JP2001002744A - Ultraviolet-curable composition and surface-functional material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a material that has excellent resistance to scratch, solvent, tipping and cracking and shows excellent fabricability and adhesion to a plurality of materials. SOLUTION: The ultraviolet-setting resin composition comprises (A) an ultraviolet-setting urethane (meth)acrylate oligomer that is prepared by allowing an isocyanate prepolymer bearing 3 or more isocyanate groups in one molecule to react with a polycaprolatonemodified hydroxyethyl (meth)acrylate and (B) a 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 composition and a surface functional material useful mainly as a paint, a coating agent and the like used in fields requiring abrasion resistance.

[0002]

BACKGROUND OF THE INVENTION Plastic molded articles such as polyvinyl chloride, acrylic resin, polycarbonate and polyethylene terephthalate have poor physical properties such as hardness, solvent resistance and weather resistance. Surface treatment may be applied. Such surface treatments include plating, vapor deposition, metal surface treatments such as sputtering, and the metal surface treatment film is easily damaged,
There is a problem that the scratches are conspicuous.

Further, the surface of products such as mobile phones, touch panels, compact discs, and audio equipment is easily scratched, and even when scratched on woodwork products such as stairs, floors, and furniture, the scratches are easily noticeable. . In recent years, there has been an increasing trend toward high durability so as to maintain the surface state of these products for a long period of time, and there is a demand for scratch resistance that does not damage even with some external stimulus.

[0004] As a coating having scratch resistance, a UV-curable hard coat agent, an electron beam-curable hard coat agent, a silica-based hard coat agent, a two-pack acrylic urethane-based soft paint, and the like are conventionally known. .

[0005]

However, in the above-mentioned ultraviolet-curable hard coat agent, electron beam-curable hard coat agent and silica-based hard coat agent, use of a hard monomer for increasing the hardness and increase of the crosslink density are required. As a result, an increase in distortion during curing shrinkage tends to cause problems such as a decrease in adhesion to a material and generation of chipping and cracking depending on a coating film thickness. Further, when these hard coat agents are applied to a plastic film / sheet or the like, the formed coating film is too hard and brittle, so that secondary processing after coating becomes extremely difficult.

On the other hand, the two-pack type acrylic urethane-based soft paint has no problem of chipping and cracking, but has a problem in that the work efficiency is low because the two-pack type is limited in the pot life and the like. In addition, there are problems such as productivity such as long curing and drying time, and problems such as poor solvent resistance and blocking resistance. In order to improve the blocking resistance, it is conceivable to add polydimethylsiloxane oil to the two-pack type acrylic urethane-based soft paint, but the transparency of the coating film, the solvent resistance, and the adhesion to the substrate are considered. Problems such as lowering occur.

Accordingly, an object of the present invention is to provide a material having excellent scratch resistance, solvent resistance, chipping resistance, and crack resistance, as well as excellent secondary workability and adhesion to various materials. That is.

[0008]

In order to solve the above problems, the present invention provides an isocyanate prepolymer compound having three or more isocyanate groups in one molecule and a polycaprolactone-modified hydroxyethyl (meth) acrylate. An ultraviolet-curable composition comprising an ultraviolet-curable urethane (meth) acrylate oligomer obtained by the reaction and a photoinitiator, and further comprising the ultraviolet-curable composition. The present invention provides a surface functional material obtained by curing the above.

[0009] The above-mentioned ultraviolet-curable composition may be, if desired,
Further, it may contain a compound having an ultraviolet-curable functional group and / or an ultraviolet-curable silicone graft or block copolymer which can be copolymerized with the ultraviolet-curable urethane (meth) acrylate oligomer. By containing a compound having an ultraviolet-curable functional group that can be copolymerized with the ultraviolet-curable urethane (meth) acrylate-based oligomer, it is possible to reduce the viscosity of the obtained ultraviolet-curable composition and increase the solidity of the composition. As well as being able to impart water resistance to the cured coating film, the adhesion to the substrate can be further improved. Further, copolymerizable with the ultraviolet-curable urethane (meth) acrylate oligomer,
By containing an ultraviolet-curable silicone graft or block copolymer, the cured coating film can be imparted with properties such as lubricity, water repellency, weather resistance, stain resistance, and blocking resistance.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The ultraviolet curable composition of the present invention is obtained by reacting an isocyanate prepolymer compound (A) having three or more isocyanate groups in one molecule with a polycaprolactone-modified hydroxyethyl (meth) acrylate (B). It contains a curable urethane (meth) acrylate oligomer (C) and a photoinitiator (F).
Further contains a compound (D) having a UV-curable functional group and / or a UV-curable silicone graft or block copolymer (E) copolymerizable with the UV-curable urethane (meth) acrylate oligomer (C). I do.

(A) Isocyanate prepolymer compound The isocyanate prepolymer compound (A) in the present invention can be usually obtained by modifying a diisocyanate monomer (a) having two isocyanate groups. Examples of the method for modifying the diisocyanate monomer (a) include isocyanurate modification, trimethylolpropane (TMP) modification, and biuret modification.

As the diisocyanate monomer (a), for example, tolylene diisocyanate represented by the following formula (1):

Embedded image Naphthalenediisocyanate represented by the following formula (2),

Embedded image Diphenylmethane diisocyanate represented by the following formula (3),

Embedded image Isophorone diisocyanate represented by the following formula (4),

Embedded image Xylylene diisocyanate represented by the following formula (5),

Embedded image Hexamethylene diisocyanate represented by the following formula (6),

Embedded image Dicyclohexylmethane diisocyanate represented by the following formula (7),

Embedded image Other examples include those having two isocyanate groups in one molecule, such as 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate methyl and the like.

The isocyanate prepolymer compound (A1) obtained by modifying the diisocyanate monomer (a) with isocyanurate includes, for example, those represented by the following general formula (8).

Embedded image

The above diisocyanate monomer (a) is
MP-modified isocyanate prepolymer compound (A
Examples of 2) include those represented by the following general formula (9).

Embedded image

Examples of the isocyanate prepolymer compound (A3) obtained by biuret-modifying the diisocyanate monomer (a) include those represented by the following formula (10).

Embedded image

(B) Polycaprolactone-modified hydroxy
Ethyl (meth) acrylate The polycaprolactone-modified hydroxyethyl (meth) acrylate (B) in the present invention is a compound represented by the following general formula (11).

Embedded image The compound is capable of reacting with an isocyanate group,
It has an ultraviolet curable functional group (CH ₂ ＝).

(D) Compound Having UV-Curable Functional Group The compound (D) in the present invention is a UV-curable urethane (meth) acrylate-based oligomer (C) (the isocyanate prepolymer compound (A) and the polycaprolactone-modified hydroxy Ethyl (meth) acrylate (B)
Is a compound having an ultraviolet-curable functional group that can be copolymerized with the compound (a), and a typical example thereof is a compound having a (meth) acryloyl group in the molecule.
As such a compound, a commercially available compound can be used, and if necessary, a monofunctional or polyfunctional monomer or oligomer may be appropriately selected.

Representative monomers include 2-ethylhexyl acrylate, phenoxyethyl acrylate,
-Ethoxyethyl acrylate, 2-ethoxyethoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, polycaprolactone-modified hydroxyethyl acrylate, dicyclopentenyloxyethyl acrylate, N-vinylpyrrolidone, acryloylmorpholine, isobornyl acrylate , Vinyl acetate, monofunctional ones such as styrene, neopentyl glycol diacrylate, 1,9-nonanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol diacrylate,
Bifunctional ones such as diethylene glycol diacrylate, triethylene glycol diacrylate, propylene glycol diacrylate, and dipropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, and 3 mol propylene oxide adduct of trimethylolpropane Polyfunctional compounds such as triacrylate, triacrylate of a 6 mol ethylene oxide adduct of trimethylolpropane, glycerin propoxy triacrylate, dipentaerythritol hexaacrylate, and hexaacrylate of a caprolactone adduct of dipentaerythritol are exemplified.

Typical oligomers include unsaturated polyester, polyester acrylate, polyether acrylate, acryl acrylate, urethane acrylate, epoxy acrylate and the like. The above examples do not limit the present invention.

(E) UV-curable silicone graft or
Is a block copolymer. In the present invention, the ultraviolet-curable silicone graft or block copolymer (E) comprises a polydimethylsiloxane moiety (graft or block) and an ultraviolet-curable urethane (meth) acrylate oligomer (C) (the above isocyanate). Prepolymer compound (A) and polycaprolactone-modified hydroxyethyl (meth) acrylate (B)
And a compound having an ultraviolet-curable functional group that can be copolymerized, and may be a graft copolymer or a block copolymer.

The ultraviolet-curable silicone graft or block copolymer (E) is obtained by combining a graft type reactive silicone (e1-1) or a block type reactive silicone (e1-2) with a glycidyl group, an isocyanate group,
A vinyl monomer (e2-1,2-2,2-3,2-4) having a functional group such as a hydroxyl group or a carboxyl group, and if necessary, the reactive silicone (e1-1 and / or e1-2) is copolymerized with another copolymerizable vinyl monomer (e3), and a functional group of the vinyl monomer (e2-1,2-2,2-3,2-4) is obtained. And can be obtained by adding a compound (e4-1, 4-2, 4-3, 4-4) having a UV-curable functional group.

Graft-type reactive silicone (e1-
Examples of 1) include a compound having an unsaturated double bond at one end, such as a compound represented by the following formula (12).

Embedded image

The block type reactive silicone (e1-2) includes, for example, a compound represented by the following formula (13).

Embedded image

A vinyl monomer having a glycidyl group (e2-
Examples of 1) include glycidyl acrylate, glycidyl methacrylate, and glycidyl allyl ether. Vinyl monomers having an isocyanate group (e)
Examples of 2-2) include 2-isocyanatoethyl (meth) acrylate, methacryloyl isocyanate, and vinyl isocyanate. Examples of the hydroxyl-containing vinyl monomer (e2-3) include 2-hydroxyethyl ( (Meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, phenoxyhydroxypropyl acrylate, and the like. Examples of the vinyl monomer having a carboxyl group (e2-4) include acrylic acid,
Methacrylic acid, itaconic acid, crotonic acid, maleic acid,
Maleic anhydride and the like can be mentioned.

Another vinyl monomer (e3) copolymerizable with the reactive silicone (e1-1 and / or e1-2).
Examples include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, octyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, methyl methacrylate, ethyl methacrylate, n -Butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, stearyl methacrylate, lauryl methacrylate, or other aliphatic or cyclic 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-methyl styrene; nitrile monomers such as acrylonitrile and methacrylonitrile; vinyl fatty acids such as vinyl acetate and vinyl propionate; vinyl chloride; Examples include halogen-containing monomers such as vinylidene, vinyl fluoride, and vinylidene fluoride; olefins such as ethylene and propylene; and dienes such as isoprene, chloroprene, and butadiene. These vinyl monomers (e3) have no reactivity with the functional groups of the vinyl monomer (e2-1, 2-2, 2-3, 2-4).

And capable of reacting with a glycidyl group,
Examples of the compound (e4-1) having an ultraviolet-curable functional group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, and maleic anhydride having a carboxyl group, and can react with an isocyanate group. Examples of the compound (e4-2) having an ultraviolet-curable functional group include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and polyethylene glycol mono (having a hydroxyl group). Examples include alcohol type such as (meth) acrylate, epoxy type such as butoxyhydroxyacrylate and phenoxyhydroxypropyl acrylate, and compounds having an amino group such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate. Examples of the compound (e4-3) capable of reacting with a hydroxyl group and having an ultraviolet curable functional group include 2-isocyanateethyl (meth) acrylate, methacryloyl isocyanate, and vinyl isocyanate, and are capable of reacting with a carboxyl group. The compound (e4-4) having a UV-curable functional group includes glycidyl acrylate, glycidyl methacrylate, glycidyl allyl ether and the like. The above examples do not limit the present invention.

(F) Photoinitiator As the photoinitiator (F) in the present invention, for example, isopropylbenzoin ether, isobutyl benzoin ether, benzophenone, Michler's ketone, o-benzoylmethylbenzoate, acetophenone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, ethylanthraquinone, p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, 1-hydroxycyclohexyl phenyl ketone (for example, Irgacure 18 manufactured by Ciba Geigy Corporation)
4), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (for example, Darocure 1173 manufactured by Ciba-Geigy Corporation), 2,2-dimethoxy-1,2-
Diphenylethan-1-one (for example, Irgacure 651 manufactured by Ciba-Geigy), 2-benzyl-2-
Dimethylamino-1 (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, methylbenzyl formate and the like.

Next, a method for producing the ultraviolet curable composition of the present invention will be described. (1) UV-curable urethane (meth) acrylate
Synthesis of Gomer (C) The UV-curable urethane (meth) acrylate oligomer (C) in the present invention is obtained by reacting an isocyanate prepolymer compound (A) with a polycaprolactone-modified hydroxyethyl (meth) acrylate (B). Is obtained by The reaction can be usually performed in a solution, toluene, an aromatic hydrocarbon solvent such as xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, a ketone solvent such as cyclohexanone, ethyl acetate,
Ester solvents such as propyl acetate, isobutyl acetate, and butyl acetate are used alone or as a mixed solvent.
The above reaction can be carried out in a solvent-free system or in a compound having an ultraviolet-curable functional group, for example, styrene, isobornyl acrylate, acryloyl morpholine, diethylene glycol diacrylate, triethylene glycol diacrylate, or the like. You can also. The reaction temperature is preferably from room temperature to 100 ° C., and the reaction time is preferably from 1 to 10 hours.

The mixing ratio of the isocyanate prepolymer compound (A) and the polycaprolactone-modified hydroxyethyl (meth) acrylate (B) is 10 to 60 parts by weight of the isocyanate prepolymer compound (A) and the polycaprolactone-modified hydroxyethyl ( The amount of the (meth) acrylate (B) is preferably 40 to 90 parts by weight, and if necessary, dibutyltin dilaurate, dibutyltin diethylhexoate, dibutyltin sulfite, or the like can be used as a catalyst. The amount of these catalysts added
It is preferably 0.01 to 1 part by weight, particularly 0.1 to 1 part by weight.
It is preferably 0.5 parts by weight. Further, a polymerization inhibitor such as hydroquinone monomethyl ether may be used, and the amount of the polymerization inhibitor to be added is preferably 0.01 to 1 part by weight.

(2) Production of Ultraviolet-Curable Composition To produce the ultraviolet-curable composition of the present invention, the ultraviolet-curable urethane (meth) acrylate oligomer (C) obtained as described above, The photoinitiator (F) and, if desired, a compound (D) having an ultraviolet-curable functional group and / or an ultraviolet-curable silicone graft or block copolymer (E) are mixed. If necessary,
You may mix | blend a solvent, additives, such as a leveling agent and an ultraviolet absorber. Here, when the compound (D) having the ultraviolet-curable functional group is mixed, the viscosity of the obtained ultraviolet-curable composition can be reduced, and the amount of the solvent can be reduced to a high solid. Examples of the solvent include aromatic hydrocarbon solvents such as toluene and xylene, alcohol solvents such as methanol, ethanol, isopropyl alcohol, n-butanol and isobutanol, and ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. Ester solvents such as ethyl acetate, propyl acetate, butyl acetate and isobutyl acetate are used alone or as a mixed solvent. As the leveling agent, an acrylic copolymer or a silicone-based or fluorine-based one is used. As the ultraviolet absorber, a benzophenone-based, benzotriazole-based, oxalic anilide-based, triazine-based, or hindered amine-based one is used. Can be used.

The above-mentioned UV-curable urethane (meth) acrylate oligomer (C), compound (D) having a UV-curable functional group, UV-curable silicone graft or block copolymer (E) and photoinitiator (F) Is 20 to 99: 0 to 40: 0 in terms of solid content ratio (weight).
~ 40: preferably 0.5 to 10, more preferably 30 to
The ratio is preferably 90: 5 to 35: 5 to 35: 1 to 5.

The composition obtained as described above is irradiated with ultraviolet light.
Alternatively, the composition may be cured by irradiation with an electron beam.
You. Irradiation conditions when irradiating ultraviolet rays include mercury
Curing energy using a lamp, metal halide lamp, etc.
Is 100 to 1000 mj / cm ^TwoIt is preferred that
The irradiation conditions when irradiating the electron beam include acceleration
With a voltage of 150 to 250 keV and a dose of 1 to 5 Mrad
Preferably, there is.

As described above, by curing the ultraviolet curable composition of the present invention, the composition is excellent in adhesion to various materials, solvent resistance, chipping resistance, and secondary workability.
A surface functional material having excellent scratch resistance and also excellent self-healing properties when a scratch occurs is obtained. Here, when the compound (D) having the UV-curable functional group is contained in the UV-curable composition, the surface functional material becomes excellent in water resistance and adheres to the substrate. In addition, when the ultraviolet-curable silicone graft or block copolymer (E) is contained, the surface functional material has lubricity, water repellency, weather resistance, stain resistance, and blocking resistance. And so on.

The ultraviolet-curable composition of the present invention can be used for mobile phones, watches, compact discs, audio equipment,
Electrical and electronic equipment such as A equipment; Electronic material parts such as touch panels and anti-reflection plates of cathode ray tubes; Household appliances such as refrigerators, vacuum cleaners, microwave ovens; Interiors such as instrument panels and dashboards of automobiles; Body, bumper, spoiler, door knob, handle, headlamp, gasoline tank for motorcycle; automotive parts such as plated, evaporated and sputtered aluminum wheels and door mirrors; carport roof, daylighting roof; polyvinyl chloride, acrylic resin Plastic products such as polyethylene terephthalate, polycarbonate, and ABS resin, films and sheets; woodwork products such as stairs, floors, desks, chairs, closets, and other furniture; surface of sheet-like base materials such as cloth and paper, etc. Paints or coatings used in fields where abrasion resistance is required It is suitable as grayed agent.

The UV-curable composition may be applied to the substrate by a conventional method, and may be applied by, for example, air spray, airless spray, electrostatic coating, roll coater, flow coater, spin coating, or the like. The thickness of the coating film is preferably about 1 to 100 μm.

[0036]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples and the like, but the scope of the present invention is not limited to these Examples. [Synthesis Example 1] Synthesis of ultraviolet-curable urethane acrylate (C) -1 92 parts by weight of xylene (hereinafter simply referred to as "parts" ) was placed in a 500 ml flask equipped with a stirrer, a thermometer and a condenser.
That. ), Isocyanurate modified type of tolylene diisocyanate (Takeda Pharmaceutical Co., Ltd., Takenate D-212, active ingredient: 50%, NCO: 7.6%) 1
00 parts, polycaprolactone-modified hydroxyethyl acrylate (Placcel F, manufactured by Daicel Chemical Industries, Ltd.)
A3) 92 parts, dibutyltin dilaurate 0.02 parts,
And 0.2 part of hydroquinone monomethyl ether were charged, and the temperature was raised to 70 ° C. Thereafter, the temperature was maintained at the same temperature for 3 hours to terminate the reaction, thereby obtaining urethane acrylate C-1 having a solid content of 50% by weight.

Synthesis Example 2 Synthesis of ultraviolet-curable urethane acrylate (C) -2 In a flask similar to Synthesis Example 1, 170 parts of toluene and a TMP adduct-modified type of tolylene diisocyanate (Coronate, manufactured by Nippon Polyurethane Industry Co., Ltd.) L, active ingredient: 75%, NCO: 13.2%), 100 parts, polycaprolactone-modified hydroxyethyl acrylate (Placcel FA2, manufactured by Daicel Chemical Industries, Ltd.), 120 parts,
0.03 part of dibutyltin dilaurate and 0.3 part of hydroquinone monomethyl ether were charged and heated to 70 ° C. Thereafter, the temperature was maintained at the same temperature for 3 hours to terminate the reaction, thereby obtaining urethane acrylate C-2 having a solid content of 50% by weight.

Synthesis Example 3 Synthesis of ultraviolet-curable urethane acrylate (C) -3 In a flask similar to Synthesis Example 1, 108 parts of toluene and an isocyanurate-modified type of hexamethylene diisocyanate (Takenate, manufactured by Takeda Pharmaceutical Co., Ltd.) D-170
N, active ingredient: 100%, NCO: 20.9%) 50
Part, polycaprolactone-modified hydroxyethyl acrylate (Placcel FA, manufactured by Daicel Chemical Industries, Ltd.)
1) 58 parts, 0.02 part of dibutyltin dilaurate, and 0.2 part of hydroquinone monomethyl ether were charged and heated to 70 ° C. Thereafter, the temperature was maintained at the same temperature for 3 hours to terminate the reaction, thereby obtaining urethane acrylate C-3 having a solid content of 50% by weight.

[Synthesis Example 4] Synthesis of UV-curable urethane acrylate (C) -4 In a flask similar to Synthesis Example 1, 145 parts of toluene and an isocyanurate-modified type of hexamethylene diisocyanate (Takenate, manufactured by Takeda Pharmaceutical Co., Ltd.) D-170
N, active ingredient: 100%, NCO: 20.9%) 50
Part, polycaprolactone-modified hydroxyethyl acrylate (Placcel FA, manufactured by Daicel Chemical Industries, Ltd.)
2) 95 parts, 0.02 part of dibutyltin dilaurate, and 0.2 part of hydroquinone monomethyl ether were charged and heated to 70 ° C. Thereafter, the temperature was maintained at the same temperature for 3 hours to terminate the reaction, thereby obtaining urethane acrylate C-4 having a solid content of 50% by weight.

Synthesis Example 5 Synthesis of UV-Curable Urethane Acrylate (C) -5 In a flask similar to Synthesis Example 1, 95 parts of toluene and an isocyanurate-modified type of hexamethylene diisocyanate (Takenate, manufactured by Takeda Pharmaceutical Co., Ltd.) D-170
N, active ingredient: 100%, NCO: 20.9%) 20
Part, polycaprolactone-modified hydroxyethyl acrylate (Placcel FA, manufactured by Daicel Chemical Industries, Ltd.)
5) 75 parts, 0.02 part of dibutyltin dilaurate, and 0.3 part of hydroquinone monomethyl ether were charged and heated to 70 ° C. Thereafter, the temperature was maintained at the same temperature for 3 hours to complete the reaction, and urethane acrylate C-5 having a solid content of 50% by weight was obtained.

[Synthesis Example 6] Synthesis of UV-curable urethane acrylate (C) -6 In a flask similar to Synthesis Example 1, 80 parts of ethyl acetate and a TMP adduct-modified type of hexamethylene diisocyanate (Dainippon Ink Chemical Industry Co., Ltd.) Made, Barnock DN
-950, active ingredient: 75%, NCO: 12%) 50
Part, polycaprolactone-modified hydroxyethyl acrylate (Placcel FA, manufactured by Daicel Chemical Industries, Ltd.)
2) 55 parts, 0.03 part of dibutyltin dilaurate, and 0.2 part of hydroquinone monomethyl ether were charged and heated to 60 ° C. Thereafter, the temperature was maintained at the same temperature for 4 hours to terminate the reaction, thereby obtaining urethane acrylate C-6 having a solid content of 50% by weight.

[Synthesis Example 7] Synthesis of UV-curable urethane acrylate (C) -7 In a flask similar to Synthesis Example 1, 78 parts of methyl isobutyl ketone and a TMP adduct modified type of hexamethylene diisocyanate (Dainippon Ink and Chemicals, Inc.) Made by the company, Barnock DN-950, active ingredient: 75%, NCO: 1
2%) 40 parts, polycaprolactone-modified hydroxyethyl acrylate (Placcel FA3, manufactured by Daicel Chemical Industries, Ltd.) 58 parts, dibutyltin dilaurate 0.0
2 parts and 0.2 part of hydroquinone monomethyl ether were charged and heated to 70 ° C. Thereafter, the temperature was maintained at the same temperature for 3 hours to terminate the reaction, and urethane acrylate C-7 having a solid content of 50% by weight was obtained.

Synthesis Example 8 Synthesis of UV-Curable Urethane Acrylate (C) -8 In a flask similar to Synthesis Example 1, 124 parts of toluene and a biuret-modified type of hexamethylene diisocyanate (Takenate D, manufactured by Takeda Pharmaceutical Co., Ltd.) -165N,
Active ingredient: 100%, NCO: 23.3%) 40 parts, polycaprolactone-modified hydroxyethyl acrylate (Placcel FA2, manufactured by Daicel Chemical Industries, Ltd.) 8
4 parts, dibutyltin dilaurate 0.02 parts and hydroquinone monomethyl ether 0.2 parts
The temperature was raised to ° C. Thereafter, the reaction was terminated by holding at the same temperature for 3 hours, and urethane acrylate C having a solid content of 50% by weight.
-8 was obtained.

Synthesis Example 9 Synthesis of UV-Curable Urethane Acrylate (C) -9 In a flask similar to Synthesis Example 1, 114 parts of toluene and a biuret-modified type of hexamethylene diisocyanate (Takenate D, manufactured by Takeda Pharmaceutical Co., Ltd.) -165N,
Active ingredient: 100%, NCO: 23.3%) 30 parts, polycaprolactone-modified hydroxyethyl acrylate (Placcel FA3, manufactured by Daicel Chemical Industries, Ltd.) 8
4 parts, dibutyltin dilaurate 0.02 parts and hydroquinone monomethyl ether 0.2 parts
The temperature was raised to ° C. Thereafter, the reaction was terminated by holding at the same temperature for 3 hours, and urethane acrylate C having a solid content of 50% by weight.
-9 was obtained.

[Synthesis Example 10] Synthesis of UV-curable urethane acrylate (C) -10 In a flask similar to Synthesis Example 1, 120 parts of toluene and a TMP adduct modified type of xylylene diisocyanate (Takenate, manufactured by Takeda Pharmaceutical Co., Ltd.) D-110N,
100 parts of active ingredient: 75%, NCO: 11.5%), polycaprolactone-modified hydroxyethyl acrylate (Placcel FA1 manufactured by Daicel Chemical Industries, Ltd.) 7
0 parts, dibutyltin dilaurate 0.02 parts, and hydroquinone monomethyl ether 0.2 parts.
The temperature was raised to ° C. Thereafter, the reaction was terminated by holding at the same temperature for 3 hours, and urethane acrylate C having a solid content of 50% by weight.
-10 was obtained.

Synthesis Example 11 Synthesis of UV-Curable Urethane Acrylate (C) -11 In a flask similar to Synthesis Example 1, 148 parts of toluene and a TMP adduct modified type of isophorone diisocyanate (Takenate D, manufactured by Takeda Pharmaceutical Co., Ltd.) −140N,
100 parts of active ingredient: 75%, NCO: 10.8%), polycaprolactone-modified hydroxyethyl acrylate (Placcel FA2, manufactured by Daicel Chemical Industries, Ltd.) 9
8 parts, dibutyltin dilaurate 0.02 parts and hydroquinone monomethyl ether 0.2 parts
The temperature was raised to ° C. Thereafter, the reaction was terminated by holding at the same temperature for 3 hours, and urethane acrylate C having a solid content of 50% by weight.
-11 was obtained.

Synthesis Example 12 Synthesis of UV-Curable Urethane Acrylate (C) -12 In a flask similar to Synthesis Example 1, 98 parts of toluene and a TMP adduct modified type of isophorone diisocyanate (Takenate D, manufactured by Takeda Pharmaceutical Co., Ltd.) -140N, 40 parts of active ingredient: 75%, NCO: 10.8%), 78 parts of polycaprolactone-modified hydroxyethyl acrylate (Placcel FA5, manufactured by Daicel Chemical Industries, Ltd.), 0.02 part of dibutyltin dilaurate, and hydroquinone monomethyl ether 0.2 part was charged and the temperature was raised to 70 ° C. Thereafter, the temperature was maintained at the same temperature for 3 hours to terminate the reaction, and a urethane acrylate C-12 having a solid content of 50% by weight was used.
I got

Synthesis Example 13 Synthesis of ultraviolet-curable silicone copolymer (E) -1 In a 500 ml flask equipped with a stirrer, thermometer, condenser and nitrogen gas inlet tube, 50 parts of toluene and 50 parts of methyl isobutyl ketone were placed. Parts and 20 parts of a polydimethylsiloxane macromonomer (FM0721, manufactured by Chisso Corporation, active ingredient: 100%, molecular weight 5000),
Under reflux at 113 ° C., 30 parts of methyl methacrylate, 30 parts of butyl methacrylate, and 20 isocyanateethyl methacrylate (Karenz MOI, manufactured by Showa Denko KK)
Part and 2,2-azobis-2-methylbutyronitrile 5
Part of the mixed solution was added dropwise over 2 hours. afterwards,
The polymerization was terminated at the same temperature for 5 hours to obtain a copolymer solution having a solid content of 50% by weight.

To 200 parts of the obtained copolymer solution, 80 parts of toluene, 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 And heated to 70 ° C. Thereafter, the temperature was maintained at the same temperature for 5 hours to terminate the reaction, and an ultraviolet-curable silicone copolymer E-1 having a solid content of 50% by weight was obtained.

[Synthesis Example 14] Synthesis of UV-curable silicone copolymer (E) -2 In a flask similar to Synthesis Example 13, 50 parts of toluene, 50 parts of methyl isobutyl ketone, and a polydimethylsiloxane-based polymer initiator ( VPS-501, manufactured by Wako Pure Chemical Industries, Ltd.)
20 parts, 30 parts of methyl methacrylate, 30 parts of butyl methacrylate, and 20 parts of isocyanatoethyl methacrylate (Karenz MOI, manufactured by Showa Denko KK) were charged and heated to 90 ° C. Thereafter, the temperature was maintained at the same temperature for 6 hours to terminate the polymerization, thereby obtaining a copolymer solution having a solid content of 50% by weight.

To 200 parts of the obtained copolymer solution, 80 parts of toluene, 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 And heated to 70 ° C. Thereafter, the temperature was maintained at the same temperature for 5 hours to terminate the reaction, and an ultraviolet-curable silicone copolymer E-2 having a solid content of 50% by weight was obtained.

Example 1 80 parts of the urethane acrylate C-1 obtained in Synthesis Example 1, 10 parts of the ultraviolet-curable silicone copolymer E-1 obtained in Synthesis Example 13, and 9 parts of acryloylmorpholine , And 1 part of a photoinitiator (Irgacure 184, manufactured by Ciba Geigy Co., Ltd.), and this was dried on a polycarbonate plate and an aluminum plate to a film thickness of 1%.
It was coated so as to have a thickness of 0 to 15 μm. 60 ℃
Drying process in a drying oven for 5 minutes, then one lamp output
It was cured at a conveyor speed of 3 m / min by a 20 W / cm UV drying oven, and this was used as a test plate.

Example 2 85 parts of the urethane acrylate C-2 obtained in Synthesis Example 2, 10 parts of the ultraviolet-curable silicone copolymer E-2 obtained in Synthesis Example 14, and 4 parts of acryloylmorpholine , And 1 part of a photoinitiator (Darocur 1173, manufactured by Ciba Geigy Corporation). Using this mixture, a test plate was manufactured in the same manner as in Example 1.

Example 3 89 parts of the urethane acrylate C-3 obtained in Synthesis Example 3 were mixed with an ultraviolet-curable silicone graft copolymer (GUA23 manufactured by Toa Gosei Co., Ltd.).
5) and 1 part of a photoinitiator (Darocur 1173, manufactured by Ciba Geigy). Using this mixture, a test plate was manufactured in the same manner as in Example 1.

Example 4 80 parts of the urethane acrylate C-4 obtained in Synthesis Example 4, 10 parts of the ultraviolet-curable silicone copolymer E-1 obtained in Synthesis Example 13, 9 parts of styrene, And 1 part of a photoinitiator (Irgacure 184, manufactured by Ciba Geigy Co., Ltd.). Using this mixture, a test plate was manufactured in the same manner as in Example 1.

Example 5 80 parts of the urethane acrylate C-5 obtained in Synthesis Example 5, 10 parts of the ultraviolet-curable silicone copolymer E-1 obtained in Synthesis Example 13, triethylene glycol diacrylate 9 parts (Kyoeisha Chemical Co., Ltd., light acrylate 3EG-A) and a photoinitiator (Ciba Geigy Co., Ltd., Irgacure 184)
Was blended in one part. Using this mixture, a test plate was manufactured in the same manner as in Example 1.

Example 6 89 parts of the urethane acrylate C-6 obtained in Synthesis Example 6 were mixed with an ultraviolet-curable silicone graft copolymer (GUA23 manufactured by Toa Gosei Co., Ltd.).
5) and 1 part of a photoinitiator (Darocur 1173, manufactured by Ciba Geigy). Using this mixture, a test plate was manufactured in the same manner as in Example 1.

Example 7 89 parts of the urethane acrylate C-7 obtained in Synthesis Example 7, 10 parts of the ultraviolet-curable silicone copolymer E-2 obtained in Synthesis Example 14, and a photoinitiator ( Circa Geigy Co., Ltd., Irgacure 18
4) was blended in an amount of 1 part. Using this mixture, Example 1
A test plate was manufactured in the same manner as described above.

Example 8 99 parts of the urethane acrylate C-8 obtained in Synthesis Example 8 and 1 part of a photoinitiator (Darocur 1173, manufactured by Ciba-Geigy Co., Ltd.) were blended. Using this mixture, a test plate was manufactured in the same manner as in Example 1.

Example 9 80 parts of the urethane acrylate C-9 obtained in Synthesis Example 9, 10 parts of the ultraviolet-curable silicone copolymer E-1 obtained in Synthesis Example 13, 9 parts of styrene, And 1 part of a photoinitiator (Irgacure 184, manufactured by Ciba Geigy Co., Ltd.). Using this mixture, a test plate was manufactured in the same manner as in Example 1.

Example 10 99 parts of the urethane acrylate C-10 obtained in Synthesis Example 10 and 1 part of a photoinitiator (Irgacure 184, manufactured by Ciba Geigy Co., Ltd.) were blended. Using this mixture, a test plate was manufactured in the same manner as in Example 1.

Example 11 89 parts of the urethane acrylate C-11 obtained in Synthesis Example 11 was mixed with an ultraviolet-curable silicone graft copolymer (GUV, manufactured by Toa Gosei Co., Ltd.).
235) and 1 part of a photoinitiator (Darocure 1173, manufactured by Ciba Geigy Corporation). Using this mixture, a test plate was manufactured in the same manner as in Example 1.

Example 12 80 parts of the urethane acrylate C-12 obtained in Synthesis Example 12, 10 parts of the ultraviolet-curable silicone copolymer E-1 obtained in Synthesis Example 13,
9 parts of acryloylmorpholine and 1 part of a photoinitiator (Irgacure 184, manufactured by Ciba-Geigy) were blended. Using this mixture, a test plate was manufactured in the same manner as in Example 1.

Comparative Example 1 84 parts of dipentaerythritol hexaacrylate (manufactured by Toa Gosei Co., Ltd., M-400) and N-vinylpyrrolidone (manufactured by Toa Gosei Co., Ltd.)
M-150) and 2 parts of a photoinitiator (Irgacure 184, manufactured by Ciba-Geigy). Using this mixture, a test plate was produced in the same manner as in Example 1 so that the coating thickness when dried was 5 μm.

Comparative Example 2 40 parts of dipentaerythritol hexaacrylate (M-400, manufactured by Toagosei Co., Ltd.), 58 parts of the ultraviolet-curable silicone copolymer E-1 obtained in Synthesis Example 13, and Two parts of a photoinitiator (Irgacure 184, manufactured by Ciba Geigy Corporation) was blended. Using this mixture, a test plate was produced in the same manner as in Example 1 so that the coating thickness when dried was 5 μm.

[Test Examples] Examples 1 to 12 and Comparative Examples 1 to
The test plate obtained in 2 was evaluated for adhesion, surface tackiness, water resistance, acid resistance, alkali resistance, impact resistance, bending resistance, scratch resistance, and solvent resistance. For the impact resistance and the bending resistance, a test plate of an aluminum plate was used, and for the evaluations other than the impact resistance and the bending resistance, a test plate of a polycarbonate plate was used.

The adhesion was evaluated by a cross cut cellophane tape peel test. The tackiness on the surface was determined by finger touch.
The water resistance was evaluated by immersing in tap water at 40 ° C. for 120 hours. The acid resistance was evaluated by performing a spot test at 20 ° C. for 24 hours using 0.1 N sulfuric acid. The alkali resistance was evaluated by performing a spot test at 20 ° C. for 24 hours using 0.1 N sodium hydroxide. The impact resistance was tested using a Dupont type impact tester under the conditions of 1 / 4φ, 500g × 50cm,
evaluated. Flex resistance was evaluated under the test condition of 0T. Scratch resistance was measured using steel wool of # 000 and 500
The haze value (%) after rubbing 50 times with a load of g was evaluated. The solvent resistance was evaluated by rubbing toluene 100 times. Table 1 shows the results.

[0068]

[Table 1] ：: extremely good □: generally good △: slightly problematic ×: poor

As apparent from Table 1, Examples 1 to 12
Is particularly excellent in impact resistance and bending resistance as compared with the test plates of Comparative Examples 1 and 2.

[0070]

The composition obtained by curing the ultraviolet-curable composition of the present invention has excellent scratch resistance, solvent resistance, chipping resistance,
A surface functional material having crack resistance and excellent secondary workability and adhesion to various materials.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 183/07 C09D 183/07 (72) Inventor Shigekazu Teranishi 8th Ninomachi, Mizuho-ku, Nagoya-shi, Aichi Prefecture No. 3 Inside the Research Laboratory of Natco Corporation (72) Inventor Kozo Fujii Nauchiko, Oji, Miyoshi-machi, Nishikamo-gun, Aichi Prefecture (72) Inventor Toshikatsu Miyako Utsugoe, Natsuki, Miyoshi-machi, Nishikamo-gun, Aichi Prefecture (72) ) Inventor Susumu Kawakami 8-3, Ninocho, Mizuho-ku, Nagoya-shi, Aichi F-term in the laboratory of NATCO Corporation (reference) 4J011 AA05 AC04 BA03 QA02 QA03 QA07 QA08 QA09 QA13 QA23 QA24 QA25 QA32 QA34 QA35 QA38 QA39 QB03 QB12 QB16 QB19 QB24 QB25 SA02 SA22 SA34 SA63 SA64 SA72 SA75 SA78 SA84 UA01 UA03 VA01 WA02 4J027 AA02 AB02 AB03 AB10 AB28 AC03 AC04 AC06 AE01 AF05 AF06 AG03 AG1 2 AG23 AG24 AG27 AG28 AJ02 AJ08 AJ09 BA01 BA03 BA04 BA05 BA06 BA07 BA08 BA09 BA10 BA12 BA13 BA15 BA19 BA21 BA23 BA24 BA26 CA10 CB10 CC05 CC06 CD08 4J034 CA05 CB04 CB07 CC02 FA02 FB01 FC01 FD01 FE02 GA07 HA07 HA07 HA07 HA08 HC03 HC12 HC13 HC17 HC22 HC35 HC45 HC46 HC52 HC54 HC61 HC64 HC67 HC71 HC73 JA42 LA12 LA13 LA23 LA33 RA03 RA07 RA09 RA10 RA12 RA14 4J038 DG261 FA011 FA041 FA111 FA121 FA151 FA211 FA251 FA261 FA271 FA281 KA03 NA03 NA05 NA07 NA10 PCB PC10

Claims (3)

[Claims] 1. An ultraviolet-curable urethane (meth) acrylate oligomer obtained by reacting an isocyanate prepolymer compound having three or more isocyanate groups in one molecule with a polycaprolactone-modified hydroxyethyl (meth) acrylate. And a photoinitiator. 2. The composition according to claim 1, further comprising a compound having an ultraviolet-curable functional group and / or an ultraviolet-curable silicone graft or block copolymer copolymerizable with the ultraviolet-curable urethane (meth) acrylate oligomer. 2. The ultraviolet-curable composition according to 1. 3. A surface functional material obtained by curing the ultraviolet curable composition according to claim 1.