KR20190019924A - Active energy ray curable resin composition and coating material made therefrom - Google Patents

Abstract

An active energy ray curable resin composition capable of forming a cured coating film excellent in balance in gas barrier properties such as water vapor barrier property and oxygen barrier property and in flexibility in addition to hardness and scratch resistance and having an average isocyanurate structure per molecule of 3 (Meth) acrylate compound (A) having at least one urethane (meth) acrylate compound (A).

Description

Active energy ray curable resin composition and coating material made therefrom

More particularly, the present invention relates to an active energy ray-curable resin composition and a coating agent, and more particularly, to an active energy ray-curable resin composition and a coating agent which are excellent in hardness and scratch resistance of a coating film and have gas barrier properties such as water vapor barrier property and oxygen barrier property, And a coating agent using the active energy ray curable resin composition.

Conventionally, the active energy ray-curable resin composition is extensively used as a coating agent, an adhesive agent, or an anchor coat agent for various substrates because curing is completed by irradiation of active energy rays such as ultraviolet rays or ultraviolet rays for a very short time. For example, plastic films are widely used for optical member applications such as liquid crystal displays, and these plastic films are prone to scratches on their surfaces. Therefore, in order to impart hardness and scratch resistance, A coating agent is applied and used.

In order to improve the processability such as the punching process of the plastic film having the cured coating film or to use it for the flexible display which is being developed in recent years in addition to the hardness and scratch resistance of the cured coating film, It is required to have high flexibility so that cracks do not occur even when the plastic film on which the coating film is formed is bent.

In addition, for example, in organic EL, which is under development in recent years, it is known that a display element is weak in moisture and deteriorates due to humidity in the environment. For this reason, in the plastic film used for the display device using the organic EL, the hard coat layer is required to have high water vapor barrier property so as to prevent display failure and visibility deterioration caused by intrusion of moisture.

Thus, there is a demand for an active energy ray curable resin composition capable of forming a cured coating film that satisfies all of these physical properties because many coating agents for hard coating are required.

As an active energy ray-curable resin composition that meets such a demand, for example, Patent Document 1 discloses an active energy ray curable resin composition containing urethane (meth) acrylate, tripentaerythritol octa (meth) acrylate and a polymerization initiator And shows that when the resin composition is coated on a plastic film, a hardened film can be obtained and a cured coating film excellent in flexibility can be obtained.

Patent Document 2 discloses a urethane compound having an ethylenically unsaturated double bond obtained by reacting a polyolefin polyol compound, an ethylenically unsaturated compound having a hydroxyl group and a compound having two or more isocyanate groups in one molecule, a photopolymerizable monomer, Discloses a photo-curable resin composition containing an initiator and a urethane acrylate oligomer, and exhibits flexibility, low moisture permeability, and adhesiveness to a polyethylene terephthalate (PET) base material.

Patent Document 1 JP 2013-23585 A Patent Document 2 JP 2010-144000 A

However, the cured coating film disclosed in Patent Document 1 has an evaluation of flexibility by a mandrel tester of 6 to 10 (see Table 1). Flexibility is insufficient in the cured coating film disclosed in Patent Document 1 because it is required that the evaluation of flexibility by a mandrel tester is 5 or less when the flexible display is used or when the film is folded and processed. In addition, it does not have water vapor barrier property.

The technique of Patent Document 2 has water vapor barrier properties, but hardness and scratch resistance can not be satisfied when the resin is flexible to form a cured coating film, which is difficult to apply to hard coat applications.

Therefore, in the present invention, when a cured coating film is formed under such a background, an active energy ray curing property capable of forming a cured coating film excellent in balance of gas barrier property and bending property such as water vapor barrier property and oxygen barrier property in addition to hardness and scratch resistance A resin composition and a coating agent using the same are provided.

Accordingly, the present inventors have conducted intensive studies in view of such circumstances, and as a result, have found that, in an active energy ray-curable resin composition containing a urethane (meth) acrylate compound, a urethane (Meth) acrylate compound is used, an active energy ray curable resin composition excellent in balance in hardness, scratch resistance, bendability and gas barrier property can be obtained as a cured coating film.

That is, the gist of the present invention relates to an active energy ray curable resin composition characterized by containing a urethane (meth) acrylate compound (A) having three or more average isocyanurate structures per molecule.

The present invention also relates to a coating agent prepared using the active energy ray-curable resin composition.

The active energy ray-curable resin composition of the present invention contains a urethane (meth) acrylate compound (A) having three or more isocyanurate structures per molecule, so that it has water vapor barrier properties, oxygen It is possible to obtain a cured coating film having gas barrier properties such as barrier properties and excellent balance of flexibility.

(Meth) acrylate compound (a2) having an isocyanurate structure other than the isocyanurate compound (a1) and the above component (a1) in the urethane (meth) acrylate compound The urethane (meth) acrylate compound (A1) as a reaction product is superior in balance of gas barrier property and bendability of the cured coating film.

Wherein the urethane (meth) acrylate compound (A) is an isocyanurate compound (a1), a hydroxyl group-containing (meth) acrylate compound (a2) having an isocyanurate structure other than the component (a1) (Meth) acrylate compound (A2), which is the reaction product of the curing agent and the chain extender (a3), is excellent due to the balance between the gas barrier property and the bendability of the cured coating film.

When the number average molecular weight of the hydroxyl group-containing (meth) acrylate compound (a2) having an isocyanurate structure is 200 to 2,000, the gas barrier property of the cured coating film is superior.

If the weight average molecular weight of the urethane (meth) acrylate compound (A) is 1,000 to 20,000, the balance between the flexural properties and the hardness of the cured coating film is further improved.

Wherein the urethane (meth) acrylate compound (A1) is obtained by reacting the isocyanurate compound (a1) and the hydroxyl group-containing (meth) acrylate compound (a2) having the isocyanurate structure with a2) = 1: 2 to 1: 10, the content of the urethane acrylate compound can be sufficiently obtained.

In addition, if the monomer (B1) containing an ethylenic unsaturated group having an isocyanurate structure is contained, the balance between scratch resistance, bendability and gas barrier properties of the cured coating film is further improved.

When the concentration of the isocyanurate structure in the curing component contained in the active energy ray-curable resin composition is 1.0 mmol / g or more, the gas barrier property and the bending property and hardness balance of the cured coating film are further improved.

When the active energy ray-curable resin composition is used as a coating agent, it is possible to obtain a cured coating film excellent in balance in hardness, scratch resistance, bending property and water vapor barrier property.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail, but these are only examples of preferred embodiments. In the present specification, the term "(meth) acryl" means acryl or methacryl, (meth) acrylate means acrylate or methacrylate, (meth) acryloyloxy means acryloyloxy or methacryloyloxy It means.

The active energy ray-curable resin composition of the present invention is characterized by containing urethane (meth) acrylate compound (A) having three or more average isocyanurate structures per molecule. The number of average isocyanurate structures per molecule is preferably at least 3.5, particularly preferably at least 4.0, even more preferably at least 4.5, and the upper limit is usually 100, preferably 50, Preferably 30 pieces. When the number of the average isocyanurate structures is small, gas barrier property and bending property are lowered.

<Urethane (meth) acrylate compound (A)>

The urethane (meth) acrylate compound (A) used in the present invention has three or more average isocyanurate structures per molecule, and contains an isocyanurate structure in the urethane (meth) acrylate compound (Meth) acrylate compound prepared by reacting an isocyanate compound and a hydroxyl group-containing (meth) acrylate compound with one or both of an isocyanate compound and a hydroxyl group-containing (meth) Can be reacted with an isocyanurate structure. Particularly, it is preferable to use a compound having an isocyanurate structure on both of them to react with each other in view of excellent balance between gas barrier property and bendability of the cured coating film.

Specifically, the isocyanurate compound (a1) is used as the isocyanate compound and the hydroxyl group-containing (meth) acrylate compound (a2) having an isocyanurate structure as the hydroxyl group-containing (meth) (Meth) acrylate compound (A1) obtained by reacting (a1) and (a2) with an isocyanurate compound (excluding the isocyanurate compound (a1) It is preferable from the viewpoint of excellent balance between gas barrier property and bending property.

In the present invention, it is also preferred that the urethane (meth) acrylate compound (A) is an isocyanurate compound (a1), a hydroxyl group containing (meth) acrylate compound having an isocyanurate structure (meth) acrylate compound (A2) which is a reaction product of the urethane (meth) acrylate compound (a3).

Specifically, the isocyanurate compound (a1) is used as the isocyanate compound and the hydroxyl group-containing (meth) acrylate compound (a2) having an isocyanurate structure as the hydroxyl group-containing (meth) (Meth) acrylate-based compound (a1) obtained by reacting (a1) to (a3) using a chain extender (a3) except that the isocyanurate compound (A2) is also preferable from the viewpoint of excellent balance between gas barrier property and bendability of the cured coating film.

&Lt; Isocyanate compound &gt;

The isocyanurate compound (a1) used as the isocyanate compound is a polyisocyanate having an isocyanurate structure, and examples thereof include aromatic diisocyanates (for example, tolylene diisocyanate, diphenylmethane diisocyanate , Modified diphenylmethane diisocyanate, xylene diisocyanate, tetramethyl xylene diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, etc.);

Aliphatic diisocyanates such as aliphatic diisocyanates (e.g., pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate and the like) and aliphatic triisocyanates (such as lysine triisocyanate) Isocyanate;

Alicyclic diisocyanates such as isophorone diisocyanate, hydrolyzed diphenylmethane diisocyanate, 1,3-bis (isocyanat) cyclohexane, 1,4-bis (isocyanat) cyclohexane, Alicyclic isocyanate, etc.);

And isocyanurate compounds of various polyvalent isocyanates. These may be used singly or in combination of two or more. The isocyanurate compound may be a trimer or a higher polymer, but a trimer is preferable from the viewpoint of versatility.

Of these, the isocyanurate of diisocyanate is preferable from the viewpoint of excellent balance between scratch resistance and bending property of the cured coating film, and isocyanurate of aliphatic diisocyanate is particularly preferable from the viewpoint of excellent water vapor barrier property, From the standpoint of versatility, an isocyanurate of hexamethylene diisocyanate is still more preferable.

In the present invention, when the isocyanurate structure is contained in a large amount in the hydroxyl group-containing (meth) acrylate compound, there is no need to have an isocyanurate structure in the isocyanate compound, and isocyanurate Examples of the polyisocyanate having no rate structure include aromatic diisocyanates (e.g., tolylene diisocyanate, diphenylmethane diisocyanate, diphenylmethane diisocyanate, modified diphenylmethane diisocyanate, xylene diisocyanate, tetramethyl Aromatic diisocyanates such as xylylene diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate);

Aliphatic diisocyanates such as aliphatic diisocyanates (e.g., pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate and the like) and aliphatic triisocyanates (such as lysine triisocyanate) Isocyanate;

Alicyclic diisocyanates such as isophorone diisocyanate, hydrolyzed diphenylmethane diisocyanate, 1,3-bis (isocyanat) cyclohexane, 1,4-bis (isocyanat) cyclohexane, Alicyclic isocyanate, etc.);

And allophanates and burettes obtained by using these polyisocyanates. These isocyanate compounds may be used singly or in combination of two or more.

&Lt; Hydroxyl group-containing (meth) acrylate compound &gt;

In the present invention, a hydroxyl group-containing (meth) acrylate compound (a2) having an isocyanurate structure is used as the hydroxyl group-containing (meth) acrylate compound.

Examples of the hydroxyl group-containing (meth) acrylate compound (a2) having an isocyanurate structure include isocyanuric acid ethylene oxide-modified mono (meth) acrylate, isocyanuric acid ethylene oxide-modified di (meth) , Isocyanuric acid alkylene oxide-modified mono or di (meth) acrylates such as isocyanuric acid propylene oxide-modified mono (meth) acrylate and isocyanuric acid propylene oxide-modified di (meth) acrylate;

Isocyanuric acid dipropylene oxide modified mono (meth) acrylate, isocyanuric acid dipropylene oxide modified mono (meth) acrylate, isocyanuric acid diethylene oxide modified mono (meth) acrylate, isocyanuric acid diethylene oxide modified di (meth) (Meth) acrylate, isocyanuric acid triethylene oxide modified mono (meth) acrylate, isocyanuric acid triethylene oxide modified di (meth) acrylate, isocyanuric acid tripropylene oxide modified mono (meth) Isocyanuric acid polyalkylene oxide-modified mono or di (meth) acrylates such as poly (meth) acrylate and di (meth) acrylate modified di (meth) acrylate;

And the like, and one kind or a combination of two or more kinds can be used.

(Meth) acrylate, isocyanuric acid alkylene oxide-modified di (meth) acrylate, isocyanuric acid propylene oxide-modified mono (meth) acrylate, isocyanuric acid alkylene oxide- (Meth) acrylate modified with isocyanuric acid ethylene oxide, and isocyanuric acid-modified (meth) acrylate modified with isocyanuric acid such as isocyanuric acid ethylene oxide Modified di (meth) acrylates are particularly preferred.

The number average molecular weight of the hydroxyl group-containing (meth) acrylate compound (a2) having an isocyanurate structure is preferably 200 to 2,000 from the viewpoint of excellent gas barrier properties of the cured coating film, 1,500.

In the present invention, when the isocyanurate structure is contained in a large amount in the isocyanate compound, the hydroxyl group-containing (meth) acrylate compound does not need to have an isocyanurate structure. The hydroxyl group- containing (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl Hydroxyalkyl (meth) acrylates such as hydroxyalkyl (meth) acrylate and 6-hydroxyhexyl (meth) acrylate, 2-hydroxyethyl acryloylphosphate, 2- (meth) acryloyloxyethyl- Caprolactone-modified 2-hydroxyethyl (meth) acrylate, dipropylene glycol (meth) acrylate, fatty acid-modified glycidyl (meth) acrylate, polyethylene glycol (Meth) acrylates such as mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy- (Meth) acrylate-based compounds containing one ethylenic unsaturated group such as mono (meth) acrylate;

Ethylenically unsaturated groups such as glycerin di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, pentaerythritol di (meth) acrylate and dipentaerythritol di (Meth) acrylate-based compounds containing a plurality of

(Meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tri (Meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, and ethylene oxide modified dipentaerythritol penta (meth) Methacrylate compounds;

And the like. These hydroxyl group-containing (meth) acrylate compounds may be used singly or in combination of two or more.

<Chain extender (a3)>

The chain extender (a3) has a function of increasing the molecular weight of the urethane (meth) acrylate compound. Specific examples thereof include ethylene glycol, propylene glycol, 1,3-propanediol, polyethylene glycol, Polypropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, 1,12-dodecanediol, Methyl-1,5-pentanediol, trimethylol propane, glycerin, pentaerythritol, dipentaerythritol, and tripentaerythritol, aliphatic polyols such as 1,1-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclo A polyol compound such as decane dimethanol, an ethylene oxide adduct of isocyanuric acid, and a cyclic structure-containing polyol such as isocyanuric acid adduct of isocyanuric acid, a polyol compound such as 3,3'-diaminodipropylamine, bis (hexamethylene) , 4,4'-diaminodiphenylmethane, diaminocyclo (3-mercaptopropionate), xylene dithiol, 1,4-butanediol bis (3-mercaptopropionate), 1,4-cyclohexane bis Mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), tris [(3-mercaptopropionyloxy) -ethyl] -isocyanurate, pentaerythritol tetrakis (3-mercapto Propionate), and dipentaerythritol hexaquis (3-mercaptopropionate). Among them, a polyol compound is preferable, and an aliphatic polyol and a cyclic structure-containing polyol are preferable from the viewpoint of excellent gas barrier properties. In particular, a cured film having a high glass transition temperature (Tg) Of the polyols, neopentyl glycol is preferred among the polyol having a cyclic structure, 1,1-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, ethylene oxide adduct of isocyanuric acid, propylene oxide of isocyanuric acid Adducts are preferred. These chain extender (a3) may be used alone or in combination of two or more.

The number average molecular weight of the chain extender (a3) is preferably 30 to 500, more preferably 50 to 400, and particularly preferably 70 to 300. If it is too large, the hardness and gas barrier properties tend to decrease. If too small, the flexibility tends to decrease.

The urethane (meth) acrylate compound (A1) used in the present invention has a functional group-to-isomer ratio of the isocyanate group of the isocyanurate compound (a1) to the hydroxyl group of the hydroxyl group-containing (meth) (A1) is reacted with a hydroxyl group-containing (meth) acrylate compound (a2) using a reaction catalyst such as dibutyltin dilaurate or a polymerization inhibitor, if necessary, to obtain an isocyanurate compound .

Specifically, the reaction molar ratio of the isocyanurate compound (a1) to the hydroxyl group-containing (meth) acrylate compound (a2) can be determined, for example, by reacting the isocyanurate compound (a1) Acrylate compound (a2) is preferably reacted at a molar ratio of (a1) :( a2) = 1: 2 to 1:10, more preferably 1: 2.1 to 1: 8, furthermore 1: 2.2 to 1: to be.

In the addition reaction between the isocyanurate compound (a1) and the hydroxyl group-containing (meth) acrylate compound (a2), the reaction is terminated when the residual isocyanate group content in the reaction system becomes 0.1 wt% (Meth) acrylate compound (A1) can be obtained.

In the reaction between the isocyanurate compound (a1) and the hydroxyl group-containing (meth) acrylate compound (a2), it is preferable to use a reaction catalyst for the purpose of promoting the reaction. For example, organic metal compounds such as dibutyltin dilaurate, trimethyltin hydroxide, tetra-n-butyltin and the like, zinc octenoate, tin octenoate, tin octylate, cobalt naphthenate, Tin and the like, metal salts such as triethylamine, benzyldiethylamine, 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] undecene, N, N , N ', N'-tetramethyl-1,3-butane diamine, N-ethylmorpholine, and the like, bismuth acetate, bismuth bromide, bismuth iodide and bismuth sulfide, Organic bismuth compounds such as dioctyl bismuth dilaurate, Bismuth salt of stannic acid, bismuth salt of linoleic acid, bismuth salt of bismuth, bismuth salt of bismuth, bismuth salt of bismuth salt, bismuth salt of bismuth salt, bismuth salt of bismuth A bismuth-based catalyst such as a bismuth salt of an organic acid such as a bismuth salt of di-salicylic acid, a zirconium-based catalyst such as an inorganic zirconium, an organic zirconium or a zirconium group, a zinc-2-ethylhexanoate / zirconium tetraacetylacetone Dibutyl tin dilaurate and 1,8-diazabicyclo [5,4,0] undecene are very suitable. Among these, dibutyl tin dilaurate and 1,8-diazabicyclo [5,4,0] undecene are particularly suitable. These catalysts may be used alone or in combination of two or more.

In the reaction of the isocyanurate compound (a1) with the hydroxyl group-containing (meth) acrylate compound (a2), the polymerization inhibitor is preferably used from the viewpoint of the reaction stability at the time of production, For example, 4-methoxyphenol, 2,6-di-tert-butylcresol, pentaerythritol tetraquiz [3- (3,5-di- tert -butyl-4-hydroxyphenyl) propionate (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], and the like. Of these, 4-methoxyphenol and 2,6-di-tert-butylcresol are preferred. These may be used alone or in combination of two or more.

In the reaction of the isocyanurate compound (a1) with the hydroxyl group-containing (meth) acrylate compound (a2), an organic solvent having no functional group reactive with the isocyanate group, such as ethyl acetate, butyl acetate Ketones such as methyl ethyl ketone and methyl isobutyl ketone, and aromatic solvents such as toluene and xylene. When the ethylenically unsaturated compound (B) described later is contained, the ethylenically unsaturated compound (B) may be reacted in the presence of a diluting monomer.

The urethane (meth) acrylate compound (A2) used in the present invention may also be an isocyanurate compound (a1) having an isocyanate group, a hydroxyl group of the hydroxyl group-containing (meth) acrylate compound (a2) (A1), a hydroxyl group-containing (meth) acrylate compound (a1), and a polymerization initiator are used in the presence of a reaction catalyst such as dibutyltin dilaurate or a polymerization inhibitor by adjusting the molar ratio of functional groups of the chain extender (Meth) acrylate compound (a2) and a chain extender (a3). The reaction conditions and the like can be carried out in the same manner as in the case of the urethane (meth) acrylate compound (A1).

The concentration of the isocyanurate structure-containing urethane (meth) acrylate compound (A) used in the present invention is preferably 1.3 mmol / g or more, particularly preferably 1.5 to 3.0 mmol / g, and more preferably 1.8 To 2.5 mmol / g.

If the isocyanurate structure-containing concentration of the urethane (meth) acrylate compound (A) is too high, the cured coating tends to soften and scratch resistance tends to deteriorate. If too low, the gas barrier property tends to deteriorate, Further, since the cured coating film becomes hard, the flexibility tends to be lowered.

The isocyanurate structure-containing concentration of the urethane (meth) acrylate compound (A) is preferably in the range of from 0.1 to 30 parts by weight, preferably from 10 to 100 parts by weight, per 100 parts by weight of the constituent materials (isocyanate compound, (meth) (A chain extender, if necessary)) is calculated by the following formula (1).

[Formula 1]

Concentration of isocyanurate structure (mmol / g) = 1000 x? (N x W / M)

N: number of average isocyanurate structures included in each constituent raw material

W: weight ratio of each constituent material to the urethane (meth) acrylate compound (A)

M: Number average molecular weight of each constituent raw material

The number N _i of the average isocyanurate structures contained in the isocyanate compound is determined by the following formula 2.

[Formula 2]

N _i = (A _i x M _i / 4202) -2

A _i : weight ratio of isocyanate group contained in isocyanate compound

M _i : Number average molecular weight of isocyanate compound

The number average molecular weight is a number average molecular weight in terms of standard polystyrene molecular weight conversion. For example, the number of columns is ACQUITY APC XT 450 × 1, ACQUITY APC (manufactured by Waters Corporation, "ACQUITY APC System" XT 200 × 1, and ACQUITY APC XT 45 × 2.

The isocyanurate structure-containing concentration of the urethane (meth) acrylate compound (A) can be determined, for example, by adjusting the ratio of the amount of the reaction raw material containing an isocyanurate structure to the reaction raw material containing no isocyanurate structure And the like.

The urethane (meth) acrylate compound (A) used in the present invention preferably has a weight average molecular weight of 1,000 to 20,000, particularly preferably 1,200 to 18,000, more preferably 1,500 to 15,000, particularly preferably 2,000 ~ 10,000. If the weight average molecular weight is too large, the viscosity tends to become high and handling becomes difficult. When the weight average molecular weight is too small, the balance between the flexibility and hardness of the cured coating film tends to decrease.

The above weight average molecular weight refers to a weight average molecular weight in terms of standard polystyrene molecular weight equivalents. For example, in a high-performance liquid chromatography ("ACQUITY APC system", manufactured by Waters Corporation), columns: ACQUITY APC XT 450 × 1 , ACQUITY APC XT 200 × 1, and ACQUITY APC XT 45 × 2.

The urethane (meth) acrylate compound (A) may be used alone or in combination of two or more.

&Lt; Active energy ray curable resin composition &gt;

The active energy ray-curable resin composition of the present invention may further contain an ethylenically unsaturated compound (B).

Examples of the ethylenically unsaturated compound (B) include an ethylenic unsaturated group-containing monomer (monofunctional monomer) having one ethylenic unsaturated group, and an ethylenic unsaturated group-containing monomer (multifunctional monomer) having two or more ethylenic unsaturated groups have.

Examples of the monofunctional monomer include styrene monomers such as styrene, vinyltoluene, chlorostyrene and? -Methylstyrene, monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, acrylonitrile, Acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) Phenoxyethyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2-hydroxy- Acrylate such as propyl (meth) acrylate, glycerol mono (meth) acrylate, glycidyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, isobonyl Decanyl (meth) acrylate, dicyclopentenyl (meta) (Meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, (2-methyl- (Meth) acrylate, 3-ethyl-3-oxetanylmethyl (meth) acrylate, cyclohexane spiro-2- (Meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (Meth) acrylate, n-stearyl (meth) acrylate, benzyl (meth) acrylate, phenol ethylene oxide modified (n = 2) (meth) acrylate, nonylphenol Propylene oxide modified (n = 2.5) (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, 2- (meth) acryloyloxy- (Meth) acrylate, carboxy (meth) acrylate, benzyl (meth) acrylate, butoxy (meth) acrylate of a phthalic acid derivative such as hydroxyethyl (Meth) acrylate monomers such as ethyl (meth) acrylate, aryl (meth) acrylate, (meth) acryloylmorpholine and polyoxyethylene secondary alkyl ether acrylate, , N-methylol (meth) acrylamide, N-vinylpyrrolidone, 2-vinylpyridine, vinyl acetate and the like.

Examples of the bifunctional monomer include bifunctional monomers and trifunctional monomers. Examples of the bifunctional monomers include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene Propylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (Meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, propylene oxide modified bisphenol A (meth) acrylate, cyclohexanedimethanol di Acrylate, ethoxylated cyclohexanedimethanol di (meth) acrylate, dimethyloliglycopentane di (meth) acrylate, tricyclodecane dimethacrylate, (Meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (Meth) acrylate, hydroxypivalic acid-modified neopentyl glycol di (meth) acrylate, isocyanuric acid di (meth) acrylate, Ethylene oxide-modified diacrylate, and the like.

Examples of the monomer having three or more functional groups include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta Pentaerythritol hexa (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylol propane, glycerin polyglyceryl ether (meth) acrylate, isocyanuric acid ethylene oxide modified triacrylate, caprolactone Caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (metha) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, caprolactone-modified pentaerythritol tetra Modified dipentaerythritol penta (meth) acrylate, ethylene oxide (Meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol tetra (meth) acrylate, ethoxylated glycerin triacrylate, and the like.

Also, a Michael addition product of acrylic acid or 2-acryloyloxyethyl dicarboxylic acid monoester can be used in combination. Examples of the Michael addition product of acrylic acid include acrylic acid dimer, methacrylic acid dimer, acrylic acid trimmer, methacrylic acid trimmer, Acrylic acid tetramer, and methacrylic acid tetramer.

Examples of the 2-acryloyloxyethyl dicarboxylic acid monoester include carboxylic acid having a specific substituent, such as 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid mono ester, 2 - acryloyloxyethyl phthalate monoester, 2-methacryloyloxyethyl phthalate monoester, 2-acryloyloxyethylhexahydrophthalic acid monoester, 2-methacryloyloxyethyl hexahydrophthalic acid Monoester and the like. Other oligomeric ester acrylates may also be mentioned.

Among these, from the viewpoint of the hardness, it is preferable to use a copolymer of trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, and the like.

From the viewpoint of bending property, it is preferable to use 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, isobonyl (meth) acrylate, Containing monomers containing a monofunctional ethylenic unsaturated group such as acrylate, (meth) acryloylmorpholine and the like.

In addition, from the viewpoint of excellent balance between hardness and bending property, it is preferable that isocyanuric acid ethylene oxide modified triacrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexa (metha) acrylate, caprolactone (Meth) acrylate, ethylene oxide-modified dipentaerythritol penta (meth) acrylate, ethylene oxide-modified dipentaerythritol hexa (metha) acrylate, caprolactone-modified pentaerythritol tetra Containing monomer having a high molecular weight, such as modified pentaerythritol tri (meth) acrylate and ethylene oxide-modified pentaerythritol tetra (meth) acrylate.

From the viewpoint of gas barrier properties, it is preferable to contain an ethylenic unsaturated group-containing monomer (B1) having an isocyanurate structure.

It is preferable that the cured coating film contains an ethylenically unsaturated group-containing monomer (B1) having an isocyanurate structure from the viewpoint of excellent balance between scratch resistance, bending property and gas barrier property, and it is preferable that the cured coating film has hardness, scratch resistance, , And gas barrier properties, it is preferable to use an isocyanuric acid such as isocyanuric acid ethylene oxide diacrylate, isocyanuric acid ethylene oxide modified triacrylate and the like having 2 to 6 functional groups, particularly 2 to 3 functional isocyanurate structures It is particularly preferable to contain an ethylenic unsaturated group-containing monomer.

These ethylenically unsaturated compounds (B) may be used alone or in combination of two or more.

Here, it is preferable that the ethylenically unsaturated compound (B) contains 50% by weight or more of an ethylenic unsaturated group-containing monomer (B1) having an isocyanurate structure from the viewpoint of excellent balance between gas barrier property and bendability of the cured coating film , And more preferably at least 60 wt%, especially at least 70 wt%. The upper limit is usually 100% by weight.

The content of the ethylenically unsaturated compound (B) is preferably 10 to 900 parts by weight, particularly preferably 25 to 400 parts by weight, more preferably 25 to 400 parts by weight, per 100 parts by weight of the urethane (meth) Is 40 to 250 parts by weight.

If the content of the ethylenically unsaturated compound (B) is too large, the balance between scratch resistance and bendability of the obtained cured coating film tends to be impaired. If the content is too small, the hardness of the cured coating film tends to decrease.

Such an ethylenically unsaturated compound (B) may be separately added to the active energy ray-curable resin composition of the present invention. The ethylenically unsaturated compound (B) may be blended separately in the active energy ray-curable resin composition of the present invention and used as a raw material for producing the urethane (meth) Or may be left in the system.

The isocyanurate structure-containing concentration ratio of the urethane (meth) acrylate compound (A) and the ethylenic unsaturated group-containing monomer (B1) having an isocyanurate structure was (A) / (B1) = 20/80 More preferably 30/70 to 70/30, and even more preferably 40/60 to 60/40.

The active energy ray curable resin composition of the present invention preferably further contains a photopolymerization initiator (C) in order to efficiently perform curing by an active energy ray.

The photopolymerization initiator (C) is not particularly limited as long as it can generate a radical by the action of light, and examples thereof include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan- Dimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1- hydroxycyclohexyl phenyl ketone, 2- 2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1- Phenyl] propanol oligomer, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy- 4- (2-hydroxy-2-methylpropionyl) -benzyl] -phenyl} -2-methyl-propan-1-one;

Benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether;

Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, 3,3 ', 4,4'-tetra (t- butylperoxycarbonyl) benzophenone , 2,4,6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2- propenyloxy) ethyl] benzenemethanium bromide, Benzophenones such as trimethylammonium chloride, etc .; benzophenones such as 2- isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, Thioxanthones such as propoxythioxanthone and 2- (3-dimethylamino-2-hydroxy) -3,4-dimethyl-9H-thioxanthone 9-one mesochloride;

(2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) - phenylphosphine oxide, 1,2-octadiene-1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone 1- [9- - (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime);

And the like.

These photopolymerization initiators (C) may be used alone or in combination of two or more.

Examples of the preparation of these photopolymerization initiators (C) include triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Mihira ketone), 4,4'-diethylaminobenzophenone, 2- Dimethylaminoethylbenzoic acid, 4-dimethylaminobenzoic acid (n-butoxy) ethyl, 4-dimethylaminobenzoic acid isoamyl, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethyl Thioxanthone, 2,4-diisopropylthioxanthone and the like can be used in combination.

These preparations may be used alone or in combination of two or more.

The content of such a photopolymerization initiator (C) is preferably 0.1 to 100 parts by weight based on 100 parts by weight of the urethane (meth) acrylate compound (A) (in the case of containing the ethylenically unsaturated compound (B) To 20 parts by weight, particularly preferably 1 to 10 parts by weight, still more preferably 2 to 5 parts by weight. If the content is too small, the curing rate tends to decrease or the adhesive force tends to deteriorate. If the content is too large, the curing property does not improve, and yellowing tends to occur under high temperature conditions.

In addition, the active energy ray-curable resin composition of the present invention may contain a polythiol compound from the viewpoints of inhibition of unreacted components and improvement of adhesion.

The polythiol compound is not particularly limited but is preferably a compound having 2 to 6 mercapto groups in the molecule, and examples thereof include aliphatic polythiols such as alkane dithiol having about 2 to 20 carbon atoms, , Polythiols obtained by substituting mercapto groups for halogen atoms of halohydrin adducts of alcohols, polythiols composed of hydrogen sulfide reaction products of polyepoxy group compounds, polythiols composed of 2 to 6 hydroxyl groups And polythiols composed of esters of thioglycolic acid,? -Mercaptopropionic acid or? -Mercaptobutanoic acid, and the like, and these may be used singly or in combination of two or more kinds .

The content of the polythiol compound is preferably 0.01 to 10 wt% based on 100 wt% of the urethane (meth) acrylate compound (A) (the sum of (A) and (B) when the ethylenically unsaturated compound And particularly preferably 0.1 to 5 parts by weight.

The active energy ray-curable resin composition of the present invention may contain urethane (meth) acrylate compound (A), optionally ethylenically unsaturated compound (B) and photopolymerization initiator (C) A urethane (meth) acrylate compound other than the acrylate compound (A), other crosslinkable group compound (D), an acrylic resin, a surface modifier, a leveling agent and a polymerization inhibitor , An oil, an antioxidant, a flame retardant, an antistatic agent, a filler, a stabilizer, a reinforcing agent, a quencher, a softener, an organic fine particle and an inorganic particle.

Examples of other crosslinkable group-containing compounds (D) include epoxy compounds, oxetane compounds, carboxylic acid compounds, aziridine compounds, polyisocyanate compounds, polyol compounds, and polyamine compounds.

The content of the other crosslinkable group-containing compound (D) is preferably from 0.1 to 20 parts by weight, more preferably from 0.5 to 20 parts by weight, more preferably from 0.5 to 5 parts by weight based on 100 parts by weight of the curing component contained in the active energy ray- To 15 parts by weight, more preferably 1 to 10 parts by weight.

The active energy ray-curable resin composition of the present invention may preferably contain an organic solvent for dilution, if necessary, in order to adjust the viscosity at the time of coating. Examples of such organic solvents include alcohols such as methanol, ethanol, propanol, n-butanol and i-butanol, ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone, Aromatic hydrocarbons such as toluene and xylene, glycol ethers such as propylene glycol monomethyl ether, acetic acid esters such as methyl acetate, ethyl acetate and butyl acetate, and diacetone alcohol. These organic solvents may be used alone or in combination of two or more. When two or more of them are used in combination, it is preferable to select at least two of glycol ethers, ketones, acetic acid esters, and alcohols from the viewpoint of coating film appearance.

Thus, the active energy ray-curable resin composition of the present invention can be obtained.

In the active energy ray-curable resin composition of the present invention, the concentration of the isocyanurate structure in the curing component contained in the active energy ray-curable resin composition is usually 1.0 mmol / g or more, preferably 1.4 to 3.0 mmol / g, More preferably 1.6 to 2.5 mmol / g, and particularly preferably 1.8 to 2.2 mmol / g. If the isocyanurate structure-containing concentration is too high, the cured coating film becomes soft and the scratch resistance is lowered. If the concentration is too low, the water vapor barrier property is deteriorated and the cured coating film becomes hard.

The curing component may contain a urethane (meth) acrylate compound (A), and if necessary, a urethane (meth) acrylate compound other than the ethylenically unsaturated compound (B) or (A) When the compound (D) is contained, they are considered to be included.

The concentration of the isocyanurate structure contained in the curing component contained in the active energy ray-curable resin composition is preferably in the range of 1 to 100 parts by weight based on 100 parts by weight of the urethane (meth) acrylate compound (A), the ethylenically unsaturated compound (B) ) &Lt; / RTI &gt;

[Formula 3]

Concentration of isocyanurate structure (mmol / g) = 1000 x? (N x W / M)

N: number of average isocyanurate structures contained in each curing component

W: weight ratio of each curing component to the curing component

M: Number average molecular weight of each curing component

The number N _i of the average isocyanurate structures contained in the isocyanate compound is determined by the following formula 4.

[Formula 4]

N _i = (A _i x M _i / 4202) -2

A _i : weight ratio of isocyanate group contained in isocyanate compound

M _i : Number average molecular weight of isocyanate compound

In the case where the urethane (meth) acrylate compound other than the urethane (meth) acrylate compound (A) is contained, the urethane (meth) acrylate compound is calculated based on the respective constituent materials.

In such an active energy ray-curable resin composition, the urethane (meth) acrylate compound (A) is preferably 25% by weight or more, particularly preferably 30% by weight or more, more preferably 35% by weight or more, Is at least 40% by weight. The upper limit is usually 100% by weight from the viewpoint of flexibility.

The viscosity (60 캜) of the active energy ray-curable resin composition of the present invention is preferably from 100 to 200,000 mPa,, particularly preferably from 500 to 100,000 mPa s, more preferably from 1 , 000 to 50,000 mPa · s. If the viscosity is too low, control of the film thickness tends to be difficult at the time of coating, while if it is too high, handling becomes difficult or the coating property tends to deteriorate. The viscosity is a viscosity measured using an E-type viscometer.

The active energy ray-curable resin composition of the present invention is effectively used as a curable resin composition for forming a coating film, such as an overcoat agent and an anchor coat agent for various substrates.

In particular, the active energy ray-curable resin composition of the present invention is useful for applications requiring flexibility and gas barrier properties in addition to hardness and scratch resistance in a cured coating film. For example, A surface coating agent for a protective film, a coating agent for a punching process, or an adhesive between optical members for optical display.

The active energy ray-curable resin composition of the present invention can be cured by irradiating an active energy ray after coating the substrate (when the composition diluted with an organic solvent is coated, and after drying).

Examples of the base material to which the active energy ray-curable resin composition of the present invention is applied include polyolefin resin, polyester resin, polycarbonate resin, acrylic resin acrylonitrile butadiene styrene copolymer (ABS), polystyrene resin, (Aluminum, copper, iron, SUS, zinc, magnesium, alloys thereof, etc.) such as a plastic substrate such as a metal substrate (film, sheet, And includes a metal film such as a metal vapor deposition film) or a substrate provided with a primer layer on a substrate such as glass.

Examples of coating methods include wet coating methods such as spraying, showering, dipping, roll, spin, curtain, flow, slit, die, gravure, comma, dispenser, screen printing, inkjet printing, It is possible to coat the substrate under the condition of room temperature.

As the active energy ray, it is possible to use not only electromagnetic waves such as far-ultraviolet ray, ultraviolet ray, near-ultraviolet ray and infrared ray, electromagnetic waves such as X-ray and gamma ray but also electron ray, It is advantageous to cure by ultraviolet irradiation from ease, cost and the like. In addition, when electron beam irradiation is performed, curing can be performed without using a photopolymerization initiator (C).

A metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless discharge lamp, an LED, or the like, which emits light in a wavelength range of 150 to 450 nm when ultraviolet rays are irradiated, It is possible to irradiate ultraviolet rays of usually 30 to 3000 mJ / cm 2 (preferably 100 to 1500 mJ / cm 2).

After the ultraviolet ray irradiation, the curing may be completed by heating according to need.

The thickness of the coating film after curing is usually 1 to 1000 占 퐉, preferably 2 to 500 占 퐉, and particularly preferably 5 to 200 占 퐉.

The water vapor permeability of the coating film after curing is preferably 100 g / m 2 day or less, more preferably 90 g / m 2 day or less, and further preferably 80 g / m 2 day or less. Usually, the lower limit value of the water vapor permeability is 0 g / m 2 · day.

The water vapor permeability was measured by a cylinder-plate method in accordance with JIS Z 0208 using a cured coating film layer having a thickness of about 50 탆 and measured at 40 캜 under a 90% RH atmosphere.

The oxygen permeability of the coated film after curing is preferably 20 cc / m 2 · day · atm or less, more preferably 15 cc / m 2 · day · atm or less and further preferably 10 cc / m 2 · day · atm or less. Normally, the lower limit value of the oxygen permeability is 0 cc / m 2 day-atm.

The oxygen permeability was measured using an oxygen permeability tester ("Oxtran100A" manufactured by MOCON Co., Ltd.) at 23 ° C and 80% RH using a PET film provided with a coating layer having a film thickness of about 70 μm. Thereafter, the oxygen permeability (cc / m 2 · day · atm) of the 100 μm thick cured coating film monolayer was calculated.

(Example)

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded. In the examples, &quot; part &quot; and &quot;% &quot; The measurement of the weight average molecular weight and the concentration of the isocyanurate structure were carried out in accordance with the method described above.

[Production Example 1: urethane (meth) acrylate compound (A1-1)]

(A1-1) of hexamethylene diisocyanate having an isocyanurate structure (isocyanate group content: 21.1%, average number of isocyanate groups (average number of isocyanate groups)) was added to a four-necked flask equipped with a thermometer, a stirrer, 14.7 g (0.025 mole) of isocyanuric acid ethylene oxide diacrylate (a2-1) and isocyanuric acid ethylene oxide-modified triacrylate (B1-1 ) (A weight ratio of (a2-1) / (B1-1) = 35/65, hydroxyl value of 49.7 mg KOH / g, average number of isocyanurate structures of 1.0, number average molecular weight of 532) ), 0.03 g of dibutyltin dilaurate as a reaction catalyst and 0.08 g of 2,6-di-tert-butylcresol as a polymerization inhibitor were added and reacted at 70 ° C for 6 hours. The reaction was terminated when the residual isocyanate group became 0.1%, and 44.6 g (weight average molecular weight (Mw): 3,300) of urethane (meth) acrylate compound (A1-1) and isocyanuric acid ethylene oxide (B1-1).

[Production Example 2: urethane (meth) acrylate compound (A1-2)]

A hexamethylene diisocyanate trimer (a1-2) having an isocyanurate skeleton (isocyanate group content: 23.4%, average number of isocyanate groups (number of isocyanate groups)) was added to a four-necked flask equipped with a thermometer, a stirrer, 13.5 g (0.025 mole) of isocyanuric acid ethylene oxide diacrylate (a2-1) and isocyanuric acid ethylene oxide-modified triacrylate (B1-1 (Weight ratio of (a2-1) / (B1-1) = 35/65, hydroxyl value of 49.7 mg KOH / g, average number of isocyanurate structures of 1.0, number average molecular weight of 532) ), 0.03 g of dibutyltin dilaurate as a reaction catalyst and 0.08 g of 2,6-di-tert-butylcresol as a polymerization inhibitor were added and reacted at 70 ° C for 6 hours. The reaction was terminated when the residual isocyanate group became 0.1%, and 43.8 g (weight average molecular weight (Mw): 2,400) of urethane (meth) acrylate compound (A1-2) and isocyanuric acid ethylene oxide modified triacrylate (B1-1).

[Production Example 3: urethane (meth) acrylate compound (A1-3)]

To a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen gas inlet was added a hexamethylene diisocyanate trimer (a1-3) having an isocyanurate skeleton (isocyanate group content: 23.0%, average isocyanate group (A1-1), isocyanuric acid ethylene oxide diacrylate (a2-1), isocyanuric acid ethylene oxide-modified triacrylate (B1-1), isocyanuric acid ethylene oxide diacrylate (Weight ratio of (a2-1) / (B1-1) = 35/65, hydroxyl value of 49.7 mg KOH / g, average number of isocyanurate structures of 1.0, number average molecular weight of 532) ), 0.03 g of dibutyltin dilaurate as a reaction catalyst and 0.08 g of 2,6-di-tert-butylcresol as a polymerization inhibitor were added and reacted at 70 ° C for 6 hours. The reaction was terminated when the residual isocyanate group became 0.1%, and 43.9 g (weight average molecular weight (Mw): 2,300) of urethane (meth) acrylate compound (A1-3) and isocyanuric acid ethyleneoxide modified triacrylate B1-1).

[Production Example 4: urethane (meth) acrylate compound (A1-4)]

To a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen gas inlet was added a hexamethylene diisocyanate trimer (a1-3) having an isocyanurate skeleton (isocyanate group content: 23.0%, average isocyanate group 28.4 g (0.052 mol) of isocyanuric acid ethylene oxide diacrylate (a2-1) and isocyanuric acid ethylene oxide-modified monoacrylate (a2-2 (A2-1) / (a2-2) / (B1-1) = 50/13/37, a hydroxyl value of 124 mg, and an isocyanuric acid ethylene oxide modified triacrylate 71.6 g (0.158 mol) of a polyoxyalkylene-polyoxyalkylene copolymer (KOH / g, number average structure of isocyanurate of 1.0, number average molecular weight of 524), 0.03 g of dibutyltin dilaurate as a reaction catalyst, And 0.08 g of cresol were added and reacted for 6 hours at 70 ° C. The residual isocyanate group was 0.1% The reaction was terminated at the point of time, and 73.5 g of a urethane (meth) acrylate compound (A1-4) (weight average molecular weight (Mw): 5,200), 26.5 g of isocyanuric acid ethyleneoxide modified triacrylate &Lt; / RTI &gt;

[Production Example 5: urethane (meth) acrylate compound (A2-1)]

 To a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen gas inlet was added a hexamethylene diisocyanate trimer (a1-3) having an isocyanurate skeleton (isocyanate group content: 23.0%, average isocyanate group 20.3 g (0.037 mol) of isocyanuric acid ethylene oxide diacrylate (a2-1) and isocyanuric acid ethylene oxide-modified triacrylate (B1-1 ) (A weight ratio of (a2-1) / (B1-1) = 35/65, hydroxyl value of 49.7 mg KOH / g, average number of isocyanurate structures of 1.0, number average molecular weight of 532) ), 0.03 g of dibutyltin dilaurate as a reaction catalyst and 0.08 g of 2,6-di-tert-butylcresol as a polymerization inhibitor were added and reacted at 70 ° C for 3 hours. Then, cyclohexanedimethanol 3.2 g (0.022 mol) of a3-1) were added and reacted at 70 DEG C for 3 hours. (Weight ratio of (a2-1) / (B1-1) = 35/65) containing isocyanuric acid ethylene oxide diacrylate (a2-1) and isocyanuric acid ethylene oxide modified triacrylate (B1-1) , Hydroxyl value of 49.7 mg KOH / g, average number of isocyanurate structures of 1.0, number average molecular weight of 884), and the reaction was carried out for 3 hours. , And a mixture of 50.8 g of a urethane (meth) acrylate compound (A2-1) (weight average molecular weight (Mw): 8, 600) and 49.2 g of isocyanuric acid ethylene oxide modified triacrylate (B1-1) .

[Comparative Preparation Example 1: urethane (meth) acrylate compound (A'-1)]

(A1-1) of hexamethylene diisocyanate having an isocyanurate skeleton (isocyanate group content: 21.1%, average number of isocyanate groups (number average molecular weight of isocyanate group 28.7 g (0.048 mole) of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (hydroxyl value: 117.2 mg KOH / g), 71.3 g 0.149 moles), 0.03 g of dibutyltin dilaurate as a reaction catalyst and 0.08 g of 2,6-di-tert-butylcresol as a polymerization inhibitor were added and reacted at 70 ° C for 6 hours. The reaction was terminated when the remaining isocyanate group became 0.1%, and the reaction was carried out with 70.0 g of a urethane (meth) acrylate compound (A'-1) (weight average molecular weight (Mw): 9,900) and 30.0 g of pentaerythritol tetraacrylate A mixture was obtained.

[Comparative Preparation Example 2: urethane (meth) acrylate compound (A'-2)]

To a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen gas inlet, 6.6 g (0.03 mol) of isophorone diisocyanate, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate 48 mg KOH / g) as a polymerization inhibitor, 0.06 g of 2,6-di-tert-butylcresol as a polymerization inhibitor and 0.02 g of dibutyltin dilaurate as a reaction catalyst were added and reacted at 60 ° C to obtain a residual isocyanate group (A'-2) (weight average molecular weight (Mw): 2,200) having no isocyanurate structure and 44.0 g of dipentaerythritol pentaacrylate A mixture of 8.6 g of unreacted portion of the cryate (B-3) and 47.4 g of dipentaerythritol hexaacrylate (B-2) was obtained.

[Comparative Preparation Example 3: urethane (meth) acrylate compound (A'-3)]

(0.081 mole) of isophorone diisocyanate, a bifunctional hydrogenated polybutadiene polyol (hydroxyl value of 65.5 mg KOH / g, number average molecular weight of 1,700) was added to a four-necked flask equipped with a thermometer, a stirrer, a water- And 0.02 g of dibutyltin dilaurate as a reaction catalyst were placed and reacted at 80 ° C for 6 hours. Then, 12.0 g (0.083 mol) of 4-hydroxybutyl acrylate and 2.6 g Tert-butylcresol were added and reacted at 60 ° C for 3 hours. When the residual isocyanate group became 0.3%, the reaction was terminated and urethane acrylate (A'-3) having no isocyanurate structure was obtained. (Weight average molecular weight (Mw): 7, 800).

&Lt; Example 1 &gt;

A mixture of 45 parts of the urethane (meth) acrylate compound (A1-1) obtained in Production Example 1 and 55 parts of isocyanuric acid ethylene oxide-modified triacrylate (B1-1) 4 parts of hydroxy-cyclohexyl-phenyl-ketone (IRGACURE 184, manufactured by BASF Japan) and 150 parts of ethyl acetate as a diluting solvent were uniformly mixed to obtain an active energy ray curable resin composition. The concentration of the isocyanurate structure in the curing component contained in the obtained active energy ray-curable resin composition was 2.02 mmol / g.

&Lt; Example 2 &gt;

A mixture of 44 parts of the urethane (meth) acrylate compound (A1-2) obtained in Production Example 2 and 56 parts of isocyanuric acid ethylene oxide-modified triacrylate (B1-1) as the photopolymerization initiator (C) 4 parts of hydroxy-cyclohexyl-phenyl-ketone ("IRGACURE 184" manufactured by BASF Japan) and 150 parts of ethyl acetate as a diluting solvent were uniformly mixed to obtain an active energy ray curable resin composition. The concentration of the isocyanurate structure in the curing component contained in the obtained active energy ray-curable resin composition was 1.97 mmol / g.

&Lt; Example 3 &gt;

A mixture of 44 parts of the urethane (meth) acrylate compound (A1-3) obtained in Preparation Example 3 and 56 parts of isocyanuric acid ethylene oxide-modified triacrylate (B1-1) as the photopolymerization initiator (C) (IRGACURE 184, manufactured by BASF Japan) and 150 parts of ethyl acetate as a diluting solvent were uniformly mixed to obtain an active energy ray curable resin composition. The concentration of the isocyanurate structure in the curing component contained in the obtained active energy ray-curable resin composition was 1.94 mmol / g.

<Example 4>

A mixture of 73 parts of the urethane (meth) acrylate compound (A1-4) obtained in Production Example 4 and 27 parts of isocyanuric acid ethylene oxide-modified triacrylate (B1-1) as the photopolymerization initiator (C) (IRGACURE 184, manufactured by BASF Japan) and 150 parts of ethyl acetate as a diluting solvent were uniformly mixed to obtain an active energy ray curable resin composition. The concentration of the isocyanurate structure in the curing component contained in the obtained active energy ray-curable resin composition was 2.02 mmol / g.

&Lt; Example 5 &gt;

A mixture of 51 parts of the urethane (meth) acrylate compound (A2-1) obtained in Production Example 5 and 49 parts of isocyanuric acid ethylene oxide-modified triacrylate (B1-1) 4 parts of hydroxy-cyclohexyl-phenyl-ketone ("IRGACURE 184" manufactured by BASF Japan) and 150 parts of ethyl acetate as a diluting solvent were uniformly mixed to obtain an active energy ray curable resin composition. The concentration of the isocyanurate structure in the curing component contained in the obtained active energy ray-curable resin composition was 1.91 mmol / g.

&Lt; Comparative Example 1 &

A mixture of 70 parts of the urethane (meth) acrylate compound (A'-1) obtained in Comparative Preparation Example 1 and 30 parts of pentaerythritol tetraacrylate (B-1), 1 part of a mixture of 1-hydroxy 4 parts of cyclohexyl-phenyl-ketone (IRGACURE 184, manufactured by BASF Japan) and 150 parts of ethyl acetate as a diluting solvent were uniformly mixed to obtain an active energy ray curable resin composition. The concentration of the isocyanurate structure in the curing component contained in the obtained active energy ray-curable resin composition was 0.82 mmol / g.

&Lt; Comparative Example 2 &

44 parts of the urethane (meth) acrylate compound (A'-2) obtained in Comparative Preparation Example 2, 47 parts of dipentaerythritol hexaacrylate (B-2), 45 parts of dipentaerythritol pentaacrylate (B- 3), 4 parts of 1-hydroxy-cyclohexyl-phenyl-ketone ("IRGACURE 184" manufactured by BASF Japan) as a photopolymerization initiator (C) and 150 parts of ethyl acetate as a diluting solvent To obtain an active energy ray curable resin composition. The concentration of the isocyanurate structure in the curing component contained in the obtained active energy ray-curable resin composition was 0 mmol / g.

&Lt; Comparative Example 3 &

100 parts by weight of a mixture of isocyanuric acid ethylene oxide diacrylate (B1-2) and isocyanuric acid ethylene oxide modified triacrylate (B1-1) (content ratio by weight: (B1-2) / (B1-1) = 10 / , 4 parts of 1-hydroxy-cyclohexyl-phenyl-ketone ("IRGACURE 184" manufactured by BASF Japan) as a photopolymerization initiator (C) And 150 parts of ethyl acetate as a solvent were uniformly mixed to obtain an active energy ray curable resin composition. The concentration of the isocyanurate structure in the curing component contained in the obtained active energy ray-curable resin composition was 1.88 mmol / g.

&Lt; Comparative Example 4 &

100 parts of the urethane (meth) acrylate-based compound (A'-3) obtained in Comparative Preparation Example 3, 1 part of 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF Japan Ltd., IRGACURE 184 ) And 150 parts of toluene as a diluting solvent were uniformly mixed to obtain an active energy ray curable resin composition. The concentration of the isocyanurate structure in the curing component contained in the obtained active energy ray-curable resin composition was 0 mmol / g.

The active energy ray-curable resin compositions of Examples 1 to 5 and Comparative Examples 1 to 4 were evaluated as follows. The results are shown in Table 1.

[Preparation of evaluation coating film sample]

The active energy ray curable resin composition obtained in Examples 1 to 5 and Comparative Examples 1 to 4 was applied onto a 125 μm thick PET film provided with a reverse adhesive layer using a bar coater and the film thickness after curing was measured in accordance with the following evaluation , And dried at 60 DEG C for 3 minutes. Thereafter, 2 passes of ultraviolet irradiation (cumulative dose: 500 mJ / cm 2) was carried out from a height of 18 cm to a conveyor speed of 5.1 m / min using a high pressure mercury lamp 80 W, 1 lamp or the like to form a cured coating film.

The active energy ray curable resin composition obtained in Comparative Example 4 was applied onto a 125 占 퐉 thick PET film provided with a reverse adhesion layer by means of a bar coater so that the film thickness after curing became a thickness conforming to each evaluation as described below And dried at 90 캜 for 3 minutes. Thereafter, a 2-pass ultraviolet ray irradiation (cumulative dose: 800 mJ / cm 2) was carried out from a height of 18 cm to a conveyor speed of 3.4 m / min using a high-pressure mercury lamp 80 W, 1 or the like to form a cured coating film.

<Pencil hardness>

The pencil hardness of the cured coating film (film thickness 10 mu m) obtained above was measured according to JIS K 5600-5-4.

(evaluation)

○ · · · H or more

X ... F or less

<Scratch resistance>

The cured coating film (film thickness 10 mu m) obtained above was reciprocated five times by using a brass second-order brush, and the coating film was scratched. The degree of surface damage was visually observed and evaluated as follows did.

(evaluation)

○ · · · There was no scratch.

× ... There was a scratch.

<Flexibility>

The cured coating film (film thickness: 5 mu m) obtained above was evaluated in accordance with JIS K 5600-5-1 using a cylindrical mandrel bending test machine. The maximum diameter (integer value, mm) at which cracking or peeling occurred when the cured coating film for evaluation was wound on the test rod was measured and evaluated as follows.

(evaluation)

&Amp;bull; &amp;bull; 2 &amp;le; (no cracking or peeling occurs even at a diameter of 2 mm)

X 2 or more

<Water vapor barrier property>

The amount of the diluting solvent was changed to 11 parts per 100 parts in total of the urethane (meth) acrylate compound (A) or (A ') and the ethylenically unsaturated compound (B) in Examples 1 to 5 and Comparative Examples 1 to 4 The same operation as in Example 1 was carried out except for changing the composition to obtain an active energy ray curable resin composition.

(How to measure)

The active energy ray-curable resin compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 3 were coated on an untreated PET film with an applicator so that the film thickness after curing became approximately 50 占 퐉 and dried at 60 占 폚 for 20 minutes And then laminated with a peelable PET film. Thereafter, it was cut into a circle having a diameter of 7 cm, and irradiated with 2 passes of ultraviolet rays (cumulative dose: 500 mJ / cm 2) at a conveyor speed of 5.1 m / min from a height of 18 cm using a high pressure mercury lamp 80 W, Thereby forming an attachment sheet. The untreated PET film and the peelable PET film were peeled off from the sheet, and the cured coating film monolayer was taken out to obtain a sample for measurement of steam permeability.

The active energy ray-curable resin composition obtained in Comparative Example 4 was coated on an untreated PET film with an applicator so that the film thickness after curing became approximately 50 占 퐉, dried at 90 占 폚 for 20 minutes, (Total irradiation amount 800 mJ / cm 2) at a conveyor speed of 3.4 m / min from a height of 18 cm using a high-pressure mercury lamp 80 W, a first lamp, and the like. To form a cured coated film-attached sheet. The untreated PET film and the peelable PET film were peeled off from the sheet, and the cured coating film monolayer was taken out to obtain a sample for measurement of steam permeability.

The measurement of the water vapor permeability was carried out by a cylindrical flat plate method conforming to JIS Z 0208 and evaluated in an atmosphere of 40 ° C and 90% RH. The evaluation criteria are as follows.

(evaluation)

○ · · · Water vapor permeability is less than 50g / ㎡ · day

× · · · The water vapor transmission rate is greater than 50 g / m 2 · day

&Lt; Oxygen barrier property &

The amount of the diluting solvent was changed to 11 parts with respect to 100 parts in total of the urethane (meth) acrylate compound (A) or (A ') and the ethylenically unsaturated compound (B) in Examples 1 to 5 and Comparative Examples 1 to 4 , An active energy ray curable resin composition was obtained.

(How to measure)

The active energy ray-curable resin compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 4 were coated on an untreated PET film so as to have a film thickness after curing of about 70 μm using an applicator, After drying for several minutes, two passes of ultraviolet irradiation (cumulative dose: 500 mJ / cm 2) were carried out from a height of 18 cm at a conveyor speed of 5.1 m / min using a high pressure mercury lamp of 80 W and 1 to obtain a sample for measurement of oxygen permeability.

The active energy ray-curable resin composition obtained in Comparative Example 4 was coated on the untreated PET film with an applicator so as to have a film thickness after curing of about 70 탆 and dried at 90 캜 for 20 minutes. Then, a high-pressure mercury lamp 80 W , And the like were used to conduct 2 pass ultraviolet irradiation (cumulative dose: 800 mJ / cm 2) at a conveyor speed of 3.4 m / min from a height of 18 cm to obtain a sample for measurement of oxygen permeability.

The measurement was carried out at 23 DEG C and 80% RH using an oxygen permeability tester (Oxtran100A, manufactured by MOCON CORPORATION). Thereafter, the oxygen permeability (cc / m 2 · day · atm) of the cured coating membrane layer after 100 μm was calculated. The oxygen permeability was measured by the method according to JIS K 7126 and evaluated under an atmosphere of 23 ° C and 80% RH. The evaluation criteria are as follows.

(evaluation)

Oxygen permeability less than 10 cc / m 2 day atm

× · · · The oxygen permeability is greater than 10 cc / m 2 · day · atm

From Table 1, it can be seen that the active energy ray-curable resin compositions of Examples 1 to 5 can obtain a cured coating film excellent in balance in hardness, scratch resistance, flexibility, water vapor barrier property and oxygen barrier property. Therefore, even when the active energy ray-curable resin compositions of Examples 1 to 5 were used as a coating agent, they were well balanced in hardness, scratch resistance, flexibility, water vapor barrier property and oxygen barrier property.

On the other hand, in Comparative Example 1 in which the number of isocyanurate structures per molecule in the composition was lower than that defined in the present invention, the flexibility of the cured coating film could not be sufficiently obtained.

In Comparative Example 2, which contained a urethane (meth) acrylate compound having no isocyanurate structure and no urethane (meth) acrylate compound having an isocyanurate structure, the water vapor permeability and The oxygen permeability was high, the gas barrier property was poor, and the flexibility was also not obtained.

In Comparative Example 3 using only an ethylenically unsaturated monomer having an isocyanurate structure and containing no urethane (meth) acrylate compound, the flexibility of the cured coating film was not sufficient.

Further, it is preferable that the urethane (meth) acrylate compound having no isocyanurate structure is contained, and the urethane (meth) acrylate compound having an isocyanurate structure is not contained. On the other hand, And Comparative Example 4, which did not contain an ethylenically unsaturated monomer having a hydroxyl group, was poor in hardness and scratch resistance.

That is, in the active energy ray-curable resin composition of the comparative example which does not satisfy the constituent requirements of the present invention, a cured coating film satisfying all of the hardness, scratch resistance, flexibility and gas barrier property can not be obtained.

Although the embodiment has been described in the concrete form of the present invention, the embodiment is merely an example and is not to be construed as limiting. Various modifications that are obvious to those skilled in the art are expected to be within the scope of the present invention.

The active energy ray-curable resin composition of the present invention is useful as various film-forming materials. In particular, it is useful as various coating agents such as optical display members, coatings for protective films of touch panels, and undercoats. It is also useful as an adhesive layer between optical display members and an encapsulating material of an organic EL display element. A gas barrier film or sheet may be molded.

Claims (9)

(Meth) acrylate compound (A) having at least three isocyanurate structures per molecule. The method according to claim 1,
(Meth) acrylate compound (a2) having an isocyanurate structure other than the isocyanurate compound (a1) and the above component (a1) in the urethane (meth) acrylate compound Wherein the active energy ray-curable resin composition is a urethane (meth) acrylate compound (A1) as a reaction product. The method according to claim 1,
Wherein the urethane (meth) acrylate compound (A) is an isocyanurate compound (a1), a hydroxyl group-containing (meth) acrylate compound (a2) having an isocyanurate structure other than the component (a1) Wherein the urethane (meth) acrylate compound (A2) is a reaction product of a urethane (meth) acrylate compound and a chain extender (a3). The method according to claim 2 or 3,
Wherein the hydroxyl group-containing (meth) acrylate compound (a2) having an isocyanurate structure has a number average molecular weight of 200 to 2,000. 5. The method according to any one of claims 1 to 4,
Wherein the urethane (meth) acrylate compound (A) has a weight average molecular weight of 1,000 to 20,000. The method of claim 2,
The (meth) acrylate compound (A1) is obtained by reacting the isocyanurate compound (a1) and the hydroxyl group-containing (meth) acrylate compound (a2) having the isocyanurate structure with (a1) :( a2) = 1: 2 to 1: 10. The active energy ray-curable resin composition according to claim 1, 7. The method according to any one of claims 1 to 6,
And an ethylenically unsaturated group-containing monomer (B1) having a socyanurate structure is further contained in the active energy ray-curable resin composition. The method according to any one of claims 1 to 7,
Wherein the concentration of the isocyanurate structure in the curing component contained in the active energy ray-curable resin composition is 1.0 mmol / g or more. A coating agent comprising the active energy ray-curable resin composition according to any one of claims 1 to 8.