JPH08151420A - Actinic-radiation-curing resin composition - Google Patents

Abstract

PURPOSE: To obtain an actinic-radiation-curing resin composition which has high curability even in an atmosphere containing oxygen and can give a cured coating film having high surface hardness. CONSTITUTION: This composition comprises a major amount of a radical- polymerizable compound and a phosphorous ester having a tert. amino group (e.g. tri 2-(ethylphenylamino)ethyl} phosphite).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an active energy ray-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 An active energy ray-curable resin which is cured by an active energy ray is widely used for paints, inks, adhesives, coating agents and the like because of its fast curing characteristic. In particular, in a process that has a post-process such as stacking or winding a cured product immediately after curing, the feature that curing is particularly rapid can be utilized, and the use of active energy ray-curable resins is progressing.

However, when the active energy ray-curable resin is cured in the air, the surface layer cures slowly, and the surface is contaminated or scratched in a subsequent process. Further, the active energy ray curable resin in a thin state of 2 to 3 μm, which can be produced by spray coating, gravure printing, etc., has a drawback that it does not cure in air. Many proposals have been made to overcome these drawbacks. For example, by blowing an inert gas such as nitrogen gas, the atmosphere at the time of curing,
It is known to replace air with inert gas,
In addition, the active energy ray-curable resin is used in combination with a photopolymerization initiator and a phosphite compound such as diphenylisodecyl phosphite or cyclic neopentatetraylbis (octadecyl) phosphite. Use as a composition is disclosed in JP-A-63-
No. 72740, Japanese Patent Laid-Open No. 64-79213, and the like.

[0004]

The above-mentioned curing method using an inert gas has a drawback that the inert gas is expensive, and is not generally used in active energy ray curing. Further, the method of adding the phosphite ester compound and the photopolymerization initiator into the active energy ray-curable resin is a simple method, but the addition of the photopolymerization initiator reduces the physical properties of the coating film, for example, the surface. There is a drawback that the hardness decreases.

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

[0006]

Means for Solving the Problems As a result of earnest studies in view of such a situation, the present inventors have found that an active energy ray-curable resin containing a compound having radical polymerizability as a main component has a tertiary amino group. When a phosphite compound having is added as an essential component, it is found that even in an atmosphere in which oxygen is present, the curability is extremely high as compared with the above method, and a cured coating having a high surface hardness can be obtained. The present invention has been completed.

That is, the present invention is an active energy ray-curable resin composition comprising a radically polymerizable compound (A) as a main component, which comprises a phosphite compound (B) having a tertiary amino group. The present invention provides an active energy ray-curable resin composition containing the same.

The active energy ray-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 a phosphite ester compound (B) having a tertiary amino group as an essential component, and further contains a non-reactive resin, an additive, a filler, other Components, for example, those to which a photopolymerization initiator or the like is added in the case of ultraviolet curing, can be mentioned. The radical-polymerizable prepolymer (A ₁ ) and the radical-polymerizable monomer (A ₂ ) may be appropriately mixed and used.

The radical-polymerizable prepolymer (A ₁ ) is, for example, urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, polybutadiene (meth) acrylate or silicone (having a molecular weight of 500 or more). (Meth) acrylate, polyether (meth) acrylate, melamine (meth) acrylate, phosphazene (meth) acrylate, (meth) acrylic compound such as acrylic copolymer having (meth) acryloyl group introduced therein; polybutadiene or unsaturated polyester Compounds having unsaturated bonds in the main chain and side chains such as compounds; compounds having radically polymerizable double bonds such as allyl group, vinyl group, vinyl ether group, maleimide group, (meth) acrylamide group; thiol compounds, amination Compounds, and the like to cause radical addition reaction of an object or the like. These compounds may be appropriately selected and used so as to satisfy the required physical properties, and usually those having a molecular weight of about 500 to 30,000 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 these radically polymerizable monomers (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, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane di (meth) acrylate, bisphenol A dioxydiethylene glycol di (meth) acrylate, tricyclodecane di Methanol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 1,4-butanediol di (meth) acrylate, N-vinylpyrrolidone, tripropylene glycol divinyl ether and the like can be mentioned. .

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 at the time of curing, more than the above blending ratio is required. It is preferably used in a small amount, for example, a proportion of 3 to 15% by weight.

As the phosphite compound (B) used in the present invention, any phosphite compound having a tertiary amino group can be used. However, when a phosphite compound having a primary and / or secondary amino group instead of the tertiary amino group is used, the radical polymerizable compound and the amino group contained in the active energy ray resin composition are combined with each other. Active hydrogen causes an addition reaction,
There is a drawback that the storage stability of the resin composition becomes poor.

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

[0015]

Embedded image

[In the above general formula (1), n is an integer of 1 to 3, R is an atomic group having a tertiary amino group, and R ₁ is an alkyl group, an aryl group or an aralkyl group. However, R
₁ may have a substituent, and as the substituent, for example, a halogen, an alkoxy group, an alkoxycarbonyl group,
Examples thereof include an acyloxy group, an alkanoyl group, a cyano group and a hydroxyl group. ]

[0017]

Embedded image

[In the above general formula (2), n is an integer of 1-2, m is an integer of 0-2, R is an atomic group having a tertiary amino group, R ₁ is an alkyl group, an aryl group or an aralkyl group. Is. However, R ₁ may have a substituent, and as the substituent, for example, halogen, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, an alkanoyl group,
Examples thereof include a cyano group and a hydroxyl group. R ₂ is an alkylene group, an arylene group or an aralkylene group. However, R ₂ 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 ₂ 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 and a hydroxyl group. ]

[0019]

Embedded image

[In the above general formula (3), R is an atomic group having a tertiary amino group, 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 and a hydroxyl group. ]

[0021]

[Chemical 4]

[In the above general formula (4), m is an integer of 0 to 1, R is an atomic group having a tertiary amino group, and R ₁ is an alkyl group, an aryl group or an aralkyl group. However, R
₁ may have a substituent, and as the substituent, for example, a halogen, an alkoxy group, an alkoxycarbonyl group,
Examples thereof include an acyloxy group, an alkanoyl group, a cyano group and a hydroxyl group. R ₄ is an aliphatic hydrocarbon group, an aromatic group or a cycloaliphatic group. However, R ₄ 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 ₄ 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 and a hydroxyl group. ]

[0023]

Embedded image

[In the general formula (5), n is an integer of 0 to 2, m is an integer of 0 to 2, R is an atomic group having a tertiary amino group, and R ₅ is a divalent group having a tertiary amino group. R ₁ is an alkyl group, an aryl group or an aralkyl group. However, R ₁ may have a substituent, and as the substituent, for example, halogen, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, an alkanoyl group, a cyano group,
Examples thereof include a hydroxyl group. The R in the general formulas (1) to (5), that is, the atomic group having a tertiary amino group is, for example, the following general formula (6).
The atomic group represented by.

[0025]

[Chemical 6]

[In the above general formula (6), R ₆ is an alkylene group, an arylene group or an aralkylene group. However, R ₆ 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 ₇ and R ₈ are an alkyl group, an aryl group or an aralkyl group, and these may be the same or different. R ₆ , R
₇ and R ₈ may further have a substituent, and examples thereof include a halogen atom, an alkoxy group, an alkoxycarbonyl group, a cyano group and a hydroxyl group. Among them, R ₆ is preferably an alkylene group having 1 to 9 carbon atoms, a cycloalkylene group having 1 to 9 carbon atoms, or an arylene group having 6 to 12 carbon atoms, and may have a substituent. R ₇ ,
R ₈ is an alkyl group having 1 to 9 carbon atoms, 1 carbon atom
A cycloalkyl group having 9 to 9 or an aryl group having 6 to 12 carbon atoms is preferable, and may have a substituent. ] Specific examples of the atomic group represented by the general formula (6) include:
(N, N-dimethylamino) 1-propyl, (N, N-
Dimethylamino) 2-propyl, N, N-diethylaminoethyl, N, N-dimethylaminoethyl, N, N-diisopropylaminoethyl, N, N-dibutylaminoethyl, N, N-dihydroxyethylaminoethyl, (N
-Ethyl-N-phenylamino) ethyl, (N, N-diethylamino) phenyl, (N-hydroxyethyl-N)
-Phenylamino) ethyl and the like.

Further, as R ₅ in the general formula (5), that is, the divalent atomic group having a tertiary amino group, for example, an atomic group represented by the following general formula (7) can be mentioned.

[0028]

[Chemical 7]

[In the general formula (7), R ₆ and R ₉ are an alkylene group, an arylene group or an aralkylene group,
These may be the same or different.
However, R ₆ and R ₉ are carbon-carbon bond, ether bond,
It may optionally contain at least one bond selected from the group consisting of an ester bond, an amide bond, a urethane bond, a thioether bond and an imide bond. R ₇ is an alkyl group, an aryl group or an aralkyl group. R ₆ ,
R ₇ and R ₉ may further have a substituent, for example, a halogen atom, an alkoxy group, an alkoxycarbonyl group,
Examples thereof include a cyano group and a hydroxyl group. Among them, R ₆ , R
₉ is an alkylene group having 1 to 9 carbon atoms, 1 carbon atom
The cycloalkylene group having 9 to 9 or the arylene group having 6 to 12 carbon atoms is preferable, and may have a substituent. R ₇ is preferably an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group having 1 to 9 carbon atoms or an aryl group having 6 to 12 carbon atoms, and may have a substituent. ] Specific examples of the atomic group represented by the general formula (7) include:
(N-methylamino) diethyl, (N-butylamino)
Diethyl, (N-methylamino) diisopropyl, (N
-Phenylamino) diethyl, {N- (3-phenyl)
Amino} diethyl, (N-hydroxyethyl) aminodiethyl and the like can be mentioned.

Specific examples of the phosphite compound (B) having a tertiary amino group used in the present invention include 3- (dimethylamino) propyl-diisodecyl phosphite,
Tri {3- (dimethylamino) propyl} phosphite, di {2- (dimethylamino) propyl} pentaerythritol-diphosphite, tetra {2- (diethylamino) ethyl} dipropyleneglycol-diphosphite, tri {2- (dimethylamino) ) Ethyl} phosphite, compounds represented by the following structural formulas (8) to (10), and the like.

[0031]

Embedded image

The phosphite compound (B) used in the present invention is, among others, a tertiary amino group having a structure in which one or more aromatic rings are directly bonded to a tertiary nitrogen atom (hereinafter, aromatic tertiary It is preferable to use a phosphite compound (B ₁ ) having an amino group) because the storage stability of the active energy ray-curable resin composition is improved and a cured coating film having higher surface hardness can be obtained. .

The preferred phosphite compound (B
Examples of ₁ ) include 2- (ethylphenylamino) ethyl-didecylphosphite, 2- (ethylphenylamino) ethyl} -decylphosphite, di {2- (ethylphenylamino) ethyl} -pentaerythritol diphosphite. Fight, tri {2- (ethylphenylamino) ethyl} phosphite, 2- {ethyl (3-methylphenyl) amino} ethyl-diisodecylphosphite, tetra- {2- (ethylphenylamino) ethyl-tetradecyl-pentaerythritol Tetraphosphite, 3-
Examples thereof include (diethylamino) phenyl-diisodecylphosphite, tri {3- (diethylamino) phenyl-phosphite, and compounds represented by the following structural formulas (11) to (13).

[0034]

[Chemical 9]

Further, the phosphite ester compound used in the present invention
Examples of the product (B) include> P with a tertiary amino group.
-O- aromatic ring unit, a group having photopolymerization initiation ability, and a group
Having one or more selected from dical polymerizable unsaturated bonds
Phosphite compound (B ₂ ), The curability is
In terms of improving and providing a cured coating with higher surface hardness,
Compound of phosphite having aromatic tertiary amino group
Thing (B₁ As well as). In addition, phosphite
Compound (B₂ ) Has a tertiary amino group, an aromatic tertiary amine
It is more preferable if it is a no group.

The above preferable phosphite compound (B
_{As 2} ), first, a phosphite compound (B ₂₁ ) having a> PO-aromatic ring unit together with a tertiary amino group.
And 3- (dimethylamino) propyl-
Diphenylphosphite, di {2- (dimethylamino)
Propyl} -phenylphosphite, 2- (diethylamino) ethyl-diphenylphosphite, di {2- (dimethylamino) ethyl} -phenylphosphite, 2
-(Ethylphenylamino) ethyl-diphosphite,
3- (diethylamino) phenyl-diisodecylphosphite, tri {3- (diethylamino) phenyl-phosphite, 3- (diethylamino) phenyl-diphenylphosphite, compounds represented by the following structural formulas (14) and (15), and the like. To be

[0037]

[Chemical 10]

Among these phosphorous acid ester compounds (B ₂₁ ), di {3- (diethylamino) phenyl-diisodecyl phosphite and 3- (diethylamino)
Phenyl-diisodecyl phosphite, such as tri {3- (diethylamino) phenyl-phosphite> P-
The compound having a structure in which the aromatic ring of the O-aromatic ring unit is directly bonded to the tertiary nitrogen atom is a compound having the above-mentioned phosphite ester (B
_Since it has the same structure as ₁ ), it can be referred to as a phosphite compound (B ₁ ) having an aromatic tertiary amino group.

Examples of preferable phosphite compounds (B ₂ ) include phosphite compounds (B ₂₂ ) having a group having photopolymerization initiating ability together with a tertiary amino group, which are usually used for UV curing. It is used by adding it to the resin composition. The group capable of initiating photopolymerization may be any group that takes any reaction reaction mode as long as it is a group that generates an active species that initiates a reaction involving a radical, such as ultraviolet light, visible light, and infrared light. Is a group that produces an active species that initiates reactions such as radical polymerization and radical addition reaction. Examples of the generation reaction mode include a group that produces an active species by cleavage of a bond in the molecule by light, a group that produces an active species by causing a hydrogen abstraction reaction between molecules, and the like.

Specific examples of the group capable of initiating photopolymerization include benzoin ether group, benzyl ketal group and α-
Hydroxyacetophenone group, chloroacetophenone group, α-aminoacetophenone group, acylphosphine oxide group, α-dicarbonyl group, α-acyloxime group, benzophenone group, thioxanthone group, biimidazole group, acridone group, anthraquinone group, camphorquinone group. Examples of the phosphite compound (B ₂₂ ) having a group having a photopolymerization initiation ability together with the above-mentioned tertiary amino group having a group and the like include compounds represented by the following structural formulas (16) to (20). To be

[0041]

[Chemical 11]

[0042]

[Chemical 12]

Further, a phosphite compound (B ₂₃ ) having a> PO-aromatic ring unit and a group having photoinitiating ability together with the tertiary amino group is also a preferable phosphite compound, and examples thereof include the following. Examples thereof include compounds represented by Structural Formulas (21) to (24).

[0044]

[Chemical 13]

[0045]

Embedded image

Other preferable phosphite compound (B ₂ ) is a phosphite compound (B ₂₄ ) having a radically polymerizable unsaturated bond together with a tertiary amino group.
Is mentioned. The phosphite ester compound (B ₂₄ ) having a radical-polymerizable unsaturated bond has less bleeding on the surface of the coating film, and a cured coating film having higher surface hardness can be obtained. The group having a radically polymerizable unsaturated bond,
Examples thereof include a (meth) acryloyl group, a vinyl group, a vinyl ether group, an aryl group, a maleimide group, and a (meth) acrylamide group.

Examples of the phosphite compound (B ₂₄ ) having a radical-polymerizable unsaturated bond include compounds represented by the following structural formulas (25) to (29).

[0048]

[Chemical 15]

[0049]

Embedded image

Furthermore, together with a group having a tertiary amino group,
A phosphite compound (B ₂₆ ) having a> PO-aromatic ring unit and a radical-polymerizable unsaturated bond is also a preferable phosphite compound, for example, the following structural formula (3
0) to (35) and the like.

[0051]

[Chemical 17]

[0052]

Embedded image

The addition amount of the phosphite compound (B) having a group having a tertiary amino group is 100 parts by weight based on 100 parts by weight of the total amount of the radically polymerizable compound (A).
Usually 0.0001 to 30 parts by weight, preferably 0.05 to
It is in the range of 10 parts by weight.

However, the phosphite compound (B ₂₅ )
The phosphite compound having a radical-polymerizable unsaturated bond such as (B ₂₆ ) and (B ₂₆ ) itself also serves as the compound (A) having radical-polymerizability, and thus can be used in a range other than the above range. The compound (A) having radical polymerizability is usually used in an amount of 0 to 300 parts by weight, preferably 0 to 200 parts by weight, based on 100 parts by weight of the phosphite compound having a polymerizable unsaturated bond.
For example, as the phosphite compound (B), a phosphite compound having a radically polymerizable unsaturated bond such as phosphite compounds (B ₂₅ ) and (B ₂₆ ) alone or in this type In some cases, the required properties can be satisfied only by the combination of acid ester compounds.

When ultraviolet rays are used as a curing means for the resin composition of the present invention, it is usually necessary to add a photopolymerization initiator (C) to the composition. Photopolymerization initiator (C)
The amount of addition of the compound (A) 10 having radical polymerizability
It is usually 0.01 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 0 parts by weight. However, when a phosphite compound having a group having a photopolymerization initiation ability such as a phosphite compound (B ₂₃ ) or (B ₂₄ ) is used as the phosphite compound (B), The addition of the polymerization initiator (C) can be stopped or the addition amount can be reduced.

The photopolymerization initiator (C) can be roughly 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-methylpropane-.
1-one, 4- (2-hydroxyethoxy) phenyl-
(2-Hydroxy-2-propyl) ketone, 1-hydroxycyclohaxyl-phenyl ketone, 2-methyl-2
-Morpholino (4-thiomethylphenyl) propane-1
-One, 2-benzyl-2-dimethylamino-1- (4
-Morpholinophenyl) -acetophenone such as butanone; benzoin such as benzoin, benzoin isopropyl ether, benzoin isobutyl ether;
Acylphosphine oxides such as 4,6-trimethylbenzoyldiphenylphosphine oxide; benzyl, methylphenylglyoxy ester and the like can be mentioned. On the other hand, examples of the latter include benzophenone, methyl 2-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 Thioxanthones such as diethylthioxanthone and 2,4-dichlorothioxanthone; aminobenzophenones such as Michler's ketone and 4,4'-diethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10- Examples thereof include phenanthrenequinone and camphorquinone.

The active energy ray-curable resin composition of the present invention is cured by irradiation with active energy rays only by adding the phosphite (B) having a group having a tertiary amino group. However, in order to further improve the curability, it is also possible to use a photosensitizer (D) in combination, and the compounding amount thereof is usually 0 with respect to 100 parts by weight of the compound (A) having radical polymerizability. 0.01 to 5 parts by weight, preferably 0.0
5 to 2 parts by weight. As the photosensitizer (D),
For example, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate,
Isoamyl 4-dimethylaminobenzoate, benzoic acid (2
Examples thereof include amines such as -dimethylamino) ethyl, (n-butoxy) ethyl 4-dimethylaminobenzoate, and 2-ethylhexyl 4-dimethylaminobenzoate.

In addition to the above, the active energy ray-curable resin composition of the present invention contains non-reactive oligomers and resins, pigments, dyes, inorganic fillers, organic fillers, polymerization inhibitors, defoamers, and leveling agents. , A plasticizer, and an adhesion improver such as coupling may be added. Further, in applications such as paints and coating agents, the viscosity can be adjusted by adding an organic solvent, if necessary, but in this case, it is preferable to remove the organic solvent before or after curing with an active energy ray.

Examples of the non-reactive oligomer or resin include liquid or solid oligomers or 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,
Examples thereof include polyether oligomers, liquid polyamides, polyisocyanate oligomers, xylene resins, ketone resins, petroleum resins, fluorine-based oligomers, silicon-based oligomers and polysulfide-based oligomers. These non-reactive oligomers and resins include halogens, epoxy groups,
You may have functional groups, such as an amino group, a hydroxyl group, a thiol group, and an amide group.

As the pigments and dyes, oil-degradable 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. The inorganic filler, a silane coupling agent, a titanate-based coupling agent, an aluminum-based coupling agent, a zirconate-based coupling agent or the like is added and reacted by a method such as a halogen group, an epoxy group, an amino group, a hydroxyl group, It may have a functional group such as a thiol group and an amide group.

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, nylon 6
/ 66, phenol resin, epoxy resin, urethane resin, polyimide resin and the like. 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, N-β- (N-vinylbenzylaminoethyl). -Γ-aminopropyltrimethoxysilane, silane coupling agent having 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, isopropyldimethacrylisostearoyl titanate, isopropyldiacrylisostearoyl titanate, isopropyltriisostearoyl titanate, Bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl tridodecyl benzene sulfo Examples thereof include titanate-based coupling agents such as nil titanate and isopropyl tricumylphenyl titanate; aluminum-based coupling agents such as acetoalkoxyaluminum diisopropylate and zirconium-based coupling agents such as acetylacetone-zirconium complex.

To obtain the active energy ray-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 active energy ray-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 active energy rays.

The active energy ray refers to ultraviolet rays, electron rays, ionizing radiation such as α rays, β rays, γ rays, microwaves, high frequencies, etc., but any energy can be used as long as radical active species can be generated. You can use seeds. Visible light, infrared light or argon laser may be used. Examples of the substance that generates ultraviolet rays include ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, metal halide lamps, chemical lamps, black light lamps, mercury-xenon lamps, and short arc lamps, which generate radical active species. Considering the absorption wavelength of the compound,
Just select it.

The active energy ray-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, aluminum, iron, copper or the like can be obtained. Metal, vinyl chloride, acrylic,
Polycarbonate, polyethylene terephthalate, AB
S resin, polyethylene, polypropylene, polystyrene and other plastics, glass and other ceramics, wood,
It is applicable to applications requiring coating of various materials such as paper, printing paper, fibers, surface treatment agents, binders, plastic materials, molding materials, laminated plates, etc., 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 active energy ray-curable resin composition of the present invention may be used.

[0067]

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.

In the Examples and Comparative Examples, the ultraviolet curability, electron beam curability and surface height were measured by the following methods. (1) UV curability: Each resin composition was applied onto a glass plate so that the film thickness after curing was 10 μm, and then 120 W / cm high pressure mercury lamp (manufactured by Eye Graphics Co., Ltd.) in the atmosphere. ), Ultraviolet irradiation was performed under conditions of a lamp height of 15 cm and a conveyor speed of 30 m / min to determine the number of irradiations required to make the surface tack-free, and the number of irradiations was evaluated.

(2) Electron beam curability: Each resin composition was applied on a glass plate so that the film thickness after curing was 10 μm, and then an electron beam irradiation apparatus CB175 (manufactured by ESI, USA) was used. Acceleration voltage 170KV, oxygen concentration in irradiation atmosphere 50
Electron beam irradiation S was performed under the condition of 0 ppm to obtain the irradiation dose required to make the surface tack-free, and the irradiation dose was evaluated.

(3) Surface hardness: A coating film was prepared in the same manner as in the above-mentioned measurement of active energy ray curability, and was subjected to JIS.
Based on K-5400, surface property measuring instrument TYPE: 14D
The pencil hardness was measured using (TYPE: 14D manufactured by Shinto Scientific Co., Ltd.).

Reference Example 1 [Phosphite compound (B)
Production] In a four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, 100 ml of diethyl ether, 8.91 g (0.10 mol) of N, N-dimethylethanolamine and 10.3 g (0.102 mol of triethylamine) were prepared. ) Was added and dissolved, and after cooling with cold water, 4.7 g of phosphorus trichloride was added.
(0.034 mol) was added dropwise, and after completion of the addition, the mixture was kept at 40 ° C. with stirring and reacted for 3 hours. Next, this was cooled to room temperature, triethylamine hydrochloride was removed by filtration, and diethyl ether was distilled off from the obtained filtrate under reduced pressure to obtain a phosphite compound having an aliphatic tertiary amino group [triethyl {2- (Dimethylamino) ethyl} phosphite] was obtained as a colorless liquid. Hereinafter, this is abbreviated as a phosphorous acid ester compound (B-1).

Reference Example 2 (same as above) In a recovery flask, 31.0 g of triphenyl phosphite was added.
(0.1 mol), 49.5 g (0.3 mol) of N-ethyl-N- (2-hydroxyethyl) -aniline and 0.2 g of diphenyl phosphite were added, and the mixture was stirred while stirring 11
After holding at 0 to 120 ° C. and reacting for 30 minutes, the inside of the flask was kept under reduced pressure of 10 to 15 mmHg, and the reaction was allowed to proceed while distilling phenol off. The condition at the end of the reaction is 1
40 ° C., 10 mmHg, the amount of phenol distilled off was 27.
It was 8 g. A phosphite compound having an aromatic tertiary amino group [tri {2- (ethylphenylamino) ethyl} phosphite] was obtained in the flask as a pale yellow liquid. Hereinafter, this is referred to as a phosphite compound (B-
2) is abbreviated.

Reference Example 3 (same as above) In a recovery flask, 62.0 g of triphenyl phosphite was added.
(0.2 mol), N, N-di (2-hydroxyethyl)
Aniline 18.1 g (0.1 mol), 4- (2, isodecyl alcohol 31.6 g (0.2 mol) and diphenyl phosphite 0.2 g were added, and the mixture was stirred at 110
After the reaction was carried out for 30 minutes while keeping at 120 ° C, the inside of the flask was kept under a reduced pressure of 10 to 15 mmHg to allow the reaction to proceed while distilling phenol off. The condition at the end of the reaction is 140
℃, 10mmHg, the amount of phenol distilled off is 27.3g
Thus, a phosphite compound having an aromatic tertiary amino group [a compound represented by the above structural formula (9)] was obtained in the flask as a light brown liquid. Hereinafter, this is abbreviated as a phosphorous acid ester compound (B-3).

Reference Example 4 (same as above) Instead of 49.5 g (0.3 mol) of N-ethyl-N- (2-hydroxyethyl) -aniline, 17.8 g (0.2 mol) of N, N-dimethylaminoethanol was used. Mol) was used in the same manner as in Reference Example 1 to prepare a phosphite compound having an aliphatic tertiary amino group and a> PO-aromatic ring unit [di {2- (dimethylamino) ethyl} -phenylphosphine. [Fight] 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, 62.0 g of triphenyl phosphite was added.
(0.2 mol), 4,4'-isopropylidene diphenol (22.8 g, 0.1 mol) and diphenylphosphite (0.2 g) were added, and the mixture was stirred at 110 to 120 ° C.
After holding for 30 minutes to react,
It was kept under a reduced pressure of 15 mmHg and the reaction was allowed to proceed while distilling phenol. The conditions at the end of this reaction are 140
℃, 10mmHg, the amount of phenol distilled off 18.2g
Met. Then, in the flask, N, N-dimethyl-m
-Adding 33.2 g (0.201 mol) of aminophenol, maintaining the mixture at 110 to 120 ° C. for 30 minutes while stirring, and then again maintaining the inside of the flask under a reduced pressure of 10 to 15 mmHg to distill the phenol off. It was made to react while doing. Conditions at the end of the reaction were 140 ° C., 10 mmHg, the amount of phenol distilled off was 9.2 g, and the phosphite compound having an aromatic tertiary amino group and a> PO-aromatic ring unit in the flask [the above structure The compound represented by the formula (14)] was obtained as a pale brown liquid. Hereinafter, this is abbreviated as a phosphorous acid ester compound (B-5).

Reference Example 6 (same as above) In a recovery flask, 31.0 g of triphenylphosphite was added.
(0.1 mol), N-ethyl-N- (2-hydroxyethyl) -aniline 33.2 g (0.201 mol), 4-
22.4 g (0.1 mol) of (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone and 0.2 g of diphenylphosphite were added, and the mixture was maintained at 110 to 120 ° C. for 30 minutes while stirring. After the reaction, the inside of the flask is kept under a reduced pressure of 10 to 15 mmHg,
The reaction was allowed to proceed while the phenol was distilled off. The conditions at the end of the reaction are 140 ° C., 10 mmHg, the amount of phenol distilled off is 27.7 g, and the phosphite compound having an aromatic tertiary amino group and a group having photoinitiating ability in the flask [the above structural formula The compound represented by (23)] was obtained as a pale brown liquid. Hereinafter, this is abbreviated as a phosphorous acid ester compound (B-6).

Reference Example 7 (Same as above) In a recovery flask, 31.0 g of triphenyl phosphite was added.
(0.1 mol), P-hydroxybenzophenone 19.
8 g (0.1 mol), 33.2 g (0.201 mol) of N, N-dimethyl-m-aminophenol and 0.2 g of diphenyl phosphite were added, and 110-110 with stirring.
After maintaining at 120 ° C. and reacting for 30 minutes, the inside of the flask was kept under reduced pressure of 10 to 15 mmHg, and the reaction was allowed to proceed while distilling phenol off. The condition at the end of the reaction is 140
℃, 10mmHg, the amount of phenol distilled off is 27.5g
And an aromatic tertiary amino group,> P-O- in the flask.
A phosphite compound having an aromatic ring unit and a group having photoinitiating ability [a compound represented by the structural formula (24)] was obtained as a light brown liquid. Hereinafter, this is abbreviated as a phosphorous acid ester compound (B-7).

Reference Example 8 (same as above) 31.0 g of triphenyl phosphite was placed in an eggplant flask.
(0.1 mol), N, N-dimethyl-m-aminophenol 16.5 g (0.1 mol), 2-hydroxyethyl acrylate 23.4 g (0.2 mol) and diphenyl phosphite 0.2 g were added. , Stirring 110
After maintaining at 120 ° C. and reacting for 30 minutes, the inside of the flask was kept under reduced pressure of 10 to 15 mmHg, and the reaction was allowed to proceed while distilling phenol off. The condition at the end of the reaction is 140
℃, 10mmHg, the amount of phenol distilled off is 27.9g
And an aromatic tertiary amino group,> P-O- in the flask.
A phosphite compound having an aromatic ring unit and a radical-polymerizable unsaturated bond [a compound represented by the structural formula (32)] was obtained as a light brown liquid. Hereinafter, this is abbreviated as a phosphorous acid ester compound (B-8).

Example 1 Synthesized with 98 parts of Kayarad R684 (tricyclodecane dimethanol diacrylate manufactured by Nippon Kayaku Co., Ltd.), 2 parts of Irgacure 184 (photopolymerization initiator manufactured by Ciba-Geigy, Switzerland) and Reference Example 1. 2 parts of the phosphite ester compound (B-1) was added and mixed to obtain an active energy ray-curable resin composition, and then UV curability and surface hardness were evaluated. Table 1 shows the evaluation results.

Example 2 Instead of 2 parts of the phosphite compound (B-1), the phosphite compound (B-2) 2 synthesized in Reference Example 2 was used.
An active energy ray-curable resin composition was obtained in the same manner as in Example 1 except that parts were used, and then ultraviolet ray curability and surface hardness were evaluated. Table 1 shows the evaluation results.

Example 3 Instead of 2 parts of the phosphite compound (B-1), the phosphite compound (B-2) 4 synthesized in Reference Example 2 was used.
An active energy ray-curable resin composition was obtained in the same manner as in Example 1 except that parts were used, and then ultraviolet ray curability and surface hardness were evaluated. Table 1 shows the evaluation results.

Examples 4 to 8 Instead of 2 parts of the phosphite compound (B-1), the phosphite compound (B-) synthesized in Reference Examples 3 to 7 was used.
3) to (B-7) An active energy ray-curable resin composition was obtained in the same manner as in Example 1 except that 2 parts were used, and then ultraviolet ray curability and surface hardness were evaluated. Table 1 shows the evaluation results
Shown in

Example 9 To 98 parts of Kayarad R684, 2 parts of the phosphite compound (B-7) synthesized in Reference Example 7 was added and mixed to obtain an active energy ray-curable resin composition, and then UV curing. The properties and surface hardness were evaluated. Table 1 shows the evaluation results.

Example 10 Instead of 2 parts of the phosphite compound (B-1), the phosphite compound (B-8) 2 synthesized in Reference Example 8 was used.
An active energy ray-curable resin composition was obtained in the same manner as in Example 1 except that parts were used, and then ultraviolet ray curability and surface hardness were evaluated. Table 1 shows the evaluation results.

Example 11 Instead of 2 parts of the phosphite compound (B-1), the phosphite compound (B-8) 2 synthesized in Reference Example 8 was obtained.
An active energy ray-curable resin composition was obtained in the same manner as in Example 1 except that 0 part was used, and then UV curability and surface hardness were evaluated. Table 1 shows the evaluation results.

Example 12 Instead of 2 parts of the phosphite compound (B-1), the phosphite compound (B-2) 2 synthesized in Reference Example 2 was used.
Parts and 1 part of triethanolamine (photosensitizer) were used in the same manner as in Example 1 to obtain an active energy ray-curable resin composition, and then ultraviolet ray curability and surface hardness were evaluated. Table 1 shows the evaluation results.

Comparative Example 1 An active energy ray-curable resin composition was prepared in the same manner as in Example 1 except that 2 parts of diphenylisodecyl phosphite was used instead of 2 parts of the phosphite compound (B-1). Then, the active energy ray curability and the surface hardness were evaluated. Table 1 shows the evaluation results.

Comparative Example 2 Instead of 2 parts of the phosphite compound (B-1), cyclic neopentatetraylbis (octadecyl) was used.
An active energy ray-curable resin composition was obtained in the same manner as in Example 1 except that 2 parts of phosphite was used, and then the active energy ray curability and the surface hardness were evaluated. Table 1 shows the evaluation results.

[0089]

[Table 1]

Example 13 98 parts of TMP3A (trimethylolpropane triacrylate manufactured by Osaka Organic Co., Ltd.) was added with Irgacure 18
4 parts (photopolymerization initiator manufactured by Ciba-Geigy, Switzerland) and the phosphite compound (B-1) 3 synthesized in Reference Example 1
Parts were added and mixed to obtain an active energy ray-curable resin composition, and then UV curability and surface hardness were evaluated. Table 2 shows the evaluation results.

Example 14 Instead of 3 parts of the phosphite compound (B-1), the phosphite compound (B-2) 3 synthesized in Reference Example 2 was used.
An active energy ray-curable resin composition was obtained in the same manner as in Example 13 except that the parts were used, and then the ultraviolet curability and the surface hardness were evaluated. Table 2 shows the evaluation results.

Comparative Example 3 An active energy ray-curable resin composition was prepared in the same manner as in Example 13 except that 2 parts of diphenylisodecyl phosphite was used instead of 3 parts of the phosphite compound (B-1). Then, the active energy ray curability and the surface hardness were evaluated. Table 2 shows the evaluation results.

[0093]

[Table 2]

Example 15 To 98 parts of Kayarad R684, 2 parts of the phosphite compound (B-1) synthesized in Reference Example 1 was added and mixed to obtain an active energy ray-curable resin composition, and then an electron beam. The curability and surface hardness were evaluated. The evaluation results are shown in Table 3.

Example 16 2 parts of the phosphite compound (B-2) synthesized in Reference Example 2 was added to 98 parts of Kayarad R684 to prepare Example 1
An active energy ray-curable resin composition was obtained in the same manner as in 5, and then electron beam curability and surface hardness were evaluated. The evaluation results are shown in Table 3.

Comparative Example 4 An active energy ray-curable resin composition was prepared in the same manner as in Example 15 except that diphenylisodecyl phosphite was used instead of 2 parts of the phosphite compound (B-1). Then, the electron beam curability and the surface hardness were evaluated.
The evaluation results are shown in Table 3.

Comparative Example 5 Instead of 2 parts of the phosphite compound (B-1), cyclic neopentatetraylbis (octadecyl) was used.
An active energy ray-curable resin composition was obtained in the same manner as in Example 15 except that phosphite was used, and then electron beam curability and surface hardness were evaluated. The evaluation results are shown in Table 3.

[0098]

[Table 3]

[0099]

The active energy ray-curable resin composition of the present invention has high curability even in an atmosphere containing oxygen,
Moreover, a cured coating film having high surface hardness can be obtained.

Claims (6)

[Claims] 1. An active energy ray-curable resin composition comprising a radically polymerizable compound (A) as a main component, which contains a phosphite compound (B) having a tertiary amino group. A characteristic active energy ray-curable resin composition. 2. The phosphite compound (B) is a phosphite compound (B) having an aromatic tertiary amino group.
The composition according to claim _1, which is ₁ ). 3. The phosphite compound (B) contains, together with a tertiary amino group, at least one selected from a> PO-aromatic ring unit, a group having photoinitiating ability and a radical-polymerizable unsaturated bond. The composition according to claim 1 or 2, which is a phosphite compound (B ₂ ). 4. The addition amount of the phosphite compound (B) is 0.05 to 10 parts by weight with respect to 100 parts by weight of the compound (A) having radical polymerizability. Composition. 5. The composition according to claim 4, which further comprises a photopolymerization initiator (C). 6. The composition according to claim 5, which further comprises a photosensitizer (D).