JP2019104907A - Active energy ray-curable resin composition and coating agent - Google Patents

Abstract

To provide an active energy ray-curable resin composition capable of forming a coated film which is excellent in storage stability of a coating liquid, and is excellent in antifouling performance (contamination resistance and its persistence) and characteristics (appearance, hardness and scratch resistance).SOLUTION: An active energy ray-curable resin composition contains an urethane (meth)acrylate composition [I] obtained by reaction of a hydroxyl group in a (meth)acrylic acid adduct (A) of dipentaerythritol and an isocyanate group of a polyisocyanate compound (B), a fluorine-containing (meth)acrylate compound [II] and a polymerization initiator [III], in which a content of the polymerization initiator [III] is 800-10,000 ppm based on the weight with respect to the total of the urethane (meth)acrylate composition [I], the fluorine-containing (meth)acrylate compound [II] and the polymerization initiator [III].SELECTED DRAWING: 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 more specifically, antifouling performance (contamination resistance and its durability) and a cured coating The present invention relates to an active energy ray-curable resin composition capable of forming a coating film excellent in the properties (appearance, hardness, scratch resistance) of the above, and a coating agent containing 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. In recent years, when the active energy ray-curable resin composition is used as a coating agent, particularly as a coating agent for a hard coat, those having high surface hardness and scratch resistance to replace glass are required.

  As described above, as a hard coating agent having high surface hardness and scratch resistance as a cured coating film, for example, one obtained by blending a fluorine compound in a curing component mainly composed of dipentaerythritol hexaacrylate and N-substituted acrylamide Has been proposed (see, for example, Patent Document 1). A film obtained by applying this hard coating agent on a laminated film to a film thickness of 11 μm and curing it does not get scratched even if it is reciprocated 500 times with a hardness of about 5H with a pencil hardness of about 5H It develops scratch resistance.

JP, 2017-141416, A

  However, although the disclosed technique of Patent Document 1 is excellent in surface hardness of a 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 further improvement is required. There is.

  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. And 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 when top coating with a coating agent is carried out The scuff resistance of the surface has been studied, etc., and the demand for the antifouling performance and the scuff resistance of the coating film surface is increasing more and more. Furthermore, although a fluorine compound is often used to develop antifouling property and scratch resistance, a coating agent containing a fluorine compound may be easily gelled during storage of the coating liquid, and thus storage stability is obtained. Further improvement of sexuality is required.

  Therefore, in the present invention, under such background, the storage stability of the coating liquid is excellent, and the antifouling performance (contamination resistance and its persistence), the characteristics of the cured coating (appearance, hardness, scratch resistance) The object of the invention is to provide an active energy ray-curable resin composition capable of forming a coating film excellent in the following properties) and a coating agent using the same.

  However, as a result of extensive research under these circumstances, the present inventors have made urethane (meth) acrylates obtained by reacting a (meth) acrylic acid adduct of dipentaerythritol with a polyisocyanate compound as a curing component. In an active energy ray curable resin composition containing a composition, a fluorine-containing (meth) acrylate compound and a polymerization inhibitor, the active energy ray curable resin composition contains a larger amount of the above-mentioned polymerization inhibitor than usual. It is found that a cured coating film is obtained which is excellent in storage stability with the following solution and is excellent in coating physical properties such as antifouling performance and scratch resistance when the cured coating film is formed, and the present invention is completed. did.

That is, according to the present invention, a urethane (meth) acrylate composition [I] in which the hydroxyl group in the (meth) acrylic acid adduct (A) of dipentaerythritol and the isocyanate group of the polyisocyanate compound (B) have reacted. A fluorine-containing (meth) acrylate compound [II] and a polymerization inhibitor [III], wherein the content of the polymerization inhibitor [III] is urethane (meth) acrylate composition [I], fluorine-containing An active energy ray-curable resin composition having a weight of 800 to 10,000 ppm by weight based on the total of the (meth) acrylate compound [II] and the polymerization inhibitor [III] is the first aspect. .
Moreover, the coating agent formed by containing the active energy ray curable resin composition of the said 1st summary makes it a 2nd summary.

  Generally, when producing a urethane (meth) acrylate composition, a polymerization inhibitor is contained in the reaction system for the purpose of suppressing the polymerization reaction of the (meth) acryloyl group during the urethanization reaction and improving the storage stability. Although it is carried out, it is usually considered that the compounding amount should be as small as possible, as it will lower the active energy ray curability by the presence of a polymerization inhibitor or cause coloration. is there. However, in the present invention, surprisingly, the use of the polymerization inhibitor more than the amount used at the time of production of the urethane (meth) acrylate composition reduces the active energy ray curability, and the coating solution There is no coloring problem of the cured coating film, the storage stability of the coating solution is excellent, the antifouling performance (stain resistance and its persistence), and the properties of the cured coating film (appearance, hardness, scratch resistance) are excellent. It has been found that a coating can be formed.

  The active energy ray-curable resin composition of the present invention is a urethane (meth) wherein the hydroxyl group in the (meth) acrylic acid adduct (A) of dipentaerythritol and the isocyanate group of the polyisocyanate compound (B) have reacted. Acrylate composition [I], fluorine-containing (meth) acrylate compound [II] and polymerization inhibitor [III], and the content of polymerization inhibitor [III] is urethane (meth) acrylate composition The amount is 800 to 10,000 ppm by weight based on the total of the compound [I], the fluorine-containing (meth) acrylate compound [II] and the polymerization inhibitor [III]. Therefore, it is excellent in the storage stability in a coating liquid, and also excellent in the antifouling performance and abrasion resistance at the time of setting it as a cured coating film. In addition, because of these excellent properties, they are particularly useful in applications of hard coat coatings or optical film coatings.

  Further, among the present invention, in particular, when the fluorine-containing (meth) acrylate compound [II] has a siloxane bond, it becomes more excellent in antifouling performance.

  Furthermore, among the present invention, in particular, 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.

  Further, among the present invention, in particular, when the hydroxyl value of the (meth) acrylic acid adduct (A) of dipentaerythritol is 10 to 120 mg KOH / g, with the fluorine-containing (meth) acrylate compound [II] It becomes more excellent by compatibility, and becomes further excellent by hardness and abrasion resistance at the time of setting it as a cured coating film.

  And, among the present invention, in particular, when the weight average molecular weight of the urethane (meth) acrylate composition [I] is 900 to 30,000, the phase with the fluorine-containing (meth) acrylate compound [II] It is excellent in solubility, and it becomes more excellent also in abrasion resistance at the time of setting it as a cured coating film.

  In addition, when the active energy ray curable resin composition of the present invention further contains a coloration inhibitor [IV], the storage stability in the coating liquid is further improved.

  Further, when the active energy ray-curable resin composition of the present invention further contains an organic solvent having a boiling point of 80 ° C. or higher, the above urethane (meth) acrylate composition [I] and the fluorine-containing (meth) acrylate compound [ Since the compatibility with [II] is excellent, the storage stability in the coating liquid, the antifouling performance and the appearance of the cured coating film are further excellent.

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 urethane (meth) acrylate composition [I], a fluorine-containing (meth) acrylate compound [II] and a polymerization inhibitor [III]. The details will be described below.

<Urethane (Meth) Acrylate Composition [I]>
The urethane (meth) acrylate composition [I] used in the present invention causes the hydroxyl group in the (meth) acrylic acid adduct (A) of dipentaerythritol to react with the isocyanate group of the polyisocyanate compound (B). Thus, a urethane bond can be formed.

[(Meth) acrylic acid adduct of dipentaerythritol (A)]
Generally, the (meth) acrylic acid adduct of dipentaerythritol refers to dipentaerythritol in which (meth) acrylic acid is added to all six of the six hydroxyl groups possessed by dipentaerythritol in the component. Erythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate monool having 5 (meth) acrylic acid added thereto, and dipentaerythritol tetra (meth) acrylate having 4 (meth) acrylic acid added 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 (Meth) acrylic acid added to dipentaerythritol (meth) It is a mixture containing chestnut rate pentaols.
The (meth) acrylic acid adduct (A) of dipentaerythritol used in the present invention may be obtained by reacting dipentaerythritol and (meth) acrylic acid according to a generally known method.

The hydroxyl value of the (meth) acrylic acid adduct (A) of dipentaerythritol is preferably 10 to 120 mg KOH / g, more preferably 20 to 80 mg KOH / g, particularly preferably 30 to 70 mg KOH / g, Particularly preferably, it is 40 to 60 mg KOH / g.
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 It tends to be easier. If the hydroxyl value is 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 resulting urethane acrylate becomes large. Since the viscosity is increased, it tends to be difficult to handle.

The hydroxyl value of the (meth) acrylic acid adduct (A) of dipentaerythritol mentioned above means the hydroxyl value of the mixture of (meth) acrylic acid adducts of dipentaerythritol as a whole.
Moreover, the said hydroxyl value can be calculated | required by the method according to JISK1557-1.

  The adjustment of the hydroxyl value of the (meth) acrylic acid adduct (A) of dipentaerythritol can be performed, for example, by adjusting the ratio of (meth) acrylic acid to be added to dipentaerythritol.

[Polyisocyanate Compound (B)]
The polyisocyanate compound (B) that reacts with the hydroxyl group of the (meth) acrylic acid adduct (A) of dipentaerythritol described above is generally known in general, which is used for producing a urethane (meth) acrylate composition These polyisocyanate compounds can be used.

  Examples of the polyisocyanate compound (B) include aromatic compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, phenylene diisocyanate and naphthalene diisocyanate. -Based polyisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, aliphatic diisocyanates such as lysine diisocyanate and lysine triisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, etc. of Cyclic polyisocyanates or trimeric compound or multimeric compounds of these polyisocyanates, allophanate type polyisocyanate, buret type polyisocyanate, water dispersible polyisocyanate, and the like. These polyisocyanate compounds (B) can be used alone or in combination of two or more.

  The polyisocyanate compound (B) may be selected from various polyols, for example, low molecular weight polyols and high molecular weight polyols, particularly polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, polybutadiene polyols ( It may be a reaction product of a polyol such as a meth) acrylic polyol and a polyisocyanate compound.

  Among these, aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate and lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene, in terms of excellent yellowing resistance and versatility. Alicyclic diisocyanates such as diisocyanates are preferred, and isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate and hexamethylene diisocyanate are more preferred, and isophorone diisocyanate and hexamethylene diisocyanate are more preferred.

[Method of producing urethane (meth) acrylate composition [I]]
The urethane (meth) acrylate composition [I] used in the present invention reacts the hydroxyl group in the (meth) acrylic acid adduct (A) of dipentaerythritol with the isocyanate group of the polyisocyanate compound (B). It is obtained by
In the urethane (meth) acrylate composition [I] used in the present invention, a (meth) acrylic acid adduct of dipentaerythritol having a hydroxyl value of 60 mg KOH / g or more, xylylene diisocyanate, hydrogenated xylylene It excludes the urethane (meth) acrylate composition which the at least 1 sort (s) of polyisocyanate system compound selected from the group which consists of isocyanate and these derivatives reacted.

  Specifically, the functional group molar ratio between the isocyanate group of the above-mentioned polyisocyanate compound (B) and the hydroxyl group of the (meth) acrylic acid adduct of dipentaerythritol (A) is adjusted, and as necessary, dibutyltin A urethane (meth) acrylate composition [I] is obtained by reacting a polyisocyanate compound (B) with a (meth) acrylic acid adduct of dipentaerythritol (A) using a catalyst such as dilaurate. Can.

  The reaction molar ratio [(B) :( A)] of the preparation of the polyisocyanate compound (B) and the (meth) acrylic acid adduct (A) of dipentaerythritol is about 1: 2 to 1: 5. is there.

  A low molecular weight monomer which does not react with the polyisocyanate compound (B) such as dipentaerythritol hexa (meth) acrylate if the proportion of the (meth) acrylic acid adduct (A) of dipentaerythritol is too large at this reaction molar ratio The cured film tends to have a large amount of curling due to a large content of curing shrinkage and a large amount of curing shrinkage. If the proportion of the (meth) acrylic acid adduct (A) of dipentaerythritol is too small, unreacted poly The isocyanate compound (B) tends to remain, 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 polyisocyanate compound (B) is usually carried out by the above (meth) acrylic acid adduct of dipentaerythritol (A), a polyisocyanate compound (A) B) may be charged to 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-tert-butylhydroquinone, methylhydroquinone, mono-tert-butylhydroquinone, 4-methoxyphenol, 2,6-di-tert-butylcresol, pt-butylcatechol, etc. And phenols. Among them, phenols are preferable, and 4-methoxyphenol and 2,6-di-t-butylcresol are particularly preferable. These can be used alone or in combination of two or more.

  The content of the polymerization inhibitor [III '] in the above reaction is 0.005 to about 100 parts by weight in total of the (meth) acrylic acid adduct of dipentaerythritol (A) and the polyisocyanate compound (B). It is 0.075 parts by weight, preferably 0.02 to 0.07 parts by weight. If the content of the polymerization inhibitor [III '] is too small, polymerization of acryloyl group may occur during the reaction. In addition, the liquid stability of the urethane (meth) acrylate composition [I] also tends to decrease, and the composition tends to gel during storage. On the other hand, when the content of the polymerization inhibitor [III '] is too large, coloring tends to occur, and curing tends to be difficult even when irradiated with active energy rays.

  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 of the above reaction 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 (meth) acrylic acid adduct of polyisocyanate compound (B) and unreacted dipentaerythritol. (A) dipentaerythritol mono (meth) acrylate pentaol, dipentaerythritol di (meth) acrylate tetraol, dipentaerythritol tri (meth) acrylate triol, dipentaerythritol tetra (meth) acrylate diol, dipentaerythritol Penta (meth) acrylate monool, dipentaerythritol hexa (meth) acrylate, and further, polypentaerythritol poly (meth) acrylate which is a polymer of (meth) acrylic acid adduct (A) of dipentaerythritol Which may contain over bets like.

The weight average molecular weight of the urethane (meth) acrylate composition [I] is preferably 900 to 30,000, more preferably 1,000 to 15,000, and particularly preferably 1,100 to 6,000. It is.
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.

  The weight average molecular weight in the present invention is a weight average molecular weight based on standard polystyrene molecular weight conversion, 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 500 to 300,000 mPa · s, in particular 750 to 100,000 mPa · s, and further preferably 1,000 to 30. The viscosity is preferably 1,000 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 10% by weight or more, particularly preferably 20% by weight or more, and further preferably 30% by weight or more. Particularly preferably, it is 50% by weight or more. The upper limit is usually 80% by weight.

<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. The structure other than the (meth) acryloyl group and the fluorine atom is not particularly limited, and may further have a heteroatom 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” and “SUA1900L6” manufactured by Chemical Company, “UT3971” manufactured by Japan Synthetic Chemical Industry Co., Ltd. “KNS5300” and “KY-1203” manufactured by Shin-Etsu Chemical Co., Ltd. "," Viscoat 8F "," Viscoat " FM "," BISCOAT 13F ", AGC Corp." IRX-380 ", 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 in that they are more excellent in antifouling performance, and “KY-1203” is particularly preferable preferable.

  The weight average molecular weight of the fluorine-containing (meth) acrylate compound [II] is preferably 1,000 to 100,000, more preferably 5,000 to 70,000, and particularly preferably 10,000 to It is 50,000, More preferably, it is 15,000-40,000. When the weight average molecular weight of the fluorine-containing (meth) acrylate compound [II] is too small, the scratch resistance and the antifouling performance tend to decrease, and when the weight average molecular weight is too large, the urethane acrylate composition [I] and the solvent There is a tendency for the compatibility with

  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 decrease, and when the content is too large, the urethane (meth) acrylate composition [I There is a tendency for the compatibility with

<Polymerization inhibitor [III]>
The active energy ray curable resin composition of the present invention contains the polymerization inhibitor [III] more than a general active energy ray curable resin composition. Usually, in the active energy ray-curable resin composition, the addition of a large amount of the polymerization inhibitor [III] causes reduction in active energy ray curability, coloring, etc. The content of the polymerization inhibitor [III] is an amount such that the content of the polymerization inhibitor [III] is generally used in the production of the above-mentioned urethane (meth) acrylate composition [I]. However, in the present invention, in the active energy ray curable resin composition containing the specific urethane (meth) acrylate composition [I] and the fluorine-containing (meth) acrylate compound [II], generally, the active energy ray curing is carried out The content of the polymerization inhibitor [III] is larger than the amount used for the water-soluble resin composition, the liquid energy stability of the active energy ray-curable resin composition is free from the problem of decrease in the active energy ray curability and coloring problems The effect is to improve and to suppress gelation during storage.

  As the polymerization inhibitor [III] used in the present invention, known general ones can be used, and specifically, the same compounds as the compounds listed in the above-mentioned polymerization inhibitor [III '] can be used . Further, 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.

  In addition, the content of the polymerization inhibitor [III] is relative to the total of the urethane (meth) acrylate composition [I], the fluorine-containing (meth) acrylate compound [II] and the polymerization inhibitor [III]. It is important that it is 800 to 10,000 ppm by weight, preferably 1,000 to 8,000 ppm, more preferably 1,500 to 7,000 ppm, still more preferably 2,000 to 6,000 ppm, in particular Preferably, it is 3,100 to 5,000 ppm. When the content of the polymerization inhibitor [III] is too small, the liquid stability of the active energy ray-curable resin composition before curing is reduced, and the composition becomes easy to gel during storage. In addition, when the content of the polymerization inhibitor [III] is too large, it becomes difficult to cure even when irradiated with an active energy ray. 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 the polymerization inhibitor of this invention [ Included in the content of III].

<Colorant [IV]>
In the present invention, in order to prevent the coloration of the urethane (meth) acrylate composition [I] and to make the storage stability of the liquid of the active energy ray curable resin composition more excellent, a coloring inhibitor is further added. It is preferable to contain [IV].
As said coloring inhibitor [IV], for example, aryl phosphine compounds such as triphenyl phosphine, 1,1,3,3-tetramethyldisilazane, 1,1,3,3,3-hexamethyldisilazane etc. Examples thereof include silazane compounds, and hydrazine compounds such as phenylhydrazine, benzophenylhydrolazine, and diacetylhydrazine. One of these coloring inhibitors may be used alone, or two or more thereof may be used in combination. Among these, aryl phosphine compounds are preferable, and triphenyl phosphine is particularly preferable, in that the coloring of the urethane (meth) acrylate composition [I] can be further prevented.

  In addition, the content of the above-mentioned coloring inhibitor [IV] is the total of urethane (meth) acrylate composition [I], fluorine-containing (meth) acrylate compound [II] and polymerization inhibitor [III], It is usually 10 to 10,000 ppm, preferably 100 to 5,000 ppm, and more preferably 250 to 2,000 ppm by weight.

[Other optional components]
It is preferable that the active energy ray curable resin composition of the present invention further 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 blended within a range that does not impair the effects of the present invention. Oils, 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 and the like can also be blended. These may be used alone or in combination of two or more.

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-hydroxy Acetophenones such as 2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomers; benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, o -Benzoylbenzoic acid methyl, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 2,4,6- Trimethyl benzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzene metanaminium bromide, benzopheno such as (4-benzoylbenzyl) trimethylammonium chloride 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3 Thioxanthones such as 4-dimethyl-9H-thioxanthone-9-one meso chloride; 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl- Acyl phosphine oxides such as pentyl phosphine oxide, bis (2,4,6-trimethyl benzoyl) -phenyl phosphine oxide, 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyl] Oxime)], Etano And oxime esters such as 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime).
These photopolymerization initiators may be used alone or in combination of two or more.

  Among these, preferred are acetophenones, and more preferred are benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoin isopropyl ether, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, particularly preferably 1-hydroxycyclohexyl phenyl ketone.

When the photopolymerization initiator is contained, the content thereof is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the curing component contained in the active energy ray curable resin composition, and in particular The amount is preferably 0.5 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 an auxiliary agent of the said photoinitiator, for example, triethanolamine, triisopropanolamine, 4,4'- dimethylamino benzophenone (Michler's ketone), 4,4'- diethylamino benzophenone, 2- dimethylamino ethyl benzoic acid, Ethyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2, It is also possible to use 4-diisopropylthioxanthone and the like 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, Vinyl acetate etc. are mentioned.

  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 an ethylenically unsaturated monomer other than urethane (meth) acrylate, a Michael adduct of (meth) acrylic acid or 2-acryloyloxyethyl dicarboxylic acid monoester can be used in combination. Examples of such Michael adducts of (meth) acrylic acid include (meth) acrylic acid dimers, (meth) acrylic acid trimers, and (meth) acrylic acid tetramers. 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 90% by weight or less, particularly preferably 80% by weight, based on the total curing components contained in the active energy ray curable resin composition. % Or less, more preferably 70% 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 the effect of improving the surface smoothness of the coating film, and the alkyd resin has the effect of improving the 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.

  The active energy ray curable resin composition of the present invention comprises a mixture of a urethane (meth) acrylate composition [I], a fluorine-containing (meth) acrylate compound [II], a polymerization inhibitor [III] and other optional components. It can be obtained by 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 is excellent in storage stability in a coating liquid, and further excellent in abrasion resistance when formed into a cured coating film and antifouling property after abrasion. It is a thing.

  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. In the case of dilution, the solid content concentration may be usually 3 to 90% by weight (preferably 5 to 60% by weight) using an organic solvent.

  Examples of the organic solvent include alcohols such as methanol, ethanol, propanol, n-butanol and i-butanol, ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone, and 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.

  Moreover, among these, it is excellent in compatibility with urethane (meth) acrylate type composition [I] and fluorine-containing (meth) acrylate [II], and is excellent in the stability of the liquid of an active energy ray curable resin composition. Solvents having a boiling point of 80 ° C. or higher, particularly 100 ° C. or higher, more preferably 120 to 170 ° C. are preferred, glycol ethers are more preferred, and 1-methoxy-2-propanol is particularly preferred. Propylene glycol monomethyl ether acetate.

  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 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 15 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.

  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 (in the case where the active energy ray-curable resin composition diluted with an organic solvent is applied, after further drying), the active energy ray is cured to cure it. Be done.

  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. Base materials such as acrylic 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 composite substrates of the above materials mixed with glass fibers and inorganic substances, metals (aluminium, copper, iron, SUS, zinc, magnesium, alloys thereof, etc.) or glasses, or primer layers on these substrates The base material etc. which were provided are mentioned.

  The coating method of the active energy ray-curable resin composition of the present invention includes, for example, wet coating methods such as spray, shower, gravure, dipping, roll, spin, screen printing, etc. It may be coated on the substrate under the condition of temperature range without heating.

  Moreover, as a drying condition at the time of applying the active energy ray curable resin composition which diluted with the said organic solvent, temperature is a temperature, usually 40-120 degreeC (preferably 50-100 degreeC), and drying time And usually 1 to 20 minutes (preferably 2 to 10 minutes).

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 electromagnetic waves described above, electron beams, proton beams, neutron beams and the like can be used, but ultraviolet rays or electron beams, particularly ultraviolet rays are preferable in view of curing speed, availability of an irradiation apparatus, cost 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 irradiation with ultraviolet light, use 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 electrode discharge lamp, an LED lamp etc. In general, 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 from the viewpoint of transmitting light so that the photopolymerization initiator reacts uniformly as an active energy ray-curable coating film. The thickness is preferably 2 to 500 μm, particularly preferably 3 to 200 μm.

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

  Thus, the active energy ray-curable resin composition of the present invention is excellent in the storage stability of the solution, and further excellent in the scratch resistance when formed into a cured coating film and the antifouling property after scratching. In particular, it is useful as a coating agent (further, a coating agent for a hard coat or a coating agent for an optical film), and is also useful as a paint, an 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.

  First, the following were prepared as a urethane (meth) acrylate composition [I].

<Production Example 1>
[Production of Urethane Acrylate Composition [I-1]]
66.2 parts of isophorone diisocyanate (B-1) and acrylic acid adduct of dipentaerythritol (A-1) [hydroxyl value in a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet] C .: 933.8 parts of 48 mg KOH / g], 0.6 parts of 2,6-di-t-butylcresol as a polymerization inhibitor [III'-1], 0.2 parts of dibutyltin dilaurate as a reaction catalyst, 50.degree. The reaction was terminated when the residual isocyanate group reached 0.3%, and a urethane acrylate composition [I-1] was obtained (resin concentration 100%).
The weight average molecular weight of the resulting urethane acrylate composition [I-1] was 1,700, and the viscosity at 60 ° C. was 1,500 mPa · s.

<Production Example 2>
[Production of Urethane Acrylate Composition [I-2]]
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port, 237.8 parts of a trimer compound (B-2) of hexamethylene diisocyanate having an isocyanurate skeleton [isocyanate group content 21 %, Acrylic acid adduct of dipentaerythritol (A-1) [hydroxyl value: 50 mg KOH / g] 639.5 parts, 122.7 parts of 2-hydroxypropyl acrylate, 2 as a polymerization inhibitor [III'-1] 0.8 parts of 2,6-di-t-butylcresol and 0.2 parts of dibutyltin dilaurate as a reaction catalyst are charged and reacted at 60 ° C., and the reaction is completed when the residual isocyanate group reaches 0.3%. The urethane acrylate composition [I-2] was obtained (resin concentration 100%).
The weight average molecular weight of the resulting urethane acrylate composition [I-2] was 3,700, and the viscosity at 60 ° C. was 3,000 mPa · s.

  Next, an active energy ray curable resin composition was produced using the above-mentioned urethane acrylate compositions [I-1] and [I-2].

[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 (boiling point 120 ° C.), the fluorine-containing acrylate compound [II- 1) “KY-1203” (20% active ingredient, weight-average molecular weight (measured value) 27,000 manufactured by Shin-Etsu Chemical Co., Ltd.) 0.2 part (1 part including solvent ingredient) active ingredient, polymerization prohibited 0.3 part of 2,6-di-t-butylcresol as agent [III-1] (urethane acrylate composition [I-1], fluorine-containing acrylate compound [II-1] and polymerization inhibitor [III 0.1 parts of "CSP" (made by SEIKO CHEMICAL CO., LTD.) As a coloring inhibitor [IV-1] with respect to a total of 2,990 ppm with respect to the total of 1], and an active energy ray curable resin composition was obtained .
Further, 4 parts of an α-hydroxyalkylphenone photopolymerization initiator (“OMNI RAD 184” manufactured by IGM Co., Ltd.) is blended as a photopolymerization initiator to obtain an active energy ray curable resin composition containing the photopolymerization initiator The
In the above, the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III ′] used in the production of the urethane acrylate composition) is the urethane acrylate composition [I], the fluorine-containing acrylate compound [I] It was 3,580 ppm with respect to the sum total of II] and polymerization inhibitor [III].

Example 2
An active energy ray-curable resin composition in the same manner as in Example 1 except that the urethane acrylate composition [I-2] is used instead of the urethane acrylate composition [I-1] in Example 1, and An active energy ray-curable resin composition containing a photopolymerization initiator was obtained.
In the above, the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III ′] used in the production of the urethane acrylate composition [I]) is a urethane acrylate composition [I], a fluorine-containing acrylate The amount was 3,780 ppm based on the total of the compound [II] and the polymerization inhibitor [III].

Example 3
An active component was prepared in the same manner as in Example 1, except that the content of the fluorine-containing acrylate compound [II-1] was changed to 0.05 parts (0.25 parts by solvent). An active energy ray-curable resin composition containing an energy ray-curable resin composition and a photopolymerization initiator was obtained.
In the above, the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III ′] used in the production of the urethane acrylate composition [I]) is a urethane acrylate composition [I], a fluorine-containing acrylate It was 3,590 ppm with respect to the total of the compound [II] and the polymerization inhibitor [III].

Example 4
The active energy ray curability is obtained in the same manner as in Example 1 except that the compounding amount of the fluorine-containing acrylate compound [II-1] is changed to 1 part (5 parts in terms of solvent) including the active ingredient in Example 1. An active energy ray curable resin composition containing a resin composition and a photopolymerization initiator was obtained.
In the above, the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III ′] used in the production of the urethane acrylate composition [I]) is a urethane acrylate composition [I], a fluorine-containing acrylate It was 3,550 ppm relative to the total of the compound [II] and the polymerization inhibitor [III].

Example 5
In Example 1, in place of the fluorine-containing acrylate compound [II-1], “Optool DAC-HP” (active ingredient 20%, manufactured by Daikin Industries, weight average molecular weight Measured value: 2,300) The active energy ray-curable resin composition and the photopolymerization initiator were prepared in the same manner as in Example 1 except that 0.2 parts of the active ingredient (1 part of solvent ingredient included) was used. The active energy ray curable resin composition to be contained was obtained.
In the above, the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III ′] used in the production of the urethane acrylate composition [I]) is a urethane acrylate composition [I], a fluorine-containing acrylate It was 3,580 ppm with respect to the total of the compound [II] and the polymerization inhibitor [III].

Example 6
In Example 1, as a fluorine-containing acrylate compound [II-3] instead of the fluorine-containing acrylate compound [II-1], “IRX-380” (10% active ingredient, manufactured by AGC, weight average molecular weight (measured value) The active energy ray-curable resin composition and the photopolymerization initiator are contained in the same manner as in Example 1 except that 0.2 parts (2 parts by solvent included) of 1,300) is used as an active ingredient. An active energy ray-curable 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 acrylate composition [I]) is a urethane acrylate composition [I], a fluorine-containing acrylate It was 3,580 ppm with respect to the total of the compound [II] and the polymerization inhibitor [III].

Example 7
An active energy ray-curable resin composition and a photopolymerization initiator are contained in the same manner as in Example 1 except that the blending amount of the polymerization inhibitor [III-1] is changed to 0.9 part in Example 1. An active energy ray-curable 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 acrylate composition [I]) is a urethane acrylate composition [I], a fluorine-containing acrylate It was 9,500 ppm based on the total of the compound [II] and the polymerization inhibitor [III].

Example 8
An active energy ray-curable resin composition in the same manner as in Example 1 except that 4-methoxyphenol was used as the polymerization inhibitor [III-2] in place of the polymerization inhibitor [III-1] in Example 1. Energy curable resin composition containing the polymer and the photopolymerization initiator was obtained.
In the above, the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III ′] used in the production of the urethane acrylate composition [I]) is a urethane acrylate composition [I], a fluorine-containing acrylate It was 3,580 ppm with respect to the total of the compound [II] and the polymerization inhibitor [III].

Example 9
An active energy ray-curable resin composition containing an active energy ray-curable resin composition and a photopolymerization initiator in the same manner as in Example 1 except that the coloring inhibitor [IV-1] is not used in Example 1. I got a thing.
In the above, the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III ′] used in the production of the urethane acrylate composition [I]) is a urethane acrylate composition [I], a fluorine-containing acrylate It was 3,580 ppm with respect to the total of the compound [II] and the polymerization inhibitor [III].

Comparative Example 1
An active energy ray-curable composition containing an active energy ray-curable resin composition and a photopolymerization initiator in the same manner as in Example 1 except that the fluorine-containing acrylate compound [II-1] is not used in Example 1. A 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 acrylate composition) is the urethane acrylate composition [I], the fluorine-containing acrylate compound [I] It was 3,590 ppm with respect to the sum total of II] and polymerization inhibitor [III].

Comparative Example 2
In Example 1, it replaced with urethane acrylate composition [I-1], and except having used trimethylol propane triacrylate (made by Toagosei Co., Ltd., "Alonix M-309", 100 ppm of polymerization inhibitors containing), In the same manner as in Example 1, an active energy ray curable resin composition containing an active energy ray curable resin composition and a photopolymerization initiator was obtained.
In the above, the content of the polymerization inhibitor [III] (including the polymerization inhibitor contained in trimethylolpropane triacrylate) is trimethylolpropane triacrylate, fluorine-containing acrylate compound [II] and polymerization inhibitor [III] It was 3,090 ppm with respect to the sum of

Comparative Example 3
An active energy ray curable resin composition containing an active energy ray curable resin composition and a photopolymerization initiator in the same manner as in Example 1 except that the polymerization inhibitor [III-1] is not used in Example 1. I got a thing.
In the above, the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III ′] used in the production of the urethane acrylate composition [I]) is a urethane (meth) acrylate composition [I], The amount was 600 ppm based on the total of the fluorine-containing (meth) acrylate compound [II] and the polymerization inhibitor [III].

The storage stability of the liquid of the active energy ray curable resin composition obtained above was evaluated by the following method.
[Liquid storage stability]
The Hazen color number (APHA) of the above-mentioned active energy ray-curable resin composition was measured using a spectrocolorimeter "SE6000: manufactured by Nippon Denshoku Kogyo Co., Ltd.". Furthermore, the active energy ray-curable resin composition was placed in a closed glass test container, and subjected to a heat resistance test under heat resistance conditions (stored for 4 weeks in a 60 ° C. environment) to measure the value of APHA after the heat resistance test.

  Moreover, a sample for evaluation is manufactured from the active energy ray-curable resin composition containing the photopolymerization initiator obtained above, and the pencil hardness, the scratch resistance, the stain resistance, the water contact angle and the oleic acid contact angle The evaluation of The results are shown in Table 1 below.

[Method of producing sample for evaluation]
Using a bar coater, the active energy ray-curable resin composition containing the photopolymerization initiator obtained above is applied onto an easily-adhered PET film (Toyobo Co., Ltd., “Cosmo Shine A4300, thickness 125 μm) substrate, The coating is applied so that the film thickness after drying is 5 μm, and after drying at 90 ° C. for 3 minutes, using a 80 W high-pressure mercury lamp, 1 lamp, from a height of 18 cm to a conveyor speed of 5.1 m / min 2 The pass was irradiated with ultraviolet light (accumulated irradiation amount: 450 mJ / cm ² ) to form a cured coating film.

[Pencil hardness]
The cured coating film formed on the easy adhesion PET film was tested according to JIS K 5600 to measure pencil hardness.

[Scratch resistance]
About the above-mentioned cured coating film formed 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) The number of reciprocations until occurrence of a wound was measured and evaluated according to the following criteria.
(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

[Stain resistance (Magic ink (registered trademark) wiping ability)]
A line was drawn on the cured coating surface in one reciprocation with black magic ink, and after standing for 24 hours, the coating after wiping with a rag was observed and evaluated as follows. Moreover, the magic ink wiping off property was similarly evaluated also about the coating film after said abrasion resistance test (after 1,000 reciprocations).
(Evaluation)
○ ········································································· Can not wipe off

[Water and oleic acid contact angle]
The contact angles of water and oleic acid with respect to the cured coating surface were measured by a contact angle measurement device (DropMaster 600, manufactured by Kyowa Interface Chemicals Co., Ltd.). Moreover, water and an oleic acid contact angle were similarly measured also about the coating film after the above-mentioned abrasion resistance test.

  The results of the above Examples and Comparative Examples are shown in Table 1.

As can be seen from the above results, the composition containing the urethane (meth) acrylate composition [I] and the fluorine-containing (meth) acrylate compound [II] further contains a predetermined amount of the polymerization inhibitor [III] In the examples, the storage stability in the coating liquid was excellent. Furthermore, the Example was excellent also in the antifouling performance and abrasion resistance at the time of setting it as a cured coating film, although it contained polymerization inhibitor [III] more than usual.
On the other hand, in Comparative Example 1 which does not contain the fluorine-containing (meth) acrylate compound [II], the antifouling performance and the scratch resistance are inferior, and a comparison in which the urethane (meth) acrylate composition [I] is not used In Example 2, the curability was insufficient. In addition, in Comparative Example 3 in which the addition of the polymerization inhibitor [III] was not performed except for the production of the urethane (meth) acrylate composition [I], the storage stability of the solution was poor, and the present invention Were not satisfied with the purpose of

  The active energy ray-curable resin composition of the present invention is excellent in the storage stability of the coating solution, and has antifouling performance (contamination resistance and its persistence), properties of the cured coating (appearance, hardness, scratch resistance) (6) can be formed, and is useful as a coating agent, in particular, a coating agent for a hard coat or a coating agent for an optical film. It is also useful as a paint, an ink and the like.

Claims (10)

  Urethane (meth) acrylate composition [I] in which the hydroxyl group in the (meth) acrylic acid adduct (A) of dipentaerythritol has reacted with the isocyanate group of the polyisocyanate compound (B), fluorine-containing (meth) Acrylate compound [II] and polymerization inhibitor [III] are contained, and the content of polymerization inhibitor [III] is urethane (meth) acrylate composition [I], fluorine-containing (meth) acrylate compound An active energy ray curable resin composition characterized by being 800 to 10,000 ppm by weight with respect to the total of [II] and the polymerization inhibitor [III].   The active energy ray curable resin composition according to claim 1, 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 composition of Claim 1 or 2 characterized by the above-mentioned.   The active energy ray curable resin according to any one of claims 1 to 3, wherein the hydroxyl value of the (meth) acrylic acid adduct (A) of dipentaerythritol is 10 to 120 mg KOH / g. Composition.   The weight average molecular weight of the said urethane (meth) acrylate type composition [I] is 900-30,000, The active energy ray curable resin composition as described in any one of Claims 1-4 characterized by the above-mentioned. .   The active energy ray curable resin composition according to any one of claims 1 to 5, further comprising a coloring inhibitor [IV].   The active energy ray curable resin composition according to any one of claims 1 to 6, further comprising an organic solvent having a boiling point of 80 ° C or higher.   A coating agent comprising the active energy ray curable resin composition according to any one of claims 1 to 7.   9. The coating agent according to claim 8, which is used as a coating agent for hard coating.   The coating agent according to claim 8, which is used as a coating agent for an optical film.