JP3436321B2 - UV curable resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet curable resin composition which gives a cured coating film having high curability and high surface hardness even in an atmosphere containing oxygen.

[0002]

2. Description of the Related Art UV curable resins that are cured by ultraviolet rays have the characteristic of rapid curing, so paints, inks,
Widely used for applications such as adhesives and coatings. In particular, in a process that has a post-process such as stacking or winding a cured product immediately after curing, it is possible to take advantage of the feature that curing is particularly rapid, and the use of ultraviolet curable resins is progressing.

However, the ultraviolet curable resin has a drawback that when it is cured in air, the curing of the surface layer is slow, and the surface is contaminated or scratched in a subsequent process. Further, the UV curable resin which can be made by spray coating, gravure printing or the like and has a thin state of 2 to 3 μm or less has a defect that it does not cure in air. Many proposals have been made to overcome these drawbacks.

For example, it is known to blow an inert gas such as nitrogen gas to replace the atmosphere at the time of curing with the inert gas. In addition, an ultraviolet curable resin is added to diphenylisodecyl phosphite, and Use of a phosphorous ester compound such as click neopentatetraylbis (octadecyl) phosphite and a photopolymerization initiator in combination as an ultraviolet-curable resin composition is disclosed in JP-A-63-72740 and JP-A-63-72740. 64
-79213 publication.

[0005]

The above curing method using an inert gas has a drawback that the inert gas is expensive, and is not generally used in ultraviolet curing. The method of adding the phosphite compound and the photopolymerization initiator to the ultraviolet curable resin is a simple method, but the addition of the photopolymerization initiator causes a decrease in the physical properties of the coating film, such as a decrease in the surface hardness. There is a drawback that

An object of the present invention is to provide an ultraviolet curable resin composition which gives a cured coating film having high curability and high surface hardness even in an atmosphere containing oxygen.

[0007]

Means for Solving the Problems The inventors of the present invention have made earnest studies in view of such circumstances, and as a result, an ultraviolet-curable resin containing a compound having radical polymerizability as a main component has photopolymerization initiation ability. When a phosphite ester compound having a group is added as an essential component, it is found that a cured coating film having extremely high curability and high surface hardness can be obtained as compared with the method in an atmosphere where oxygen is present, The present invention has been completed.

That is, the present invention relates to an ultraviolet-curable resin composition containing a radically polymerizable compound (A) as a main component, which is a phosphite compound (B) having a group capable of initiating photopolymerization. The present invention provides an ultraviolet-curable resin composition containing:

The ultraviolet-curable resin composition of the present invention includes a radically polymerizable compound (A), for example, a radically polymerizable prepolymer (A ₁ ) and / or a radically polymerizable monomer (A ₂ ). Etc. as a main component, and also contains a phosphite compound (B) having a group having a photopolymerization initiation ability as an essential component, and further contains a non-reactive resin, an additive, a filler, if necessary.
Other components, for example, a resin composition in which a photopolymerization initiator and the like are used in combination are included.

In the usual case, the radical-polymerizable prepolymer (A ₁ ) and the radical-polymerizable monomer (A ₂ ) are appropriately mixed and used. Examples of the radical-polymerizable prepolymer (A ₁ ) include urethane (meth) acrylates having a molecular weight of 500 or more,
Polyester (meth) acrylate, epoxy (meth)
Acrylate, polybutadiene (meth) acrylate,
Silicone (meth) acrylate, polyether (meth) acrylate,

(Meth) acrylic compounds such as melamine (meth) acrylate, phosphazene (meth) acrylate, and acrylic copolymers having (meth) acryloyl group introduced therein; main chains and sides of polybutadiene, unsaturated polyester compounds, etc. Compounds having an unsaturated bond in the chain; allyl group, vinyl group, vinyl ether group, maleimide group,
A compound having a radically polymerizable double bond such as a (meth) acrylamide group;

Examples thereof include compounds which cause a radical addition reaction such as thiol compounds and amino compounds. These compounds may be appropriately selected and used so as to satisfy the required physical properties, and usually have a molecular weight of 500 to 30,000.
Those of different grades are used alone or as a mixture.

The radical-polymerizable monomer (A ₂ ) may be a compound having a molecular weight of less than 500 and capable of radical polymerization or radical addition reaction in a bulk or liquid state, such as a (meth) acrylic compound, Examples thereof include unsaturated polyester compounds, vinyl compounds, vinyl ether compounds, maleimide compounds, (meth) acrylamide compounds, thiol compounds and amino compounds. Among them, a (meth) acrylic compound, a (meth) acrylamide compound, and a vinyl ether compound are preferable because of their high reactivity.

Specific examples of the radically polymerizable monomer (A ₂ ) include (meth) acrylamide,
(Meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,

Glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, N-methylmaleimide, N-phenylmaleimide, diethyleneglycol di (meth). Acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanedi (meth) acrylate
Acrylate,

Bisphenol A dioxydiethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 1,4-butanediol di (meth) acrylate, N-vinylpyrrolidone, tripropylene. Examples thereof include glycol divinyl ether.

Prepolymer (A ₁ ) having radical polymerizability and monomer (A ₂ ) having radical polymerizability
The mixing ratio in the case of mixing and using is not particularly limited, but in the total 100% by weight of the radical-polymerizable prepolymer (A ₁ ) and the radical-polymerizable monomer (A ₂ ), the radical-polymerizable Having monomer (A
₂ ) The content is usually 50% by weight or less, preferably 3 to 3
The ratio is 0% by weight.

When a volatile monomer such as (meth) acrylic acid lower alkyl ester is used, in order to prevent problems such as bad odor and toxicity caused by evaporation during curing,
Smaller amount than the above blending ratio, for example 3 to 15% by weight
It is preferable to use it in a ratio such that

As the phosphite compound (B) used in the present invention, any phosphite compound having a group capable of initiating photopolymerization can be used. The group capable of initiating photopolymerization may be any group that takes any reaction mode as long as it is a group capable of generating an active species that initiates a reaction involving a radical. It refers to a group or the like that produces an active species that starts a reaction such as an addition reaction.

There are two types of reaction modes for generating active species that initiate a reaction involving a radical. One is a group that is cleaved in the molecule by light to generate an active species, for example, a benzoin ether group, benzyl ketal. Group, acetophenone group, α-hydroxyacetophenone group, chloroacetophenone group, α-aminoacetophenone group, acylphosphine oxide group, α-dicarbonyl group, α-acyl oxime group and the like.

The other is a group that causes an intermolecular hydrogen abstraction reaction to generate an active species, for example, a benzophenone group, a thioxanthone group, a biimidazole group, an acridone group, an anthraquinone group, a phenanthrenequinone group, and camphorquinone. Groups and the like. Preferably, it is a group in which the bond is cleaved in the molecule by light to generate an active species, and among them, the α-hydroxyacetophenone group is easy to introduce into the phosphite compound and excellent in photopolymerization initiation ability. Particularly preferred.

Typical examples of the phosphite compound (B) having a group having a photopolymerization initiating ability used in the present invention are shown by the general formulas (1) to (5).

[0023]

[Chemical 2]

[In the above general formula (1), n is an integer of 1 to 3, R is a group having a photopolymerization initiating ability, and R ₁ is an alkyl group, an aryl group or an aralkyl group. However, R ₁ may have a substituent, and examples of the substituent include halogen, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, an alkanoyl group, a cyano group, a hydroxyl group and an amino group. ]

[0025]

[Chemical 3]

[In the above general formula (2), n is an integer of 1 to 2, m is an integer of 0 to 2, R is a group having a photopolymerization initiating ability, and R is
₁ is an alkyl group, an aryl group or an aralkyl group. However, R ₁ may have a substituent, and examples of the substituent include halogen, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, an alkanoyl group, a cyano group, a hydroxyl group and an amino group. R ₂ is an alkylene group, an arylene group or an aralkylene group,
Also, carbon-carbon bond, ether bond, ester bond,

It may optionally contain at least one bond selected from the group consisting of an amide bond, a urethane bond, a thioether bond and an imide bond. R ₂ may further have a substituent, and examples of the substituent include halogen,
Examples thereof include an alkoxy group, an alkoxycarbonyl group, an acyloxy group, an alkanoyl group, a cyano group, a hydroxyl group and an amino group. ]

[0028]

[Chemical 4]

[In the above general formula (3), R is a group having a photopolymerization initiating ability, and R ₃ is an alkylene group, an arylene group or an aralkylene group. However, R ₃ may optionally contain at least one bond selected from the group consisting of a carbon-carbon bond, an ether bond, an ester bond, an amide bond, a urethane bond, a thioether bond and an imide bond. R ₃ may further have a substituent, and examples of the substituent include halogen, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, an alkanoyl group, a cyano group, a hydroxyl group and an amino group. ]

[0030]

[Chemical 5]

[In the above general formula (4), m is an integer of 0 to 1, R is a group having a photopolymerization initiating ability, and R ₁ is an alkyl group, an aryl group or an aralkyl group. However, R ₁ may have a substituent, and examples of the substituent include halogen, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, an alkanoyl group, a cyano group, a hydroxyl group and an amino group. R ₄ is a tetravalent aliphatic hydrocarbon group, 4
A valent aromatic group or a tetravalent cycloaliphatic group, and a carbon-carbon bond, an ether bond, an ester bond,

It may optionally contain at least one bond selected from the group consisting of an amide bond, a urethane bond, a thioether bond and an imide bond. R ₄ may further have a substituent, and examples of the substituent include halogen,
Examples thereof include an alkoxy group, an alkoxycarbonyl group, an acyloxy group, an alkanoyl group, a cyano group, a hydroxyl group and an amino group. ]

[0033]

[Chemical 6]

[In the above general formula (5), n is an integer of 0 to 2, m is an integer of 0 to 2, R is a group having a photopolymerization initiation ability,
R ₅ is a group capable of initiating photopolymerization, and R ₁ is an alkyl group, an aryl group or an aralkyl group. However, R ₁ may have a substituent, and examples of the substituent include halogen, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, an alkanoyl group, a cyano group, a hydroxyl group and an amino group. ]

Specific examples of R in the above general formulas (1) to (5), that is, a group having a group capable of initiating photopolymerization include 2-phenylketonepropyl and 2- (4-isopropylphenylketone). Propyl, 2- (4-dodecylphenylketone) propyl, 2-nonylphenylketonepropyl, 4- (2-hydroxy-2-propylketone)
Phenoxyethyl, cyclohexyl phenyl ketone, phenylacetophenone,

Nonylphenylacetophenone, 2-methoxy-2-phenylacetophenone, 4- (phenylketone) phenyl, 4- (4-phenylphenylketone)
Examples thereof include phenyl, thioxanthone, 2-ethylanthraquinone, 4- (2,4,6-trimethylbenzoylphenylphosphine oxide) phenyl and the like.

The phosphite compound (B) used in the present invention has, as described above, a group having a group capable of initiating photopolymerization and having a group which is cleaved in the molecule by light to produce an active species. The phosphoric acid ester compound (B ₁ ) is preferable, and for example, the following structural formulas (6) to (9)

[0038]

[Chemical 7]

Examples thereof include compounds represented by the following. Among them, a phosphite compound having an α-hydroxyacetophenone group as a group capable of initiating photopolymerization, for example, the following structural formulas (10) to (12)

[0040]

[Chemical 8]

Compounds represented by are preferred. In addition,
Examples of the phosphite compound (B) having a group capable of generating an active species by causing a hydrogen abstraction reaction between molecules as a group having a photopolymerization initiation ability include, for example, tri (4-benzoylphenyl) phosphite and di (4 -Benzoylphenyl) -isodecylphosphite, (4-benzoyl-
Phenyl) -diisodecyl phosphite, di (4-benzoylphenyl) pentaerythritol diphosphite and the like can be mentioned.

As the phosphite compound (B) used in the present invention, any phosphite compound having a group having a photopolymerization initiation ability as described above can be used. It is preferable to use a phosphite compound (B ₂ ) having a group having photopolymerization initiation ability and a> P-O-aromatic ring unit, since curability is improved and a compound having high surface hardness is obtained. .

Further, it is more preferable that the group having a photopolymerization initiating ability of the phosphite compound (B ₂ ) is a group capable of cleaving a bond in the molecule by light to generate an active species.
The preferred phosphite compound as the (B _2), for example the following structural formulas (13) to (19)

[0044]

[Chemical 9]

[0045]

[Chemical 10]

[0046]

[Chemical 11]

And the like. Further, the phosphite compound (B) used in the present invention has a high content of a group having a photopolymerization initiation ability, is easy and inexpensive to produce, and has improved curability and high surface hardness. From the viewpoint of obtaining, the phosphite ester compound (B ₃ ) represented by the general formula (1) is also preferable, and for example, the following structural formulas (20) to (21)

[0048]

[Chemical 12]

Examples thereof include compounds represented by The addition amount of the phosphite compound (B) having a group capable of initiating photopolymerization is usually 0.0001 with respect to 100 parts by weight of the total amount of the compound (A) having radical polymerizability.
-30 parts by weight, preferably 0.1-10 parts by weight.

Further, the photopolymerization initiator (C) can be added to the ultraviolet curable resin composition of the present invention, but the addition amount thereof is a cured film having extremely high curability and high surface hardness. It is necessary that the range is not contrary to the gist of the present invention to provide the obtained ultraviolet curable resin composition. The compounding amount of the photopolymerization initiator (C) is usually 0.0 with respect to 100 parts by weight of the compound (A) having radical polymerizability.
It is 1 to 10 parts by weight, preferably 0.05 to 3 parts by weight.

The photopolymerization initiator (C) used here can be broadly classified into two types: intramolecular bond cleavage type and intramolecular hydrogen abstraction type. Examples of the former include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 1- (4
-Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone,

1-Hydroxycyclohaxyl-phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Acetophenone type such as butanone; benzoin type such as benzoin, benzoin isopropyl ether and benzoin isobutyl ether; acylphosphine oxide type such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide;

Examples thereof include benzyl and methylphenylglyoxyester. On the other hand, examples of the latter include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone,

4-benzoyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,
Benzophenone compounds such as 3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone and 3,3'-dimethyl-4-methoxybenzophenone; 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4 A thioxanthone system such as diethylthioxanthone or 2,4-dichlorothioxanthone;

Aminobenzophenone type compounds such as Michler's ketone and 4,4'-diethylaminobenzophenone; 10-
Butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone and the like can be mentioned.

The UV-curable resin composition of the present invention is cured by UV irradiation even if only the phosphite ester (B) having a group capable of initiating photopolymerization is added, but in order to further improve the curability, The photosensitizer (D) may be used in combination, but the addition amount thereof is, as in the case of using the photopolymerization initiator (C) in combination, a cured coating film having extremely high curability and high surface hardness. It is necessary that the range is not contrary to the gist of the present invention to provide the obtained ultraviolet curable resin composition.

The photosensitizer (D) is used in an amount of usually 0.01 to 10 parts by weight, preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the radically polymerizable compound (A). is there. Examples of the photosensitizer (D) used here include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate.

Isoamyl 4-dimethylaminobenzoate,
Examples include amines such as (2-dimethylamino) ethyl benzoate, (n-butoxy) ethyl 4-dimethylaminobenzoate, and 2-ethylhexyl 4-dimethylaminobenzoate.

In addition to the above, the UV-curable resin composition of the present invention contains non-reactive oligomers and resins, pigments, dyes, inorganic fillers, organic fillers, polymerization inhibitors, defoamers, leveling agents, plasticizers. Adhesives such as agents and couplings may be added. Furthermore, in applications such as paints and coating agents, the viscosity can be adjusted by adding an organic solvent as needed, but in this case, it is preferable to remove the organic solvent before or after curing with ultraviolet rays.

Examples of the non-reactive oligomers and resins include liquid or solid oligomers and resins having low radical reactivity or no radical reactivity.
For example, alkyl (meth) acrylate copolymer, epoxy resin, liquid polybutadiene, liquid polybutadiene derivative, liquid chloroprene, liquid polypentadiene, dicyclopentadiene derivative, saturated polyester oligomer,
Polyether oligomer, liquid polyamide, polyisocyanate oligomer, xylene resin, ketone resin,

Examples include petroleum resins, fluorine-based oligomers, silicon-based oligomers and polysulfide-based oligomers. These non-reactive oligomers and resins may have functional groups such as halogen, epoxy groups, amino groups, hydroxyl groups, thiol groups, and amide groups.

As the pigment and the dye, oil-soluble dyes are suitable because of their excellent solubility, but any dye may be used. Inorganic fillers and organic fillers generally have strength,
Used to improve mechanical properties such as cushioning and slipperiness.

As the inorganic filler, for example, silicon dioxide,
Silicon oxide, calcium carbonate, calcium silicate, magnesium carbonate, magnesium oxide, talc, kaolin clay, calcined clay, zinc oxide, zinc sulfate, aluminum hydroxide, aluminum oxide, glass, mica, barium sulfate, alumina white, zeolite, silica balloon ,
Examples thereof include glass balloons.

As the inorganic filler, a silane coupling agent,
Having a functional group such as a halogen group, an epoxy group, an amino group, a hydroxyl group, a thiol group and an amide group by a method such as adding and reacting a titanate coupling agent, an aluminum coupling agent, a zirconate coupling agent, etc. It doesn't matter if you give it.

Examples of the organic filler include benzoguanamine resin, melamine resin, benzoguanamine / melamine resin, urea resin, silicone resin, low density polyethylene, high density polyethylene, polyolefin resin, ethylene / acrylic acid copolymer, polystyrene and crosslinked polystyrene. , Polydivinylbenzene, styrene-divinylbenzene copolymer, acrylic copolymer, crosslinked acrylic resin,
Polymethylmethacrylate resin, vinylidene chloride resin,
Fluororesin, nylon 12, nylon 11,

Examples include nylon 6/66, phenol resin, epoxy resin, urethane resin, and polyimide resin. The organic filler may have a functional group such as a halogen group, an epoxy group, an amino group, a hydroxyl group, a thiol group and an amide group.

Examples of the coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane and N-β- (N-vinylbenzylaminoethyl). -Γ-aminopropyltrimethoxysilane, silane coupling agent having an amino group such as hexamethylsilazane, γ-glycidoxypropyltrimethoxysilane,

Β- (3,4-epoxycyclohexyl)
Silane coupling agent having an epoxy group such as ethyltrimethoxysilane, silane coupling agent having a mercapto group such as γ-mercaptopropyltrimethoxysilane, and silane coupling having a halogen group such as γ-chloropropyltrimethoxysilane Silane coupling agents such as agents; tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, isopropyl dimethacryl isostearoyl titanate,

Titanates such as isopropyldiacrylisostearoyl titanate, isopropyltriisostearoyl titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tricumylphenyl titanate. System coupling agent;

Examples include aluminum-based coupling agents such as acetoalkoxyaluminum diisopropylate and zirconium-based coupling agents such as acetylacetone-zirconium complex. In order to obtain the ultraviolet curable resin composition of the present invention, the above-mentioned components may be mixed, and the order and method of mixing are not particularly limited.

The ultraviolet-curable resin composition of the present invention thus obtained is shaped by various methods such as coating and printing, and then cured by irradiation with ultraviolet rays. Examples of the ultraviolet light generator include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a chemical lamp, a black light lamp, a mercury-xenon lamp and a short arc lamp.

The ultraviolet-curable resin composition of the present invention can give a cured coating film having high curability and high surface hardness even in an atmosphere in which oxygen is present. Therefore, metals such as aluminum, iron and copper can be obtained. , Vinyl chloride, acrylic, polycarbonate, polyethylene terephthalate, ABS resin,
Plastics such as polyethylene, polypropylene and polystyrene, ceramics such as glass, wood, paper, printing paper,

The present invention can be applied to coating materials of various materials such as fibers, surface treatment agents, binders, plastic materials, molding materials, laminated plates and the like which require hard surfaces. Even in applications such as adhesives, pressure-sensitive adhesives, and binders where the surface is not required to be hard, there is an advantage in that the curability is improved, and the application is acceptable. Even when the curing atmosphere is replaced with an inert gas, the ultraviolet curable resin composition of the present invention may be used.

[0074]

The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. All parts in the examples are parts by weight unless otherwise specified. Further, in the examples and comparative examples, the measurement of the ultraviolet curability and the surface height is
The procedure was as follows.

(1) UV curability: Each resin composition was applied on a glass plate so that the film thickness after curing was 10 μm, and then 120 W / cm high pressure mercury lamp (eye graphics) in air. Product), the lamp height is 15 cm, and the conveyor speed is 30 m / min.
The number of irradiations required to make the surface tack-free was evaluated.

(2) Surface hardness: A coating film was prepared in the same manner as in the above-mentioned measurement of ultraviolet curability, and JIS K-540 was used.
Based on 0, the pencil hardness was measured using a surface property measuring instrument TYPE: 14D (manufactured by Shinto Kagaku).

(Reference Example 1) [Production of phosphite compound (B)] 31.0 g of triphenyl phosphite was placed in an eggplant flask.
(0.1 mol), 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone 45.7
g (0.204 mol), diphenylphosphite 0.2
g, and the mixture was maintained at 110 to 120 ° C. for 30 minutes while stirring. Then, the inside of the flask was kept under reduced pressure of 10 to 15 mmHg to distill off phenol.

The conditions at the end of the reaction are 140 ° C. and 10 mmH.
The amount of phenol distilled off was 18.6 g. In the flask, a group capable of initiating photopolymerization (a group that is cleaved in the molecule by light to generate an active species) and> PO
A phosphite compound having an aromatic ring unit [di {4- (2-hydroxy-2-propylketone)}
Phenoxyethyl-phenylphosphite] [a compound represented by the structural formula (20)] was obtained as a pale yellow liquid. Hereinafter, this is a phosphite compound (B-1)
Is abbreviated.

Reference Example 2 (Same as above) 31.0 g of triphenyl phosphite was placed in an eggplant flask.
(0.1 mol), 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone 22.8
g (0.102 mol), diphenylphosphite 0.2
g, and the mixture was maintained at 110 to 120 ° C. for 30 minutes while stirring. Then, the inside of the flask was kept under reduced pressure of 10 to 15 mmHg to distill off phenol.

Conditions at the end of the reaction are 140 ° C. and 10 mmH
The amount of phenol distilled off was 9.3 g.
Phosphorous acid ester compound [2- {4- (2-hydroxy-2-propylketone)} phenoxy having a group capable of initiating photopolymerization (group that is cleaved in the molecule by light to generate active species) Ethyl-diphenyl phosphite]
[Compound represented by the structural formula (21)] was obtained as a pale yellow liquid. Hereinafter, this is abbreviated as a phosphorous acid ester compound (B-2).

Reference Example 3 (Same as above) In a recovery flask, 31.0 g of triphenylphosphite was added.
(0.1 mol), 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone 22.8
g (0.102 mol) and isodecyl alcohol 3
1.6 g (0.2 mol) of diphenylphosphite.
2 g was added, and the mixture was maintained at 110 to 120 ° C. for 30 minutes while stirring.

Then, the inside of the flask is heated to 10 to 15 mmHg.
It was kept under reduced pressure and the phenol was distilled off. The conditions at the end of the reaction were 140 ° C. and 10 mmHg, and the amount of phenol distilled off was 27.1 g. A phosphite compound having a group capable of initiating photopolymerization (a group that is cleaved in the molecule by light to generate an active species) [2- {4- (2
-Hydroxy-2-propylketone)} phenoxyethyl-diisodecyl phosphite] [the structural formula (1
The compound shown in 1)] was obtained as a pale yellow liquid. Hereinafter, this is abbreviated as a phosphorous acid ester compound (B-3).

Reference Example 4 (same as above) Instead of 45.7 g (0.204 mol) of 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, 39.P-hydroxybenzophenone was used.
A phosphite compound having a group having a photopolymerization initiation ability (a group that produces an active species by causing a hydrogen abstraction reaction between molecules) in the same manner as in Reference Example 1 except that 6 g (0.2 mol) was used. [Di (4-benzoylphenyl) -phenylphosphite] [compound represented by the structural formula (13)] was obtained as a colorless liquid. Hereinafter, this is abbreviated as a phosphorous acid ester compound (B-4).

Reference Example 5 (Same as above) In a recovery flask, 31.0 g of triphenylphosphite was added.
(0.1 mol), P-hydroxybenzophenone 39.
6 g (0.2 mol) and isodecyl alcohol 15.
8 g (0.1 mol), diphenyl phosphite 0.2 g
Was added, and the mixture was maintained at 110 to 120 ° C. for 30 minutes while stirring. Then, the inside of the flask was kept under reduced pressure of 10 to 15 mmHg to distill off phenol.

The conditions at the end of the reaction are 140 ° C. and 10 mmH.
The amount of phenol distilled off was 26.9 g. A phosphite compound [di (4-benzoylphenyl) -isodecyl phosphite] having a group capable of initiating photopolymerization (a group that produces an active species by causing a hydrogen abstraction reaction between molecules) as a colorless liquid Obtained. Hereinafter, this is abbreviated as a phosphorous acid ester compound (B-5).

Reference Example 6 (Same as above) Instead of 45.7 g (0.204 mol) of 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, 2-hydroxythioxanthone 45 was used. ．
In the same manner as in Reference Example 1, except that 4 (0.2 mol) was used, a phosphite compound having a group having a photopolymerization initiation ability (a group that produces an active species by causing a hydrogen abstraction reaction between molecules) [Di (thioxanthone) -phenylphosphite] [compound represented by the structural formula (14)] was obtained as a pale yellow liquid. Hereinafter, this is abbreviated as a phosphorous acid ester compound (B-6).

(Example 1) Kayarad R684 (tricyclodecane dimethanol diacrylate manufactured by Nippon Kayaku Co., Ltd.)
To 98 parts, 2 parts of the phosphite compound (B-1) synthesized in Reference Example 1 was added and mixed to obtain an ultraviolet curable resin composition, and then ultraviolet curability and surface hardness were evaluated.
The evaluation results are shown in Table 1.

(Examples 2 to 5) The phosphite compounds (B-2) to (B-3) synthesized in Reference Examples 2 to 3 were used instead of 2 parts of the phosphite compound (B-1). An ultraviolet-curable resin composition was obtained in the same manner as in Example 1 except that was used in the addition amount shown in Table 1, and then the ultraviolet-curability and surface hardness were evaluated. The evaluation results are shown in Table 1.

Example 6 Phosphite compound (B
-1) In the same manner as in Example 1 except that 2 parts of the phosphite compound (B-2) synthesized in Reference Example 2 and 1 part of 1-hydroxycyclohexyl-phenylketone were used instead of 2 parts, An ultraviolet curable resin composition was obtained, and then ultraviolet curability and surface hardness were evaluated. Table 1 shows the evaluation results
Shown in.

Comparative Example 1 Phosphite ester compound (B
-1) UV curable resin composition in the same manner as in Example 1 except that 2 parts of 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone was used instead of 2 parts. Then, UV curability and surface hardness were evaluated. The evaluation results are shown in Table 1.

Comparative Example 2 Phosphite Compound (B
-1) 1-hydroxycyclohexyl-in place of 2 parts
An ultraviolet curable resin composition was obtained in the same manner as in Example 1 except that 2 parts of phenyl ketone was used, and then the ultraviolet curability and surface hardness were evaluated. The evaluation results are shown in Table 1.

Comparative Example 3 Phosphite Compound (B
-1) In the same manner as in Example 1 except that 2 parts of 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone and 2 parts of diphenylisodecylphosphite were used instead of 2 parts. Thus, an ultraviolet curable resin composition was obtained, and then the ultraviolet curability and the surface hardness were evaluated. The evaluation results are shown in Table 1.

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[Table 1]

(Examples 7 to 9) Instead of 2 parts of the phosphite compound (B-1), the phosphite compounds (B-4) to (B-5) synthesized in Reference Examples 4 to 6 were obtained. An ultraviolet curable resin composition was obtained in the same manner as in Example 1 except that 2 parts were used, and then the ultraviolet curability and the surface hardness were evaluated. The evaluation results are shown in Table 2.

Example 10 Instead of 2 parts of phosphite compound (B-1), 2 parts of phosphite compound (B-4) synthesized in Reference Example 4 and N, N-dimethylethanolamine An ultraviolet curable resin composition was obtained in the same manner as in Example 1 except that 1 part was used, and then the ultraviolet curability and surface hardness were evaluated. The evaluation results are shown in Table 1.

Comparative Example 4 Phosphite Compound (B
-1) An ultraviolet curable resin composition was obtained in the same manner as in Example 1 except that 2 parts of benzophenone was used instead of 2 parts, and then the ultraviolet curability and surface hardness were evaluated. The evaluation results are shown in Table 2.

Comparative Example 5 Phosphite Compound (B
-1) An ultraviolet curable resin composition was obtained in the same manner as in Example 1 except that 2 parts of benzophenone and 2 parts of diphenylisodecyl phosphite were used instead of 2 parts, and then the ultraviolet curability and surface hardness Evaluated. The evaluation results are shown in Table 2.

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[Table 2]

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EFFECT OF THE INVENTION The ultraviolet curable resin composition of the present invention can give a cured coating film having high curability and high surface hardness even in an atmosphere containing oxygen.

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Claims (8)

(57) [Claims] 1. A UV-curable resin composition comprising a radically polymerizable compound (A) as a main component, which comprises a phosphite compound (B) having a group capable of initiating photopolymerization.
An ultraviolet ray curable resin composition comprising: 2. The resin according to claim _{1, wherein the} phosphite compound (B) is a phosphite compound (B ₁ ) having a group in which a bond is cleaved in the molecule by light to generate an active species. Composition. 3. The phosphite compound (B) is α-
The resin composition according to claim 1, which is a phosphite compound having a hydroxyacetophenone group. 4. The phosphite compound (B) is a phosphite compound (B ₂ ) having a> PO aromatic ring unit together with a group having a photopolymerization initiation ability.
The resin composition according to 2 or 3. 5. The phosphite compound (B) has the general formula (1): [In the above general formula (1), n is an integer of 1 to 3, R is a group having a photopolymerization initiation ability, and R ₁ is an alkyl group, an aryl group or an aralkyl group. However, R ₁ may have a substituent. ] The phosphite compound (B
₃ ) The resin composition according to claim 1, 2 or 3. 6. The addition amount of the phosphite compound (B) is 0.1 to 10 parts by weight with respect to 100 parts by weight of the compound (A) having radical polymerizability. The resin composition according to one. 7. The method according to claim 6, further comprising a photoinitiator (C).
The resin composition described. 8. The resin composition according to claim 6, further comprising a photosensitizer (D).