoat agent for a resin plate for a substrate, and a cured product thereof.

[0002]

2. Description of the Related Art In general, plastic products such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, vinyl chloride resin, ABS resin and cellulose acetate are excellent in light weight, easy processability, impact resistance and the like. It is used for various applications. However, these plastic products are easily damaged due to their low surface hardness, and transparent resins such as polycarbonate have the drawback of significantly impairing the original transparency or appearance of the resin. It makes the use of plastic products in the field difficult. Therefore, there is a need for an active energy ray-curable hard coat material that imparts abrasion resistance to the surface of these plastic products.

[0003] A polycarbonate plate is used for an optical disk substrate, and a surface treatment with a hard coat agent has been performed so far to prevent damage. Conventional optical discs have an optical head provided on the opposite side of the recording layer of the optical disc substrate, so that the reading light and the recording light emitted from the optical head pass through the substrate and reach the recording layer. Although the incident method has been adopted, recently, an optical head is provided so as to face the recording layer, and light is irradiated from the recording layer side without passing through the substrate, that is, recording and reproduction are performed by so-called film surface incidence, so that the objective is It has been proposed to increase the capacity by increasing the numerical aperture of the lens and reducing the light spot. However, in this method, the distance between the optical disk and the head is reduced to 2 to 10 μm as compared with 1 mm in the conventional substrate surface incidence method. In this method, since the distance between the optical disk and the head is small, dust entering between the optical disk and the head is more likely to damage the surface of the optical disk than before. For this reason, as an overcoat agent for an optical disk, a hard coat agent having a slip property for facilitating removal of dust between the optical disk and the head and having a higher abrasion resistance than before has been required.

[0004] Further, conventionally used liquid crystal display panels use a glass plate as a substrate. However, there is a limit to the reduction in glass density and the improvement in mechanical strength of a glass substrate panel. There is a situation where it is not possible to sufficiently cope with the demand for weight reduction and thickness reduction. For this reason, it has been studied to use a resin plate that can be reduced in weight and thickness as a liquid crystal substrate instead of glass.However, the resin plate is inferior in gas barrier properties and abrasion resistance as compared with a glass plate. A method of forming a hard coat layer after forming a gas barrier film of silicon oxide such as SiOx has been considered. In addition, in the process of producing a liquid crystal display panel using this resin plate, the surface of the resin plate is required to have slipperiness in order to improve workability when laminating the polarizing plates. For these reasons, as an overcoat agent for a resin plate for a liquid crystal substrate, a hard coat agent having slip properties and high abrasion resistance is required.

As a hard coat agent having high abrasion resistance, a composition using a silica sol as an inorganic material in addition to a polyfunctional acrylate as an ultraviolet-curable resin is disclosed in JP-A-57-500984, JP-A-3-56514. JP 5
-179157 and JP-A-5-287215. However, since these hard coat agents are not supposed to be applied by a spin coater, when applied by a spin coater, a good coating surface cannot be obtained, for example, the drying property of the solvent is high and lines are formed on the coating surface. On the other hand, when propylene glycol monomethyl ether or propylene glycol monomethyl ether acetate, which can be suitably used in a spin coater, is used as a solvent, silica sol using these solvents as a dispersion medium causes a problem that secondary aggregation occurs when a polyfunctional acrylate is added. was there.

[0006]

DISCLOSURE OF THE INVENTION The present invention relates to an ultraviolet curable resin composition for forming a film having a high level of abrasion resistance and excellent slip properties, and to an optical disk and a liquid crystal substrate which are excellent in coating properties with a spin coater. It is an object of the present invention to provide a hard coating agent such as a resin plate for use.

[0007]

Means for Solving the Problems As a result of intensive studies to achieve these objects, silica-sol is hydrolyzed and condensed with an acrylate compound having an alkoxysilyl group to form an organic-inorganic composite. The present inventors have found that the surface of a silica sol is surface-treated, and that propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate can coexist with a polyfunctional acrylate even when used as a dispersion medium for the silica sol, thereby completing the present invention.

That is, the present invention relates to (a) an organic-inorganic composite obtained by hydrolyzing and condensing an acrylate having an alkoxysilyl group and silica sol, and (b) a polyfunctional acrylate having three or more acryloyl groups in a molecule. ,
A resin composition containing (c) an acrylic resin having an organopolysiloxane skeleton, (d) propylene glycol monomethyl ether and / or propylene glycol monomethyl ether acetate, and (e) a photopolymerization initiator, wherein (a) An ultraviolet-curable resin composition characterized in that the content of the organic-inorganic composite is 15 to 80% by weight of the solid content of the resin composition.

The present invention also provides a resin plate for an optical disk or a liquid crystal substrate, comprising a cured layer of the above-mentioned ultraviolet-curable resin composition. The present invention also provides an organic compound obtained by hydrolyzing and condensing an acrylate having an alkoxysilyl group and a silica sol at a ratio of 1 to 20 parts by weight of an alkoxysilyl group of an acrylate to 100 parts by weight of a silica sol (solid content). The present invention provides an inorganic composite.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail. (A) Organic / inorganic composite obtained by hydrolytic condensation of an acrylate having an alkoxysilyl group and silica sol:
The acrylate having an alkoxysilyl group of the present invention is
It is obtained by reacting a compound having a functional group and an alkoxysilyl group (silane coupling agent) with an acrylate. Examples of the functional group of the silane coupling agent include an isocyanate group, an epoxy group, and an amino group.

Specifically, for example, a silane coupling agent having an isocyanate group such as isocyanatopropyltrimethoxysilane, isocyanatopropyltriethoxysilane, isocyanatopropylmethyldimethoxysilane, and isocyanatopropylmethyldiethoxysilane: γ
-Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4 epoxycyclohexyl) ethyl Silane coupling agents having an epoxy group such as trimethoxysilane: γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-
Silane coupling agents having an amino group such as phenyl-γ-aminopropyltrimethoxysilane;

For a silane coupling agent having an isocyanate group, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, bis (acryloxyethyl) A hydroxyl group-containing acrylate such as hydroxyethyl isocyanurate, pentaerythritol triacrylate, dipentaerythritol tetraacrylate, or dipentaerythritol pentaacrylate is subjected to an addition reaction.

For a silane coupling agent having an epoxy group, a hydroxyl group-containing acrylate such as bis (acryloxyethyl) hydroxyethyl isocyanurate, pentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and anhydride A carboxyl group-containing acrylate obtained by reacting an acid anhydride such as succinic acid, maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, and pyromellitic anhydride is subjected to an addition reaction.

For silane coupling agents having an amino group, bis (acryloxyethyl) hydroxyethyl isocyanurate, tris (acryloxyethyl) isocyanurate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate,
An addition reaction (Michael addition) of pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, or the like is performed.

The above isocyanate group, epoxy group,
The acrylate to be reacted with the silane coupling agent having an amino group is preferably a polyfunctional acrylate having 2 to 5 acryloyl groups in one molecule from the viewpoint of photopolymerization curability, abrasion resistance of a coating film, and the like.

Next, as the silica sol, a silica sol having a particle diameter of about 5 to 100 nm using an organic solvent as a dispersion medium can be used. Specifically, for example, methyl alcohol, isopropyl alcohol, ethylene glycol,
Examples of the dispersion medium include ethylene glycol mono-n-propyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dimethylacetamide, methyl ethyl ketone, methyl isobutyl ketone, and a mixed solvent of xylene and n-butyl alcohol. Further, silica sol using water as a dispersion medium can also be used by substituting the above organic solvent with a solvent.

The organic-inorganic composite (a) comprises an acrylate having an alkoxysilyl group, silica sol, water,
It is obtained by blending a hydrolysis catalyst and performing a hydrolysis condensation reaction at room temperature to 80 ° C. for 1 hour to 7 days. The amount of water to be added may be an amount at which the alkoxysilyl group can be hydrolyzed by 100% as a theoretical amount or more. An amount equivalent to 100 to 300%, preferably 100 to 200% is added. As the hydrolysis catalyst, for example, aluminum acetylacetone, butoxide borate, acetic acid, hydrochloric acid, maleic acid,
Oxalic acid, fumaric acid, dibutyltin dilaurate, dibutyltin dioctate, p-toluenesulfonic acid and mixtures thereof can be used. The amount is 0.1 to 5 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the acrylate having an alkoxysilyl group.

The mixing ratio of the acrylate having an alkoxysilyl group and the silica sol is determined by the alkoxysilyl group of the acrylate (-SiR _m (OR) _n : R = alkyl group such as methyl group, ethyl group, aromatic hydrocarbon such as phenyl group, etc. And m + n = 3, n = 1 to 3) and the solid content of silica sol is usually 0.01 to 0.2.
0, preferably 0.02 to 0.15. When the weight ratio of the alkoxysilyl group to the silica sol exceeds 0.20,
In addition to the reaction between the alkoxysilyl group and the silica sol, a cross-linking reaction (side reaction) between the alkoxysilyl groups increases and gels, and thus cannot be used as a hard coating agent. On the other hand, when the amount is 0.01 or less, the amount of the obtained organic-inorganic composite decreases, and when the solvent is replaced with propylene glycol monomethyl ether or propylene glycol monomethyl ether acetate, secondary aggregation of the silica sol occurs in the presence of acrylate and the hard coat agent. Can not be used as

The solid content of the silica sol is preferably from 10 to 60 with respect to 100% by weight of the solid content of the ultraviolet curable resin.
%, More preferably 20 to 50% by weight. If the solid content of the silica sol is less than 10% by weight, the resulting cured film has insufficient abrasion resistance. When the solid content of the silica sol exceeds 60% by weight, the viscosity of the ultraviolet-curable resin composition increases, and the viscosity of the ultraviolet-curable resin composition decreases to a viscosity that can be applied by a spin coater. Will be lowered, and accordingly, the drying property will worsen,
Further, it is difficult to secure a sufficient coating film thickness, which is not preferable. When the silica sol is used in the above range, the content of the organic-inorganic composite (a) in the solid content of the ultraviolet-curable resin composition is 15 to 80% by weight.

(B) Polyfunctional acrylate having three or more acryloyl groups in the molecule: Examples of the polyfunctional acrylate having three or more acryloyl groups in the molecule include tris (acryloxyethyl) isocyanurate,
Examples thereof include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate. In addition to the organic / inorganic composite, a polyfunctional acrylate having three or more acryloyl groups in these molecules is added to the UV-curable resin composition at a solid content of 20 to 20%.
By using 85% by weight, preferably 25-80% by weight, high wear resistance can be exhibited.

(C) Acrylic resin having an organopolysiloxane skeleton: The acrylic resin having an organopolysiloxane skeleton is an organopolysiloxane compound having one radical polymerizable group in a molecule or a mercapto group in a molecule. An organopolysiloxane compound;
It is obtained by copolymerizing a compound having a (meth) acryloyl group. The organopolysiloxane compound has an organopolysiloxane skeleton represented by the following general formula (I).

[0022]

Embedded image

(Wherein R ¹ and R ² may be the same or different and each is a methyl group or a phenyl group;
Represents an integer of 300. )

The organopolysiloxane compound having one radically polymerizable group in the molecule is a compound having one radically polymerizable group in the molecule such as a (meth) acryloyl group, a styryl group, a vinyl group and an allyl group. Preferably it is.
Considering the easiness of copolymerization with a compound having one (meth) acryloyl group in the molecule, an organopolysiloxane compound having a (meth) acryloyl group and a styryl group at the terminal is preferable. Further, when a compound having one (meth) acryloyl group in a molecule is polymerized, an organopolysiloxane compound having a mercapto group in the molecule, which is introduced into the polymer via a sulfide bond by chain transfer, is also preferable. Can be used. As the number of mercapto groups, those having one or two in the molecule can be used.

Examples of the compound having one (meth) acryloyl group in a molecule include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate,
Isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxy Ethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, ethyl carbitol (meth) acrylate, butoxyethyl (meth) acrylate, cyanoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) ) Acrylate, N, N-diethylaminoethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4- Dorokishibuchiru (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and glycidyl (meth) acrylate.

An organopolysiloxane compound having one radically polymerizable group in the molecule copolymerized with a compound having one (meth) acryloyl group in the molecule or an organopolysiloxane compound having a mercapto group in the molecule The amount used is usually from 0.5 to the copolymerizable monomer.
It is 30% by weight, preferably 1 to 20% by weight.

The copolymerization of the organopolysiloxane compound and the compound having a (meth) acryloyl group is carried out in a solvent using a usual radical polymerization initiator. As the solvent, aromatic hydrocarbons such as toluene and xylene; ethyl alcohol, isopropyl alcohol, n-
Alcohols such as butyl alcohol and isobutyl alcohol; esters such as ethyl acetate, propyl acetate and butyl acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether and propylene Ethers such as glycol monomethyl ether; ether esters such as 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, and propylene glycol monomethyl ether acetate; and these may be used in combination. .

Examples of the radical polymerization initiator used in the polymerization reaction include peroxides such as benzoyl peroxide, di-t-butyl peroxide and cumene hydroperoxide; 2,2'-azobisisobutyronitrile; ,
Azo compounds such as 2'-azobis- (2,4-dimethylvaleronitrile) and 2.2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) are preferably used. The monomer concentration in the polymerization solution is usually 10 to 60% by weight,
Preferably it is 15 to 50% by weight. The polymerization initiator is used in an amount of usually 0.1 to 5% by weight, preferably 0.3 to 2% by weight, based on the monomer mixture.

Among the acrylic resins having an organopolysiloxane skeleton obtained by these methods, particularly when applied by a spin coater, an organopolysiloxane compound having a mercapto group in the molecule and a (meth) acryloyl group are used. An acrylic resin obtained by polymerizing a compound having one compound therein is preferable. In this product, an organopolysiloxane skeleton was introduced into the main chain of an acrylic resin, and an organopolysiloxane skeleton was introduced into a side chain obtained from an organopolysiloxane compound having one radical polymerizable group in the molecule. Compared to acrylic resin,
It is more preferable as a slip agent because it easily comes out on the coated surface.

The obtained acrylic resin having an organopolysiloxane skeleton has a solid content of usually 0.5 to 10% by weight, preferably 1 to 5% by weight, based on the solid content of the ultraviolet-curable resin composition. Can be If the content of the acrylic resin having an organopolysiloxane skeleton is less than 0.5% by weight, sufficient slip properties cannot be obtained. On the other hand, 10
Exceeding the weight percent is not preferred because the abrasion resistance of the cured film is reduced.

(D) Propylene glycol monomethyl ether and / or propylene glycol monomethyl ether acetate: As the solvent for the ultraviolet-curable resin of the present invention, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and a mixture thereof are used. When a spin coater is used as a coating method, it is preferable to use a solvent having a boiling point of 120 to 130 ° C. from the viewpoint of drying properties, and a good coating film can be obtained by using these solvents.

In preparing the organic-inorganic composite of the component (a), when a silica sol using propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, or a mixture thereof as a dispersion medium is used.
The resulting solvent of component (a) is propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, or a mixture thereof, and can be used as it is as the solvent for the ultraviolet-curable resin of the present invention. On the other hand, when the dispersion medium of the silica sol is not one of these solvents, after preparing the organic-inorganic composite of the component (a) or adding the component (b) to the component (a), the solvent is changed to propylene glycol. Monomethyl ether,
Solvent replacement with propylene glycol monomethyl ether acetate or a mixture thereof.

When the acrylic resin having an organopolysiloxane skeleton of the component (c) is prepared using a solvent other than propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate or a mixture thereof, the solvent may be propylene glycol. Monomethyl ether, propylene glycol monomethyl ether acetate, or a mixture thereof is used after solvent replacement. After adding the component (c) to the components (a) and (b), the solvent may be replaced with propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate or a mixture thereof.

As described above, when preparing an organic-inorganic composite in which the solvent is propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate or a mixture thereof, the organic-inorganic composite is preferably prepared by using a silica sol having a dispersion medium of methyl ethyl ketone. After preparing the body and adding the component (b), it is more preferable to replace the solvent with propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate or a mixture thereof. Until the organic-inorganic composite was formed, the ultraviolet-curable resin composition thus obtained did not cause aggregation of silica sol because the solvent was methyl ethyl ketone, and the organic-inorganic composite was formed. Since post-solvent replacement is performed, the secondary aggregation of the silica sol is small, and when coated with a spin coater, a good coating film without generation of streaks is obtained.

When the ultraviolet curable resin composition of the present invention is applied by a spin coater, the viscosity at 25 ° C. is preferably 100 mPa · s or less. The solid content of the ultraviolet curable resin composition is preferably higher within the above viscosity range, and the solid content is 30 to 60% by weight.

(E) Photopolymerization initiator: Examples of the photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, diethoxyacetophenone, benzyldimethyl ketal, and 2-hydroxy-2-methylpropio. Phenone, 1-hydroxycyclohexylphenyl ketone, benzophenone, 2,4,6-trimethylbenzoindiphenylphosphine oxide, 2-methyl- [4
-(Methylthio) phenyl] -2-morpholino-1-
Propanone, 2-benzyl-2-dimethylamino-1-
(4-morpholinophenyl) -butan-1-one, Michler's ketone, isoamyl N, N-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, and the like. More than one kind can be used in combination as appropriate, and it is used at 5% by weight or less, preferably 1 to 3% by weight in the composition for forming a film.

The ultraviolet-curable resin composition of the present invention contains an ultraviolet absorber (for example,
Benzotriazole-based, benzophenone-based, salicylic acid-based, cyanoacrylate-based UV absorbers, UV stabilizers (eg, hindered amine-based UV stabilizers), antioxidants (eg, phenolic, sulfur-based, phosphorus-based antioxidants), Various additives such as an anti-blocking agent and a leveling agent may be incorporated in the composition for forming a film in an amount of 0.01 to 2% by weight, respectively.

The ultraviolet-curable resin composition of the present invention can be applied to a base material such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, cellulose acetate, vinyl chloride resin, ABS resin, synthetic paper and paper by dipping, flow coating, or the like. The solvent is dried by a coating method using a coating method such as gravure coating, roll coating, blade coating, air knife coating, etc. 1-50 μm on the surface, preferably 1-2
Coating is performed so that a film having a thickness of 0 μm is obtained. Then
After drying the solvent, the coating composition layer applied is irradiated with ultraviolet light from a light source such as a 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, etc. To form a coating.

The ultraviolet-curable resin composition of the present invention is suitably used as a hard coat agent for optical discs, resin plates for liquid crystal substrates, etc., but may be used for hard coats on display surfaces such as liquid crystal displays, plasma displays, projection TVs, and plastics. It can be used for a hard coat of a member, an OP varnish, a vehicle for UV printing ink, and the like.

When used as a hard coat agent for an optical disk, it is used on a recording layer and an insulating layer of an optical disk, and when used as a hard coat agent for a resin plate for a liquid crystal substrate,
A hard coat layer is formed on the SiOx gas barrier layer provided on the liquid crystal resin substrate by spin coating and irradiating with ultraviolet rays to cure the coating. The thickness is usually preferably about 1 to 20 μm. By using the ultraviolet curable resin of the present invention, a cured film having high abrasion resistance and slip properties can be obtained.

[0041]

EXAMPLES The present invention will be described more specifically with reference to Synthesis Examples and Examples below. Components, ratios, procedures, and the like described in the following synthesis examples and examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples described below. Parts and% described in Synthesis Examples and Examples mean parts by weight and% by weight, respectively.

Synthesis Example of Polyfunctional Acrylate Having Alkoxysilyl Group: (Synthesis Example 1) 3-isocyanatopropyltriethoxysilane (Shin-Etsu Chemical Co., Ltd. product name: KBE9007)
And dipentaerythritol pentaacrylate (4
6.7% by weight) and dipentaerythritol hexaacrylate (53.3% by weight) (trade name: Kayarad DPHA, manufactured by Nippon Kayaku Co., Ltd., hydroxyl value 50 mg KOH)
/ G) and 18.0 parts and 82.0 parts of each were placed in a flask such that -NCO group / OH group = 1, and 0.05 part of dibutyltin dilaurate and 0.05 part of p-methoxyphenol were added. The reaction was carried out at 80 ° C. for 2 hours (the disappearance of the absorption of the isocyanate group at 2250 cm ⁻¹ was confirmed in the infrared absorption spectrum), and the alkoxysilyl group which was a reaction product of 3-isocyanatopropyltriethoxysilane and dipentaerythritol pentaacrylate was obtained. 56.3 parts of a polyfunctional acrylate (I) having an alkoxysilyl group 11.
9 parts) and dipentaerythritol hexaacrylate 4
3.7 parts of a mixture were obtained.

Synthesis Example 2 Succinic anhydride, dipentaerythritol pentaacrylate (46.7% by weight) and dipentaerythritol hexaacrylate (53.3%)
% By weight) (trade name: Kayarad DPHA, hydroxyl value 50 mgKOH / g, manufactured by Nippon Kayaku Co., Ltd.)
Place 6.9 parts and 76.9 parts of each in a flask so that OOCO-group / -OH group = 1, add 0.05 parts of p-methoxyphenol, react at 110 ° C. for 3 hours, and obtain an acid value of 46 mg KOH. / G reaction was obtained. Then, γ-glycidoxypropyltrimethoxysilane (trade name: KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.) 16.2
And 0.5 part of tetramethylammonium bromide, and reacted at 110 ° C. for 10 hours.
KOH / g. As a result, a polyfunctional acrylate (II) having an alkoxysilyl group, which is a reaction product of succinic anhydride, dipentaerythritol pentaacrylate, and γ-glycidoxypropyltrimethoxysilane 59.
A mixture of 0 parts (8.3 parts of an alkoxysilyl group) and 41.0 parts of dipentaerythritol hexaacrylate was obtained.

Acrylic resin having an organopolysiloxane skeleton: (Synthesis Example 3) 90 parts of methyl methacrylate, an organopolysiloxane compound having a mercapto group at both ends (trade names: X-22-167B, manufactured by Shin-Etsu Chemical Co., Ltd.) A mixture of 10 parts of number average molecular weight 3,340) and 300 parts of propylene glycol monomethyl ether was heated to 8 parts.
When the temperature was raised to 0 ° C., and two hours after the temperature was raised, 0.3 parts of azobisisobutyronitrile was added, and the mixture was reacted at 80 ° C. for 8 hours. An acrylic resin (III) having a siloxane skeleton was obtained.

(Synthesis Example 4) Methyl methacrylate 80
Part, an organopolysiloxane compound having a methacryloyl group at one end (trade name: FM072, manufactured by Chisso Corporation)
5, a mixture of 20 parts of a number average number molecular weight 10,000) and 300 parts of propylene glycol monomethyl ether was heated to 80 ° C., and two hours after the temperature was raised, azobisisobutyro was obtained. 0.3 of nitrile
The reaction was carried out at 80 ° C. for 8 hours, and the solid content was 25%.
Acrylic resin (IV) having an organopolysiloxane skeleton was obtained.

(Examples 1 to 8, Comparative Examples 1 to 5) Production Examples of Ultraviolet Curable Resin Composition: Polyfunctional acrylate having alkoxysilyl group, polyfunctional acrylate, silica sol, water, hydrolysis catalyst, and (b) ) A polyfunctional acrylate was blended at the ratio shown in Table 1 or Table 3
Reaction was carried out for a time to obtain a mixture of an organic / inorganic composite and a polyfunctional acrylate. (C) an acrylic resin having an organopolysiloxane skeleton, (d) a substitution solvent,
(E) After adding the photopolymerization initiator at the ratio shown in Table 2 or Table 4, the temperature was raised under reduced pressure, and methyl ethyl ketone and a part of the substitution solvent were distilled off to obtain an ultraviolet-curable resin composition having a solid content of 60%. Was prepared. In Comparative Example 2, gelation occurred during solvent replacement. In Comparative Example 3, when the hydrolysis treatment was performed at 75 ° C., gelation occurred 30 minutes later.

[0047]

[Table 1]

[0048]

[Table 2]

[0049]

[Table 3]

[0050]

[Table 4]

Table 5 shows the properties of the obtained ultraviolet curable resin composition. Using a spin coater, 8 ml of the ultraviolet curable resin composition was supplied onto a 5.25 inch transparent polycarbonate plate at 300 rpm for 5 seconds, and then 4 ml.
After shaking off at 000 rpm for 10 seconds, it was dried by heating at 60 ° C. for 2 minutes. Using a high-pressure mercury lamp with an output density of 120 W / cm, this was 600 mJ / cm 2 at a position 10 cm below the light source.
Irradiation with UV light of cm ² was performed to form a coating. Table 5 shows the evaluation results of the obtained films.

Each evaluation item was evaluated according to the following method. (Applicability) The presence or absence of streaks, wrinkles, aggregates, etc. on the coating film surface was visually confirmed. (Abrasion resistance) Using a worn wheel of CS-10F manufactured by Caliberase, a 100-rotation Taber abrasion test was performed under a load of 500 g and evaluated by the difference ΔH% between haze after the Taber abrasion test and haze before the Taber abrasion test. (Slip property) Using a slip tester, JIS K-
The dynamic friction coefficient was measured according to 7125. In addition, the dynamic friction coefficient of the polycarbonate plate as the base material was 0.51.

[0053]

[Table 5]

In each of Examples 1 to 8, a hard coat film having high abrasion resistance and slip properties can be formed on a polycarbonate plate by using a spin coater. Among these, a silica sol of methyl ethyl ketone as a dispersion medium is subjected to hydrolysis treatment with a polyfunctional acrylate having an alkoxysilyl group, and then the solvent is replaced with propylene glycol monomethyl ether and / or propylene glycol monomethyl ether acetate. The film surface was good.

In Examples 5 and 6, a large thickening phenomenon was observed at the beginning of the hydrolysis, and thereafter, the viscosity decreased as the organic-inorganic composite was formed. This is presumed to be because silica sol before the formation of the organic-inorganic composite is secondarily aggregated in propylene glycol monomethyl ether or propylene glycol monomethyl ether acetate in the presence of a polyfunctional acrylate. For this reason, the viscosity decreases as the hydrolysis treatment proceeds, but secondary aggregation is not completely eliminated, which is considered to have affected the state of the coated surface.

Comparative Example 1 does not contain silica sol and thus has insufficient abrasion resistance. Comparative Example 2 gels at the stage of solvent substitution, but since this system does not contain an alkoxysilyl group-containing polyfunctional acrylate, an organic-inorganic composite is not formed,
It is considered that secondary aggregation of the silica sol proceeded in the presence of the polyfunctional acrylate as the solvent was replaced with propylene glycol monomethyl ether. In Comparative Example 3, since the amount of the alkoxysilyl group relative to the silica sol was large, it is presumed that the organic-inorganic composite was crosslinked and gelled. In Comparative Example 4, since a solvent, methyl isobutyl ketone, has a high drying property, a good coating film cannot be obtained with a spin coater.

Example 9 8 ml of the ultraviolet-curable resin composition prepared in Example 3 was supplied to the surface of a 5.25 inch optical disk composed of a polycarbonate plate / recording layer / insulating layer using a spin coater, and 300 rpm. For 5 seconds, then at 4000 rpm for 10 seconds, then at 60 ° C. for 2 seconds.
Heat and dry for minutes. This was converted to an output density of 120 W / c.
m using a high-pressure mercury lamp of 600 m at a position 10 cm below the light source.
Ultraviolet irradiation of mJ / cm ² was performed. As a result, a film having a sufficient performance as a film surface incidence type optical disk having high abrasion resistance and slip property was obtained.

[0058]

The acrylate having an alkoxysilyl group and the silica sol are hydrolyzed and condensed to form an organic-inorganic composite, so that the propylene glycol monomethyl ether or propylene glycol monomethyl ether acetate, which is preferably used in spin coating, is used. The inorganic components of the silica sol could be introduced. The ultraviolet-curable resin of the present invention has high abrasion resistance and slip properties, and is useful as a hard coating agent for optical disks, resin plates for liquid crystal substrates, and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 292/00 C08F 292/00 4J038 C08J 7/04 CFD C08J 7/04 CFDK 5D029 G02F 1/1333 500 G02F 1 / 1333 500 G11B 7/24 534 G11B 7/24 534D 534C 534E // C09D 4/06 C09D 4/06 5/00 5/00 Z 183/07 183/07 F term (reference) 2H090 HB02X HB07X HC01 HC19 HD01 HD02 JB03 4F006 AA02 AA11 AA17 AA22 AA35 AA36 AA58 AB24 AB39 AB43 AB76 BA02 CA01 DA04 4F100 AK22A AK25A AK52A AL05A AT00B BA02 CC00A EJ54 GB90 JB14 4J011 PA13 PA26 PA69 PA99 QA21 SA24AA SAA QA23 SAA AB44 BA28 BB01 DA02 GA07 4J038 AA011 AA012 CG141 CG142 CJ291 CJ292 CR061 CR062 D L121 DL122 DL131 DL132 FA111 FA112 FA241 FA242 HA441 HA442 JA26 JA57 KA03 LA02 LA06 NA11 PA17 PB08 PB11 5D029 LA03 LA04 LA05 LA06 LC21

Claims (9)

[Claims] 1. An organic compound obtained by hydrolyzing and condensing (a) an acrylate having an alkoxysilyl group and a silica sol.
An inorganic composite, (b) a polyfunctional acrylate having three or more acryloyl groups in a molecule, (c) an acrylic resin having an organopolysiloxane skeleton, (d) propylene glycol monomethyl ether and / or propylene glycol monomethyl ether acetate, And (e) a resin composition containing a photopolymerization initiator, wherein the content of the (a) organic-inorganic composite is 15 to 80% by weight based on the solid content of the resin composition. Ultraviolet curable resin composition. 2. An organic-inorganic composite (a) obtained by hydrolytic condensation at a ratio of 1 to 20 parts by weight of an alkoxysilyl group of an acrylate with respect to 100 parts by weight of a silica sol (solid content). The ultraviolet-curable resin composition according to claim 1. 3. The acrylate having an alkoxysilyl group has a plurality of alkoxy groups in one molecule.
Or the ultraviolet-curable resin composition according to 2. 4. The ultraviolet-curable resin composition according to claim 1, wherein the acrylate having an alkoxysilyl group has a plurality of acryloyl groups in one molecule. 5. The method according to claim 1, wherein (c) the acrylic resin having an organopolysiloxane skeleton is obtained by copolymerizing an organopolysiloxane compound having a mercapto group and a compound having a (meth) acryloyl group. The ultraviolet-curable resin composition according to any one of Items 1 to 4. 6. The hydrolytic condensation of an acrylate having an alkoxysilyl group and silica sol in the presence of methyl ethyl ketone as a solvent, and then the solvent is replaced with propylene glycol monomethyl ether and / or propylene glycol monomethyl ether acetate, 2. A composition according to claim 1, characterized in that a composition containing a) and (d) is prepared, and then (b), (c) and (e) are mixed thereafter or at any earlier stage. A method for producing an ultraviolet-curable resin composition. 7. An article comprising a cured product layer of the ultraviolet-curable resin composition according to claim 1. 8. A resin plate for an optical disk or a liquid crystal substrate, comprising a cured product layer of the ultraviolet-curable resin composition according to any one of claims 1 to 5. 9. An organic / inorganic compound obtained by hydrolyzing and condensing an acrylate having an alkoxysilyl group and a silica sol in a ratio of 1 to 20 parts by weight of an alkoxysilyl group of an acrylate to 100 parts by weight of a silica sol (solid content). Complex.