JP3442255B2 - UV curable composition and material having functional surface - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention mainly relates to weather resistance,
Effective paints in the fields where lubricity and releasability are required, such as paints for preventing ice and snow accretion, paints for preventing sticking, and films such as polyvinyl chloride and polyester, plastics such as acrylic and polycarbonate. The present invention relates to an ultraviolet-curable composition useful as a coating agent that imparts functions such as water repellency, lubricity, and releasability to the surface or the back surface of a base material such as a molded article, cloth or paper, and a material having a functional surface .

[0002]

2. Description of the Related Art In general, paints having releasability are used to prevent icing and snow, or to prevent graffiti and paper sticking. Further, polyethylene terephthalate (PET) or polyethylene naphthalate (PEN) used as a base material for magnetic tapes, thermal transfer ink ribbons, etc.
For the purpose of imparting water repellency, lubricity, heat resistance and the like to the surface of plastic films such as and plastic molded products such as acrylic and polycarbonate, treatment with a coating agent is performed. As a paint or coating agent having such a releasing property, a coating composition to which reactive silicone, polydimethylsiloxane, etc. have been added has been conventionally used.

[0003]

However, the coating composition containing the above-mentioned reactive silicone, polydimethylsiloxane, etc., has a reduced adhesiveness and transparency of the coating film, and has a tackiness on the surface of the coating film. However, there are problems that the effect of imparting water repellency, lubricity, heat resistance, etc. to the surface of the base material is not sufficient and that it is not durable. Therefore, an object of the present invention is to provide a material which is excellent in adhesion, transparency, etc. of a coating film, has no surface tackiness, and is capable of imparting sufficient water repellency, lubricity, heat resistance, etc. in a durable manner. It is to be.

[0004]

As a result of intensive studies in view of the above problems, the present inventors have found that by curing an ultraviolet curable composition containing a polymer having a polydimethylsiloxane moiety incorporated in its structure, Materials that have functions such as water repellency, lubricity, and heat resistance, as well as excellent weather resistance, solvent resistance, surface tackiness, film transparency, or water repellency and lubricity persistence The inventors have found that they can be obtained and completed the present invention.

That is, according to the present invention, one or more polydimethylsiloxane-based graft or block copolymers (A) having a polydimethylsiloxane moiety and a vinyl polymer moiety having an isocyanate group are reacted with an isocyanate group. One or two UV curable silicone graft or block copolymers (C) obtained by reacting with one or more compounds (B) capable of having two or more UV reactive functional groups. And above, if desired,
One or more kinds of the compound (D) having a UV-reactive functional group capable of copolymerizing with the UV-curable silicone graft or block copolymer (C), and one or more kinds of the photoinitiator (E). relates ultraviolet-curable composition characterized by containing the bets, further the present invention comprises a substrate
And a material having a functional surface comprising a coating layer formed by applying and curing the above-mentioned ultraviolet-curable composition on the front or back surface of the substrate.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The ultraviolet-curable composition of the present invention is a polydimethylsiloxane copolymer (A) having a polydimethylsiloxane portion and a vinyl polymer portion having an isocyanate group.
And a UV-curable silicone copolymer (C) obtained by reacting a compound (B) capable of reacting with an isocyanate group and having a UV-reactive functional group, and containing a photoinitiator (E) And, if desired, it contains a compound (D) having a UV-reactive functional group capable of copolymerizing with the UV-curable silicone copolymer (C).

(A) Polydimethylsiloxane Copolymer The polydimethylsiloxane copolymer (A) in the present invention has a polydimethylsiloxane part (graft or block) and a vinyl polymer part having an isocyanate group. It is a copolymer, and may be a graft copolymer or a block copolymer. This polydimethylsiloxane-based copolymer (A) comprises a graft type reactive silicone (a1) or a block type reactive silicone (a1 ′) and a vinyl monomer (a2) having an isocyanate group, and if necessary. Then, it is obtained by copolymerizing the above-mentioned reactive silicone (a1 and / or a1 ′) with another vinyl monomer (a3) which is copolymerizable.

Graft-type reactive silicone (a
As 1), for example,

[Chemical 1]

[Chemical 2] And the like having an unsaturated double bond at one end.

Further, as the block type reactive silicone (a1 '), for example,

[Chemical 3] Etc.

Examples of the vinyl monomer (a2) having an isocyanate group include 2-isocyanate ethyl (meth) acrylate, methacryloyl isocyanate, m-isopropenyldimethylbenzyl isocyanate and vinyl isocyanate.

Reactive silicone (a1 and / or a
As the other vinyl monomer (a3) copolymerizable with 1 '), for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2 -Ethylhexyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, stearyl acrylate,
Aliphatic or cyclic compounds such as lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, stearyl methacrylate, lauryl methacrylate Acrylate or methacrylate, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, n
-Vinyl ethers such as butyl vinyl ether and isobutyl vinyl ether, styrenes such as styrene and α-methylstyrene, nitrile monomers such as acrylonitrile and methacrylonitrile, vinyl acetate, fatty acid vinyl such as vinyl propionate, vinyl chloride and chloride. Halogen-containing monomers such as vinylidene, vinyl fluoride, vinylidene fluoride, olefins such as ethylene, propylene and isoprene, dienes such as chloroprene and butadiene, epoxy group-containing single monomers such as glycidyl acrylate, glycidyl methacrylate and glycidyl allyl ether. There is a quantity. The above-mentioned monomers have no reactivity with the isocyanate group of the vinyl monomer (a2), and are used alone or in an appropriate mixture. It should be noted that the above examples do not limit the present invention.

The graft type or block type reactive silicone (a1, a1 '), the vinyl monomer having an isocyanate group (a2) and, if desired, other copolymerizable vinyl monomer (a3) are copolymerized. The polydimethylsiloxane-based copolymer (A) obtained by polymerization preferably has a siloxane content of 1 to 70% by weight, particularly preferably 10 to 50% by weight. The content ratio is preferably 1 to 60% by weight, particularly preferably 10 to 50% by weight, and the content ratio of the other copolymerizable vinyl monomer is 0 to 98% by weight, particularly 5 to 80% by weight. Is preferred.

(B) is capable of reacting with an isocyanate group
Examples of the compound (B) having two or more UV-reactive functional groups and capable of reacting with an isocyanate group and having two or more UV-reactive functional groups include, for example, glycerol di (meth) acrylate and glycerol methacrylate. Acrylate, isocyanuric acid ethylene oxide-modified diacrylate, bifunctional compound (B) such as pentaerythritol diacrylate monostearate, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate Multifunctional compounds such as (B)
Etc.

(D) Compound Having Ultraviolet Reactive Functional Group The compound (D) in the present invention comprises an ultraviolet curable silicone copolymer (C) (two or more of the above polydimethylsiloxane copolymer (A) and A compound having an ultraviolet-reactive functional group capable of copolymerization with a compound (B) having an ultraviolet-reactive functional group), which is a compound having a (meth) acryloyl group in the molecule as a representative example. Is mentioned. As such a compound, a commercially available compound can be used, and a monofunctional monomer or oligomer or a polyfunctional monomer or oligomer may be appropriately selected depending on the required physical properties.

For example, when the surface hardness after curing of the composition is required, a polyfunctional monomer or oligomer having three or more functional groups may be selected as a main component.

Typical monomers are 2-ethylhexyl acrylate, phenoxyethyl acrylate, 2
-Ethoxyethyl acrylate, 2-ethoxyethoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, dicyclopentenyloxyethyl acrylate, N-vinylpyrrolidone, vinyl acetate and other monofunctional compounds, neopentyl glycol di Difunctional ones such as acrylate, 1,6-hexanediacrylate, 1,4-butanediacrylate, diethylene glycol (400) diacrylate,
Trimethylolpropane triacrylate, pentaerythritol triacrylate, triacrylate of 6 mol ethylene oxide adduct of trimethylolpropane, triacrylate of 3 mol propylene oxide adduct of trimethylolpropane, glycerin propoxytriacrylate, dipentaerythritol hexaacrylate, Examples thereof include polyfunctional ones such as hexaacrylate which is a caprolactone adduct of dipentaerythritol.

Typical oligomers include unsaturated polyesters, polyester acrylates, polyether acrylates, acrylic acrylates, urethane acrylates and epoxy acrylates. The above examples do not limit the present invention.

(E) Photoinitiator The photoinitiator (E) used in the present invention includes isopropyl benzoin ether, isobutyl benzoin ether, benzophenone, Michler's ketone, o-benzoylmethyl benzoate, xanthone, thioxanthone, 2
-Chlorothioxanthone, acetophenone, diethoxyacetophenone, 1-phenyl-2-hydroxy-2-
Methylpropan-1-one (for example, Darocure 1173 manufactured by Ciba-Geigy Co., Ltd.), 1-hydroxycyclohexyl phenyl ketone (for example, Irgacure 184 manufactured by Ciba-Geigy Co., Ltd.), 2-methyl-1- (4-
Methylthiophenyl) -2-morpholino-propane-1
-ON (for example, Irgacure 907 manufactured by Ciba Geigy Co., Ltd.), 2-ethylanthraquinone, and methylbenzyl formate (for example, Vicure 55 manufactured by Stouffer Co., Ltd.).

Next, a method for producing the ultraviolet curable composition of the present invention will be described. (1) Synthesis of Polydimethylsiloxane Copolymer (A) The polydimethylsiloxane copolymer (A) is a graft type or block type reactive silicone (a1,
a1 ′) and a vinyl monomer (a2) having an isocyanate group, and optionally, another vinyl monomer (a3) copolymerizable with the above-mentioned reactive silicone (a1 and / or a1 ′). It can be synthesized by Graft type (a
When 1) is selected, benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, dicumyl peroxide, t-butyl peroxyisopropyl carbonate, t-butyl perbenzoate, di-t-butyl peroxide, azo A polymerization initiator such as bisisobutyronitrile or azobisvaleronitrile can be used.

When the block type (a1 ') is selected as the reactive silicone, the synthesis can be carried out by a living polymerization method or a polymer initiator method.
Industrially, it is preferably synthesized by the polymer initiator method. In the polymer initiator method, for example,

[Chemical 4] It is possible to use a high molecular weight azo initiator having a polydimethylsiloxane moiety introduced therein, which makes it possible to efficiently produce a block copolymer. Further, if a polymeric initiator such as a peroxide type polymer initiator or an azo type polymer initiator is used, the polymerization can be carried out in two steps.

Examples of the peroxide type polymer initiator include:

[Chemical 5]

[Chemical 6]

[Chemical 7] Etc. can be used. Examples of the azo type polymer initiator include

[Chemical 8] Can be used. In the formula, as an example of R,

[Chemical 9] Or

[Chemical 10] And so on.

When this azo type polymer initiator is used,
Polymerization proceeds according to the following reaction formula.

[Chemical 11] Here, M ₁ and M ₂ represent a reactive silicone oil, and m, n, n ′ and l represent an integer of 1 or more. that's all,
Although the case where a polymerization initiator is used for copolymerization has been described as an example, it is not always necessary to use a polymerization initiator in the present invention.

Polymerization reaction of graft type or block type reactive silicone (a1, a1 ') and vinyl monomer having an isocyanate group (a2) and, if desired, other copolymerizable vinyl monomer (a3). Is usually performed in solution. In this solution polymerization, an aromatic hydrocarbon solvent such as toluene and xylene, a ketone solvent such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and an ester solvent such as ethyl acetate, propyl acetate, isobutyl acetate and butyl acetate are used alone. Alternatively, it is used as a mixed solvent.

The reaction temperature is preferably 50 to 150 ° C., and the reaction time is preferably 3 to 12 hours. In the above polymerization, the content ratio of siloxane in the obtained polydimethylsiloxane copolymer (A) is 1 to 70.
%, Particularly 10 to 50% by weight, and the content ratio of the vinyl monomer having an isocyanate group is 1 to 60% by weight,
Particularly, it is 10 to 50% by weight, and the content ratio of other copolymerizable vinyl monomer is 0 to 98% by weight, particularly 5 to 80% by weight.
Each raw material (a1, a1 ', a2, a
It is preferable to blend 3).

(2) UV curable silicone copolymer
Synthesis of (C) The obtained polydimethylsiloxane-based graft or block copolymer (A) is reacted with the compound (B) having two or more UV-reactive functional groups to obtain a UV-curable silicone graft or A block copolymer is synthesized. The reaction can usually be carried out in a solution, such as an aromatic hydrocarbon solvent such as toluene or xylene, a ketone solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone, an ester such as ethyl acetate, propyl acetate, isobutyl acetate or butyl acetate. A system solvent or the like is used alone or as a mixed solvent. The reaction temperature is preferably room temperature to 100 ° C., and the reaction time is preferably 1 to 10 hours.

The mixing ratio of the polydimethylsiloxane-based graft or block copolymer (A) and the compound (B) having two or more UV-reactive functional groups is 50% by weight of the polydimethylsiloxane-based copolymer (A). To 90 parts by weight, compounds (B) 10 to 50 having two or more UV-reactive functional groups
It is preferably 0.01 part by weight, if necessary, 0.01 to 1 part by weight of a catalyst such as dibutyltin dilaurate, and 0.01 to 1 part of a polymerization inhibitor such as hydroquinone monomethyl ether.
It is preferable to mix 1 part by weight.

(3) Production of UV-Curable Composition The UV-curable silicone copolymer (C) and photoinitiator (E) obtained and optionally a compound (D) having an UV-reactive functional group are mixed. To do. Also, if necessary,
You may mix | blend a solvent or additives, such as a leveling agent and an ultraviolet absorber. As the solvent, toluene, an aromatic hydrocarbon solvent such as xylene, a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone,
Ester-based solvents such as ethyl acetate, propyl acetate, isobutyl acetate and butyl acetate, alcohol-based solvents such as methanol, isopropyl alcohol, ethanol, n-butanol and isobutanol are used alone or as a mixed solvent. As the leveling agent, silicone-based or fluorine-based ones, and as the ultraviolet absorber, benzophenone-based, benzotriazole-based, oxalic acid anilide-based, cyanoacrylate-based, triazine-based, hindered amine-based ones and the like can be used.

UV curable silicone copolymer (C),
The compounding ratio of the compound (D) having an ultraviolet reactive functional group and the photoinitiator (E) is 1 to 5: 0 in terms of solid content ratio (weight).
It is preferable that it is -99: 0.5-10, especially 10-
It is preferably 40:60 to 90: 1 to 5.

By curing the composition of the present invention obtained as described above by irradiating it with ultraviolet rays, it has functions such as water repellency, lubricity, and heat resistance, as well as weather resistance, solvent resistance and surface tack. A material having a functional surface excellent in feeling, film transparency, or water repellency and durability of lubricity can be obtained. The ultraviolet irradiation conditions are as follows:
It is preferably ˜3000 mj / cm ² .

The ultraviolet-curable composition of the present invention can be used as various coating agents. For example, a back coat agent applied on the front surface or the back surface of a plastic film such as a thermal transfer recording sheet, a thermal transfer ink ribbon, or a magnetic tape, and a surface protective coat for a plastic card such as a magnetic card, an IC card, a cash card, a prepaid card, and a telephone card Agent, automobile head lamp, tail lamp, meter cover, cover for center panel, helmet windshield, eyeglass lens, surface protective coating agent for plastic molded products such as goggles, road sign, guide plate, indicator light, reflector plate, It can be used for antifouling of wall materials, snowfall prevention, icing / condensation prevention, graffiti prevention, paper coating prevention, release paper, paper such as process paper. Application of the ultraviolet curable composition to the substrate may be carried out by a conventional method,
For example, it can be applied using a spray for painting, an electrostatic spray, a roll coater, spin coating, or the like. The film thickness is preferably about 1 to 100 μm.

The UV-curable composition of the present invention is different from the conventional UV-curable coating composition in which only polydimethylsiloxane oil is added, and the polydimethylsiloxane component is incorporated into the vinyl polymer portion as a graft or block structure. Since it has a surface concentration function, it is more excellent in water repellency, lubricity and heat resistance than the conventional UV-curable coating composition. Therefore, the surface tack feeling peculiar to the conventional ultraviolet curable coating composition, a decrease in transparency and solvent resistance,
Alternatively, the sustainability of various effects can be improved.
Further, the copolymerization component also improves the adhesion to the substrate. Furthermore, by curing with ultraviolet rays, surface hardness, scratch resistance, weather resistance, heat resistance and solvent resistance are improved, and at the same time, water repellency and durability of lubricity are significantly improved. In particular, when a compound having two or more UV-reactive functional groups (bifunctional or polyfunctional monomer or oligomer) is used as the compound (B) capable of reacting with an isocyanate group and having a UV-reactive functional group, Also significantly improves the ultraviolet curability.

[0032]

The present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to these examples. [Production Example 1] Production of polydimethylsiloxane copolymer (A) -1 To a flask of 500 ml equipped with a stirrer, a thermometer, a condenser and a nitrogen gas introducing tube, 60 parts by weight of toluene (hereinafter, simply referred to as "part"). And polydimethylsiloxane macromonomer (AK-3, manufactured by Toagosei Co., Ltd.)
0, active ingredient 50%, molecular weight about 30,000) 80 parts,
Under reflux at 110 ° C., 30 parts of methyl methacrylate, 20 parts of butyl methacrylate, and isocyanate ethyl methacrylate (Showa Denko KK, Karens MOI) 10
And 5 parts of 2,2-azobis-2-methylbutyronitrile (Wako Pure Chemical Industries, Ltd., V-59) were added dropwise over 2 hours. Then, the temperature was maintained for 5 hours to complete the polymerization, and a copolymer solution having a solid content of 50% by weight was obtained. This copolymer solution is called resin A-1.

Production Example 2 Production of Polydimethylsiloxane Copolymer (A) -2 In the same flask as in Production Example 1, 100 parts of toluene and polydimethylsiloxane macromonomer (manufactured by Chisso Corporation, FM0721, molecular weight 5000 ) were prepared. ) Prepare 40 parts,
Mixture consisting of 30 parts of methyl methacrylate, 10 parts of butyl methacrylate, 20 parts of methacryloyl isocyanate and 5 parts of 2,2-azobis-2-methylbutyronitrile (Wako Pure Chemical Industries, Ltd., V-59) under reflux at 110 ° C. The liquid was added dropwise over 2 hours. Then, the temperature was maintained for 5 hours to complete the polymerization, and a copolymer solution having a solid content of 50% by weight was obtained. This copolymer solution is called resin A-2.

Production Example 3 Production of Polydimethylsiloxane Copolymer (A) -3 In a flask similar to that of Production Example 1, 60 parts of toluene and polydimethylsiloxane polymer initiator (manufactured by Wako Pure Chemical Industries, Ltd.) , VPS-0501, siloxane chain length 5000) 40
Parts, 30 parts of methyl methacrylate, 20 parts of butyl methacrylate and 10 parts of isocyanate ethyl methacrylate (Showa Denko KK, Karens MOI),
The temperature was raised to 95 ° C. Then, the temperature was maintained for 5 hours to complete the polymerization, and a copolymer solution having a solid content of 50% by weight was obtained. This copolymer solution is called resin A-3.

Production Example 4 Production of UV-Curable Silicone Copolymer (C) -1 In the same flask as in Production Example 1, 200 parts of Resin A-1 obtained in Production Example 1, 40 parts of toluene, 40 parts of pentaerythritol triacrylate (Aronix M305 manufactured by Toagosei Co., Ltd.), 0.02 part of dibutyltin dilaurate and 0.2 part of hydroquinone monomethyl ether were charged, and the temperature was raised to 70 ° C. Then, the reaction was terminated by maintaining the same temperature for 3 hours to obtain a copolymer solution having a solid content of 50% by weight. This copolymer solution is called resin C-1.

[Production Example 5] Production of UV-curable silicone copolymer (C) -2 In a flask similar to Production Example 1, 200 parts of Resin A-2 obtained in Production Example 2 and 80 parts of toluene were added. 80 parts of pentaerythritol triacrylate (Aronix M305 manufactured by Toagosei Co., Ltd.), 0.03 part of dibutyltin dilaurate and 0.2 part of hydroquinone monomethyl ether were charged, and the temperature was raised to 70 ° C. Then, the reaction was terminated by maintaining the same temperature for 3 hours to obtain a copolymer solution having a solid content of 50% by weight. This copolymer solution is designated as resin C-2.

Production Example 6 Production of UV-Curable Silicone Copolymer (C) -3 In the same flask as in Production Example 1, 200 parts of Resin A-3 obtained in Production Example 3 and 80 parts of toluene were added. 80 parts of isocyanuric acid ethylene oxide modified diacrylate (Toagosei Co., Ltd., Aronix M215), 0.02 part of dibutyltin dilaurate and 0.2 part of hydroquinone monomethyl ether were charged, and the temperature was raised to 70 ° C.
Then, the reaction was terminated by maintaining the same temperature for 3 hours to obtain a copolymer solution having a solid content of 50% by weight. This copolymer solution is referred to as resin C-3.

Example 1 16 parts of resin C-1 obtained in Production Example 4 and dipentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd.,
M-400) 21 parts, N-vinylpyrrolidone (manufactured by Toagosei Co., Ltd., M-150) 2 parts, isobutanol 40 parts, 3-methoxybutyl acetate 20 parts and photoinitiator (manufactured by Ciba Geigy Co., Ltd.). , Irgacure 18
4 parts of 4) was blended, and this was spray-coated on a polycarbonate plate so that the film thickness when dried was 5 μm. This coated plate was treated in a hot air drying oven at 60 ° C for 5 minutes, and then a lamp output of 120 W / cm (distance from lamp: 25 m
m) UV drying furnace, conveyor speed 3m / m
cured in. The coated plate thus obtained,
It is called test plate 1.

Example 2 16 parts of the resin C-2 obtained in Production Example 5, 21 parts of ditrimethylolpropane tetraacrylate (M-408 manufactured by Toagosei Co., Ltd.), ethoxydiethylene glycol acrylate (Kyoeisha Chemical Co., Ltd.) Company-made, EC-A)
2 parts, 40 parts of isobutanol, 20 parts of 3-methoxybutyl acetate and 1 part of a photoinitiator (Darocur 1173 manufactured by Ciba-Geigy Co., Ltd.). Using this, a coated plate was manufactured in the same manner as in Example 1. The obtained coated plate is referred to as test plate 2.

Example 3 16 parts of Resin C-3 obtained in Production Example 6, 18 parts of ditrimethylolpropane tetraacrylate (M-305 manufactured by Toagosei Co., Ltd.), ethoxydiethylene glycol acrylate (Kyoeisha Chemical Co., Ltd.) Company-made, EC-A)
5 parts, isobutanol 40 parts, 3-methoxybutyl acetate 20 parts, and a photoinitiator (manufactured by Ciba-Geigy Co., Ltd., Darocure 1173) were mixed. Using this, a coated plate was manufactured in the same manner as in Example 1. The obtained coated plate is referred to as test plate 3.

Comparative Example 1 21 parts of dipentaerythritol hexaacrylate (M-400 manufactured by Toagosei Co., Ltd.), 2 parts of N-vinylpyrrolidone (M-150 manufactured by Toagosei Co., Ltd.) and isobutanol were added. 48 parts, 20 parts of 3-methoxybutyl acetate, 1 part of photoinitiator (Ciba Geigy Co., Ltd., Irgacure 184), and 8 parts of polydimethylsiloxane macromonomer (Toagosei Co., Ltd., active ingredient 50%, molecular weight 30000). Parts. Using this, a coated plate was manufactured in the same manner as in Example 1. The obtained coated plate is referred to as test plate 4.

Comparative Example 2 18 parts of ditrimethylolpropane tetraacrylate (manufactured by Toagosei Co., Ltd., M-305) and ethoxydiethylene glycol acrylate (manufactured by Kyoeisha Chemical Co., Ltd.,
EC-A) 5 parts, isobutanol 48 parts, 3-methoxybutyl acetate 23 parts, photoinitiator (Ciba Geigy Ltd., Darocur 1173) 1 part and side chain ether type epoxy modified polydimethylsiloxane (Toray). 5 parts of Silicone Co., Ltd., SF-8411) was blended. Using this, a coated plate was manufactured in the same manner as in Example 1. The obtained coated plate is referred to as test plate 5.

[Test Example] With respect to the test plates 1 to 5 obtained as described above, adhesion, contact angle, friction coefficient, film transparency, surface tackiness, peeling property, scratch resistance, water resistance and The solvent resistance was evaluated. The adhesiveness was evaluated by a cross-cut cellophane tape peeling test. The contact angle was measured using a contact angle meter manufactured by Kyowa Interface Science. The friction coefficient was measured using a HEIDON type friction tester. The film transparency was visually evaluated.
Regarding the peelability, using an autograph manufactured by Shimadzu Corporation, using a cloth tape with a width of 25 mm and peeling at 90 degrees, 300
The peeling force was measured at a speed of mm / min. For abrasion resistance, use steel wool # in a taper abrasion tester
Haze value was measured by carrying out 50 cycles under a load of 500 g using 000. For water resistance, after dipping in water at 80 ° C. for 1 hour and drying at room temperature for 1 hour, the adhesiveness is the same as above.
It was evaluated by measuring the contact angle and the peeling property. Regarding the solvent resistance, after performing a spot test with toluene at room temperature for 24 hours, the contact angle was measured in the same manner as above.
The results are shown in Table 1.

[0044]

[Table 1] Tackiness on the surface: ○… No ×… Yes

As is apparent from Table 1, the test plates 1 to 3 obtained by curing the ultraviolet curable composition of the present invention showed good adhesion,
As shown in the evaluation of the dynamic friction coefficient (lubricity) and the contact angle, the orientation of the silicone is effectively expressed, and there is no problem in the appearance of the film. Moreover, the contact angle and the peeling property in the water resistance test are hardly decreased. On the other hand, in Test Plates 4 and 5, although the effect of silicone was observed to some extent, the tackiness of the surface and the decrease in the transparency of the film which were caused by the addition of a large amount of silicone were observed, and the contact angle in the water resistance test was Also, the releasability is lowered, and the effect persistence is not sufficient.

[0046]

According to the present invention, the functions of silicone such as water repellency, lubricity, heat resistance, etc. can be fully exerted, and the weather resistance, solvent resistance, surface tackiness, film transparency, or repellency can be improved. Functionality with excellent water resistance and lubricity
A material having a surface is obtained.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C08F 290/06 C08F 290/06 (72) Inventor Susumu Kawakami 8-3 Ninomachi, Mizuho-ku, Nagoya-shi, Aichi Natco Paint Co., Ltd. (56) References JP-A-2-247210 (JP, A) JP-A-2-247211 (JP, A) JP-A-8-176504 (JP, A) JP-A-8-283362 (JP, A) ) JP-A-62-513 (JP, A) JP-A-4-275319 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 290/00-290/14 C08F 299 / 00-299/08 C09D 1/00-201/10

Claims (3)

(57) [Claims] 1. A polydimethylsiloxane-based graft or block copolymer having a polydimethylsiloxane moiety and a vinyl polymer moiety having an isocyanate group,
An ultraviolet-curable silicone graft or block copolymer obtained by reacting with a compound capable of reacting with an isocyanate group and having two or more ultraviolet-reactive functional groups, and a photoinitiator. UV curable composition. 2. The ultraviolet-curable composition according to claim 1, further comprising a compound having an ultraviolet-reactive functional group capable of copolymerizing with the ultraviolet-curable silicone graft or block copolymer. The 3. A functional surface of a substrate as defined in Claim 1 or 2 ultraviolet-curable composition according to any one characterized by comprising a coating layer formed by coating cured on the surface or back surface of said substrate
Material to have .