JP2003137964A - Urethane (meth)acrylate containing ultraviolet- absorbing functional group, and composition thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ultraviolet-curable composition capable of forming a coated film having excellent weatherability over a long period. SOLUTION: This urethane (meth)acrylate containing an ultraviolet-absorbing functional group is obtained by reacting an ultraviolet-absorber with a polyol, a polyisocyanate and a hydroxy group-containing (meth)acrylate. The ultraviolet- curable resin composition contains the urethane (meth)acrylate.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a urethane (meth) acrylate and a composition containing the urethane (meth) acrylate as a curing component, which is useful mainly in paints and coating agents and in outdoor applications where weather resistance is particularly required. It is about.

[Prior art]

In recent years, solvent-free active energy ray-curable coating materials that cure with active energy rays have been widely used in place of organic solvent-based coating materials due to environmental pollution problems and energy saving. It contains a resin curable by active energy rays and a curable monomer,
Since the curable monomer also functions as a solvent, there is an advantage that it is not necessary to volatilize the solvent when forming a coating film. As the resin and the curable monomer that can be cured by this active energy ray, two or more (meth) acryloyl groups such as urethane (meth) acrylate, polyester (meth) acrylate, and epoxy (meth) acrylate are attached to the molecular terminals. Used are oligomers and various (meth) acrylic monomers.
Such paints and coatings have begun to be used outdoors.

However, the conventional ones have the drawback that when the cured coating film is exposed to light including ultraviolet rays such as sunlight, it undergoes deterioration and discoloration due to the ultraviolet rays, resulting in a decrease in the molecular weight and a decrease in the strength. In order to improve the weather resistance of paints and coating agents to ultraviolet rays, it is usual to add ultraviolet absorbers. Examples of such an ultraviolet absorber include 2- (2′-hydroxy-).
5'-methylphenyl) benzotriazole, 5-chloro-2- (2'-hydroxy-3 ', 5'-di-ter
benzotriazoles such as t-butylphenyl) benzotriazole and 2,4-dihydroxybenzophenone,
Benzophenone and the like such as 2-hydroxy-4-octyloxybenzophenone are known (see, for example, Japanese Patent Application Laid-Open Publication No. Sho-Sho).
62-181360, JP-A-2-173163, 3-2 81685
Gazette, and 9-157315 gazette, etc.).

[0004]

However, since these conventional ultraviolet absorbers are low-molecular-weight, low-boiling compounds, various disadvantages arise when they are simply added to paints or coating agents. For example, if a large amount of these low molecular weight ultraviolet absorbers are added, inhibition occurs during ultraviolet curing, making it difficult to cure. Therefore, the addition of the ultraviolet absorber is suppressed to a minimum amount, but in that case, the weather resistance of the paint or coating agent is not improved to a satisfactory degree. In addition, just adding an ultraviolet absorber causes bleed-out over time and oozes out from the surface of the coating film, so that the ultraviolet absorption effect becomes small and it becomes impossible to maintain stable weather resistance for a long period of time.

[0005]

Therefore, as a result of intensive studies to solve the above problems, the present inventor has found that, instead of simply adding an ultraviolet absorber, it is used as a molecule of a urethane (meth) acrylate compound. It has been found that weather resistance can be maintained for a long period of time without being lost due to bleeding or evaporation of the ultraviolet absorber by chemically bonding it inside, and the present invention has been completed.

That is, the present invention relates to "the ultraviolet absorber (A) represented by the following formula (1), a polyol (B) optionally added, a polyisocyanate (C) and a hydroxy group-containing (meth) acrylate. UV-absorbing functional group-containing urethane (meth) acrylate obtained by reacting with (D)

[Chemical 2] <In the formula (1), R ¹ and R ² are a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, n and n ′ are integers of 4 to 8, respectively, and m and m ′ are 0 or 1 respectively. Is an integer of 20 and is nm, n'm 'or nm + n'm'
R ¹ and R ² may be the same or different from each other. >, And “the above-mentioned UV-absorbing functional group-containing urethane (meth) acrylate and (meth) acryloyl group-containing monomer and / or (meth) acryloyl group-containing oligomer (E), It is a functional group-containing active energy ray-curable urethane (meth) acrylate composition ".

The ultraviolet absorber (A) used in the present invention is a compound represented by the above formula (1). In the above formula (1), R ¹ and R ² are hydrogen atoms or have 1 to 10 carbon atoms.
Is an alkyl group. n and n'are 4 to 8 respectively
, M and m ′ are 0 or 1 to 20, respectively,
Preferably, it is an integer of 0-10. Where nm,
Of course, n'm 'and nm + n'm' R ¹ and R ² may be the same or different from each other. Particularly, in the above formula (1), it is preferable that R ¹ and R ² are hydrogen atoms, n and n ′ are 5, m + m ′ is 1 to 4, or both m and m ′ are 0. As long as they are within the above range, they can be used without particular limitation.

In the ultraviolet absorber (A) represented by the above formula (1), a compound having an alcoholic hydroxyl group, which is a compound in which m and m'in the formula (1) are represented by 0, is represented by the following formula (2): )

[Chemical 3] <In Formula (2), R ¹ and R ² are a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and n R ¹ and R ² may be the same or different from each other. n is also an integer obtained by subjecting a lactone represented by an integer of 4 to 8> to ring-opening addition polymerization. The method for producing the ultraviolet absorber is described in, for example, JP-A-10-265557, JP-A-2000-95849 and JP-A-2000-3.
No. 27736, etc. The compound having an alcoholic hydroxyl group, which is a compound in which m and m ′ in formula (1) are 0, is bis [3- (2H-benzotriazol-2-yl) -4-hydroxy-benzeneethanol] methane. Therefore, a synthetic product or a commercially available product (for example, a product name "MBEP" manufactured by Otsuka Chemical Co., Ltd.) can be used.

Examples of the lactone represented by the above formula (2) include ε-caprolactone, trimethyl-ε-caprolactone, monomethyl-ε-caprolactone, γ-butyrolactone and δ-valerolactone. Above all,
In the formula (2), R ¹ and R ² are hydrogen atoms, and n is 5 ε
-Caprolactone is industrially mass-produced and preferred because it is easily available. In addition, when only ε-caprolactone is used, both n and n ′ in the formula (1) are 5. An ultraviolet absorber in which at least one of m and m represented by the formula (1) is not 0 is a synthetic product or a commercially available product (for example, trade name “UVA1” manufactured by Daicel Chemical Industries, Ltd.).
03 ”or“ UVA 105 ”) can be used.

Urethane (meth) containing a UV-absorbing functional group
The ratio of the ultraviolet absorber (A) component in the acrylate is 0.1 to 0.1 of the number of moles of the hydroxy group-containing (meth) acrylate (D) added to the polyisocyanate.
It is an amount obtained by replacing 50%, preferably 1 to 30%. If it is less than 0.1%, the weather resistance cannot be exhibited,
If it exceeds 50%, the acrylic group content will decrease, and the curability and coating strength will decrease.

Examples of the polyol (B) added to the present invention as needed include polyester diols, polyether diols, polyadipate diols, polybutadiene diols, polycarbonate diols, ethoxylated bisphenol A and the like, without any particular limitation. A commercial item can be used. The molecular weight of the polyol (B) is 200 to 10,000, preferably 500 to 3000.
Is. More specific examples include polycaprolactone-based polyols, aromatic polyether-based polyols, aliphatic polyether-based polyols, and the like.

The polycaprolactone type polyols include ethylene glycol, diethylene glycol, 1,
It is obtained by reacting ε-caprolactone with 4-butanediol or the like. Triethylene glycol, dipropylene glycol, tripropylene glycol and the like may be used as well. Among these, polycaprolactone-based polyols are particularly preferable. These may be used alone or in combination of two or more. Further, the same type may be used in an amount of 2 mol or more.

Polyisocyanate (C) used in the present invention
Known polyisocyanates such as aromatic, aliphatic or alicyclic polyisocyanates or mixtures, adducts, modified products and polymers thereof can be used. Above all,
Tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hydrogenated diphenylmethane diisocyanate (H12MDI), polyphenylmethane polyisocyanate (crude MDI), modified diphenylmethane diisocyanate (modified MDI), xylylene diisocyanate (XDI), hydrogenated Xylylene diisocyanate (H-XDI), hexamethylene diisocyanate (HMDI), trimethylhexamethylene diisocyanate (TMXDI), isophorone diisocyanate (IPDI), norbornene diisocyanate (N
DI) and other polyisocyanates or trimer compounds of these isocyanates.

Hydroxy group-containing (meth) used in the present invention
As the acrylate (D), 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate, tripropylene glycol (meth) ) Acrylate, glycerol mono (meth) acrylate, glycerol di (meth) acrylate, glycerol methacrylate acrylate, polyhydric alcohols such as pentaerythritol triacrylate or mixed radical (meth) acrylate; caprolactone modified 2
Examples thereof include caprolactone-modified products of the above-mentioned hydroxy group-containing (meth) acrylates such as hydroxy (meth) acrylate. In the present invention, the description of (meth) acrylate means acrylate and / or methacrylate.

As the method for producing the urethane (meth) acrylate of the present invention, the ultraviolet absorber (A), the polyol (B) optionally added, the polyisocyanate (C), and the hydroxy group-containing (meth) are used. ) There is no particular limitation as long as it is a method of reacting the acrylate (D), and it can be produced by a known method. For example, (A), (B),
A method in which (C) and (D) are collectively mixed and reacted, (B)
And (C) are reacted to form a urethane isocyanate prepolymer containing one or more isocyanate groups per molecule, and then the prepolymer and (A) and (D) are reacted, or (C ) And (D)
To form a urethane isocyanate prepolymer containing one or more isocyanate groups per molecule, and then reacting the prepolymer with (A) and (B).

Depending on the order of the reaction, a mixture of compounds having the following structures is obtained. That is, the components (A), (B),
When (C) and (D) are mixed together and reacted, D-(-CB-) _n
A mixture of compounds represented by -CD and D-(-CB-) _n'- CA is obtained [n and n'1-15].

The above components (A), (B), (C), (D)
The mixing ratio of (A) / (B) / (C) / (D) =
0.005-1.0 / 0-2.0 / 2.0 / 0.5-2.
It is 0. If the ratio of the component (A) is less than 0.005 mol with respect to 2.0 mol of the component (C), the amount of the UV-absorbing functional group becomes relatively small, resulting in poor weather resistance.
Not preferable. On the contrary, if the ratio of the component (A) is more than 2.0 mol, the ultraviolet absorbing effect is not so improved and the physical properties of the cured coating film are adversely affected, which is not preferable. Ingredient (B)
If the ratio is larger than 2.0 mol with respect to 2.0 mol of the component (C), the curing characteristics will be deteriorated, which is not preferable.
When the ratio of the component (D) is less than 0.5 mol with respect to 2.0 mol of the component (C), the curing property is deteriorated, which is not preferable. On the contrary, if the ratio of the component (D) is more than 4.0 mol, the amount of the free component (D) becomes large and the physical properties of the cured coating film are adversely affected, which is not preferable. When (A), (C) and (D) are mixed together and reacted without using the above component (B), a mixture of DCD, DCA and D-(-CA-) mCD is obtained.

The reaction is preferably carried out in the presence of a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether or phenothiazine. The amount of these polymerization inhibitors is 1 to 1 with respect to the urethane (meth) acrylate produced.
0000 ppm, preferably 100-1000 pp
m, and more preferably 400 to 500 ppm.
If the amount of the polymerization inhibitor is less than 1 ppm with respect to the urethane (meth) acrylate, a sufficient polymerization inhibiting effect may not be obtained, and if it exceeds 10,000 ppm, various physical properties of the product may be adversely affected.

For the same reason, this addition reaction is preferably carried out in a molecular oxygen-containing gas atmosphere. The oxygen concentration is appropriately selected by mixing it with air or an inert gas in consideration of safety and the like. In this reaction, in order to obtain a sufficient reaction rate, this reaction is preferably carried out using a catalyst. As the catalyst, dibutyltin dilaurate, tin octylate, tin chloride, dibutyltin diethylhexoate and the like can be used, but dibutyltin dilaurate and dibutyltin diethylhexoate are preferable from the viewpoint of reaction rate. The amount of these catalysts is usually 1 to 3000 pp relative to urethane (meth) acrylate.
m, preferably 50 to 1000 ppm. When the amount of the catalyst is less than 1 ppm, a sufficient reaction rate may not be obtained, and when it is more than 3000 ppm, various physical properties of the product may be adversely affected.

The reaction is preferably carried out at a temperature of 130 ° C. or lower, more preferably 50 ° C. to 130 ° C. If it is lower than 50 ° C., a practically sufficient reaction rate may not be obtained, and if it is higher than 130 ° C., a double bond may be crosslinked by radical polymerization due to heat, and a gelled product may be formed. The reaction is usually carried out with 0.1% residual isocyanate groups.
Perform while analyzing by gas chromatography, titration method, etc. until it becomes less than or equal to%.

The active energy ray-curable urethane (meth) acrylate composition containing an ultraviolet absorbing functional group of the present invention contains urethane (meth) acrylate, which is a compound having each of the above structures, as a curable component. . It is not always necessary to use a photopolymerization initiator when curing this composition by electron beam irradiation, but a photopolymerization initiator is added when curing this composition by ultraviolet irradiation. As the photopolymerization initiator, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, 1-
(4-Isopropylphenyl) -2-hydroxy-2-
Methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-
Hydroxy-2-propyl) ketone, 2-methyl-1-
[4- (Methylthio) phenyl] -2-morpholinopropane-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, benzyl dimethyl ketal, benzophenone, benzoyl benzoic acid, benzoyl Methyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-
4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone,
2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,
4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate, benzyl, camphorquinone and the like can be mentioned. The content of the photopolymerization initiator is 1 to 10% by weight, preferably 1 to 5% by weight, more preferably about 3% by weight, based on the entire composition. If it is less than 1% by weight, the curing rate is slow, and conversely, even if it is used in an amount exceeding 10% by weight, the curing rate is not improved, and the physical properties of the cured product are impaired, which is not preferable.

The active energy ray-curable urethane (meth) acrylate composition of the present invention is the above urethane (meth)
It is obtained by blending a (meth) acryloyl group-containing monomer or a (meth) acryloyl group-containing oligomer (both may be abbreviated as (meth) acryloyl group-containing monomer (E) hereinafter) with acrylate. The (meth) acryloyl group-containing monomer (E) is not particularly limited, and a known (meth) acryloyl group-containing monomer can be used. Examples of the (meth) acryloyl group-containing monomer (E) include phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, polycaprolactone-modified hydroxyethyl acrylate, and dicyclopentenyl. Oxyethyl acrylate, acryloyl morpholine, 1,6
Hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane 3 mol propylene oxide Adduct tri (meth) acrylate, trimethylolpropane 6 mol propylene oxide adduct tri (meth) acrylate, glycerin propoxytri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol caprolactone modified product And polyfunctional monomers such as hexa (meth) acrylate.
A typical oligomer is urethane (meth).
Examples thereof include acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, acrylic (meth) acrylate, and unsaturated polyester. The blending amount of the (meth) acryloyl group-containing monomer (E) is 1 to 100 parts by weight of the ultraviolet absorbing functional group-containing urethane (meth) acrylate.
The amount is 1000 parts by weight, preferably 1 to 500 parts by weight, more preferably 1 to 100 parts by weight. If it is less than 1 part by weight, it is meaningless to add it as a solvent. Conversely, 1000
If it is more than parts by weight, the weather resistance of the cured coating film formed from the composition will be poor, which is not preferable.

In the present invention, it is possible to add an organic solvent or the like to adjust the viscosity, if necessary. Such organic solvents include ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate and methoxyethyl acetate; ether solvents such as diethyl ether, ethylene glycol methyl ether and dioxane. Solvents; aromatic solvents such as toluene and xylene; aliphatic solvents such as pentane and hexane; halogen solvents such as methylene chloride, chlorobenzene and chloroform; alcohol solvents such as isopropanol and butanol. The blending amount of this organic solvent is preferably 0 to 30% by weight based on the whole composition.

Further, the urethane (meth) acrylate composition is blended with various other additives within a range that does not impair the characteristics of the urethane (meth) acrylate composition as the active energy ray-curable resin composition. can do. Examples of such additives include fillers, dyes and pigments, leveling agents, ultraviolet absorbers, light stabilizers,
Examples thereof include antifoaming agents, dispersants, and thixotropic agents. The amount of these additives added is 0 with respect to the resin composition.
10 to 10 parts by weight, preferably 0.05 to 5 parts by weight.
The urethane (meth) acrylate composition is applied to an object and then cured by irradiation with active energy rays such as ultraviolet rays or electron rays.

A high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp or the like is used as a light source for ultraviolet irradiation. The irradiation time is
Although it depends on the type of light source, the distance between the light source and the coating surface, and other conditions, it is several tens of seconds at the longest, and usually several seconds. After irradiation with ultraviolet rays, heating can be performed as necessary to complete curing. In the case of electron beam irradiation, 50-
It is preferable to use an electron beam having an energy in the range of 1,000 KeV and to set the irradiation dose to 2 to 5 Mrad. Usually, an irradiation source with a lamp output of about 80 to 300 W / cm is used. The thickness of the cured coating film is usually about 50 to 300 μm.

As the object to be coated, plastics such as polyethylene terephthalate (PET), polymethacrylate, polycarbonate, ABS resin and vinyl chloride resin and those obtained by subjecting the plastics to metal vapor deposition,
Examples thereof include glass, wood, metal plate, paper and the like. The above plastics in which the urethane (meth) acrylate resin composition of the present invention is used as a paint or a coating agent,
Glass, wood, metal, paper, etc. are useful for various building materials for exterior and interior, window glass for houses, transportation equipment, daylighting glass and plastic lenses, contact lenses, inks, automobile headlamp covers, and the like. The urethane (meth) acrylate composition of the present invention is particularly useful for paints and coating agents having excellent weather resistance.

[0027]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In this example, bis [3- (2H-benzotriazol-2-yl) -4-, in which m and m ′ are both 0 among the ultraviolet absorbers represented by the formula (1),
Hydroxy-benzene ethanol] methane (Otsuka Chemical, trade name “MBEP”) was used. In the formula (1), R ¹ and R ² are hydrogen atoms, and n and n ′ are 5, m
+ M ′ is 6 and an ultraviolet absorber (trade name “UVA 103”) manufactured by Daicel Chemical Industries, Ltd. is used, wherein R ¹ and R ² in the formula (1) are hydrogen atoms, and n and n ′.
The ultraviolet absorber (trade name “UVA 105”) manufactured by Daicel Chemical Industries, Ltd. was used as the one having a value of 5 and m + m ′ of 10.

Example 1 <Synthesis of Urethane Acrylate (1)> Isophorone diisocyanate 444 g (2 mol) was charged into a 3 L flask equipped with a stirrer, a thermometer and a condenser, and the internal temperature was adjusted to 70 ° C., and then the number average molecular weight was 1000. 1000 g (1 mol) of polycaprolactone diol (trade name: Praxel 210, manufactured by Daicel Chemical Industries, Ltd.) was added, and when the residual isocyanate group became 5.7%, the ultraviolet absorber [m and m in the formula (1)] Compounds where'is 0 '
104 g (0.2 mol), 2-hydroxyethyl acrylate 209 g (1.8 mol), dibutyl tin laurate 0.25 g (150 ppm, addition amount to urethane acrylate) and hydroquinone monomethyl ether 0.84 g (500 ppm, addition to urethane acrylate) The amount of residual isocyanate groups is 0.1
The reaction was carried out until the content became not more than%, to obtain urethane acrylate (1).

Example 2 <Synthesis of Urethane Acrylate (2)> Only the amounts of the main components charged are shown below. The catalyst and the polymerization inhibitor have the same ppm numbers as in Example 1, and the reaction conditions are the same as in Example 1. Isophorone diisocyanate: 444 g (2 mol), polycaprolactone diol having a number average molecular weight of 1000 (Placcel 210, manufactured by Daicel Chemical Industries) 100
0 g (1 mol), UV absorber [R ¹ and R ² in the formula (1) are hydrogen atoms, n and n ′ are 5, and m + m ′ is 6; manufactured by Daicel Chemical Industries, trade name “UVA 10”
3 "]: 240 g (0.2 mol) and 2-hydroxyethyl acrylate: 209 g (1.8 mol) were used to obtain urethane acrylate (2).

Example 3 <Synthesis of Urethane Acrylate (3)> Only the amounts of the main components charged are shown below. The catalyst and the polymerization inhibitor have the same ppm numbers as in Example 1, and the reaction conditions are the same as in Example 1. Isophorone diisocyanate: 444 g (2 mol), polycaprolactone diol having a number average molecular weight of 1000 (Placcel 210, manufactured by Daicel Chemical Industries) 100
0 g (1 mol), ultraviolet absorber [in the formula (1), R ¹ and R ² are hydrogen atoms, n and n ′ are 5 and m + m ′ is 10]
Compound, manufactured by Daicel Chemical Industries, Ltd., trade name "UVA 10
5 ″]: 332 g (0.2 mol) and 2-hydroxyethyl acrylate: 209 g (1.8 mol) were used to obtain urethane acrylate (3).

Example 4 <Synthesis of urethane acrylate (4)> Only the amounts of the main components charged are shown below. The catalyst and the polymerization inhibitor have the same ppm numbers as in Example 1, and the reaction conditions are the same as in Example 1. Isophorone diisocyanate: 444 g (2 mol), polycaprolactone diol having a number average molecular weight of 1000 (Placcel 210, manufactured by Daicel Chemical Industries) 100
0 g (1 mol), UV absorber [R ¹ and R ² in the formula (1) are hydrogen atoms, n and n ′ are 5, and m + m ′ is 6; manufactured by Daicel Chemical Industries, trade name “UVA 10”
3 "]: 120 g (0.1 mol) and 2-hydroxyethyl acrylate: 220.4 g (1.9 mol) were used to obtain urethane acrylate (4).

Example 5 <Synthesis of Urethane Acrylate (5)> Only the amounts of the main components charged are shown below. The catalyst and the polymerization inhibitor have the same ppm numbers as in Example 1, and the reaction conditions are the same as in Example 1. Isophorone diisocyanate: 444 g (2 mol), polycaprolactone diol having a number average molecular weight of 1000 (Placcel 210, manufactured by Daicel Chemical Industries) 100
0 g (1 mol), UV absorber [R ¹ and R ² in the formula (1) are hydrogen atoms, n and n ′ are 5, and m + m ′ is 6; manufactured by Daicel Chemical Industries, trade name “UVA 10”
3 ″]: 480 g (0.4 mol) and 2-hydroxyethyl acrylate: 185.6 g (1.6 mol) were used to obtain urethane acrylate (5).

Example 6 <Synthesis of Urethane Acrylate (6)> Only the amounts of the main components charged are shown below. The catalyst and the polymerization inhibitor have the same ppm numbers as in Example 1, and the reaction conditions are the same as in Example 1. Isophorone diisocyanate: 444 g (2 mol), polycaprolactone diol having a number average molecular weight of 1000 (Placcel 210, manufactured by Daicel Chemical Industries) 100
0 g (1 mol), ultraviolet absorber [a compound in which R ¹ and R ² in the formula (1) are hydrogen atoms, n and n ′ are 5, and m + m ′ is 6] manufactured by Daicel Chemical Industries, Ltd., trade name “UVA 10
3 ”: 240 g (0.2 mol) and caprolactone-modified hydroxyethyl acrylate (Placcel FA2D, manufactured by Daicel Chemical Industries, Ltd.): 619 g (1.8 mol) were used to obtain urethane acrylate (6).

Example 7 <Synthesis of Urethane Acrylate (7)> Only the amounts of the main components charged are shown below. The catalyst and the polymerization inhibitor have the same ppm numbers as in Example 1, and the reaction conditions are the same as in Example 1. Isophorone diisocyanate: 444 g (2 mol), polycaprolactone diol having a number average molecular weight of 1000 (Placcel 210, manufactured by Daicel Chemical Industries) 100
0 g (1 mol), UV absorber [R ¹ and R ² in the formula (1) are hydrogen atoms, n and n ′ are 5, and m + m ′ is 6; manufactured by Daicel Chemical Industries, trade name “UVA 10”
3 ″]: 240 g (0.2 mol) and pentaerythritol triacrylate: 538.2 g (1.8 mol) were used to obtain a urethane acrylate (7).

Example 8 <Synthesis of Urethane Acrylate (8)> Only the amounts of the main components charged are shown below. The catalyst and the polymerization inhibitor have the same ppm numbers as in Example 1, and the reaction conditions are the same as in Example 1. Isophorone diisocyanate: 222 g (1 mol), ultraviolet absorber [R ¹ and R ² in the formula (1) are hydrogen atoms, n and n ′ are 5, and m + m ′ is 6 compound, manufactured by Daicel Chemical Industries, trade name “UVA 103 "]: 240 g
(0.2 mol), 2-hydroxyethyl acrylate:
Urethane acrylate (8) was obtained using 209 g (1.8 mol).

Example 9 <Synthesis of Urethane Acrylate (9)> Only the amounts of the main components charged are shown below. The catalyst and the polymerization inhibitor have the same ppm numbers as in Example 1, and the reaction conditions are the same as in Example 1. Hexamethylene diisocyanate isocyanurate-modified type (Takenate D-170N, manufactured by Takeda Pharmaceutical Co., Ltd.): 603 g (1 mol), ultraviolet absorber [R ¹ and R ² in the formula (1) are hydrogen atoms, and n and n ′ are 5] , M +
Compound with m'6, manufactured by Daicel Chemical Industries, Ltd., trade name "UV
A 103 "]: 360 g (0.3 mol) and 2-hydroxyethyl acrylate: 313.2 g (2.7 mol) were used to obtain urethane acrylate (9).

Example 10 <Synthesis of Urethane Acrylate (10)> Only the amounts of the main components charged are shown below. The catalyst and the polymerization inhibitor have the same ppm numbers as in Example 1, and the reaction conditions are the same as in Example 1. Ultraviolet absorber [Compound in which R ¹ and R ² in the formula (1) are hydrogen atoms, n and n ′ are 5 and m + m ′ is 6, manufactured by Daicel Chemical Industries, Ltd., trade name “UVA 103”]: 1200
g (1 mol), isophorone diisocyanate: 444 g
(2 mol), 2-hydroxyethyl acrylate: 23
Urethane acrylate (10) using 2 g (2 mol)
Got

Comparative Example 1 <Synthesis of Urethane Acrylate (11)> Only the amounts of the main components charged are shown below. The catalyst and the polymerization inhibitor have the same ppm numbers as in Example 1, and the reaction conditions are the same as in Example 1. Polycaprolactone diol having a number average molecular weight of 1000 (Plaxel 210, manufactured by Daicel Chemical Industries) 100
0 g (1 mol), isophorone diisocyanate: 444
g (2 mol), 2-hydroxyethyl acrylate: 2
32 g (2 mol) of urethane acrylate (1
1) was obtained. With respect to the urethane acrylates 1 to 11 obtained in Examples 1 to 10 and Comparative Example 1, the weather resistance of the cured coating film was examined in the following manner.

Example 11, Comparative Example 2 100 parts by weight of each urethane acrylate obtained in the above Examples and Comparative Examples and a photoinitiator (Irgacure 18
(4, manufactured by Ciba Specialty Chemicals) was mixed and applied so that the film thickness would be 100 microns, and then irradiation was performed 3 times at a conveyor speed of 5 m / min using a high pressure mercury lamp with a lamp output of 120 W / cm. Thus, a cured coating film was obtained.

Example 12 80 parts by weight of each urethane acrylate obtained in the above Examples and Comparative Examples, 20 parts by weight of tripropylene glycol diacrylate (TPGDA) and a photoinitiator (IRGACURE 184, manufactured by Ciba Specialty Chemicals) 3
After blending parts by weight and coating so as to have a film thickness of 100 microns, a high-pressure mercury lamp with a lamp output of 120 W / cm was used for irradiation twice at a conveyor speed of 5 m / min to obtain a cured coating film.

Test Example First, as initial data, the breaking elongation and color difference (ΔYI) of each coating film were measured. As a weather resistance test, a sunshine weather meter was used for 3000 hours. The test conditions are shown below. Model used: Ducycle sunshine weather meter WEL-SUN-DC, manufactured by Suga Test Instruments Co., Ltd. Light source:
Carbon arc, rainfall cycle: rain for 18 minutes every 120 minutes, temperature: black panel 80 ° C. The breaking elongation of each urethane acrylate was examined and the retention rate was calculated. The retention rate was calculated by the following formula. Retention rate (%) =
Elongation at break after 3000 hours / initial elongation at break * 100 with sunshine weather meter. The evaluation results are shown below. ⊚: 100% to 90%, ∘: 90% to 80%, Δ: 80
% -60%, x: 60% or less. Further, each urethane acrylate and the compound containing each urethane acrylate were tested for color difference (ΔY
I) and haze (ΔH) are shown, and the evaluation results are shown below. Regarding color difference and haze: ⊚: 5% or less, ∘: 5% to 10%, Δ: 10% to 1
5%, x: 15% or more The results of Examples 11 and 12 are shown in Tables 1 and 2.

[0042]

[Table 1]

[0043]

[Table 2]

[0044]

EFFECTS OF THE INVENTION From the ultraviolet-absorbing functional group-containing urethane (meth) acrylate of the present invention and the composition thereof, a coating film having excellent weather resistance is formed over a long period of time.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J027 AG03 AG10 AG23 AG27 BA07                       BA11 BA19 BA25 BA28 CB10                       CC05 CD08                 4J034 BA08 CA02 CA03 CA04 CB01                       CB02 CB03 CB07 CC12 CC30                       CC35 CC44 CC54 CC62 CC67                       DA01 DB03 DB07 DC02 DC12                       DC35 DC43 DF12 DG01 DG16                       FA01 FB01 FC01 FD01 HA01                       HA07 HC03 HC12 HC17 HC22                       HC46 HC52 HC63 HC67 HC71                       HC73 LA13 LA32 QB11 QB19                       RA07

Claims (4)

[Claims] 1. An ultraviolet absorber (A) represented by the following formula (1), a polyol (B) optionally added, a polyisocyanate (C) and a hydroxy group-containing (meth) acrylate (D). Ultraviolet absorbing functional group-containing urethane (meth) acrylate obtained by the reaction. [Chemical 1] <In the formula (1), R ¹ and R ² are a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, n and n ′ are integers of 4 to 8, respectively, and m and m ′ are 0 or 1 respectively. Is an integer of 20 and is nm, n'm 'or nm + n'm'
R ¹ and R ² may be the same or different from each other. > 2. The urethane (meth) containing an ultraviolet absorbing functional group according to claim 1, wherein R ¹ and R ² in the formula (1) are hydrogen atoms, n and n ′ are 5, and m + m ′ is 6 or 10. Acrylate. 3. The urethane (meth) acrylate containing an ultraviolet absorbing functional group according to claim 1, wherein m and m ′ in the formula (1) are 0. 4. An ultraviolet absorbing functional group-containing urethane (meth) acrylate and a (meth) acryloyl group-containing monomer and / or a (meth) acryloyl group-containing oligomer (E) according to claim 1 are contained. A UV-absorbing functional group-containing active energy ray-curable urethane (meth) acrylate composition.