JPH06100799A - Abrasion-resistant ultraviolet curable coating composition - Google Patents

Abstract

PURPOSE:To provide the subject composition comprising an acrylic resin, a specific compound, a specified acrylate, silica sol. an organic solvent, and a photopolymerization initiator in a specific ratio, capable of forming a coating film just when the solvent is dried, and permitting to be molded, printed, transferred, etc., before the irradiation of UV light. CONSTITUTION:The objective composition comprises (A) an acrylic resin such as a (meth)acrylate ester (co)polymer, (B) a compound produced by reacting an isocyanate group-containing silane coupling agent of the formula (R<1>, R<2> are monovalent hydrocarbon; R<3> is 2-8C divalent hydrocarbon; (a) is 2, 3; (b) is 0,1; (c) is 4-a-b) such as 3-isocyanatopropyltrimethoxysilane with a hydroxy group-containing multifunctional acrylate having a hydroxyl group and three or more acryloyl groups, (C) a multifunctional acrylate, (D) silica sol, (E) an organic solvent, and (F) a photopolymerization initiator, the components A, B+C, and D (as solid content) being 5-35wt.%, 26-60wt.%, and 20-70wt.%, respectively, based on the total amount of the components A-D, and the ratio of the components B/C being >=0.2.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a UV-curable coating composition which forms a coating film having excellent abrasion resistance by being UV-cured. More specifically, a UV-curable coating composition that forms a coating film when the solvent is dried and can be processed such as molding, printing, and transferring before irradiation with ultraviolet rays, and forms a coating film having excellent abrasion resistance. It is about.

[0002]

BACKGROUND OF THE INVENTION Generally, plastic products,
For example, polycarbonate, polymethylmethacrylate, polyethylene terephthalate, vinyl chloride resin, A
BS resins and the like are used for various purposes because they are excellent in lightness, easy workability, impact resistance and the like. However, since these plastic products have low surface hardness, they are easily scratched, which makes them difficult to use in fields requiring abrasion resistance. Therefore, an ultraviolet curable hard coat material that imparts abrasion resistance to these plastic products and enhances the surface hardness is required. Furthermore, when the surface of these plastic products is hard-coated, it is molded before UV curing, or the hard-coating agent is not applied directly to the surface of plastic products, but applied to other substrates. However, after processing such as printing and coating of adhesive layer if necessary, the hard coat layer is transferred to the surface of plastic products, so a coating film is formed when the solvent is dried. There is a need for excellent UV curable resins.

As an ultraviolet curable hard coat agent, 3
A hard coating agent using a polyfunctional (meth) acrylate having a functionality or higher is disclosed in JP-B-53-43553 and JP-B-57-20968. Further, in order to improve the wear resistance of these hard coat agents, it is possible to add a fine powdery inorganic filler or colloidal silica to JP-A-59-41366 and JP-A-63-92675, and Announcement of addition of colloidal silica and various silane coupling agents
It is disclosed in JP-A-57-500984 and JP-A-59-204669. These UV-curable hard coating agents are excellent in abrasion resistance, but of course solvent-free, as well as those containing a solvent do not have a film-forming property when the solvent is dried, therefore, before UV irradiation, molding However, processing such as printing and transfer could not be performed. In order to impart a film forming property to these hard coating agents, it is conceivable to add a thermoplastic resin such as a (meth) acrylic acid ester copolymer, which dissolves in the hard coating agent, but it is sufficient. Simply adding a sufficient amount to impart film-forming properties will result in a significant decrease in the abrasion resistance originally required as a hard coating agent, and a hard coat with excellent film-forming properties and abrasion resistance. The drug has not been obtained yet.

[0004]

As a result of earnest studies, the present inventors were able to solve the above-mentioned conventional problems. That is, the present invention includes (a) an acrylic resin, (b) the following general formula (1):

[0005]

[Chemical 2]

(Wherein R ¹ and R ² are the same or different monovalent hydrocarbon groups, R ³ is a divalent hydrocarbon group having 2 to 8 carbon atoms,
a is an integer of 2 to 3, b is an integer of 0 to 1, and c is 4-ab
A compound obtained by reacting an isocyanate group-containing silane coupling agent represented by the formula) with a hydroxyl group-containing polyfunctional acrylate having a hydroxyl group and three or more acryloyl groups in the molecule, (c) molecule Containing a polyfunctional acrylate having 3 or more acryloyl groups therein, (d) a silica sol having an organic solvent as a dispersion medium, (e) an organic solvent, and (f) a photopolymerization initiator, and (a) component, ( b) component,
The ratio of the silica sol solid content of the component (c) and the component (d) is
Based on the total weight of these components, (a) component 5 to 35% by weight (b) component + (c) component 25 to 60% by weight (b) component / (c) component 0.2 or more (d) component silica sol solid The present invention provides an abrasion-resistant UV-curable coating composition, characterized in that the content is 20 to 70% by weight, which forms a coating film when the solvent is dried, and is used for molding, printing, and transferring. It is possible to form a coating film having excellent abrasion resistance after being irradiated with ultraviolet rays.

The present invention will be described in more detail below. Component (a) : Examples of the acrylic resin include the following compounds (i) to (d). (A) Polymer or copolymer of (meth) acrylic acid ester: Examples of the polymer or copolymer of (meth) acrylic acid ester include methacrylic acid and acrylic acid (hereinafter referred to as (meth) acrylic acid). ), Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, Isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, cyanoethyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-
(Meth) such as hydroxypropyl (meth) acrylate
Examples thereof include a polymer of monomer (I) having an acryloyl group, or a copolymer of two or more kinds of monomer (I).

(B) A compound having a (meth) acryloyl group in the side chain of a polymer or copolymer of (meth) acrylic acid ester: in the side chain of a polymer or copolymer of (meth) acrylic acid ester ( The compound having a (meth) acryloyl group is, for example, a (meth) acrylic acid adduct to a polymer of glycidyl (meth) acrylate or a copolymer having glycidyl (meth) acrylate as a constituent, (meth)
Glycidyl (meth) acrylate adduct to copolymer containing acrylic acid as a constituent, addition of polyisocyanate and hydroxyl group containing (meth) acrylate to a copolymer containing hydroxyl group-containing (meth) acrylic acid ester Examples include adducts of products.

(C) Acrylic silicone resin having an alkoxysilyl group: An acrylic silicone resin having an alkoxysilyl group reacts with the monomer (I) having the (meth) acryloyl group and the monomer (I). It is a polymer composed of a monomer (II) having an alkoxysilyl group. Monomer (II)
As, for example, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (ethoxymethoxy) silane and the like. Those having a polymerizable unsaturated double bond that copolymerizes with the monomer (I), γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-isocyanatopropyltrimethoxysilane , Γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane , N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane and the like having a functional group capable of addition reaction with the monomer (I). . The acrylic silicone resin having an alkoxysilyl group is a monomer (I) having a (meth) acryloyl group, and a monomer having a polymerizable unsaturated double bond copolymerizing with the monomer (I) and an alkoxysilyl group. body
It is obtained by copolymerizing with (II). In addition, the acrylic silicone resin having an alkoxysilyl group includes a monomer (I) having a (meth) acryloyl group, a monomer (II) having a functional group that undergoes an addition reaction with the monomer (I), and an alkoxysilyl group (II ) And by polymerizing after addition reaction, or after polymerizing the monomer (I) having a (meth) acryloyl group, a functional group and an alkoxy group which undergoes an addition reaction with this polymer and the monomer (I). It can be obtained by addition reaction with the monomer (II) having a silyl group.

(D) Acrylic silicone resin having an alkoxysilyl group and a polyorganosiloxane unit: An acrylic silicone resin having an alkoxysilyl group and a polyorganosiloxane unit is a monomer (I) having the (meth) acryloyl group. The monomer (II) having an alkoxysilyl group that reacts with the monomer (I), and a monomer (III) having a polyorganosiloxane unit that reacts with the monomer (I)
It is a polymer composed of and. The monomer (III) having a polyorganosiloxane unit that reacts with the monomer (I),
For example, a methacryloyl group-containing polyorganosiloxane that can be copolymerized with the monomer (I), or a monomer
Examples thereof include a mercapto group-containing polyorganosiloxane which is introduced into the polymer through a sulfide bond by chain transfer when polymerizing (I). The polyorganosiloxane unit contained in these monomers (III) is represented by the following general formula (2).

[0011]

[Chemical 3]

(Wherein R may be the same or different,
A methyl group or a phenyl group, and n represents an integer of 5 or more. ) An acrylic silicone resin having an alkoxysilyl group and a polyorganosiloxane unit is composed of a monomer (I) having a (meth) acryloyl group, a polymerizable unsaturated double bond which is copolymerized with the monomer (I), and an alkoxy group. Monomer having silyl group
It can be obtained by copolymerizing (II) with a monomer (III) having a polyorganosiloxane unit that reacts with the monomer (I). Further, the acrylic silicone resin having an alkoxysilyl group and a polyorganosiloxane unit has a monomer (I) having a (meth) acryloyl group, a functional group that undergoes an addition reaction with the monomer (I), and an alkoxysilyl group. After addition reaction of the monomer (II), by copolymerizing with the monomer (III), or by copolymerizing the monomer (I) having a (meth) acryloyl group and the monomer (III) After that, this copolymer is added to the monomer (II) having an alkoxysilyl group and a functional group capable of addition-reacting with the monomer (I).

An acrylic resin of the above component (a), for example (a)
~ (D) compounds, the monomers (I), (II) and (III),
It is produced by carrying out a polymerization reaction and an addition reaction if necessary in an organic solvent which is the component (e) by a usual method.
Examples of the polymerization initiator used in the polymerization reaction include benzoyl peroxide and di-t which are usual radical polymerization initiators.
-Peroxides such as butyl peroxide and cumene hydroperoxide, and azo compounds such as azobisisobutyronitrile and azobisvaleronitrile are preferably used.
The monomer concentration is usually 10 to 60% by weight, and the polymerization initiator is usually 0.1 to 10% by weight based on the monomer mixture. Further, when performing an addition reaction, for example, when performing an addition reaction of an epoxy group and a carboxyl group, benzyldimethylamine, triethylamine, tributylamine, triethylenediamine, benzyltrimethylammonium chloride, benzyltriethylammonium bromide, tetramethylammonium bromide, A catalyst such as cetyltrimethylammonium bromide or triphenylstibine can be used. The amount used is usually 0.1 to 5% by weight based on the monomer mixture. Also,
When carrying out the addition reaction of a hydroxyl group and an isocyanate group, a catalyst such as di-n-butyltin dilaurate or triethylenediamine can be used. The amount used is usually 0.01 to 0.1% by weight based on the monomer mixture.

Component (b) : The component (b) is represented by the following general formula (1)
The compound obtained by reacting an isocyanate group-containing silane coupling agent represented by and a hydroxyl group-containing polyfunctional acrylate having a hydroxyl group and three or more acryloyl groups in the molecule.

[0015]

[Chemical 4]

In the above formula, R ¹ and R ² are the same or different monovalent hydrocarbon groups, preferably R ¹ and R ² are lower alkyl groups such as methyl, ethyl and propyl. R ³ is a divalent hydrocarbon group having 2 to 8 carbon atoms, preferably 2 to ³ carbon atoms. a is an integer of 2-3, b is 0-1
And c is an integer equal to 4-a-b.

Specific examples of the isocyanate group-containing silane coupling agent include 3-isocyanatopropyltrimethoxysilane, 2-isocyanatoethyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane,
2-isocyanatoethyltriethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 2-isocyanatoethylmethyldimethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 2-isocyanatoethylmethyldiethoxysilane and the like can be mentioned. . Specific examples of the hydroxyl group-containing polyfunctional acrylate having a hydroxyl group and three or more acryloyl groups in the molecule include pentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and mixtures thereof. These can be used as the component (c) described below, and a mixture with a polyfunctional acrylate of the component (c) containing no hydroxyl group can also be used.

The reaction between the isocyanate group-containing silane coupling agent and the hydroxyl group-containing polyfunctional acrylate is carried out by mixing each compound at a ratio of --NCO /-OH groups.ltoreq.1.
Obtained by stirring at 10 ° C. for 1 to 20 hours. In this reaction, in order to prevent polymerization due to the acryloyl group during the reaction, it is preferable to use a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, catechol, pt-butylcatechol, phenothiazine, etc. The amount is 0.01 to 1% by weight, preferably 0.05 to 0.5% by weight, based on the reaction mixture.
Is. Further, in order to accelerate the reaction, for example, a catalyst such as di-n-butyltin dilaurate or triethylenediamine can be used. Furthermore, this reaction is (c)
It can also be carried out in the presence of a polyfunctional acrylate having three or more acryloyl groups in the molecule of the component or an organic solvent of the component (e).

Component (c) : The component (c) is a polyfunctional acrylate having three or more acryloyl groups in the molecule, specifically, trimethylolpropane triacrylate, EO-modified trimethylolpropane triacrylate, PO-modified trimethylolpropane triacrylate, trimethylolpropane tetraacrylate, tris (acryloxyethyl) isocyanurate, caprolactone-modified tris (acryloxyethyl) isocyanurate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, Dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, alkyl modified dipentaerythritol triacrylate, alkyl Sex dipentaerythritol tetraacrylate, alkyl-modified dipentaerythritol pentaacrylate, caprolactone-modified dipentaerythritol hexaacrylate, and mixtures of two or more of these and the like. Among these, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and mixtures thereof are particularly desirable from the viewpoint of abrasion resistance.

Component (d) : The component (d) is a silica sol using an organic solvent as a dispersion medium, and has a particle size of 5 to 30 n, for example.
m, solid content 10 to 40%, methyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, ethylene glycol, ethyl cellosolve,
Dimethylacetamide, xylene, and a mixed solvent thereof are used as a dispersion medium, and the silica has a particle size of 5 to 30 nm and a solid content of 10 to 40%. Among these dispersion media, silica sol using isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, ethyl cellosolve, xylene and a mixed solvent thereof is an acrylic resin as the component (a) and an isocyanate group as the component (b). A compound obtained by reacting a silane coupling agent with a hydroxyl group-containing polyfunctional acrylate having a hydroxyl group and three or more acryloyl groups in the molecule, and (c) a compound having three or more acryloyl groups in the molecule It has good compatibility with polyfunctional acrylates and is particularly desirable from the viewpoint of transparency of the resulting coating film.

Next, the components (a), (b), (c),
The component ratio of the silica sol solid content of the component (d) is 5 to 35% by weight of the component (a), preferably 10 to 30% by weight, based on the total weight of these components, and the component (b) + the component (c) 25 to 60% by weight. %, Preferably 30 to 50% by weight (b) component / (c) component 0.2 or more, preferably 0.5 or more (d) component silica sol solid content 20 to 70% by weight, preferably 30 to 60% by weight That is, the film forming property of the obtained ultraviolet curable coating film,
It is also desirable from the viewpoint of wear resistance. When the amount of the component (a) is less than 5% by weight, the coating film forming property becomes insufficient, and 3
If it exceeds 5% by weight, abrasion resistance becomes insufficient. If the total amount of the components (b) and (c) is less than 25% by weight, the crosslink density due to the acryloyl group will decrease and the abrasion resistance will decrease. On the other hand, when the total amount exceeds 60% by weight, the film forming property is deteriorated. When the ratio of the component (b) and the component (c) is less than 0.2, the formation of crosslinks between the alkoxysilyl group of the component (b) and the silica sol of the component (d) is reduced, and the wear resistance and the coating film formability are reduced. descend. There is no particular upper limit to the ratio, but it is generally about 10 because of easy availability. Also,
When the silica sol solid content of the component (d) is less than 20% by weight, almost no improvement in abrasion resistance due to the silica sol is observed, while when it exceeds 70% by weight, the amount of the components (b) + (c) decreases relatively. However, since the crosslink density due to the acryloyl group decreases, the wear resistance also decreases.

Component (b) used in the present invention, that is, a compound obtained by reacting an isocyanate group-containing silane coupling agent with a hydroxyl group-containing polyfunctional acrylate having a hydroxyl group and three or more acryloyl groups in the molecule is Since it has three or more acryloyl groups and a trialkoxysilyl group or a dialkoxysilyl group in the same molecule,
Even if the component (b) is mixed with the polyfunctional acrylate as the component (c), the acryloyl group density is hardly reduced and high abrasion resistance is obtained. Further, since the trialkoxysilyl group or dialkoxysilyl group present in the component (b) reacts with the silanol group present on the particle surface of the silica sol which is the component (d), it is a substantially liquid component when the solvent is dried. Since only the polyfunctional acrylate of the component (c) is used, a small amount of the acrylic resin of the component (a) added to impart the film-forming property is required. Further, the silica sol of the component (d) has an effect of imparting abrasion resistance and at the same time having an effect of relatively reducing the component (c) which is a liquid component. From the above, the coating composition of the present invention can impart coating film-forming property without lowering abrasion resistance.

Component (e) : As the organic solvent, toluene,
Aromatic hydrocarbons such as xylene, esters such as ethyl acetate, propyl acetate, butyl acetate, ethyl alcohol,
n-propyl alcohol, iso-propyl alcohol,
Alcohols such as n-butyl alcohol, ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ethers such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and diethylene glycol dimethyl ether. Examples thereof include ether esters such as 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, and the like, and these can also be used as a mixture. These organic solvents are components (a) and
It is used during the production of the component (b) and for the purpose of adjusting the viscosity of the ultraviolet curable coating composition.

As the component (f) photopolymerization initiator, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, diethoxyacetophenone, benzyl dimethyl ketal, 2-hydroxy-
2-methylpropiophenone, 1-hydroxycyclohexyl phenyl 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 can be mentioned, and two or more of these photopolymerization initiators can be used in combination. You can also The photopolymerization initiator includes components (a), (b) and (c)
The total amount of the components is 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight.

The abrasion-resistant ultraviolet-curable coating composition of the present invention contains an ultraviolet absorber (for example, benzotriazole-based, benzophenone-based, salicylic acid-based, cyanoacrylate-based ultraviolet absorber) for the purpose of improving the physical properties of the coating film. UV stabilizers (eg hindered amine UV stabilizers),
Various additives such as antioxidants (for example, phenol-based, sulfur-based, phosphorus-based antioxidants), anti-blocking agents, slip agents, leveling agents and the like which are compounded in this type of composition can be added.

The coating composition of the present invention is applied to a plastic substrate such as polycarbonate, polymethylmethacrylate, polyethylene terephthalate, vinyl chloride resin and ABS resin by a dipping method, a flow coating method, a spraying method, a bar coating method, and With a coating method using a coating machine such as gravure coat, roll coat, blade coat and air knife coat, after solvent drying and ultraviolet irradiation,
1 to 50 μ, preferably 3 to 2 on the surface of the plastic substrate
It can be applied under the condition that a hard coat layer of 0 μ is obtained.

After the solvent is dried, processing such as molding, printing and transfer is carried out if necessary. Molding is performed, for example, by heating a base material coated with a hard coat agent to an appropriate temperature, and then using a method such as vacuum forming, vacuum pressure forming, pressure forming, or mat forming, including the base material, interference fringes, etc. Molding of only the hard coat layer, such as when embossing the uneven shape of the above onto a hard coat agent such as duplication of a CD or a record, can be mentioned. Printing is carried out on the dried hard coat agent using an ordinary printing machine. For the transfer, for example, the hard coating agent of the present invention is applied to a substrate such as a polyethylene terephthalate film, dried, and if necessary, the above-mentioned printing or embossing is performed, and after applying an adhesive layer, another substrate is applied. Transfer to material. The ultraviolet curing is performed by irradiating with ultraviolet rays for 1 to 60 seconds using a lamp such as a xenon lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a carbon arc lamp, and a tungsten lamp.

[0028]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. The parts and% in the examples mean parts by weight and% by weight, respectively. Example 1 When a mixture of 100 parts of methyl methacrylate and 150 parts of methyl ethyl ketone was heated to 80 ° C. and after 2 hours from the same temperature, 0.3 parts of azobisisobutyronitrile was added. After reacting at 80 ° C. for 8 hours, a 40% methyl ethyl ketone solution of polymethyl methacrylate was obtained. Next, a mixture of 3-isocyanatopropyltrimethoxysilane, dipentaerythritol hexaacrylate containing 67 mol% of dipentaerythritol pentaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd .: Kayarad DP
HA, hydroxyl value 69 mg KOH / g), and 205 g and 813 g, respectively, were placed in a flask so that -NCO group / -OH group = 1, and hydroquinone monomethyl ether 1 was added.
g and 0.2 g of di-n-butyltin dilaurate are added,
The reaction was carried out at 110 ° C for 3 hours. When this reaction product was analyzed by infrared absorption spectrum, it was found that the -NCO group was 2250 cm 2.
^No absorption of ^-1 was observed, confirming the completion of the reaction. The obtained composition (I) contained a reaction product of 3-isocyanatopropyltrimethoxysilane and dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate of 71.6% and 28.4%, respectively. .

25 parts of a 40% methyl ethyl ketone solution of the polymethyl methacrylate obtained above, composition (I) 4
0 parts, silica sol having xylene and n-butyl alcohol as a dispersion medium (manufactured by Nissan Chemical Co., Ltd .: XBA-ST, solid content 30%,
Xylene 45%, n-butyl alcohol 25%) 167
Parts and 1.5 parts of benzyl dimethyl ketal were mixed to prepare an ultraviolet curable coating composition (A). This UV-curable coating composition (A) was coated on a transparent polycarbonate plate having a thickness of 2 mm with a bar coater to give a coating film thickness of 10
It was coated so as to have a thickness of μm, and dried by heating at 100 ° C. for 10 minutes. The surface of the polycarbonate plate after drying had no tack, and it was confirmed that this coating composition (A) had a film-forming property. Using a high pressure mercury lamp with an output of 7.5 kw and an output density of 120 w / cm installed vertically to the sample passage direction, this was irradiated with ultraviolet rays at a conveyor speed of 2 m / min at a position of 10 cm under the light source to be ultraviolet-cured. .

The adhesion of the hard coat layer formed on the polycarbonate plate to the polycarbonate plate was evaluated by making 100 squares at intervals of 1 mm with a cutter knife on the hard coat layer and crimping a Nichiban cellophane tape to strongly peel it off. At 100/100, good adhesion was obtained (cross-cut tape method JIS K5400). The transparency of the obtained hard coat-treated polycarbonate plate was evaluated by the haze value (%) and found to be 0.7%, which was good. 2mm before hard coating
The haze value of the thick polycarbonate plate was 0.5% (haze value = Td / Tt × 100, Td: scattered light transmittance, Tt: total light transmittance JIS K7105). Next, wear resistance is evaluated by using a wear wheel made of CS-10F manufactured by Calibrase Co., Ltd., and performing a 100-rotation Taber abrasion test with a load of 500 g. The difference between the cloudiness value after the Taber abrasion test and the cloudiness value before the Taber abrasion test is ΔH. Was 5.2%, and the abrasion resistance was good. In addition, ΔH obtained by performing the same Taber abrasion test on a polycarbonate plate having a thickness of 2 mm and not subjected to the hard coat treatment was 46.7% (Taber abrasion test method ASTM D1044).

Example 2 A mixture of 70 parts of methyl methacrylate, 20 parts of glycidyl methacrylate and 150 parts of toluene is heated to 80
When the temperature was raised to 0 ° C, 2 hours after the temperature was raised, 0.3 parts of azobisisobutyronitrile was added to each, and the temperature was raised to 80 ° C.
And reacted for 6 hours. Then, after raising the temperature to 110 ° C.,
Acrylic acid (10 parts) and trimethylammonium bromide (1 part) were added, and the mixture was reacted at 110 ° C. for 6 hours to obtain a 40% toluene solution of a compound having an acryloyl group in the side chain of a copolymer of methyl methacrylate and glycidyl methacrylate. The acid value of this product was 2 mgKOH / g. 40% toluene solution of the obtained compound 50
Parts, 30 parts of the composition (I) obtained in Example 1, silica sol having isopropyl alcohol as a dispersion medium (manufactured by Nissan Kagaku: IPA-ST, solid content 30%, isopropyl alcohol 7)
0%) 167 parts, and benzyl dimethyl ketal 1.
5 parts were mixed to obtain an ultraviolet curable coating composition (B). A hard-coated polycarbonate plate was obtained in the same manner as in Example 1 except that this ultraviolet-curable coating composition (B) was used. The surface of the polycarbonate plate after drying had no tack, and it was confirmed that this coating composition (B) had a film-forming property. Adhesion, transparency and abrasion resistance were evaluated in the same manner as in Example 1. Adhesion: 100/100, haze value: 0.6%, ΔH: 7.5%, and good results were obtained. It was

Example 3 A mixture of 90 parts of methyl methacrylate, 10 parts of γ-methacryloyloxypropyltrimethoxysilane, and 150 parts of methyl ethyl ketone was heated to 80 ° C. and 2 hours after the temperature was raised, respectively. Bisisobutyronitrile was added in an amount of 0.3 part each and reacted at 80 ° C. for 8 hours to obtain a 40% methyl ethyl ketone solution of an acrylic silicone resin having an alkoxysilyl group. next,
198 g and 813 g of 3-isocyanatopropyltriethoxysilane and Kayarad DPHA were placed in a flask so that -NCO group / -OH group = 0.8, respectively.
1 g of hydroquinone monomethyl ether and 0.2 g of di-n-butyltin dilaurate were added, and the mixture was reacted at 110 ° C. for 3 hours. When this reaction product was analyzed by infrared absorption spectrum, no absorption of -NCO group at 2250 cm ^-1 was observed, and it was confirmed that the reaction was completed. The composition (II) thus obtained contained 61.0% and 28% of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, respectively, a reaction product of 3-isocyanatopropyltriethoxysilane and dipentaerythritol pentaacrylate. It contains 0.6% and 10.4%. 37.5 parts of a 40% methyl ethyl ketone solution of the obtained acrylic silicone resin, 50 parts of the composition (II), silica sol (IPA-ST)
117 parts and 1.5 parts of benzyl dimethyl ketal were mixed to obtain an ultraviolet curable coating composition (C). A hard-coated polycarbonate plate was obtained in the same manner as in Example 1 except that this ultraviolet-curable coating composition (C) was used. The surface of the polycarbonate plate after drying has no tack,
It was confirmed that this coating composition (C) had a film-forming property. Adhesion, transparency and abrasion resistance were evaluated in the same manner as in Example 1. Adhesion: 100/100, haze value: 0.
Good results were obtained with 6% and ΔH: 6.8%.

Example 4 89 parts of methyl methacrylate, 10 parts of γ-methacryloyloxypropyltrimethoxysilane, mercaptopolyorganosiloxane having both ends (manufactured by Shin-Etsu Chemical Co., Ltd .: X-22-1)
67B) When a mixture of 1 part and 150 parts of methyl ethyl ketone is heated to 80 ° C. and 2 times from the time of heating.
After an hour, azobisisobutyronitrile was added to 0.3.
Each part was added and reacted at 80 ° C. for 8 hours to obtain a 40% methyl ethyl ketone solution of an acrylic silicon resin having an alkoxysilyl group and a polyorganosiloxane unit in its side chain. 25 parts of a 40% solution of the obtained acrylic silicone resin in methyl ethyl ketone, the composition obtained in Example 3
(II) 50 parts, silica sol (IPA-ST) 133 parts, and benzyl dimethyl ketal 1.5 parts were mixed to obtain an ultraviolet curable coating composition (D). This UV curable coating composition
A hard-coated polycarbonate plate was obtained in the same manner as in Example 1 except that (D) was used. The surface of the polycarbonate plate after drying had no tack, and the coating composition (D)
It was confirmed that the film had a film forming property. Adhesion, transparency and abrasion resistance were evaluated in the same manner as in Example 1. Adhesion: 100/100, haze value: 0.5%, ΔH: 5.3
%, Which is a good result.

Example 5 Coating composition (D) obtained in Example 4 and 100 transparent
A hard-coated polyethylene terephthalate film was obtained in the same manner as in Example 1 except that a polyethylene terephthalate film having a thickness of μm was used. When the adhesion of the hard coat layer formed on the polyethylene terephthalate film to the polyethylene terephthalate film was evaluated, a good adhesion of 100/100 was obtained.
The transparency of the obtained hard coat-treated polyethylene terephthalate film was evaluated by the haze value (%) to be 3.8%, and the transparency was good. The haze value of the polyethylene terephthalate film having a thickness of 100 μm before the hard coat treatment was 3.7%. Next, when the abrasion resistance was evaluated, ΔH was 6.4% and the abrasion resistance was good. The .DELTA.H of 100 .mu.m thick polyethylene terephthalate which had not been subjected to the hard coat treatment was 23.1%.

Application Example 1 The UV-curable coating composition (A) obtained in Example 1 was coated on offset coated paper so that the coating thickness after drying was 10 μm using a bar coater. Apply
After heating and drying at 80 ° C. for 3 minutes, embossing was performed, and then ultraviolet rays were irradiated under the same conditions as in Example 1 to form a transparent relief layer on the coated paper surface. As a result, a printed matter having a three-dimensional effect was obtained. The coating composition (A) not only provided an excellent abrasion resistant surface, but was also excellent in embossability.

Application Example 2 The ultraviolet-curable coating composition (D) obtained in Example 4 was used in an amount of 1
It is applied to a polyethylene terephthalate film of 00 μm by a bar coater so that the film thickness after drying becomes 10 μm, dried by heating at 100 ° C. for 10 minutes, and then a pattern is printed by the gravure printing method and further heat-sealed. Acrylic adhesive (hot stamping agent) was applied. Thermal transfer was performed on the plywood from the film surface side with the acrylic adhesive surface facing down, using a heat roll. Then, the film was peeled off, and ultraviolet rays were irradiated under the same conditions as in Example 1 to cure the surface ultraviolet curable coating composition (D). This product can be used as a wall material, and the coating composition (D) not only provides a smooth wear-resistant surface, but also has excellent workability for pattern printing and film peeling. It was .

Comparative Example 1 40 parts of the composition (I) obtained in Example 1, silica sol (XBA
-ST) 167 parts, and benzyl dimethyl ketal 1.5
The parts were mixed to obtain an ultraviolet curable coating composition (E). This UV-curable coating composition (E) was applied to a transparent polycarbonate plate having a thickness of 2 mm using a bar coater so that the coating film thickness after drying would be 10 μm, and dried by heating at 100 ° C. for 10 minutes. However, there was tack on the surface of the polycarbonate plate after drying, and no coating film forming property was observed in this coating composition (E).

Comparative Example 2 40% of the polymethylmethacrylate obtained in Example 1
25 parts of methyl ethyl ketone solution, Kayarad DPHA4
0 part, 167 parts of silica sol (IPA-ST), and 1.5 parts of benzyl dimethyl ketal were mixed to obtain an ultraviolet curable coating composition (F). A hard-coated polycarbonate plate was obtained in the same manner as in Example 1 except that this ultraviolet-curable coating composition (F) was used. The surface of the polycarbonate plate after drying had a slight tack, and the coating composition of this coating composition (F) was not sufficient. Further, when the adhesiveness, transparency and abrasion resistance were evaluated in the same manner as in Example 1, the adhesiveness: 1
00/100, haze value: 0.6%, ΔH: 18.5%, and wear resistance was not sufficient.

Comparative Example 3 A UV curable coating composition was prepared by mixing 37.5 parts of a 40% methyl ethyl ketone solution of the acrylic silicone resin obtained in Example 3, 50 parts of composition (II), and 1.5 parts of benzyl dimethyl ketal. The product (G) was obtained. A hard-coated polycarbonate plate was obtained in the same manner as in Example 1 except that this ultraviolet curable coating composition (G) was used. The surface of the polycarbonate plate after drying had a slight tack, and the coating composition of this coating composition (G) was not sufficiently formed. Further, the adhesion, transparency and abrasion resistance were evaluated in the same manner as in Example 1. Adhesion: 100/100, haze value: 0.7%, Δ
H: 16.4% and the abrasion resistance was not sufficient.

Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location // C08G 18/38 NDQ 8620-4J

Claims (3)

[Claims] 1. (a) an acrylic resin, (b) the following general formula (1): (In the formula, R ¹ and R ² are the same or different monovalent hydrocarbon groups, R ³ is a divalent hydrocarbon group having 2 to 8 carbon atoms, and a is 2 to 3
Is an integer of 0, b is an integer of 0 to 1, and c is an integer equal to 4-a-b), and has an isocyanate group-containing silane coupling agent and a hydroxyl group and three or more acryloyl groups in the molecule. A compound obtained by reacting with a hydroxyl group-containing polyfunctional acrylate, (c) a polyfunctional acrylate having three or more acryloyl groups in the molecule, (d) a silica sol containing an organic solvent as a dispersion medium, (e) an organic solvent, And (f) a photopolymerization initiator, and the proportion of the silica sol solids of the components (a), (b), (c) and (d) is based on the total weight of these components (a). 5 to 35 wt% (b) component + (c) component 25 to 60 wt% (b) component / (c) component 0.2 or more The solid content of the silica sol of the (d) component is 20 to 70 wt% And an abrasion-resistant ultraviolet-curable coating composition. 2. The acrylic resin (a) has the following (a) to
The composition according to claim 1, which is selected from the compound (d). (A) Polymer or copolymer of (meth) acrylic acid ester (b) Compound having a (meth) acryloyl group in the side chain of the polymer or copolymer of (meth) acrylic acid ester (c) Alkoxysilyl group Acrylic Silicone Resin Having (d) Acrylic Silicone Resin Having Alkoxysilyl Group and Polyorganosiloxane Unit 3. The polyfunctional acrylate (c) having 3 or more acryloyl groups in the molecule is selected from the group consisting of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and a mixture thereof. The composition of claim 1.