JP2019085558A - Active energy ray curable resin composition and coating agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a coating film having small curing shrinkage, difficult to curl, and excellent flexibility, antifouling performance (stain resistance and its durability), characteristics of a cured coating film (appearance). , Hardness, scratch resistance), and an active energy ray-curable resin composition containing a urethane (meth) acrylate-based composition that is also excellent in reaction efficiency during production, and the active energy ray-curable resin composition. The coating agent used is provided. SOLUTION: The group consists of a hydroxyl group in a (meth) acrylic acid adduct (A) of dipentaerythritol having a hydroxyl value of 60 mgKOH / g or more, a xylylene diisocyanate, a hydrogenated xylylene diisocyanate, and derivatives thereof. An activity comprising a urethane (meth) acrylate-based composition [I] and a fluorine-containing (meth) acrylate-based compound [II] in which the isocyanate group of at least one xylylene diisocyanate compound (B) reacted with the isocyanate group. An energy ray-curable resin composition was used. [Selection diagram] None

Description

  The present invention relates to an active energy ray curable resin composition and a coating agent comprising a urethane (meth) acrylate composition and a fluorine-containing (meth) acrylate compound, and more specifically, when a cured coating film is formed. In addition, curing shrinkage is small and it is difficult to curl, and also excellent in flexibility, and excellent in antifouling performance (stain resistance and its persistence), and properties of cured film (appearance, hardness, 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, as curing of active energy ray curable resin compositions is completed by irradiation of active energy rays such as radiation or ultraviolet rays for a very short time, as a coating agent, adhesive, anchor coating agent, etc. on various substrates It is widely used, and urethane (meth) acrylate compounds and polyfunctional monomers are used as the curing component therein. However, when the active energy ray-curable resin composition is used as a coating agent, particularly as a coating agent for a hard coat, there is a problem that curing shrinkage of the coating occurs and the cured coating tends to curl. There is a need for difficult things.

  In addition, since a coating agent for hard coat is also used as a protective film in a bent portion of a molded product or a display, it is required to have flexibility such that cracks do not easily occur even if a plastic film on which a cured coating is formed is bent. There is.

  With regard to the above-mentioned curl resistance, a curable resin composition (for example, see Patent Document 1) in which inorganic fine particles are added to a curable resin in order to suppress curing shrinkage (for example, urethane having high molecular weight as a curing component A curable resin composition (see, for example, Patent Document 2) containing a meta) acrylate has been proposed. In addition, as a method for increasing the hardness of the hard coat layer to improve abrasion resistance, for example, a resin composition containing dipentaerythritol hexaacrylate and tripentaerythritol octaacrylate is known (for example, Patent Document 3). A film obtained by applying this resin composition on an 80 μm-thick triacetyl cellulose film to a film thickness of 12 μm and curing it exhibits a hardness of about 5 H of pencil hardness. Furthermore, as a hard coating agent having surface hardness and abrasion resistance replacing glass, the abrasion resistance can be increased by blending a fluorine compound in a curing component mainly composed of dipentaerythritol hexaacrylate and N-substituted acrylamide. Is shown (see Patent Document 4). A film obtained by applying this hard coating agent on a laminated film to a film thickness of 11 μm and curing it has a hardness of about 5 H with a pencil hardness, and a scratch resistance that is not scratched even with 500 g of load with steel wool. It develops scratch resistance.

Unexamined-Japanese-Patent No. 2010-77292 Unexamined-Japanese-Patent No. 2010-180319 JP, 2009-286924, A JP, 2017-141416, A

  However, in the technology disclosed in Patent Document 1, there is a problem that the organic solvents that can be used are limited in consideration of the compatibility between the inorganic fine particles and the curable resin, and the possibility of surface abnormality of the coating film becomes high. Furthermore, since inorganic fine particles are generally expensive, resins and paints containing the inorganic particles are also expensive, and the practical use of the curable resin is limited to special applications.

  Further, in the technology disclosed in Patent Document 2 described above, since the production method for increasing the molecular weight of urethane (meth) acrylate used as the curing component is a multistage reaction, the reaction takes time, and the scratch resistance of the coating is It would have fallen.

  On the other hand, in the art disclosed in Patent Document 3, although the surface hardness of the cured coating is high, the curling generated during curing is large and the coating is bent when it is bent because it is hard and brittle. Met.

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

  Also, in recent years, when dirt such as fingerprints adheres to the surface of a display or monitor, the screen of a touch panel device, or the surface of an electric appliance such as a mobile phone, the transparency of the screen or the clarity of the screen may be degraded. , Because the appearance may be impaired, various methods of removing stains, examination of coating agents to improve stain adhesion prevention and stain removability, and coating film surface when coated with a coating agent The requirements for anti-soiling performance and scratch resistance of the coating film surface, such as examination of scratch resistance, are also increasing more and more.

  Therefore, in the present invention, when a cured coating film is formed under such a background, it is possible to form a coating film which has a small curing shrinkage, is not easily curled, and is also excellent in flexibility. Active energy containing a urethane (meth) acrylate-based composition capable of forming a coating film excellent in stain performance (stain resistance and its persistence) and properties of a cured coating (appearance, hardness, scratch resistance) It is an object of the present invention to provide a radiation curable resin composition and a coating agent using the same.

  However, as a result of extensive research under these circumstances, the present inventors have made urethane (meth) acrylate composition obtained by reacting (meth) acrylic acid adduct of dipentaerythritol and polyvalent isocyanate as a curing component. In the active energy ray-curable resin composition containing the compound, at least one xylylene diisocyanate-based compound selected from the group consisting of xylylene diisocyanate, hydrogenated xylylene diisocyanate and derivatives thereof as the polyvalent isocyanate, Production of urethane (meth) acrylate composition by using an adduct having a hydroxyl value of a (meth) acrylic acid adduct of dipentaerythritol higher than usual and further containing a fluorine-containing (meth) acrylate compound Excellent reaction efficiency when forming a cured coating It was found that a cured coating film excellent in coating physical properties such as antifouling performance and scratch resistance was obtained when curing shrinkage was small and curling was difficult, and that the present invention was completed. .

That is, the present invention relates to a group consisting of a hydroxyl group in (meth) acrylic acid adduct (A) of dipentaerythritol having a hydroxyl value of 60 mg KOH / g or more, xylylene diisocyanate, hydrogenated xylylene diisocyanate and derivatives thereof. Containing urethane (meth) acrylate composition [I] and fluorine-containing (meth) acrylate compound [II], which are reacted with the isocyanate group of at least one xylylene diisocyanate compound (B) selected from An active energy ray-curable resin composition according to the first aspect of the present invention.
Moreover, the coating agent formed by containing the active energy ray curable resin composition of the said 1st summary makes it a 2nd summary.

  The active energy ray-curable resin composition of the present invention comprises a hydroxyl group in a (meth) acrylic acid adduct (A) of dipentaerythritol having a hydroxyl value of 60 mg KOH / g or more, xylylene diisocyanate, hydrogenated xylylene diisocyanate And urethane (meth) acrylate compositions [I] and fluorine-containing (meth) acrylate compounds reacted with the isocyanate group of at least one xylylene diisocyanate compound (B) selected from the group consisting of these derivatives It contains [II]. Therefore, it is possible to form a cured coating film which has small curing shrinkage and is hardly curled and is excellent in flexibility, and is also excellent in antifouling performance and scratch resistance when it is formed into a cured coating film. Moreover, it is excellent in the use of the coating agent for hard coats, or the coating agent for optical films especially from such a thing.

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

  When the said fluorine-containing (meth) acrylate type compound [II] has a siloxane bond, it will become more excellent in antifouling performance.

In addition, when the weight average molecular weight of the fluorine-containing (meth) acrylate compound [II] is 1,000 to 100,000, the antifouling performance is further enhanced.

  And when the weight average molecular weight of the above urethane (meth) acrylate composition [I] is 3,000 to 30,000, curing shrinkage is smaller and curling is less likely, and a cured coating film excellent in flexibility is also obtained. It can form, and also it will be excellent also in abrasion resistance at the time of setting it as a cured coating film.

The present invention will be described 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 comprises a hydroxyl group in a (meth) acrylic acid adduct (A) of dipentaerythritol having a hydroxyl value of 60 mg KOH / g or more, xylylene diisocyanate, hydrogenated xylylene diisocyanate And an isocyanate group of at least one xylylene diisocyanate-based compound (B) (hereinafter sometimes referred to as "xylylene diisocyanate-based compound (B)") selected from the group consisting of these derivatives. The urethane (meth) acrylate composition [I] and the fluorine-containing (meth) acrylate compound [II] obtained by the reaction are included.

  The urethane (meth) acrylate composition [I] comprises a hydroxyl group in a (meth) acrylic acid adduct (A) of dipentaerythritol having a hydroxyl value of 60 mg KOH / g or more, and a xylylene diisocyanate compound (B) The urethane bond is formed and obtained by reacting the isocyanate group of

[(Meth) acrylic acid adduct of dipentaerythritol (A)]
Generally, (meth) acrylic acid adduct (A) of dipentaerythritol is a component in which (meth) acrylic acid is added to all six of six hydroxyl groups of dipentaerythritol. Dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate having (meth) acrylic acid added to five, and dipentaerythritol tetra (meth) acrylate having (meth) acrylic acid added to four Diol, dipentaerythritol tri (meth) acrylate triol to which (meth) acrylic acid is added to three, dipentaerythritol di (meth) acrylate tetraol to which (meth) acrylic acid is added to two, only one Dipentaerythritol (meth) acrelay in which (meth) acrylic acid is added to It is a mixture containing penta-ol.
The (meth) acrylic acid adduct (A) of such dipentaerythritol may be one obtained by reacting dipentaerythritol and (meth) acrylic acid according to a generally known method.

The (meth) acrylic acid adduct (A) of dipentaerythritol used in the present invention is characterized in that the hydroxyl value is higher than that of a normal (meth) acrylic acid adduct of dipentaerythritol.
In the present invention, the hydroxyl value of the (meth) acrylic acid adduct (A) of dipentaerythritol means the hydroxyl value of the entire mixture of (meth) acrylic acid adducts of dipentaerythritol. .

The hydroxyl value of the (meth) acrylic acid adduct (A) of dipentaerythritol needs to be 60 mg KOH / g or more, preferably 63 to 120 mg KOH / g, particularly preferably 65 to 100 mg KOH / g. is there.
If the hydroxyl value is too small, the content of dipentaerythritol hexa (meth) acrylate which has a low molecular weight and a large number of ethylenic unsaturated groups and does not react with isocyanate increases, so the cure shrinkage upon curing becomes large and curls In addition, the flexibility is lowered, which is not preferable. Generally, when the above-mentioned hydroxyl value becomes too large, the content of the polyol component such as dipentaerythritol tetra (meth) acrylate diol or dipentaerythritol tri (meth) acrylate triol increases, so the molecular weight of the urethane acrylate obtained Tends to be difficult to handle because the viscosity increases.
The adjustment of the hydroxyl value is performed, for example, by adjusting the ratio of (meth) acrylic acid to be added to dipentaerythritol.
Moreover, the said hydroxyl value can be calculated | required by the method according to JISK1557-1.

[Xylylene Diisocyanate Compound (B)]
In the present invention, the xylylene diisocyanate compound (B) is used as the isocyanate which reacts with the hydroxyl group of the (meth) acrylic acid adduct (A) of the above dipentaerythritol, and the curing is thereby performed. When the coating film is formed, a cured coating film is obtained which has a small curing shrinkage, is not easily curled, and is also excellent in flexibility. Furthermore, even when the (meth) acrylic acid adduct (A) of dipentaerythritol having a high hydroxyl value is used, the amount of the hydroxyl group and the isocyanate group in the (meth) acrylic acid adduct (A) of dipentaerythritol The reaction efficiency is improved, and the urethane (meth) acrylate composition [I] can be efficiently obtained.

  Examples of the above-mentioned xylylene diisocyanate compound (B) include xylylene diisocyanate, hydrogenated xylylene diisocyanate, tetramethyl xylylene diisocyanate, etc. However, since it does not contain an aromatic ring structure and is excellent in yellowing resistance, hydrogenated xylylene diisocyanate is preferable. Preference is given to using diisocyanates.

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

  Specifically, for the xylylene diisocyanate compound (B) used in the present invention, commercially available products "Takenate 500", "Takenate 600" and the like manufactured by Mitsui Chemicals, Inc. may be used.

  The above-mentioned xylylene diisocyanate compound (B) may be various polyols, for example, low molecular weight polyols and high molecular weight polyols, among them polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, polybutadiene polyols, It may be a reactant with a polyol such as (meth) acrylic polyol.

In addition, it is possible to use a small amount of polyvalent isocyanate type compounds other than the said xylylene diisocyanate type compound (B) in the range which does not inhibit the effect of this invention.
As polyvalent isocyanate compounds other than the above-mentioned xylylene diisocyanate compound (B), aromatic polyisocyanate, aliphatic polyisocyanate, alicyclic polyisocyanate, or trimer compound or multimer of these polyisocyanates Compounds etc. may be mentioned.

[Method of producing urethane (meth) acrylate composition [I]]
The urethane (meth) acrylate composition [I] used in the present invention has a hydroxyl group in a (meth) acrylic acid adduct (A) of dipentaerythritol having a hydroxyl value of 60 mg KOH / g or more, and a xylylene diisocyanate system It is obtained by reacting the isocyanate group of the compound (B), and the isocyanate group of the above-mentioned xylylene diisocyanate compound (B) and the hydroxyl group in the (meth) acrylic acid adduct of dipentaerythritol (A) The molar ratio of functional groups of is adjusted, and if necessary, a catalyst such as dibutyltin dilaurate is used to react xylylene diisocyanate compound (B) with (meth) acrylic acid adduct of dipentaerythritol (A) Can be obtained.

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

  When the proportion of the (meth) acrylic acid adduct (A) of such dipentaerythritol is too large, the content of low molecular weight monomer which does not react with the xylylene diisocyanate compound (B) such as dipentaerythritol hexa (meth) acrylate When the amount of (meth) acrylic acid adduct of dipentaerythritol (A) is too small, unreacted xylylene diisocyanate compound (B) And the stability and safety of the cured coating film tend to be reduced.

  The reaction of the (meth) acrylic acid adduct of dipentaerythritol (A) with the xylylene diisocyanate compound (B) is generally the above (meth) acrylic acid adduct of dipentaerythritol (A), a xylylene diisocyanate compound (B) may be charged into the 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 examples of such a catalyst include dibutyltin dilaurate, dibutyltin diacetate, trimethyltin hydroxide, tetra-n-butyltin and bisacetylacetonato zinc , Organometallic compounds such as zirconium tris (acetylacetonate) ethylacetoacetate, zirconium tetraacetylacetonate, tin octylate, tin octenate, zinc hexanoate, zinc octenate, zinc stearate, zirconium 2-ethylhexanoate, Metal salts of cobalt naphthenate, stannous chloride, stannous chloride, potassium acetate, etc., triethylamine, triethylenediamine, benzyldiethylamine, 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5 , 4, Amine catalysts such as undecene, N, N, N ', N'-tetramethyl-1,3-butanediamine, N-methylmorpholine, N-ethylmorpholine, bismuth nitrate, bismuth bromide, bismuth iodide, sulfide Organic bismuth compounds such as dibutyl bismuth dilaurate, dioctyl bismuth dilaurate, bismuth 2-ethylhexanoate, bismuth naphthenate, bismuth isodecanoate, bismuth neodecanoate, bismuth laurate, bismuth maleate other than bismuth and the like Bismuth-based catalysts such as organic acid bismuth salts such as salts, bismuth stearate, bismuth oleate, bismuth linoleate, bismuth acetate, bismuth bis bis neodecanoate, bismuth disalicylate, bismuth di gallate, bismuth salts of digallic acid, etc. And dibutyltin dilau among others. Over DOO, 1,8-diazabicyclo [5,4,0] undecene is preferred. These can be used alone or in combination of two or more.

<Polymerization inhibitor [III] '>
In the above reaction, it is preferable to further use a polymerization inhibitor [III] '. In addition, when using polymerization inhibitor [III] 'by the said reaction, it shall be included in content of polymerization inhibitor [III] mentioned later.

  As said polymerization inhibitor [III] ', the well-known thing generally used as a polymerization inhibitor can be used, For example, 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, p-t-butylcatechol, etc. Mention may be made of phenols. Among them, phenols are preferred, and particularly preferred is 2,6-di-t-butylcresol. 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 with respect to a total of 100 parts by weight of the (meth) acrylic acid adduct of dipentaerythritol (A) and the xylylene diisocyanate compound (B). It is preferable that it is 0.2 parts by weight, and 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 the composition tends to gel during storage. . In addition, when the content of the polymerization inhibitor [III] 'is too large, curing tends to be difficult even when the active energy ray is irradiated.

  In the above reaction, an organic solvent having no functional group reactive to an isocyanate group, for example, esters such as ethyl acetate, butyl acetate and 2-methoxy-1-methylethyl acetate, methyl ethyl ketone and methyl isobutyl ketone And organic solvents such as aromatics such as toluene and xylene.

  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.

Thus, the urethane (meth) acrylate composition [I] used in the present invention is obtained.
The above urethane (meth) acrylate composition [I] contains plural kinds of urethane (meth) acrylates, and further, dipentaerythritol di (meth) acrylate which is a (meth) acrylic acid adduct (A) 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 Etc. may be included.

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, and particularly preferably 3,500 to 10 , 000.
When the weight-average molecular weight is too small, the cured coating tends to be brittle, and when it is too large, the viscosity becomes high and it becomes difficult to handle.

  In the present invention, the weight average molecular weight is a weight average molecular weight in terms of standard polystyrene molecular weight, and in a high performance liquid chromatograph (manufactured by Waters, “ACQUITY APC system”), columns: ACQUITY APC XT 450 × 1, ACQUITY APC It is measured by using four XT 200 × 1 and ACQUITY APC XT 45 × 2 in series.

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 further preferably 5 It is preferable that it is 1,000-150,000 mPa * s. If the viscosity is outside the above range, the coatability tends to decrease.
In addition, the measuring method of a viscosity is based on E-type viscosity meter.

  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, and further preferably 65% by weight or more. Particularly preferably, it is 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. Further, the structure other than the (meth) acryloyl group and the fluorine atom is not particularly limited, and may further have a hetero atom such as oxygen, nitrogen, silicon, sulfur and the like.

  The fluorine-containing (meth) acrylate compound [II] is preferably a compound in which a fluorine atom is bonded to an alkyl group of a (meth) acrylic acid alkyl ester, for example, “Optool DAC” manufactured by Daikin Industries, Ltd. Optool DAC-HP ", DIC Corporation" Megafuck RS-75 "," Megafuck RS-76 "," Megafuck RS-91C "," Difensa TF3028 "," Difensa TF3001 "," Difensa TF3000 ", Shin-Nakamura “SUA1900L10” manufactured by Chemical Company, “SUA1900L6” manufactured by Nippon Synthetic Chemical Industry Co., Ltd. “UT3971” manufactured by Nippon Synthetic Chemical Industry Co., Ltd. “KNS5300” manufactured by Shin-Etsu Chemical Co., Ltd. “KY-1203” , "Viscoat 8F", "Viscoat 8F "," BISCOAT 13F "and the like. 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 in that the antifouling performance is more excellent. .

  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, Preferably it is 15,000-40,000. When the weight average molecular weight of the fluorine-containing (meth) acrylate compound [II] is too small, sufficient scratch resistance and antifouling performance tend not to be obtained, and when the weight average molecular weight is too large, the urethane acrylate composition [I The compatibility with the solvent and the solvent tends to be reduced.

  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 with respect to 100 parts by weight of the urethane (meth) acrylate compound [I]. The amount is 5 to 5 parts by weight, preferably 0.05 to 3 parts by weight, and particularly preferably 0.1 to 1 part by weight. When the content of the fluorine-containing (meth) acrylate compound [II] is too small, the scratch resistance and the antifouling performance tend to be insufficiently obtained, and when the content is too large, the urethane (meth) acrylate composition The compatibility with the substance [I] tends to decrease.

[Other optional components]
The active energy ray curable resin composition of the present invention comprises the above urethane (meth) acrylate composition [I] and the fluorine-containing (meth) acrylate compound [II], and such an active energy ray The curable resin composition preferably further contains a polymerization inhibitor [III], and further preferably contains a photopolymerization initiator. In addition, an ethylenically unsaturated monomer other than urethane (meth) acrylate, an acrylic resin, a surface control agent, a leveling agent and the like can be added as long as the effects of the present invention are not impaired. , Plasticizers, waxes, desiccants, dispersants, wetting agents, gelling agents, stabilizers, antifoaming agents, surfactants, leveling agents, thixotropic agents, antioxidants, flame retardants, antistatic agents, Fillers, reinforcing agents, matting agents, crosslinking agents, silica, water-dispersed or solvent-dispersed silica, zirconium compounds, preservatives, anti-coloring agents, etc. can also be blended. These can be used alone or in combination of two or more.

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

  The active energy ray curable resin composition of the present invention preferably contains a polymerization inhibitor [III] more than a general active energy ray curable resin composition. Usually, in the active energy ray curable resin composition, polymerization is carried out more than necessary because the active energy ray curability is lowered or colored by containing a large amount of the polymerization inhibitor [III]. The inhibitor [III] is not contained, and the content of the polymerization inhibitor [III] is an amount which is generally used at the production of the above-mentioned urethane (meth) acrylate composition [I]. However, in the present invention, by setting the content to be larger than the amount of the polymerization inhibitor generally used in the active energy ray-curable resin composition, the liquid stability is improved and the gelation during storage is suppressed. It produces an effect.

  The content of the polymerization inhibitor [III] in the active energy ray curable resin composition is urethane (meth) acrylate composition [I], fluorine-containing (meth) acrylate compound [II] and polymerization inhibitor [III] Is generally 800 to 10,000 ppm, preferably 1,000 to 7,500 ppm, particularly preferably 1,500 to 5,000 ppm, still more preferably 2,000 to 4,500 ppm, based on the total weight of Particularly preferably, it is 2,500 to 4,000 ppm. If the content of the polymerization inhibitor [III] is too small, the liquid stability of the active energy ray-curable resin composition before curing will not be sufficient, and there is a tendency for the composition to gelate easily during storage. In addition, when the content of the polymerization inhibitor [III] is too large, curing tends to be difficult even when irradiated with active energy rays. In addition, when polymerization inhibitor [III] 'is used by manufacture of said urethane (meth) acrylate type composition [I], content of this polymerization inhibitor [III]' is also a polymerization inhibitor of this invention [ Included in the content of 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-hydroxycyclohexyl phenyl ketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-one {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-hydroxyl Acetophenones such as -2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer; 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-2-propenyloxy) ethyl] benzene, metanaminium bromide, (4-benzoylbenzyl) trimethyl ammonium chloride and other benzofurans 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3 Thioxanthones such as 2,4-dimethyl-9H-thioxanthone-9-one meso chloride; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl Acyl phosphinic oxides such as pentyl phosphine oxide and bis (2,4,6-trimethyl benzoyl) -phenyl phosphine oxide, 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2 -(O-benzoyl oxime And oxime esters such as 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime), and the like.
These photopolymerization initiators may be used alone or in combination of two or more.

  Among these, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoin isopropyl ether, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-hydroxy-2-methyl-1- It is preferred to use phenylpropan-1-one.

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

  Moreover, as these auxiliary agents, triethanolamine, triisopropanolamine, 4,4'-dimethylamino benzophenone (Michler's ketone), 4,4'-diethylamino benzophenone, 2-dimethylaminoethylbenzoic acid, 4-dimethylaminobenzoic acid Ethyl, 4-dimethylaminobenzoate (n-butoxy) ethyl, 4-dimethylaminobenzoate isoamyl, 4-dimethylaminobenzoate 2-ethylhexyl, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone It is also possible to use in combination.

  As ethylenic unsaturated monomers other than the said urethane (meth) acrylate, a monofunctional monomer, a bifunctional monomer, the trifunctional or more than trifunctional polyfunctional monomer etc. are mentioned, for example. These ethylenically unsaturated monomers can be used alone or in combination of two or more.

  Examples of such monofunctional monomers include styrene-based monomers such as styrene, vinyl toluene, chlorostyrene, 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, dicyclopentenyl oxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate , (2-methyl-2-ethyl-1,3-dioxolan-4-yl) -methyl (meth) acrylate, cyclohexane spiro-2- (1,3-dioxolan-4-yl) -methyl (meth) acrylate, 3-ethyl-3-oxetanylmethyl (meth) acrylate, γ-butyrolactone (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) ) Ak Rate, 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 Half (meth) acrylates of phthalic acid derivatives such as oxide-modified (n = 2.5) (meth) acrylates, 2- (meth) acryloyloxyethyl acid phosphates, 2- (meth) acryloyloxy-2-hydroxypropyl phthalates, Furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, carbitol (meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate, allyl (meth) (Meth) acrylate monomers such as acrylate, (meth) acryloyl morpholine, polyoxyethylene secondary alkyl ether acrylate, 2-hydroxyethyl acrylamide, N-methylol (meth) acrylamide, N-vinyl pyrrolidone, 2-vinyl pyridine And vinyl acetate.

  As such a bifunctional monomer, for example, 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, di 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, cyclohexane dimethanol di (meth) acrylate, ethoxylated cyclohexane dimethanol di ( ) Acrylate, dimethylol dicyclopentadi (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 diglycidyl ester di (meth) acrylate, hydroxypivalic acid modified neopentyl glycol di (meth) acrylate, ethylene isocyanurate An oxide modified diacrylate etc. are mentioned.

  Examples of such trifunctional or higher functional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa ( Meta) acrylate, tri (meth) acryloyloxy ethoxy trimethylol propane, glycerin polyglycidyl ether poly (meth) acrylate, isocyanurate ethylene oxide modified triacrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexamer (Meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate, capro Kton modified pentaerythritol tetra (meth) acrylate, ethylene oxide modified dipentaerythritol penta (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol Tetra (meth) acrylate, ethoxylated 15 glycerin triacrylate and the like can be mentioned.

  Moreover, as ethylenic unsaturated monomers other than urethane (meth) acrylate, Michael adduct of acrylic acid or 2-acryloyloxyethyl dicarboxylic acid monoester can also be used together. As such a Michael adduct of acrylic acid, acrylic acid dimer, methacrylic acid dimer, acrylic acid trimer, methacrylic acid trimer, acrylic acid tetramer, methacrylic acid tetramer and the like can be mentioned. The 2-acryloyloxyethyl dicarboxylic acid monoester is a carboxylic acid having a specific substituent, such as 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, 2-acryloyloxyethyl Examples thereof include phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexahydrophthalic acid monoester, and 2-methacryloyloxyethyl hexahydrophthalic acid monoester. Furthermore, other oligoester acrylates and the like can be mentioned.

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

  It does not specifically limit as said surface conditioner, For example, cellulose resin, an alkyd resin, etc. can be mentioned. The cellulose resin has an effect of improving the surface smoothness of the coating film, and the alkyd resin has an effect of providing a film forming property at the time of coating.

  As the leveling agent, any generally known leveling agent can be used as long as it has the action of imparting wettability to the substrate of the coating liquid and the action of lowering surface tension. For example, silicone modified resin, fluorine modified resin And alkyl-modified resins can be used.

  Moreover, in the active energy ray-curable resin composition of the present invention, it is also preferable to use an organic solvent for dilution in order to make the viscosity at the time of coating appropriate. Such organic solvents include, for example, 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 (alias: propylene glycol monomethyl ether), propylene glycol monomethyl ether acetate, ethyl cellosolve, acetates such as methyl acetate, ethyl acetate, butyl acetate, diacetone alcohol, etc. . These organic solvents may be used alone or in combination of two or more. Among these, the boiling point is 80 ° C. or more, particularly 100 ° C. or more, and further 120 to 120 since the compatibility between the urethane (meth) acrylate composition [I] and the fluorine-containing (meth) acrylate [II] is excellent. Solvents having a high boiling point of 170 ° C. are preferred, alcohols and glycol ethers are more preferred, and 1-methoxy-2-propanol and propylene glycol monomethyl ether acetate are particularly preferred.

  When two or more of the above organic solvents are used in combination, a combination of a glycol ether such as propylene glycol monomethyl ether and a ketone such as methyl ethyl ketone or an alcohol such as methanol or a glycol ether such as propylene glycol monomethyl ether A combination of esters such as butyl acetate and a combination of ketones such as methyl ethyl ketone and alcohols such as methanol 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], as the case requires. It can be obtained by mixing other optional components. The mixing method is not particularly limited, and various methods such as a method of mixing each component at once, a method of mixing optional components, and a method of collectively or sequentially mixing the remaining components are adopted. can do.

  The active energy ray-curable resin composition of the present invention thus obtained has a hydroxyl group in a (meth) acrylic acid adduct (A) of dipentaerythritol having a hydroxyl value of 60 mg KOH / g or more, xylylene diisocyanate, and hydrogenation. Urethane (meth) acrylate composition [I] obtained by reacting with isocyanate group of at least one kind of xylylene diisocyanate compound (B) selected from the group consisting of xylylene diisocyanate and derivatives thereof It comprises the meta) acrylate type compound [II]. Therefore, it is possible to form a cured coating film which is small in curing shrinkage and difficult to curl and excellent in flexibility, and is also excellent in scratch resistance when formed into a cured coating film and antifouling property after scratching. It is.

  The active energy ray curable resin composition of the present invention is effectively used as a curable composition for forming a coating film, such as top coat agent and anchor coat agent for various substrates, and such active energy ray cure After the base resin composition is applied to the substrate (when the composition diluted with an organic solvent is applied, it is further dried), it is cured by irradiation with an active energy ray.

  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 copolymer (ABS), and polystyrene resins. Plastic substrates such as resins, acrylic resins etc. and molded products thereof (films, sheets, cups etc), optical films such as polyethylene terephthalate film, triacetyl cellulose film, cycloolefin film etc, composite substrates thereof, Or a composite substrate of the above-mentioned material mixed with glass fiber or inorganic substance, metal (aluminum, copper, iron, SUS, zinc, magnesium, alloys thereof, etc.) or glass, or a primer layer provided on these substrates And the like.

  As a coating method of the active energy ray curable resin composition of the present invention, for example, wet coating methods such as spray, shower, gravure, dipping, roll, spin, screen printing and the like can be mentioned. Below, it should just coat to a base material.

  Moreover, the active energy ray curable resin composition of the present invention may be coated as it is, or may be diluted with an organic solvent and coated. When diluting, it is preferable to make solid content concentration into 3 to 60 weight% (preferably 5 to 40 weight%) normally using the said organic solvent.

  As drying conditions at the time of performing dilution with the above-mentioned organic solvent, temperature is usually 40-120 ° C (preferably 50-100 ° C), and drying time is usually 1-20 minutes (preferably 2-10 minutes) If it is

The viscosity at 20 ° C. of the active energy ray-curable resin composition of the present invention is preferably 5 to 50,000 mPa · s, particularly preferably 10 to 10,000 mPa · s, still more preferably 50 to 5, It is 000 mPa · s. If the viscosity is outside the above range, the coatability tends to decrease.
In addition, the measuring method of a viscosity is based on E-type viscosity meter.

As an active energy ray used when hardening the active energy ray curable resin composition coated on the base material, for example, light rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, X rays, γ rays and the like In addition to the above electromagnetic waves, electron beams, proton beams, neutron beams and the like can be used, but ultraviolet rays or electron beams are preferable in view of curing speed, availability of an irradiation apparatus, price and the like.
In addition, when hardening by irradiation of an electron beam, even if it does not use a photoinitiator, it can harden | cure.

When curing by ultraviolet irradiation, a high pressure mercury lamp, an ultra high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless discharge lamp, an LED lamp, etc. emitting light in the 150 to 450 nm wavelength region Generally, ultraviolet light of 30 to 3,000 mJ / cm ² (preferably 100 to 1,500 mJ / cm ² ) may be irradiated.
After irradiation with ultraviolet light, heating may be performed as necessary to 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, Preferably it is 2 to 500 μm, and 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 coat or a coating agent for optical film.

In the present invention, the active energy ray-curable resin composition is applied to a thickness of 5 μm on a 125 μm easily-adhesive polyethylene terephthalate film and dried at a temperature of 90 ° C. for 3 minutes, and then the height is 18 cm. From the position, using a high-pressure mercury lamp at 80 W, the size of the cured film obtained becomes 10 cm × 10 cm by irradiating ultraviolet light at a speed of 5.1 m / min so that the accumulated irradiation amount is 500 mJ / cm ² It is preferable to set it as the coating agent used as the cured coating film which is 10 mm or less, and also 7 mm or less in average value of the jumping height of four corners when it cuts out like this.

In the present invention, the active energy ray-curable resin composition is applied to a thickness of 5 μm on a 125 μm easily-adhesive polyethylene terephthalate film and dried at a temperature of 90 ° C. for 3 minutes, and then the height is 18 cm. In a cured coating film obtained by irradiating ultraviolet rays from a position using an 80 W high-pressure mercury lamp at a speed of 5.1 m / min so that an accumulated irradiation amount is 500 mJ / cm ² , JIS K 5600-5-1 According to the above, the flexibility is evaluated using a cylindrical mandrel bending tester, and the maximum diameter (integer value, mm) at which cracking or peeling occurs when the cured film for evaluation is wound around a test rod is 12 mm. It is preferable to set it as the coating agent used as the cured coating film which is 8 mm or less further below.

  In the present invention, a group consisting of a hydroxyl group in a (meth) acrylic acid adduct (A) of dipentaerythritol having a hydroxyl value of 60 mg KOH / g or more, xylylene diisocyanate, hydrogenated xylylene diisocyanate, and derivatives thereof Containing urethane (meth) acrylate composition [I] and fluorine-containing (meth) acrylate compound [II], which are produced by reacting the isocyanate group of at least one xylylene diisocyanate compound (B) selected from The resulting active energy ray-curable resin composition has a small curing shrinkage, is less likely to curl, and can form a cured coating film having excellent flexibility, and further, the scratch resistance of the cured coating film. And anti-staining properties after abrasion, and in particular, a coating agent (further, a coating for a hard coat) And is useful as an optical film coating agent), also paints, it is also useful as ink or the like.

  EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In the examples, "parts" and "%" mean weight basis.

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

<Production Example 1>
[Production of Urethane Acrylate Composition [I-1]]
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port, 139.5 g (0.72 mol) of 1,3-hydroxylene diisocyanate (B-1) and a hydroxyl value of 96 mg KOH / 860.5 g (1.47 moles) of acrylic acid adduct of dipentaerythritol (A-1) g, 0.6 g of 2,6-di-t-butylcresol as a polymerization inhibitor [III-1] ', 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 residual isocyanate group became 0.1%, to obtain a urethane acrylate composition [I-1] (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.

<Production Example 2>
[Production of Urethane Acrylate Composition [I'-1]]
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 80.7 g (0.42 mol) of 1,3-hydroxylene 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) g, 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 residual isocyanate group became 0.1% to produce a urethane acrylate composition [I′-1]. .
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.

<Production Example 3>
[Production of Urethane Acrylate Composition [I′-2]]
A four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, dipentaerythritol with 156.0 g (0.70 mol) of isophorone diisocyanate (B'-1) and a hydroxyl value of 96 mg KOH / g. 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 a reaction catalyst .05g was charged and reacted at 60 ° C, and when the remaining isocyanate group was 0.1%, the reaction was terminated to produce a 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 at the time of reaction of urethane (meth) acrylate composition [I]]
When manufacturing the urethane acrylate compositions [I-1], [I'-1], and [I'-2] obtained above, all raw materials are charged and the internal temperature reaches 60 ° C as a standard. The content of the flask is sampled after a predetermined time to measure the amount of residual isocyanate group (%), and the consumption rate (%) of isocyanate when the amount of isocyanate group in the initial preparation is 100% is shown in the table below. Shown in 1.

  As can be seen from Table 1, even when acrylic acid adduct (A-1) of dipentaerythritol having a hydroxyl value satisfying the definition of the present invention is used, the specific xylylene diisocyanate compound specified in the present invention In Production Example [I'-2] in which (B) was not used, in the production of the urethane (meth) acrylate composition [I], the production example was 30 hours or less until the residual isocyanate group became 0.1% or less. It took twice as long as 1 and was very poor in reaction efficiency and poor in productivity.

[Production of Active Energy Ray-Curable Resin Composition]
Example 1
While stirring a solution obtained by dissolving 100 parts of the urethane acrylate composition [I-1] obtained above in 100 parts of 1-methoxy-2-propanol, KY- was obtained as the fluorine-containing acrylate compound [II-1]. Amount of active ingredient: 1203 (20% active ingredient, manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight (measured value) 27,000) 0.2 part (1 part including solvent ingredient) as a polymerization inhibitor [III-1] 0.3 part 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 CHEMICAL CO., LTD.) As a color protection agent, and an α-hydroxyalkylphenone photopolymerization initiator (manufactured by IGM Co., “OM Rudd 184 ") and 4 parts of formulation to give 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 a urethane (meth) acrylate composition [ It was 3,580 ppm with respect to the sum total of I], fluorine-containing (meth) acrylate type compound [II], and 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 a urethane (meth) acrylate composition [ It was 3,590 ppm with respect to the sum total of I], fluorine-containing (meth) acrylate type compound [II], and polymerization inhibitor [III].

Comparative Example 1
The active energy ray curing is performed in the same manner as in Example 1 except that the urethane acrylate composition [I'-1] obtained above is used instead of the urethane acrylate composition [I-1] in Example 1. 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 a urethane (meth) acrylate composition [ It was 3,580 ppm with respect to the sum total of I], fluorine-containing (meth) acrylate type compound [II], and polymerization inhibitor [III].

  With respect to the active energy ray curable resin composition obtained by using the urethane acrylate composition [I-1] and [I'-1] obtained above, a cured coating film is formed as follows, Physical properties (curl value, flexibility, scratch resistance, hardness) were evaluated. The evaluation results are as shown in Table 2.

[Method of producing sample for evaluation]
The active energy ray-curable resin composition obtained above is dried on a substrate with an easy-bonding PET film (“Cosmo Shine A4300” manufactured by Toyobo Co., Ltd., 125 μm thick) using a bar coater and the film thickness after drying is 5 μm And then dried at 90 ° C for 3 minutes, then using an 80 W high-pressure mercury lamp, 1 lamp, from a height of 18 cm to a conveyor speed of 5.1 m / min for 2 passes of UV irradiation (accumulated irradiation) An amount of 500 mJ / cm ² ) was applied to form a cured coating.

[Curl value (bounce height of four corners)]
The cured coating film coated on the easy-adhesion PET film was cut out so as to have a size of 10 cm × 10 cm, and the average value (mm) of bounce heights at the four corners was measured as a curl value. The smaller the value, the smaller the curling, which means that the film is less likely to curl.

[Flexibility]
About the said cured coating film coated on the easily bonding PET film, according to JISK 5600-5-1, the flexibility was evaluated using the cylindrical-shaped mandrel bending | flexion tester. The largest diameter (integer value, mm) at which cracking or peeling occurs when the cured coating film for evaluation was wound around a test rod so that the coated film surface was on the outside was measured. The smaller the value is, the more flexible the film is.

[Scratch resistance]
About the above-mentioned cured coating film coated on easy-to-adhere PET film, after making the surface of the cured coating film reciprocate while applying a load of 1 kg using steel wool (made by Nippon Steel Wool Co., Ltd., Bonstar # 0000) Shows the number of round trips until a wound occurs.
(Evaluation)
○ · · · There was no scratch even if reciprocated 1,000 times △ · · · wound occurred in more than 600 times and less than 1,000 times · · · wound occurred in less than 600 times

[Pencil hardness]
The cured coating film coated on the easy adhesion PET film was tested in accordance with JIS K 5600 to measure pencil hardness.

[Stain resistance (Magic ink (registered trademark) wiping ability)]
After drawing a line back and forth once with black magic ink on the cured coating surface and leaving it for 24 hours, the coating after wiping with a rag was observed and evaluated as follows. Moreover, evaluation was similarly performed about the cured coating film after the said abrasion resistance test.
(Evaluation)
○ ··········· Wipe clean

  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 Small in size, difficult to curl, excellent in flexibility and pencil hardness, and scratch-free even if reciprocated 1,000 times with 1 kg load in abrasion resistance test, and further coating after abrasion resistance test It also proves that it maintains excellent antifouling performance. In addition, in the production of the urethane acrylate composition [I-1] of Example 1, the time for the remaining isocyanate group to be 0.1% or less is within 15 hours, the reaction efficiency is good, and the productivity is excellent. It turns out that it is a thing.

On the other hand, a 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] is inferior to Example 1 in the scratch resistance test, and has an antifouling performance. Did not express.
In addition, the urethane acrylate composition [I 'of Comparative Example 1 which is a urethane acrylate composition comprising an acrylic acid adduct (A'-1) of dipentaerythritol having a hydroxyl value lower than that specified in the present invention] [I' The cured coating film obtained from the fluorine-containing acrylate compound [II-1] and the fluorine-containing acrylate compound [II-1] had a large curl value and was easily curled, and furthermore, the flexibility was inferior to that of Examples.

  The active energy ray-curable resin composition of the present invention can form a cured coating film which is small in curing shrinkage and difficult to curl when formed into a cured coating film, and is also excellent in flexibility. It is excellent also in the abrasion resistance at the time of setting it as a coating film, and the antifouling property after abrasion, and it is useful as a coating agent, especially a coating agent for hard coats, and a coating agent for optical films. It is also useful as a paint, an ink and the like.

Claims (8)

  At least one selected from the group consisting of a hydroxyl group in (meth) acrylic acid adduct (A) of dipentaerythritol having a hydroxyl value of 60 mg KOH / g or more, xylylene diisocyanate, hydrogenated xylylene diisocyanate, and derivatives thereof Characterized in that it contains a urethane (meth) acrylate composition [I] and a fluorine-containing (meth) acrylate compound [II] which are reacted with the isocyanate group of the xylylene diisocyanate compound (B) of the species Active energy ray curable resin composition.   Furthermore, the polymerization inhibitor [III] is used on a weight basis with respect to the total of the above urethane (meth) acrylate composition [I], fluorine-containing (meth) acrylate compound [II] and polymerization inhibitor [III]. 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 weight average molecular weight of the said fluorine-containing (meth) acrylate type compound [II] is 1,000-100,000, The active energy ray curable resin as described in any one of Claims 1-3 characterized by the above-mentioned. Composition.   The weight average molecular weight of the said urethane (meth) acrylate type composition [I] is 3,000-30,000, The active energy ray curability as described in any one of Claims 1-4 characterized by the above-mentioned. Resin composition.   A coating agent comprising the active energy ray curable resin composition according to any one of claims 1 to 5.   7. The coating agent according to claim 6, which is used as a coating agent for hard coating.   7. The coating agent according to claim 6, which is used as a coating agent for an optical film.