JP7408910B2 - Active energy ray-curable resin composition and coating agent - Google Patents

Description

The present invention relates to active energy ray-curable resin compositions and coating agents containing a urethane (meth)acrylate composition and a fluorine-containing (meth)acrylate compound, and more specifically, when a cured coating film is formed. In addition, it has low curing shrinkage, is resistant to curling, has excellent flexibility, and has excellent antifouling performance (stain resistance and durability) and cured coating properties (appearance, hardness, and scratch resistance). The present invention relates to an active energy ray-curable resin composition capable of forming a coating film and a coating agent using the same.

Conventionally, active energy ray-curable resin compositions are cured by irradiation with active energy rays such as radiation or ultraviolet rays for a very short period of time, so they can be used as coating agents, adhesives, or anchor coating agents for various substrates. It is widely used, and urethane (meth)acrylate compounds and polyfunctional monomers are used as curing components. However, when an active energy ray-curable resin composition is used as a coating agent, especially a hard coat coating agent, there is a problem that the cured coating shrinks and the cured coating tends to curl. What is needed is something difficult.

In addition, since hard coat coating agents are used as protective films on curved parts of molded products and displays, flexibility is required so that cracks do not easily occur even when the plastic film on which the cured coating has been formed is bent. There is.

Regarding the above-mentioned difficulty in curling, in order to suppress curing shrinkage, curable resin compositions in which inorganic fine particles are added to curable resin (for example, see Patent Document 1), and urethane with high molecular weight as a curing component ( A curable resin composition containing meth)acrylate (see, for example, Patent Document 2) has been proposed. Furthermore, as a method for increasing the hardness of the hard coat layer in order to improve the scratch resistance, for example, a resin composition containing dipentaerythritol hexaacrylate and tripentaerythritol octaacrylate is known (for example, (See Patent Document 3). The film obtained by applying this resin composition to a thickness of 12 μm on a triacetyl cellulose film having a thickness of 80 μm and curing it exhibits a hardness of about 5H in pencil hardness. Furthermore, as a hard coating agent with surface hardness and scratch resistance that can replace glass, scratch resistance can be improved by adding a fluorine compound to a curing component mainly consisting of dipentaerythritol hexaacrylate and N-substituted acrylamide. is shown (see Patent Document 4). The film obtained by applying this hard coating agent to a thickness of 11 μm on a laminated film and curing it has a hardness of approximately 5H on the pencil hardness scale and is resistant to scratches even after 500 reciprocations with steel wool under a load of 500 g. Expresses scratchiness.

Japanese Patent Application Publication No. 2010-77292 Japanese Patent Application Publication No. 2010-180319 JP2009-286924A Japanese Patent Application Publication No. 2017-141416

However, the technique disclosed in Patent Document 1 has a problem in that the organic solvents that can be used are limited in consideration of the compatibility between the inorganic fine particles and the curable resin, which increases the possibility that surface abnormalities of the coating film will occur. Furthermore, since inorganic fine particles are generally expensive, resins and paints containing them are also expensive, and in reality, the use of curable resins has been limited to special uses.

In addition, in the technology disclosed in Patent Document 2, the manufacturing method for increasing the molecular weight of urethane (meth)acrylate used as a curing component involves a multi-stage reaction, which takes time and reduces the scratch resistance of the coating film. It was expected to decline.

On the other hand, in the technology disclosed in Patent Document 3, although the surface hardness of the cured coating film is high, the curling that occurs during curing is large, and the coating film is hard and brittle, so that cracks occur when the coating film is bent. Met.

Furthermore, although the technique disclosed in Patent Document 4 has excellent surface hardness of the cured coating film and scratch resistance under a load of 500 g, there is no description regarding the scratch resistance under a load of 1 kg, which is more severe, and the minimum bending radius is large, resulting in It was lacking in sex.

In addition, in recent years, if fingerprints or other dirt adheres to the surface of displays, monitors, touch-panel devices, or electronic products such as mobile phones, the transparency and sharpness of the screen may deteriorate. , the aesthetics may be impaired, so there are various methods for wiping off dirt, consideration of coating agents to improve dirt adhesion prevention and dirt removal properties, and coating film surfaces when top-coated with coating agents. There are also increasing demands for antifouling performance and scratch resistance of coating film surfaces, such as examination of scratch resistance.

Therefore, in the present invention, when a cured coating film is formed, it is possible to form a coating film that has little curing shrinkage, is resistant to curling, and has excellent flexibility. Active energy containing a urethane (meth)acrylate composition that can form a coating film with excellent stain performance (stain resistance and durability) and cured coating film characteristics (appearance, hardness, scratch resistance) The object of the present invention is to provide a line-curable resin composition and a coating agent using the same.

However, as a result of extensive research in view of the above circumstances, the present inventors have developed a urethane (meth)acrylate composition obtained by reacting a (meth)acrylic acid adduct of dipentaerythritol with a polyvalent isocyanate as a curing component. In the active energy ray-curable resin composition containing the polyvalent isocyanate, at least one xylylene diisocyanate-based compound selected from the group consisting of xylylene diisocyanate, hydrogenated xylylene diisocyanate, and derivatives thereof, Production of a urethane (meth)acrylate composition by using a (meth)acrylic acid adduct of dipentaerythritol with a higher hydroxyl value than usual and further containing a fluorine-containing (meth)acrylate compound. A cured coating film that has excellent reaction efficiency when formed, has small curing shrinkage, is resistant to curling, has excellent flexibility, and has excellent coating properties such as antifouling performance and scratch resistance. The present invention was completed based on the discovery that the following can be obtained.

That is, the present invention provides a group consisting of a hydroxyl group in the (meth)acrylic acid adduct (A) of dipentaerythritol having a hydroxyl value of 60 mgKOH/g or more, and xylylene diisocyanate, hydrogenated xylylene diisocyanate, and derivatives thereof. A urethane (meth)acrylate composition [I] reacted with the isocyanate group of at least one xylylene diisocyanate compound (B) selected from The first aspect is an active energy ray-curable resin composition.
Moreover, the second aspect is a coating agent containing the active energy ray-curable resin composition according to the first aspect.

The active energy ray-curable resin composition of the present invention combines the hydroxyl group in the (meth)acrylic acid adduct (A) of dipentaerythritol having a hydroxyl value of 60 mgKOH/g or more, xylylene diisocyanate, and hydrogenated xylylene diisocyanate. Urethane (meth)acrylate composition [I] and fluorine-containing (meth)acrylate compound reacted with the isocyanate group of at least one xylylene diisocyanate compound (B) selected from the group consisting of and derivatives thereof [II]. Therefore, it is possible to form a cured coating film that has small curing shrinkage, is hard to curl, and has excellent flexibility, and furthermore, when formed into a cured coating film, it has excellent antifouling performance and scratch resistance. Moreover, for this reason, it is particularly suitable for use as a coating agent for hard coats or a coating agent for optical films.

Furthermore, the polymerization inhibitor [III] is added to the total of the urethane (meth)acrylate composition [I], the fluorine-containing (meth)acrylate compound [II], and the polymerization inhibitor [III] on a weight basis. When the content is 800 to 10,000 ppm, the liquid stability of the active energy ray-curable resin composition is improved and gelation during storage can be suppressed.

When the fluorine-containing (meth)acrylate compound [II] has a siloxane bond, it has better antifouling performance.

Further, when the weight average molecular weight of the fluorine-containing (meth)acrylate compound [II] is 1,000 to 100,000, the antifouling performance will be even more excellent.

When the weight average molecular weight of the urethane (meth)acrylate composition [I] is 3,000 to 30,000, a cured coating film with smaller curing shrinkage, less curling, and excellent flexibility can be obtained. Furthermore, when a cured coating film is formed, it has excellent scratch resistance.

The present invention will be explained in detail below.
In the present invention, "(meth)acrylic" means acrylic or methacrylic, "(meth)acryloyl" means acryloyl or methacryloyl, and "(meth)acrylate" means acrylate or methacrylate. .

<Active energy ray curable resin composition>
The active energy ray-curable resin composition of the present invention combines the hydroxyl group in the (meth)acrylic acid adduct (A) of dipentaerythritol having a hydroxyl value of 60 mgKOH/g or more, xylylene diisocyanate, and hydrogenated xylylene diisocyanate. , and the isocyanate group of at least one xylylene diisocyanate compound (B) (hereinafter sometimes referred to as "xylylene diisocyanate compound (B)") selected from the group consisting of derivatives thereof. It contains a urethane (meth)acrylate composition [I] and a fluorine-containing (meth)acrylate compound [II] obtained by the reaction.

The urethane (meth)acrylate composition [I] is composed of a hydroxyl group in a (meth)acrylic acid adduct of dipentaerythritol (A) having a hydroxyl value of 60 mgKOH/g or more, and a xylylene diisocyanate compound (B). By reacting the isocyanate groups of , urethane bonds are formed and obtained.

[(meth)acrylic acid adduct of dipentaerythritol (A)]
In general, a (meth)acrylic acid adduct (A) of dipentaerythritol is one in which (meth)acrylic acid is added to all six of the six hydroxyl groups of dipentaerythritol. Dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate with 5 (meth)acrylic acid added, dipentaerythritol tetra(meth)acrylate with 4 (meth)acrylic acid added Diol, dipentaerythritol tri(meth)acrylate triol with (meth)acrylic acid added to 3 pieces, dipentaerythritol di(meth)acrylate tetraol with 2 pieces of (meth)acrylic acid added, only 1 piece It is a mixture containing dipentaerythritol (meth)acrylate pentaol to which (meth)acrylic acid is added.
The (meth)acrylic acid adduct of dipentaerythritol (A) may be one prepared by reacting dipentaerythritol and (meth)acrylic acid by a commonly known method.

The dipentaerythritol (meth)acrylic acid adduct (A) used in the present invention is characterized by having a higher hydroxyl value than the usual dipentaerythritol (meth)acrylic acid adduct.
Furthermore, in the present invention, the hydroxyl value of the (meth)acrylic acid adduct of dipentaerythritol (A) means the hydroxyl value of the entire mixture of the (meth)acrylic acid adduct of dipentaerythritol. .

The hydroxyl value of the dipentaerythritol (meth)acrylic acid adduct (A) needs to be 60 mgKOH/g or more, preferably 63 to 120 mgKOH/g, particularly preferably 65 to 100 mgKOH/g. be.
If the hydroxyl value is too low, the content of dipentaerythritol hexa(meth)acrylate, which has a low molecular weight and a large number of ethylenically unsaturated groups and does not react with isocyanates, will increase, resulting in large curing shrinkage and curling. This is undesirable because it becomes easy to bend, and furthermore, the flexibility decreases. In addition, normally, when the above-mentioned hydroxyl value becomes too large, the content of polyol components such as dipentaerythritol tetra(meth)acrylate diol and dipentaerythritol tri(meth)acrylate triol increases, so the molecular weight of the obtained urethane acrylate decreases. It tends to become difficult to handle because it increases in size and viscosity.
The hydroxyl value is adjusted, for example, by adjusting the ratio of (meth)acrylic acid added to dipentaerythritol.
Further, the above-mentioned hydroxyl value can be determined by a method according to JIS K 1557-1.

[Xylylene diisocyanate compound (B)]
The present invention is characterized in that a xylylene diisocyanate compound (B) is used as the isocyanate that reacts with the hydroxyl group of the (meth)acrylic acid adduct of dipentaerythritol (A), thereby curing. When a coating film is formed, a cured coating film that exhibits little curing shrinkage, is resistant to curling, and has excellent flexibility can be obtained. Furthermore, even when a (meth)acrylic acid adduct of dipentaerythritol (A) with a high hydroxyl value is used, the hydroxyl group and isocyanate group in the (meth)acrylic acid adduct of dipentaerythritol (A) are The reaction efficiency is improved, and the urethane (meth)acrylate composition [I] can be obtained efficiently.

Examples of the xylylene diisocyanate compound (B) include xylylene diisocyanate, hydrogenated xylylene diisocyanate, and tetramethylxylylene diisocyanate. Preference is given to using diisocyanates.

Such xylylene diisocyanate compounds (B) can be used alone or in combination of two or more.

As the xylylene diisocyanate compound (B) used in the present invention, specifically, commercially available products such as "Takenate 500" and "Takenate 600" manufactured by Mitsui Chemicals may be used.

In addition, the xylylene diisocyanate compound (B) may include various polyols, such as low molecular weight polyols and high molecular weight polyols, especially polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, polybutadiene polyols, It may also be a reaction product with a polyol such as (meth)acrylic polyol.

Note that it is possible to use a small amount of polyvalent isocyanate compounds other than the xylylene diisocyanate compound (B) as long as the effects of the present invention are not impaired.
Examples of polyvalent isocyanate compounds other than the xylylene diisocyanate compound (B) include aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, or trimer compounds or polymers of these polyisocyanates. Examples include compounds.

[Method for producing urethane (meth)acrylate composition [I]]
The urethane (meth)acrylate composition [I] used in the present invention consists of a hydroxyl group in the (meth)acrylic acid adduct (A) of dipentaerythritol having a hydroxyl value of 60 mgKOH/g or more, and a xylylene diisocyanate-based composition. It is obtained by reacting the isocyanate group of the compound (B) with the isocyanate group of the xylylene diisocyanate compound (B) and the hydroxyl group in the (meth)acrylic acid adduct of dipentaerythritol (A). The xylylene diisocyanate compound (B) and the (meth)acrylic acid adduct of dipentaerythritol (A) are reacted by adjusting the molar ratio of the functional groups and using a catalyst such as dibutyltin dilaurate as necessary. You can get it.

The reaction molar ratio of the xylylene diisocyanate compound (B) and the (meth)acrylic acid adduct of dipentaerythritol (A) is xylylene diisocyanate compound (B):(meth)acrylic acid adduct of dipentaerythritol. Acid adduct (A) is about 1:2 to 1:5.

If the ratio of the dipentaerythritol (meth)acrylic acid adduct (A) is too high, the content of low molecular weight monomers such as dipentaerythritol hexa(meth)acrylate that does not react with the xylylene diisocyanate compound (B) will decrease. If the ratio of dipentaerythritol (meth)acrylic acid adduct (A) is too small, unreacted xylylene diisocyanate compound (B) remains, which tends to reduce the stability and safety of the cured coating.

The reaction between the (meth)acrylic acid adduct of dipentaerythritol (A) and the xylylene diisocyanate-based compound (B) is usually carried out using the above-mentioned (meth)acrylic acid adduct of dipentaerythritol (A) and the xylylene diisocyanate-based compound. (B) may be charged into a reactor all at once or separately and reacted.

In the above reaction, it is also preferable to use a catalyst for the purpose of promoting the reaction, and such catalysts include, for example, dibutyltin dilaurate, dibutyltin diacetate, trimethyltin hydroxide, tetra-n-butyltin, zinc bisacetylacetonate. , organometallic compounds such as zirconium tris(acetylacetonate) ethyl acetoacetate, zirconium tetraacetylacetonate, tin octylate, tin octenoate, zinc hexanoate, zinc octenoate, zinc stearate, zirconium 2-ethylhexanoate, Metal salts such as cobalt naphthenate, stannous chloride, stannic chloride, potassium acetate, triethylamine, triethylenediamine, benzyldiethylamine, 1,4-diazabicyclo[2,2,2]octane, 1,8-diazabicyclo[5] ,4,0]undecene, N,N,N',N'-tetramethyl-1,3-butanediamine, N-methylmorpholine, N-ethylmorpholine and other amine catalysts, bismuth nitrate, bismuth bromide, iodine In addition to bismuth chloride and bismuth sulfide, organic bismuth compounds such as dibutyl bismuth dilaurate and dioctyl bismuth dilaurate, bismuth 2-ethylhexanoate, bismuth naphthenate, bismuth isodecanoate, bismuth neodecanoate, and bismuth laurate. , organic acid bismuth salts such as bismuth maleate, bismuth stearate, bismuth oleate, bismuth linoleate, bismuth acetate, bismuth libisneodecanoate, bismuth disalicylate, and bismuth digallate. Examples include bismuth-based catalysts, among which dibutyltin dilaurate and 1,8-diazabicyclo[5,4,0]undecene are preferred. These can be used alone or in combination of two or more.

<Polymerization inhibitor [III]'>
Moreover, in the above reaction, it is preferable to further use a polymerization inhibitor [III]'. In addition, when the polymerization inhibitor [III]' is used in the above reaction, it shall be included in the content of the polymerization inhibitor [III] which will be described later.

As the polymerization inhibitor [III]', commonly known polymerization inhibitors can be used, such as p-benzoquinone, naphthoquinone, toluquinone, 2,5-diphenyl-p-benzoquinone, etc. quinones, hydroquinone, 2,5-di-t-butylhydroquinone, methylhydroquinone, hydroquinone monomethyl ether, mono-t-butylhydroquinone, 2,6-di-t-butylcresol, pt-butylcatechol, etc. Mention may be made of phenols. Among them, phenols are preferred, and 2,6-di-t-butylcresol is particularly preferred. These can be used alone or in combination of two or more.

The content of the polymerization inhibitor [III]' in the above reaction is 0.01 parts by weight per 100 parts by weight of the (meth)acrylic acid adduct of dipentaerythritol (A) and the xylylene diisocyanate compound (B). The amount is preferably 0.2 parts by weight, particularly preferably 0.02 to 0.1 parts by weight. If the content of the polymerization inhibitor [III]' is too small, the liquid stability of the urethane (meth)acrylate composition [I] tends to decrease, and it tends to gel more easily during storage. . Furthermore, if the content of the polymerization inhibitor [III]' is too large, it tends to be difficult to cure even when irradiated with active energy rays.

In the above reaction, organic solvents that do not have functional groups that react with isocyanate groups, such as esters such as ethyl acetate, butyl acetate, and 2-methoxy-1-methylethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, etc. Organic solvents such as ketones, aromatics such as toluene and xylene can be used.

The reaction temperature is usually 30 to 90°C, preferably 40 to 80°C, and the reaction time is usually 2 to 30 hours, preferably 3 to 20 hours.

In this way, the urethane (meth)acrylate composition [I] used in the present invention is obtained.
The urethane (meth)acrylate composition [I] contains multiple types of urethane (meth)acrylates, and further contains dipentaerythritol di(meth)acrylate (A) which is a (meth)acrylic acid adduct of dipentaerythritol. ) acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, polypentaerythritol poly(meth)acrylate other than the above It may contain etc.

The weight average molecular weight of the urethane (meth)acrylate composition [I] is preferably 3,000 to 30,000, more preferably 3,200 to 20,000, particularly preferably 3,500 to 10 ,000.
If the weight average molecular weight is too small, the cured coating film tends to become brittle, while if it is too large, it tends to become highly viscous and difficult to handle.

In the present invention, the weight average molecular weight is the weight average molecular weight in terms of standard polystyrene molecular weight, and a high performance liquid chromatograph (manufactured by Waters, "ACQUITY APC System") is equipped with a column: ACQUITY APC XT 450 x 1, ACQUITY APC It is measured by using 4 units in series: 1 x XT 200 and 2 x 45 ACQUITY APC XT.

Further, the viscosity of the urethane (meth)acrylate composition [I] at 60°C is preferably 1,000 to 300,000 mPa·s, particularly 3,000 to 200,000 mPa·s, and even 5 ,000 to 150,000 mPa·s. If the viscosity is outside the above range, coating properties tend to decrease.
The viscosity was measured using an E-type viscometer.

The content of urethane (meth)acrylate in the urethane (meth)acrylate composition [I] used in the present invention is preferably 50% by weight or more, particularly preferably 60% by weight or more, even more preferably 65% by weight or more, Particularly preferably 70% by weight or more.

<Fluorine-containing (meth)acrylate compound [II]>
The fluorine-containing (meth)acrylate compound [II] used in the present invention is a compound having a (meth)acryloyl group and a fluorine atom. Furthermore, structures other than the (meth)acryloyl group and the fluorine atom are not particularly limited, and may further contain heteroatoms such as oxygen, nitrogen, silicon, and sulfur.

The fluorine-containing (meth)acrylate compound [II] is preferably a compound in which a fluorine atom is bonded to the alkyl group of an alkyl (meth)acrylic acid ester, such as "Optool DAC" manufactured by Daikin Industries, Ltd. Optool DAC-HP”, DIC “Megafac RS-75”, “Megafac RS-76”, “Megafac RS-91C”, “Defensa TF3028”, “Defensa TF3001”, “Defensa TF3000”, Shin Nakamura "SUA1900L10", "SUA1900L6" manufactured by Kagaku Co., Ltd., "UT3971" manufactured by Nippon Gosei Chemical Co., Ltd., "KNS5300", "KY-1203" manufactured by Shin-Etsu Chemical Co., Ltd., "Viscoat 3F", "Viscoat 4F" manufactured by Osaka Organic Chemical Industry Co., Ltd. , "Viscoat 8F", "Viscoat 8FM", "Viscoat 13F", etc. These fluorine-containing (meth)acrylate compounds [II] can be used alone or in combination of two or more.

Among the above-mentioned fluorine-containing (meth)acrylate compounds [II], fluorine-containing (meth)acrylate compounds having a siloxane bond in the structure are preferable, and KY-1203 is particularly preferable, since they have better antifouling properties. .

The weight average molecular weight of the fluorine-containing (meth)acrylate compound [II] is usually 1,000 to 100,000, preferably 5,000 to 70,000, particularly preferably 10,000 to 50,000, especially It is preferably 15,000 to 40,000. If the weight average molecular weight of the fluorine-containing (meth)acrylate compound [II] is too small, sufficient scratch resistance and antifouling performance will tend to not be obtained; if the weight average molecular weight is too large, the urethane acrylate composition [I ] and the compatibility with solvents tends to decrease.

The content of the fluorine-containing (meth)acrylate compound [II] in the active energy ray-curable resin composition of the present invention is usually 0.01 parts by weight per 100 parts by weight of the urethane (meth)acrylate compound [I]. ~5 parts by weight, preferably 0.05 to 3 parts by weight, particularly preferably 0.1 to 1 part by weight. If the content of the fluorine-containing (meth)acrylate compound [II] is too low, sufficient abrasion resistance and antifouling performance tend to not be obtained; if the content is too high, the urethane (meth)acrylate composition The compatibility with substance [I] tends to decrease.

[Other optional ingredients]
The active energy ray-curable resin composition of the present invention contains the urethane (meth)acrylate composition [I] and the fluorine-containing (meth)acrylate compound [II], and is curable with active energy rays. It is preferable that the curable resin composition further contains a polymerization inhibitor [III], and it is particularly preferable that the curable resin composition further contains a photopolymerization initiator. In addition, ethylenically unsaturated monomers other than urethane (meth)acrylate, acrylic resins, surface conditioners, leveling agents, etc. can be added within the range that does not impair the effects of the present invention, and fillers, dyes and pigments, oils, etc. , plasticizers, waxes, desiccants, dispersants, wetting agents, gelling agents, stabilizers, antifoaming agents, surfactants, leveling agents, thixotropic agents, antioxidants, flame retardants, antistatic agents, It is also possible to incorporate fillers, reinforcing agents, matting agents, crosslinking agents, silica, water-dispersed or solvent-dispersed silica, zirconium compounds, preservatives, color inhibitors, and the like. These can be used alone or in combination of two or more.

As the polymerization inhibitor [III], the same one as the above-mentioned polymerization inhibitor [III]' can be used. The polymerization inhibitor [III] to be added to the active energy ray-curable resin composition is the same compound as the polymerization inhibitor [III]' used in the production of the urethane (meth)acrylate composition [I]. However, different compounds may be used.

The active energy ray-curable resin composition of the present invention preferably contains more polymerization inhibitor [III] than general active energy ray-curable resin compositions. Normally, in active energy ray-curable resin compositions, polymerization occurs more than necessary due to reasons such as lowering the active energy ray curability or causing coloration by containing a large amount of polymerization inhibitor [III]. The polymerization inhibitor [III] is not contained, and the content of the polymerization inhibitor [III] is the amount normally used when producing the above-mentioned urethane (meth)acrylate composition [I]. However, in the present invention, the content of the polymerization inhibitor is higher than that normally used in active energy ray-curable resin compositions, thereby improving liquid stability and suppressing gelation during storage. It is effective.

The content of the polymerization inhibitor [III] in the active energy ray-curable resin composition is as follows: urethane (meth)acrylate composition [I], fluorine-containing (meth)acrylate compound [II], and polymerization inhibitor [III] Based on the total amount of , particularly preferably 2,500 to 4,000 ppm. If the content of the polymerization inhibitor [III] is too small, the active energy ray-curable resin composition before curing will not have sufficient liquid stability and will tend to gel easily during storage. Furthermore, if the content of the polymerization inhibitor [III] is too large, it tends to be difficult to cure even when irradiated with active energy rays. In addition, when the polymerization inhibitor [III]' is used in the production of the urethane (meth)acrylate composition [I], the content of the polymerization inhibitor [III]' is also the same as that of the polymerization inhibitor [III] of the present invention. III].

Examples of the photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy- 2-propyl)ketone, 1-hydroxycyclohexylphenylketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propane, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane -1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer, etc. Acetophenones; Benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide , 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo Benzophenones such as -2-propenyloxy)ethyl]benzenemethanaminium bromide, (4-benzoylbenzyl)trimethylammonium chloride; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichloro Thioxanthone, 1-chloro-4-propoxythioxanthone, 2-(3-dimethylamino-2-hydroxy)-3,4-dimethyl-9H-thioxanthon-9-one mesochloride; 2,4,6- Acyls such as trimethylbenzoyl-diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, etc. Phosphone oxides, 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(o-benzoyloxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl) -9H-carbazol-3-yl]-,1-(o-acetyloxime) and other oxime esters.
Note that these photopolymerization initiators may be used alone or in combination of two or more.

Among these, benzyl dimethyl ketal, 1-hydroxycyclohexylphenyl ketone, benzoin isopropyl ether, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 2-hydroxy-2-methyl-1- Preference is given to using phenylpropan-1-one.

The content of the photopolymerization initiator is preferably 0.1 to 20 parts by weight, particularly preferably 0.5 parts by weight, based on 100 parts by weight of the curing component contained in the active energy ray-curable resin composition. The amount is preferably 1 to 10 parts by weight, more preferably 1 to 10 parts by weight.
If the content of the photopolymerization initiator is too small, curing will be poor and film formation will tend to be difficult to achieve, while if it is too large, it will cause yellowing of the cured coating film and tend to cause coloring problems.

In addition, these auxiliary agents include triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michler's ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4-dimethylaminobenzoic acid. Ethyl, (n-butoxy)ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone It is also possible to use them together.

Examples of ethylenically unsaturated monomers other than the above-mentioned urethane (meth)acrylate include monofunctional monomers, bifunctional monomers, and polyfunctional monomers having trifunctionality or higher. These ethylenically unsaturated monomers can be used alone or in combination of two or more.

Examples of such monofunctional monomers include styrene monomers such as styrene, vinyltoluene, chlorostyrene, and α-methylstyrene, methyl (meth)acrylate, ethyl (meth)acrylate, acrylonitrile, 2-methoxyethyl (meth)acrylate, 2-Hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-hydroxy -3-phenoxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, glycerin mono (meth)acrylate, glycidyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl ( meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, (2-methyl-2-ethyl- 1,3-dioxolan-4-yl)-methyl(meth)acrylate, cyclohexanespiro-2-(1,3-dioxolan-4-yl)-methyl(meth)acrylate, 3-ethyl-3-oxetanylmethyl(meth)acrylate ) acrylate, γ-butyrolactone (meth)acrylate, n-butyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (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, half (meth)acrylate of phthalic acid derivatives such as 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, furfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, carbitol (meth)acrylate, benzyl (meth)acrylate, butoxyethyl (meth)acrylate, allyl (meth)acrylate, (meth)acryloylmorpholine, polyoxyethylene secondary alkyl ether acrylate, etc. Examples include meth)acrylate monomers, 2-hydroxyethylacrylamide, N-methylol(meth)acrylamide, N-vinylpyrrolidone, 2-vinylpyridine, and vinyl acetate.

Examples of such bifunctional monomers include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and di(meth)acrylate. Propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide modified bisphenol A type di(meth)acrylate, propylene oxide modified bisphenol A type di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, ethoxylated cyclohexanedimethanol di(meth)acrylate, dimethyloldicyclopentanedi(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, 1 , 6-hexanediol di(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid di(meth)acrylate Examples include glycidyl ester di(meth)acrylate, hydroxypivalic acid-modified neopentyl glycol di(meth)acrylate, and isocyanuric acid ethylene oxide-modified diacrylate.

Such trifunctional or higher functional monomers include, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa( meth)acrylate, tri(meth)acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly(meth)acrylate, isocyanuric acid ethylene oxide modified triacrylate, caprolactone modified dipentaerythritol penta(meth)acrylate, caprolactone modified dipentaerythritol hexa (meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, ethylene oxide-modified dipentaerythritol penta(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, ethylene Examples include oxide-modified pentaerythritol tri(meth)acrylate, ethylene oxide-modified pentaerythritol tetra(meth)acrylate, and ethoxylated 15-glycerol triacrylate.

Furthermore, as the ethylenically unsaturated monomer other than urethane (meth)acrylate, a Michael adduct of acrylic acid or 2-acryloyloxyethyldicarboxylic acid monoester can also be used in combination. Such Michael adducts of acrylic acid include acrylic acid dimers, methacrylic acid dimers, acrylic acid trimers, methacrylic acid trimers, acrylic acid tetramers, methacrylic acid tetramers, and the like. The above-mentioned 2-acryloyloxyethyldicarboxylic acid monoester is a carboxylic acid having a specific substituent, such as 2-acryloyloxyethylsuccinic acid monoester, 2-methacryloyloxyethylsuccinic acid monoester, 2-acryloyloxyethyl Examples include phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethylhexahydrophthalic acid monoester, and 2-methacryloyloxyethyl hexahydrophthalic acid monoester. Furthermore, other examples include oligoester acrylates and the like.

The content of ethylenically unsaturated monomers other than urethane (meth)acrylate is preferably 70% by weight or less, particularly preferably 50% by weight, based on the total curing components contained in the active energy ray-curable resin composition. % or less, more preferably 30% by weight or less.

The surface conditioner is not particularly limited, and examples thereof include cellulose resins and alkyd resins. Such cellulose resin has the effect of improving the surface smoothness of the coating film, and the alkyd resin has the effect of imparting film-forming properties during coating.

As the above-mentioned leveling agent, any known general leveling agent can be used as long as it has the effect of imparting wettability to the base material of the coating liquid and reducing the surface tension, such as silicone-modified resin, fluorine-modified resin, etc. , alkyl-modified resin, etc. can be used.

Moreover, it is also preferable to use an organic solvent for dilution of the active energy ray-curable resin composition of the present invention, if necessary, in order to maintain an appropriate viscosity during 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; aromatics such as toluene and xylene; - Glycol ethers such as methoxy-2-propanol (also known as propylene glycol monomethyl ether), propylene glycol monomethyl ether acetate, ethyl cellosolve, acetic acid esters such as methyl acetate, ethyl acetate, butyl acetate, diacetone alcohol, etc. . These organic solvents mentioned above may be used alone or in combination of two or more. Among these, because of the excellent compatibility between the urethane (meth)acrylate composition [I] and the fluorine-containing (meth)acrylate [II], the boiling point is 80°C or higher, particularly 100°C or higher, and even 120°C or higher. A high boiling point solvent of 170° C. is preferred, alcohols and glycol ethers are more preferred, and 1-methoxy-2-propanol and propylene glycol monomethyl ether acetate are particularly preferred.

In addition, when using two or more of the above organic solvents in combination, a combination of glycol ethers such as propylene glycol monomethyl ether and ketones such as methyl ethyl ketone or alcohols such as methanol, or a combination of glycol ethers such as propylene glycol monomethyl ether, etc. Combinations of esters such as butyl acetate, combinations of ketones such as methyl ethyl ketone and alcohols such as methanol, etc. can be used.

The active energy ray-curable resin composition of the present invention comprises a urethane (meth)acrylate composition [I] and a fluorine-containing (meth)acrylate compound [II], preferably further a polymerization inhibitor [III], if necessary. It can be obtained by mixing other optional ingredients. The mixing method is not particularly limited, and various methods may be used, such as a method of mixing each component at once, or a method of mixing any component and then mixing the remaining components at once or sequentially. can do.

The active energy ray-curable resin composition of the present invention obtained in this manner combines the hydroxyl group in the (meth)acrylic acid adduct (A) of dipentaerythritol with a hydroxyl value of 60 mgKOH/g or more, xylylene diisocyanate, and hydrogenated A urethane (meth)acrylate composition [I] obtained by reacting an isocyanate group of at least one xylylene diisocyanate compound (B) selected from the group consisting of xylylene diisocyanate and derivatives thereof, and a fluorine-containing ( It contains a meth)acrylate compound [II]. Therefore, it is possible to form a cured coating film that has small curing shrinkage, is resistant to curling, and has excellent flexibility.Furthermore, the cured coating film has excellent scratch resistance and antifouling properties after being scratched. It is.

The active energy ray-curable resin composition of the present invention is effectively used as a curable composition for forming coating films, such as top coating agents and anchor coating agents on various substrates, and such active energy ray-curable resin compositions After the resin composition is applied to the base material (if a composition diluted with an organic solvent is applied, the composition is further dried) and then cured by irradiation with active energy rays.

Examples of the substrate to which the active energy ray-curable resin composition of the present invention is applied include polyolefin resins, polyester resins, polycarbonate resins, acrylonitrile butadiene styrene copolymers (ABS), and polystyrene resins. Plastic base materials such as resins, acrylic resins, etc. and their molded products (films, sheets, cups, etc.), optical films such as polyethylene terephthalate film, triacetyl cellulose film, cycloolefin film, composite base materials thereof, Or, a primer layer is provided on metal (aluminum, copper, iron, SUS, zinc, magnesium, alloys of these, etc.), glass, or composite substrates of the above materials mixed with glass fibers and inorganic substances, or on these substrates. Examples include base materials such as

Examples of the coating method for the active energy ray-curable resin composition of the present invention include wet coating methods such as spraying, showering, gravure, dipping, rolling, spinning, and screen printing, usually under room temperature conditions. It can be applied to the base material below.

Moreover, the active energy ray-curable resin composition of the present invention may be applied as is, or may be diluted with an organic solvent and applied. When diluting, it is preferable to use the organic solvent to adjust the solid content concentration to usually 3 to 60% by weight (preferably 5 to 40% by weight).

The drying conditions when diluting with the organic solvent are as follows: the temperature is usually 40 to 120°C (preferably 50 to 100°C), and the drying time is usually 1 to 20 minutes (preferably 2 to 10 minutes). That's fine.

The active energy ray-curable resin composition of the present invention preferably has a viscosity of 5 to 50,000 mPa·s, particularly preferably 10 to 10,000 mPa·s, and even more preferably 50 to 5,000 mPa·s. 000mPa・s. If the viscosity is outside the above range, coating properties tend to decrease.
The viscosity was measured using an E-type viscometer.

Examples of the active energy rays used when curing the active energy ray-curable resin composition coated on the substrate include far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, etc., X-rays, γ-rays, etc. In addition to electromagnetic waves, electron beams, proton beams, neutron beams, etc. can be used, but ultraviolet rays or electron beams are preferred from the viewpoint of curing speed, availability of irradiation equipment, cost, etc.
In addition, when curing is performed by irradiation with an electron beam, curing can be performed without using a photopolymerization initiator.

When curing by ultraviolet irradiation, use a high-pressure mercury lamp, ultra-high-pressure mercury lamp, carbon arc lamp, metal halide lamp, xenon lamp, chemical lamp, electrodeless discharge lamp, LED lamp, etc. that emit light in the wavelength range of 150 to 450 nm. Usually, ultraviolet rays of 30 to 3,000 mJ/cm ² (preferably 100 to 1,500 mJ/cm ² ) may be irradiated.
After irradiation with ultraviolet rays, heating may be performed as necessary to ensure complete curing.

The coating film thickness (film thickness after curing) is usually 1 to 1,000 μm in view of light transmission so that the photopolymerization initiator reacts uniformly as an active energy ray-curable coating film. It is preferably 2 to 500 μm, particularly preferably 3 to 200 μm.

The active energy ray-curable resin composition of the present invention is preferably used as a coating agent, and particularly preferably used as a coating agent for hard coats or a coating agent for optical films.

In addition, in the present invention, the active energy ray-curable resin composition is coated to a thickness of 5 μm on a 125 μm thick easily adhesive polyethylene terephthalate film, dried at a temperature of 90° C. for 3 minutes, and then By irradiating ultraviolet rays at a speed of 5.1 m/min with an 80 W high-pressure mercury lamp from a certain position so that the cumulative irradiation amount is 500 mJ/cm ² , the resulting cured coating film has a size of 10 cm x 10 cm. It is preferable that the coating agent forms a cured coating film having an average spring-up height of 10 mm or less, more preferably 7 mm or less, when cut out.

In addition, in the present invention, the active energy ray-curable resin composition is coated to a thickness of 5 μm on a 125 μm thick easily adhesive polyethylene terephthalate film, dried at a temperature of 90° C. for 3 minutes, and then JIS K 5600-5-1 in the cured coating film obtained by irradiating ultraviolet rays at a speed of 5.1 m/min with an 80 W high-pressure mercury lamp at a position where the cumulative irradiation amount is 500 mJ/ ^cm2 . According to the above, the flexibility was evaluated using a cylindrical mandrel bending tester, and when the cured coating film for evaluation was wrapped around a test rod, the maximum diameter (integer value, mm) at which cracking or peeling occurred was 12 mm. Hereinafter, it is preferable to use a coating agent that forms a cured coating film having a thickness of 8 mm or less.

In the present invention, a group consisting of the hydroxyl group in the (meth)acrylic acid adduct (A) of dipentaerythritol having a hydroxyl value of 60 mgKOH/g or more, xylylene diisocyanate, hydrogenated xylylene diisocyanate, and derivatives thereof A urethane (meth)acrylate composition [I] obtained by reacting with the isocyanate group of at least one xylylene diisocyanate compound (B) selected from The active energy ray-curable resin composition is capable of forming a cured coating film that exhibits small curing shrinkage, is resistant to curling, and has excellent flexibility.Furthermore, the cured coating film has excellent scratch resistance. It also has excellent antifouling properties after being scratched, and is particularly useful as a coating agent (furthermore, a coating agent for hard coats and a coating agent for optical films), as well as paints, inks, and the like.

EXAMPLES 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 it exceeds the gist thereof. In addition, in the examples, "parts" and "%" mean weight basis.

The following were prepared as urethane (meth)acrylate compositions [I] (see Table 1).

<Manufacture example 1>
[Manufacture of urethane acrylate composition [I-1]]
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet, 139.5 g (0.72 mol) of 1,3-hydrogenated xylylene diisocyanate (B-1) and hydroxyl value 96 mg KOH/ 860.5 g (1.47 mol) of acrylic acid adduct of dipentaerythritol (A-1), 0.6 g of 2,6-di-t-butylcresol as polymerization inhibitor [III-1]', reaction 0.05 g of dibutyltin dilaurate was charged as a catalyst, and the reaction was carried out at 60°C. The reaction was terminated when the remaining isocyanate groups became 0.1%, and a urethane acrylate composition [I-1] was obtained (resin minute concentration 100%).
The weight average molecular weight of the obtained urethane acrylate composition [I-1] was 5,600, and the viscosity at 60°C was 33,000 mPa·s.

<Manufacture example 2>
[Manufacture of urethane acrylate composition [I'-1]]
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet, 80.7 g (0.42 mol) of 1,3-hydrogenated xylylene diisocyanate (B-1) and a hydroxyl value of 52 mg KOH/ 919.3 g (0.85 mol) of acrylic acid adduct of dipentaerythritol (A'-1), 0.6 g of 2,6-di-t-butylcresol as polymerization inhibitor [III-1]', 0.05 g of dibutyltin dilaurate was charged as a reaction catalyst, and the reaction was carried out at 60°C. The reaction was terminated when the remaining isocyanate group became 0.1%, and a urethane acrylate composition [I'-1] was produced. .
The weight average molecular weight of the obtained urethane acrylate composition [I'-1] was 2,000, and the viscosity at 60°C was 1,900 mPa·s.

<Manufacture example 3>
[Production of urethane acrylate composition [I'-2]]
In a four-neck flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet, 156.0 g (0.70 mol) of isophorone diisocyanate (B'-1) and dipentaerythritol with a hydroxyl value of 96 mg KOH/g were added. 844.0 g (1.47 mol) of acrylic acid adduct (A-1), 0.6 g of 2,6-di-t-butylcresol as polymerization inhibitor [III-1]', 0 dibutyltin dilaurate as reaction catalyst 05 g was charged and reacted at 60° C., and the reaction was terminated when the remaining isocyanate groups reached 0.1%, producing urethane acrylate composition [I'-2].
The weight average molecular weight of the obtained urethane acrylate composition [I'-2] was 5,700, and the viscosity at 60°C was 63,000 mPa·s.

[Isocyanate consumption rate during reaction of urethane (meth)acrylate composition [I]]
During the production of the urethane acrylate compositions [I-1], [I'-1], and [I'-2] obtained above, the reference point was when all the raw materials were charged and the internal temperature reached 60°C. The contents of the flask are sampled after a certain period of time to measure the amount of remaining isocyanate groups (%), and the consumption rate (%) of isocyanate is shown in the table below when the amount of isocyanate groups in the initial charge is taken as 100%. Shown in 1.

As can be seen from Table 1, even when using the acrylic acid adduct of dipentaerythritol (A-1) whose hydroxyl value satisfies the specifications of the present invention, the specific xylylene diisocyanate-based compound defined by the present invention In production example [I'-2] in which (B) was not used, it took 30 hours to produce the urethane (meth)acrylate composition [I] until the residual isocyanate group became 0.1% or less. It took twice as long as the first method, and the reaction efficiency was very low, resulting in poor productivity.

[Manufacture of active energy ray-curable resin composition]
<Example 1>
While stirring a solution in which 100 parts of the urethane acrylate composition [I-1] obtained above was dissolved in 100 parts of 1-methoxy-2-propanol, KY- 1203 (active ingredient 20%, manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight (measured value) 27,000) as an active ingredient amount of 0.2 parts (1 part including solvent component) as a polymerization inhibitor [III-1] 0.3 parts of 2,6-di-t-butylcresol (based on the total of urethane acrylate composition [I-1], fluorine-containing acrylate compound [II-1] and polymerization inhibitor [III-1]) 2,990 ppm), 0.1 part of CSP (manufactured by Seiko Kagaku Co., Ltd.) as a coloring inhibitor, and an α-hydroxyalkylphenone photopolymerization initiator (manufactured by IGM, "Omnirad 184") as a photopolymerization initiator. 4 parts were blended to obtain an active energy ray-curable resin composition.
In the above, the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III]' used in the production of the urethane (meth)acrylate composition [I]) is the same as that of the urethane (meth)acrylate composition [I]. I], the fluorine-containing (meth)acrylate compound [II], and the polymerization inhibitor [III].

<Reference example 1>
An active energy ray-curable resin composition was obtained in the same manner as in Example 1, except that the fluorine-containing acrylate compound [II-1] was not added.
In the above, the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III]' used in the production of the urethane (meth)acrylate composition [I]) is the same as that of the urethane (meth)acrylate composition [I]. I], the fluorine-containing (meth)acrylate compound [II], and the polymerization inhibitor [III].

<Comparative example 1>
In Example 1, active energy ray curing was carried out in the same manner as in Example 1, except that the urethane acrylate composition [I'-1] obtained above was used in place of the urethane acrylate composition [I-1]. A synthetic resin composition was obtained.
In the above, the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III]' used in the production of the urethane (meth)acrylate composition [I]) is the same as that of the urethane (meth)acrylate composition [I]. I], the fluorine-containing (meth)acrylate compound [II], and the polymerization inhibitor [III].

For the active energy ray-curable resin compositions obtained using the urethane acrylate compositions [I-1] and [I'-1] obtained above, a cured coating film was formed as described below. Physical properties (curl value, flexibility, scratch resistance, hardness) were evaluated. The evaluation results are shown in Table 2.

[Method for manufacturing evaluation samples]
The active energy ray-curable resin composition obtained above was coated onto an easily adhesive PET film (manufactured by Toyobo Co., Ltd., "Cosmoshine A4300", thickness 125 μm) using a bar coater to give a film thickness of 5 μm after drying. After drying at 90°C for 3 minutes, UV irradiation was carried out in 2 passes at a conveyor speed of 5.1 m/min from a height of 18 cm using one 80 W high-pressure mercury lamp (cumulative irradiation). 500 mJ/cm ² ) to form a cured coating film.

[Curl value (jump height of four corners)]
The cured coating film coated on the easily adhesive PET film was cut out to a size of 10 cm x 10 cm, and the average value (mm) of the bounce height of the four corners was measured as the curl value. The smaller the value, the smaller the curl, meaning that the coating film is less likely to curl.

[Flexibility]
Flexibility of the cured coating film coated on the easily adhesive PET film was evaluated using a cylindrical mandrel bending tester in accordance with JIS K 5600-5-1. When the cured coating film for evaluation was wound around a test rod so that the coating surface was on the outside, the maximum diameter (integer value, mm) at which cracking or peeling occurred was measured. The smaller the value, the more flexible the coating film is.

[Scratch resistance]
Regarding the cured coating film coated on the easily adhesive PET film, the surface of the cured coating film was moved back and forth using steel wool (manufactured by Nippon Steel Wool Co., Ltd., Bonstar #0000) while applying a load of 1 kg, and the surface was visually inspected. shows the number of reciprocations until scratches occur.
(evaluation)
○...No scratches occurred even after 1,000 reciprocations △...Scars occurred after 600 or more times but less than 1,000 times ×...Scars occurred after less than 600 times

[Pencil hardness]
The cured coating film coated on the easily adhesive PET film was tested in accordance with JIS K 5600, and the pencil hardness was measured.

[Stain resistance (Magic Ink (registered trademark) wipeability)]
A line was drawn back and forth with black marker ink on the surface of the cured coating film, and after being left for 24 hours, the coating film was wiped off with a waste cloth, and the coating film was observed and evaluated as follows. Furthermore, the cured coating film after the above scratch resistance test was similarly evaluated.
(evaluation)
○...Can be wiped cleanly ×...Cannot be wiped off

From the above evaluation results, the cured coating film obtained from the active energy ray-curable resin composition containing the urethane acrylate composition [I-1] and the fluorine-containing acrylate compound [II-1] of Example 1 has a curl value of It is small and does not curl easily, has excellent flexibility and pencil hardness, and in a scratch resistance test, it did not get scratched even after 1,000 reciprocations with a 1 kg load, and the coating film after the scratch resistance test It can be seen that it also maintains excellent antifouling performance. In addition, in the production of the urethane acrylate composition [I-1] of Example 1, the time until the residual isocyanate group becomes 0.1% or less is within 15 hours, and the reaction efficiency is high and the productivity is excellent. I can see that it is something.

On the other hand, the cured coating film obtained from the active energy ray-curable resin composition of Reference Example 1, which does not contain the fluorine-containing acrylate compound [II-1], was inferior to Example 1 in the scratch resistance test, and also had antifouling performance. was not expressed.
In addition, the urethane acrylate composition [I' -1] and the fluorine-containing acrylate compound [II-1] had a large curl value and was prone to curling, and was also inferior in flexibility compared to Examples.

When the active energy ray-curable resin composition of the present invention is made into a cured coating film, it is possible to form a cured coating film that exhibits small curing shrinkage, is resistant to curling, and has excellent flexibility. It has excellent scratch resistance when formed into a coating film and antifouling property after being scratched, and is useful as a coating agent, particularly as a coating agent for hard coats and a coating agent for optical films. It is also useful as paint, ink, etc.

Claims (8)

The hydroxyl group in the (meth)acrylic acid adduct (A) of dipentaerythritol having a hydroxyl value of 65 to 100 mgKOH/g and selected from the group consisting of xylylene diisocyanate, hydrogenated xylylene diisocyanate and tetramethylxylylene diisocyanate. An active energy product containing a urethane (meth)acrylate composition [I] reacted with the isocyanate group of at least one xylylene diisocyanate compound (B) and a fluorine-containing (meth)acrylate compound [II]. A linearly curable resin composition, wherein the content of the fluorine-containing (meth)acrylate compound [II] is 0.01 to 5 parts by weight based on 100 parts by weight of the urethane (meth)acrylate composition [I]. The content of ethylenically unsaturated monomers other than urethane (meth)acrylate in the active energy ray curable resin composition is the total curing component contained in the active energy ray curable resin composition. An active energy ray-curable resin composition characterized in that the content thereof is 30% by weight or less . Furthermore, the polymerization inhibitor [III] is added to the total of the urethane (meth)acrylate composition [I], the fluorine-containing (meth)acrylate compound [II], and the polymerization inhibitor [III] on a weight basis. The active energy ray-curable resin composition according to claim 1, containing 800 to 10,000 ppm. The active energy ray-curable resin composition according to claim 1 or 2, wherein the fluorine-containing (meth)acrylate compound [II] has a siloxane bond. The active energy ray-curable resin according to any one of claims 1 to 3, wherein the fluorine-containing (meth)acrylate compound [II] has a weight average molecular weight of 1,000 to 100,000. Composition. Active energy ray curable according to any one of claims 1 to 4, wherein the urethane (meth)acrylate composition [I] has a weight average molecular weight of 3,000 to 30,000. Resin composition. A coating agent comprising the active energy ray-curable resin composition according to any one of claims 1 to 5. The coating according to claim 6, characterized in that it is used as a coating agent for hard coat. The coating agent according to claim 6, which is used as a coating agent for optical films.