KR102645100B1 - Active energy ray curable resin composition and coating agent - Google Patents

Abstract

It is an active energy ray-curable resin composition that has excellent preservation stability of the coating solution and can form a coating film with excellent antifouling performance (fouling resistance and durability) and characteristics (appearance, hardness, scratch resistance), and is a polyhydric alcohol (meta) ) Urethane (meth)acrylate-based composition [I], a fluorine-containing (meth)acrylate-based compound [II], and a polymerization inhibitor in which the hydroxyl group in the acrylic acid adduct (A) reacts with the isocyanate group of the polyisocyanate-based compound (B) Contains [III], and the content of the polymerization inhibitor [III] is the sum of the urethane (meth)acrylate-based composition [I], the fluorine-containing (meth)acrylate-based compound [II], and the polymerization inhibitor [III]. For this purpose, an active energy ray-curable resin composition of 800 to 10,000 ppm by weight is provided.

Description

Active energy ray curable resin composition and coating agent

The present invention relates to an active energy ray-curable resin composition and coating agent containing a urethane (meth)acrylate-based composition, and more specifically, to antifouling performance (fouling resistance and sustainability) and properties of the cured coating film (appearance, hardness, It relates to an active energy ray-curable resin composition capable of forming a coating film with excellent scratch resistance and a coating agent containing the same.

Conventionally, active energy ray-curable resin compositions are cured by irradiation of active energy rays such as radiation or ultraviolet rays for a very short period of time, so they are widely used as coating agents, adhesives, anchor coat agents, etc. for various substrates. As components, urethane (meth)acrylate-based compounds and polyfunctional monomers are used. Recently, when using an active energy ray-curable resin composition as a coating agent, especially a coating agent for hard coats, it is required to have high surface hardness and scratch resistance as an alternative to glass.

As a hard coat agent having high surface hardness and scratch resistance as a cured film as described above, for example, a curing component mainly composed of dipentaerythritol hexaacrylate and N-substituted acrylamide mixed with a fluorine compound is proposed. (For example, see Patent Document 1). The film obtained by applying this hard coat agent to a laminated film at a film thickness of 11㎛ and curing it has a hardness of about 5H pencil hardness and scratch resistance that does not cause scratches even after applying a load of 500g with steel wool and reciprocating 500 times. It manifests.

(Patent Document 1) JP 2017-141416A

However, although the technology disclosed in Patent Document 1 is excellent in the surface hardness of the cured coating film and scratch resistance under a load of 500 g, there is no description of scratch resistance under a more stringent load of 1 kg, and further improvement is required.

Additionally, in recent years, when contaminants such as fingerprints adhere to the screens of displays, monitors, touch panel devices, or electronic products such as mobile phones, the transparency and clarity of the screen are reduced, or the aesthetics are damaged. For this reason, methods for wiping off various types of contaminants, examination of coating agents to improve the adhesion prevention and removal of contaminants, and examination of the scratch resistance of the surface of the coating film when coated with a coating agent are being conducted. Demand for anti-fouling performance and scratch resistance is increasing. In addition, fluorine compounds are often used to achieve antifouling and scratch resistance, but the coating solution containing a fluorine compound may easily gel during storage, and further improvement in storage stability is required.

Therefore, in the present invention, under this background, an active energy that can form a coating film that has excellent storage stability of the coating solution and excellent antifouling performance (fouling resistance and durability) and properties of the cured coating film (appearance, hardness, scratch resistance) is provided. A pre-curable resin composition and a coating agent using the same are provided.

However, taking these circumstances into consideration, the present inventors conducted extensive research and as a result, obtained a urethane (meth)acrylate-based composition obtained by reacting a (meth)acrylic acid adduct of a polyhydric alcohol with a polyisocyanate-based compound as a curing component, containing fluorine ( By containing a larger amount of the polymerization inhibitor than usual in an active energy ray-curable resin composition containing a meth)acrylate-based compound and a polymerization inhibitor, the storage stability of the active energy ray-curable resin composition in a liquid is excellent, and the cured coating film is also excellent. It was discovered that a cured coating film with excellent coating film properties such as antifouling performance and scratch resistance could be obtained.

That is, the present invention is a urethane (meth)acrylate-based composition [I] in which the hydroxyl group in the (meth)acrylic acid adduct of polyhydric alcohol (A) reacts with the isocyanate group of the polyisocyanate-based compound (B), a fluorine-containing (meth)acrylic Contains a rate-based compound [II] and a polymerization inhibitor [III], and the content of the polymerization inhibitor [III] is the urethane (meth)acrylate-based composition [I] and the fluorine-containing (meth)acrylate-based composition [II] The first point is an active energy ray-curable resin composition containing 800 to 10,000 ppm by weight relative to the total of the polymerization inhibitor [III].

In addition, the coating agent containing the active energy ray-curable resin composition of the first aspect is regarded as the second aspect.

Generally, when producing a urethane (meth)acrylate-based composition, a polymerization inhibitor is added to the reaction system for the purpose of suppressing the polymerization reaction of the (meth)acryloyl group during the urethanization reaction and improving storage stability. Since the presence of inhibitors reduces the curability of active energy rays or causes coloring, the mixing amount is usually as small as possible. However, in the present invention, unexpectedly, the polymerization inhibitor is used in a larger amount than that used in the production of the urethane (meth)acrylate-based composition, thereby reducing the curability of active energy rays and causing problems of coloring of the coating solution or cured coating film. It was discovered that it was possible to form a coating film with excellent storage stability of the coating solution, excellent antifouling performance (fouling resistance and durability), and cured coating film properties (appearance, hardness, scratch resistance).

The active energy ray-curable resin composition of the present invention is a urethane (meth)acrylate-based composition [I] in which the hydroxyl group in the (meth)acrylic acid adduct (A) of a polyhydric alcohol reacts with the isocyanate group of the polyisocyanate-based compound (B), and fluorine Contains (meth)acrylate-based compound [II] and polymerization inhibitor [III], and the content of polymerization inhibitor [III] is urethane (meth)acrylate-based composition [I], fluorine-containing (meth)acrylate. The total of the compound [II] and the polymerization inhibitor [III] is 800 to 10,000 ppm by weight. For this reason, it is excellent in storage stability in the coating solution, and is also excellent in antifouling performance and scratch resistance when used as a cured coating film. Moreover, because of these excellent properties, it is particularly useful for use as a coating agent for hard coats or a coating agent for optical films.

In particular, in the present invention, if the polyhydric alcohol is at least one of dipentaerythritol and pentaerythritol, it has excellent storage stability in the coating solution and also has excellent antifouling performance and scratch resistance when used as a cured coating film.

Moreover, especially in the present invention, if the fluorine-containing (meth)acrylate-based compound [II] has a siloxane bond, it also has excellent antifouling performance.

In addition, especially in the present invention, if the weight average molecular weight of the fluorine-containing (meth)acrylate compound [II] is 1,000 to 100,000, the antifouling performance is further improved.

And, especially in the present invention, if the weight average molecular weight of the urethane (meth)acrylate-based composition [I] is 900 to 30,000, it will also have excellent scratch resistance when used as a cured coating film.

Moreover, when the active energy ray-curable resin composition of the present invention further contains a discoloration inhibitor [IV], the storage stability in the coating liquid becomes more excellent.

In addition, when the active energy ray-curable resin composition of the present invention further contains an organic solvent with a boiling point of 80° C. or higher, the urethane (meth)acrylate-based composition [I] and the fluorine-containing (meth)acrylate-based compound [II] Since the compatibility is excellent, the storage stability in the coating solution becomes even more excellent.

The present invention will be described in detail below.

In addition, in the present invention, “(meth)acrylic” refers to acrylic or methacryl, “(meth)acryloyl” refers to acryloyl or methacryloyl, and “(meth)acrylate” refers to acrylate or methacryl. Each refers to a rate.

[Active energy ray curable resin composition]

The active energy ray-curable resin composition of the present invention contains a urethane (meth)acrylate-based composition [I], a fluorine-containing (meth)acrylate-based compound [II], and a polymerization inhibitor [III]. The details are explained below.

<Urethane (meth)acrylate-based composition [I]>

The urethane (meth)acrylate-based composition [I] used in the present invention is obtained by reacting the hydroxyl group in the (meth)acrylic acid adduct of polyhydric alcohol (A) with the isocyanate group of the polyisocyanate-based compound (B), so that the urethane bond is formed. It is formed and obtained. Hereinafter, each component used in the present invention will be described.

[(meth)acrylic acid adduct of polyhydric alcohol (A)]

The (meth)acrylic acid adduct (A) of a polyhydric alcohol used in the present invention is a product in which (meth)acrylic acid is added to the hydroxyl group of a polyhydric alcohol, and (meth)acrylic acid is added to all hydroxyl groups of the polyhydric alcohol. It is a mixture containing some of the hydroxyl groups of alcohol to which (meth)acrylic acid has been added.

The polyhydric alcohol is preferably a trihydric or higher polyol, but a dihydric alcohol can also be used. Moreover, examples of types of alcohol include aliphatic alcohol, alicyclic alcohol, and aromatic alcohol, and among them, aliphatic alcohol is preferable.

Examples of the trivalent or higher aliphatic polyol include pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, trimethylolpropane, trimethylolethane, 1,3,6-hexanetriol, adamantanetriol, etc. I can hear it. These can be used individually or in combination of two or more types. Among them, pentaerythritol and dipentaerythritol are preferable.

Hereinafter, about (meth)acrylic acid adducts of pentaerythritol and dipentaerythritol, which are very suitable polyhydric alcohols [(meth)acrylic acid adduct of pentaerythritol (A1) and (meth)acrylic acid adduct of dipentaerythritol (A2)]. Explain.

[(meth)acrylic acid adduct of pentaerythritol (A1)]

In general, the (meth)acrylic acid adduct of pentaerythritol is pentaerythritol tetra(meth)acrylate in which (meth)acrylic acid is added to all four of the four hydroxyl groups of pentaerythritol, and to three of the four hydroxyl groups of pentaerythritol. Pentaerythritol tri(meth)acrylate monool with (meth)acrylic acid added, pentaerythritol di(meth)acrylate diol with (meth)acrylic acid added to two parts, pentaerythritol with (meth)acrylic acid added to only one part. It is a mixture containing mono(meth)acrylate triol.

The (meth)acrylic acid adduct of pentaerythritol (A1) may be obtained by reacting pentaerythritol and (meth)acrylic acid by a known general method.

The hydroxyl value of the (meth)acrylic acid adduct (A1) of pentaerythritol is preferably 50 to 300 mgKOH/g, more preferably 70 to 200 mgKOH/g, and particularly preferably 100 to 160 mgKOH/g.

If this hydroxyl value is too small, the content of pentaerythritol tetra(meth)acrylate, which has a low molecular weight and has many ethylenically unsaturated groups and does not react with isocyanate groups, increases, so curing shrinkage during curing increases and becomes prone to curling. There is a tendency. In addition, if the hydroxyl value becomes too large, the content of polyol components such as pentaerythritol di(meth)acrylate diol or pentaerythritol mono(meth)acrylate triol increases, so the molecular weight of the obtained urethane (meth)acrylate As it grows larger, its viscosity tends to increase and it becomes difficult to handle.

The hydroxyl value of the (meth)acrylic acid adduct of pentaerythritol (A1) refers to the hydroxyl value of the entire mixture of the (meth)acrylic acid adduct of pentaerythritol.

In addition, in the present invention, the hydroxyl value is a value determined by a method according to JIS K 1557-1.

The hydroxyl value of the (meth)acrylic acid adduct of pentaerythritol (A1) can be adjusted, for example, by adjusting the ratio of (meth)acrylic acid added to pentaerythritol.

[(meth)acrylic acid adduct of dipentaerythritol (A2)]

In general, the (meth)acrylic acid adduct of dipentaerythritol includes, among its components, dipentaerythritol hexa(meth)acrylate in which (meth)acrylic acid has been added to all six of the six hydroxyl groups of dipentaerythritol; Dipentaerythritol penta(meth)acrylate monool with (meth)acrylic acid added to 5, dipentaerythritol tetra(meth)acrylate diol with (meth)acrylic acid added to 4, and (meth)acrylic acid to 3. Dipentaerythritol tri(meth)acrylate triol with this addition, dipentaerythritol di(meth)acrylate tetraol with (meth)acrylic acid added to two, and dipentaerythritol with (meth)acrylic acid added to only one. It is a mixture containing (meth)acrylate pentanol.

The (meth)acrylic acid adduct of dipentaerythritol (A2) may be obtained by reacting dipentaerythritol and (meth)acrylic acid by a known general method.

The hydroxyl value of the (meth)acrylic acid adduct (A2) of dipentaerythritol is preferably 10 to 120 mgKOH/g, more preferably 20 to 80 mgKOH/g, particularly preferably 30 to 70 mgKOH/g, especially Preferably it is 40 to 60 mgKOH/g.

If the hydroxyl value is too small, the content of dipentaerythritol hexa(meth)acrylate, which has a low molecular weight and has many ethylenically unsaturated groups and does not react with isocyanate groups, increases, so curing shrinkage during curing increases, causing curling. It tends to get easier. In addition, if the hydroxyl value becomes too large, the content of polyol components such as dipentaerythritol tetra(meth)acrylate diol or dipentaerythritol tri(meth)acrylate triol increases, so that the resulting urethane (meth)acrylate As the molecular weight increases and the viscosity increases, handling tends to become difficult.

The hydroxyl value of the (meth)acrylic acid adduct of dipentaerythritol (A2) refers to the hydroxyl value of the entire mixture of the (meth)acrylic acid adduct of dipentaerythritol.

The hydroxyl value of the (meth)acrylic acid adduct of dipentaerythritol (A2) can be adjusted, for example, by adjusting the ratio of (meth)acrylic acid added to dipentaerythritol.

[Polyisocyanate-based compound (B)]

The polyisocyanate-based compound (B) that reacts with the hydroxyl group of the (meth)acrylic acid adduct of the polyhydric alcohol (A) is a known general polyisocyanate-based compound that is usually used in the production of urethane (meth)acrylate-based compositions. can be used.

Examples of the polyisocyanate-based compound (B) include tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylene diisocyanate, tetramethylxylene diisocyanate, and phenylene diisocyanate. Aromatic polyisocyanates such as isocyanate and naphthalene diisocyanate, aliphatic polyisocyanates such as pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate, hydrogenated diphenylmethane diisocyanate, Alicyclic polyisocyanates such as hydrogenated xylene diisocyanate, isophorone diisocyanate, and norbornene diisocyanate, or trimer or multimer compounds of these polyisocyanates, arophanate-type polyisocyanate, biuret-type polyisocyanate, and water-dispersed polyisocyanate. Isocyanate, etc. can be mentioned. These polyisocyanate-based compounds (B) can be used alone or in combination of two or more types.

In addition, the polyisocyanate-based compound (B) is a variety of polyols, such as low-molecular-weight polyols and high-molecular-weight polyols, especially polyether-based polyols, polyester-based polyols, polycarbonate-based polyols, and polyolefin-based polyols. , it may be a reaction product between polyols such as polybutadiene-based polyol and (meth)acrylic-based polyol and polyisocyanate-based compounds.

Among these, from the viewpoint of excellent yellowing resistance and versatility, aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, and isophorone diisocyanate. , alicyclic diisocyanates such as norbornene diisocyanate are preferable, particularly preferably isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, and hexamethylene diisocyanate, and even more preferably iso These are phorone diisocyanate and hexamethylene diisocyanate.

[Method for producing urethane (meth)acrylate composition [I]]

As described above, the urethane (meth)acrylate-based composition [I] used in the present invention is obtained by reacting the hydroxyl group in the (meth)acrylic acid adduct (A) of a polyhydric alcohol with the isocyanate group of the polyisocyanate-based compound (B). will be.

Specifically, the functional group molar ratio between the isocyanate group of the polyisocyanate-based compound (B) and the hydroxyl group of the (meth)acrylic acid adduct of polyhydric alcohol (A) is adjusted, and if necessary, a catalyst such as dibutyltin dilaurate is adjusted. A urethane (meth)acrylate-based composition [I] can be obtained by reacting a polyisocyanate-based compound (B) with a (meth)acrylic acid adduct of a polyhydric alcohol (A).

In addition, the urethane (meth)acrylate-based composition of the present invention is an acrylic acid adduct of a polyhydric alcohol (A), an acrylic acid adduct of dipentaerythritol with a hydroxyl value of 60 mgKOH/g or more (A2), xylene diisocyanate, and hydrogenated xylene diisocyanate. and a urethane (meth)acrylate-based composition reacted with at least one polyisocyanate-based compound selected from the group consisting of these derivatives.

The injection reaction molar ratio [(B):(A)] between such a polyisocyanate-based compound (B) and the (meth)acrylic acid adduct of polyhydric alcohol (A) is about 1:2 to 1:5.

With respect to this reaction molar ratio, if the ratio of the (meth)acrylic acid adduct (A) of the polyhydric alcohol is too high, low molecular weight monomers that do not react with the polyisocyanate-based compound (B) ((meth) on all hydroxyl groups of the polyhydric alcohol As the content of (acrylic acid added) increases, curing shrinkage increases, the curl of the cured coating film tends to increase, and if the ratio of the (meth)acrylic acid adduct (A) of polyhydric alcohol is too small, unreacted poly The isocyanate-based compound (B) remains, which tends to reduce the stability and safety of the cured coating film.

The reaction between the (meth)acrylic acid adduct of a polyhydric alcohol (A) and the polyisocyanate-based compound (B) is usually performed by adding the (meth)acrylic acid adduct of the polyhydric alcohol (A) and the polyisocyanate-based compound (B) to a reactor. It can be reacted in batches or separately.

In the above reaction, it is also preferable to use a catalyst for the purpose of promoting the reaction. Examples of such catalysts include dibutyltin dilaurate, dibutyltin diacetate, trimethyltin hydroxide, tetra-n-butyltin, Organometallic compounds such as zinc bisacetylacetonate, zirconium tris(acetylacetate)ethyl acetate, zirconium tetraacetylacetate, tin octylate, tin octenoate, zinc hexanoate, zinc octenoate, zinc stearate, 2-ethyl Metal salts such as zirconium hexanoate, cobalt naphthenate, stannous chloride, stannic chloride, and potassium acetate, triethylamine, triethylenediamine, benzyldiethylamine, 1,4-diazabicyclo [2,2,2] ]octane, 1,8-diazabicyclo[5,4,0]undecene, N,N,N',N'-tetramethyl-1,3-butanediamine, N-methylmorpholine, N-ethylmorpholine In addition to amine catalysts such as polyline, bismuth acetate, bismuth bromide, bismuth iodide, and bismuth sulfide, organic bismuth compounds such as dibutyl bismuth dilaurate and dioctyl bismuth dilaurate, bismuth 2-ethylhexanoate salt, Bismuth naphthenate, bismuth isodecanoate, bismuth neodecanoate, bismuth laurate, bismuth maleate, bismuth stearate, bismuth oleate, bismuth linoleate, bismuth acetate, bismuth tribis neodecanoate, Bismuth-based catalysts such as organic acid bismuth salts, such as bismuth disalicylic acid salt and bismuth dimolic acid salt, and among them, dibutyltin dilaurate, 1,8-diazabicyclo[5,4,0] Sen is very suitable. These can be used individually or in combination of two or more types.

＜Polymerization inhibitor [III']＞

In addition, in the above reaction, it is preferable to further use a polymerization inhibitor [III']. In addition, when polymerization inhibitor [III'] is used in the above reaction, it is included in the content of polymerization inhibitor [III] described later.

As the polymerization inhibitor [III'], known and general polymerization inhibitors can be used, for example, p-benzoquinone, naphthoquinone, tolquinone, 2,5-diphenyl-p-benzo. Quinones such as quinone, hydroquinone, 2,5-di-t-butylhydroquinone, methyl hydroquinone, mono-t-butylhydroquinone, 4-methoxyphenol, 2,6-di-t-butylcresol, Phenols such as p-t-butylcatechol can be mentioned. Among these, phenols are preferable, and 4-methoxyphenol and 2,6-di-t-butylcresol are particularly preferable. These can be used individually or in combination of two or more types.

The content of the polymerization inhibitor [III'] in the above reaction is 0.005 to 0.095 parts by weight based on a total of 100 parts by weight of the (meth)acrylic acid adduct of polyhydric alcohol (A) and the polyisocyanate-based compound (B), Preferably it is 0.01 to 0.08 parts by weight. If the content of such polymerization inhibitor [III'] is too small, polymerization of the acryloyl group may occur during the reaction. Additionally, the liquid stability of the urethane (meth)acrylate-based composition [I] tends to decrease, and it tends to gel easily during storage. Additionally, if the content of the polymerization inhibitor [III'] is too high, coloring occurs or curing tends to become difficult even when irradiated with active energy rays.

In addition, in the above reaction, an organic solvent that does not have a functional group that reacts with an isocyanate group, such as esters such as ethyl acetate, butyl acetate, and 2-methoxy-1-methyl ethyl acetate, methyl ethyl ketone, and methyl isobutyl ketone. Organic solvents such as ketones and aromatics such as toluene and xylene can be used.

The reaction temperature for 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.

In this way, the urethane (meth)acrylate-based composition [I] used in the present invention can be obtained.

The urethane (meth)acrylate-based composition [I] contains multiple types of urethane (meth)acrylate, and also contains a polyisocyanate-based compound (B) and an unreacted (meth)acrylic acid adduct of a polyhydric alcohol (A) ), and may also contain a polymer of the (meth)acrylic acid adduct (A) of a polyhydric alcohol.

The weight average molecular weight of the urethane (meth)acrylate composition [I] is preferably 900 to 30,000, more preferably 1,000 to 20,000, particularly preferably 1,100 to 10,000, and particularly preferably 1,200 to 5,000.

If this weight average molecular weight is too small, the cured coating film tends to become brittle, and if it is too large, it tends to become highly viscous and difficult to handle.

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

In addition, the viscosity of the urethane (meth)acrylate composition [I] at 60°C is preferably 500 to 300,000 mPa·s, especially 750 to 100,000 mPa·s, and more preferably 1,000 to 30,000 mPa·s. do. When the viscosity is outside the above range, coatability tends to decrease.

Additionally, the viscosity is measured using an E-type viscometer.

The content of urethane (meth)acrylate in the urethane (meth)acrylate-based composition [I] used in the present invention is preferably 10% by weight or more, particularly preferably 20% by weight or more, and even more preferably 30% by weight. It is 50% by weight or more, particularly preferably 50% by weight or more. Additionally, the upper limit is usually 80% by weight.

＜Fluorine-containing (meth)acrylate compound [II]＞

The fluorine-containing (meth)acrylate-based compound [II] used in the present invention is a compound having a (meth)acryloyl group and a fluorine atom. In addition, the structure other than the (meth)acryloyl group and fluorine atom is not particularly limited, and may also have heteroatoms such as oxygen, nitrogen, silicon, and sulfur.

The fluorine-containing (meth)acrylate-based compound [II] is preferably a compound in which a fluorine atom is bonded to the alkyl group of a (meth)acrylic acid alkyl ester, for example, “Optol DAC” and “Optol” manufactured by Daikin Industries, Ltd. DAC-HP", "Megapark RS-75" manufactured by DIC, "Megapark RS-76", "Megapark RS-91 C", "Defensa TF3028", "Defensa TF3001", "Defensa TF3000" , “SUA1900L10” and “SUA1900L6” manufactured by Shinnakamura Kakagusa Co., Ltd., “UT3971” manufactured by Nippon Kosei Kogyo Co., Ltd., “KNS5300” and “KY-1203” manufactured by Shinetsu Chemical Company Limited, and “Viscott 3F” manufactured by Osaka Organic Chemical Industries Ltd., “Viscot 4F,” “Viscot 8F,” “Viscot 8FM,” “Viscot 13F,” and “IRX-380” manufactured by AGC. These fluorine-containing (meth)acrylate compounds [II] can be used individually or in combination of two or more types.

Among the above-mentioned fluorine-containing (meth)acrylate compounds [II], from the viewpoint of more excellent antifouling performance, fluorine-containing (meth)acrylate compounds having a siloxane bond in the structure are preferable, and "KY-1203" is especially desirable.

Moreover, 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, particularly preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. am. If the weight average molecular weight of the fluorine-containing (meth)acrylate-based compound [II] is too small, the scratch resistance and antifouling performance tend to decrease, and if the weight-average molecular weight is too large, the urethane (meth)acrylate-based composition [I] Compatibility with solvents tends to decrease.

The content of the fluorine-containing (meth)acrylate-based compound [II] in the active energy ray-curable resin composition of the present invention is usually 0.01 to 5 parts by weight based on 100 parts by weight of the urethane (meth)acrylate-based composition [I]. It is a part by weight, preferably 0.05 to 3 parts by weight, and particularly preferably 0.1 to 1 part by weight. If the content of the fluorine-containing (meth)acrylate-based compound [II] is too small, scratch resistance and anti-fouling performance tend to decrease, and if the content is too high, compatibility with the urethane (meth)acrylate-based composition [I] This tends to deteriorate.

＜Polymerization inhibitor [III]＞

The active energy ray-curable resin composition of the present invention contains more polymerization inhibitor [III] than a general active energy ray-curable resin composition. Usually, in active energy ray-curable resin compositions, containing a large amount of polymerization inhibitor [III] does not contain more polymerization inhibitor [III] than necessary for reasons such as lowering or coloring the active energy ray curability. The content of the polymerization inhibitor [III] is the amount normally used in the production of the above-described urethane (meth)acrylate-based composition [I]. However, the present invention is an active energy ray-curable resin composition containing a specific urethane (meth)acrylate-based composition [I] and a fluorine-containing (meth)acrylate-based compound [II], and is generally used in active energy ray-curable resin compositions. By containing the polymerization inhibitor [III] in a larger amount than the amount used, there is no problem of deterioration of active energy ray curability or coloring, the liquid stability of the active energy ray curable resin composition is improved, and the effect of suppressing gelation during storage is achieved. It represents.

As the polymerization inhibitor [III] used in the present invention, known and general ones can be used, and specifically, compounds similar to those listed in the above-mentioned polymerization inhibitor [III'] can be used. In addition, it is preferable to use the same compound as the polymerization inhibitor [III'] used in the production of the urethane (meth)acrylate-based composition [I] as the polymerization inhibitor [III] mixed in the active energy ray-curable resin composition. , different compounds may be used.

In addition, the content of the polymerization inhibitor [III] is based on weight relative to the sum of the urethane (meth)acrylate-based composition [I], the fluorine-containing (meth)acrylate-based compound [II] and the polymerization inhibitor [III]. Therefore, it is important that it is 800 to 10,000 ppm, preferably 1,000 to 8,000 ppm, more preferably 1,500 to 7,000 ppm, further preferably 2,000 to 6,000 ppm, and especially preferably 3,100 to 5,000 ppm. If the content of such polymerization inhibitor [III] is too small, the liquid stability of the active energy ray-curable resin composition before curing decreases, making it prone to gelation during storage. Additionally, if the content of the polymerization inhibitor [III] is too high, it becomes difficult to cure even when irradiated with active energy rays. In addition, when the polymerization inhibitor [III'] is used in the production of the urethane (meth)acrylate-based composition [I], the content of this polymerization inhibitor [III'] is also the same as that of the polymerization inhibitor [III] of the present invention. Included in content.

＜Discoloration inhibitor [IV]＞

In the present invention, in order to prevent discoloration of the urethane (meth)acrylate-based composition [I] and to further improve the storage stability of the liquid of the active energy ray-curable resin composition, it is preferable to further contain a discoloration inhibitor [IV]. do.

Examples of the discoloration inhibitor [IV] include arylphosphine compounds such as triphenylphosphine, 1,1,3,3-tetramethyldisirazane, and 1,1,3,3,3-hexamethyldisirazane. and sirazan compounds, and hydrazine compounds such as phenylhydrazine, benzophenylhydrolazine, and diacetylhydrazine. These anti-coloring agents may be used individually, or two or more types may be used together. Among these, aryl phosphine compounds are preferable from the viewpoint of further preventing coloring of the urethane (meth)acrylate-based composition [I], and triphenylphosphine is especially preferable.

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

[Other optional ingredients]

It is preferable that the active energy ray-curable resin composition of the present invention further contains a photopolymerization initiator. In addition, within the range that does not impair the effect of the present invention, ethylenically unsaturated monomers other than urethane (meth)acrylate, acrylic resin, surface conditioners, leveling agents, etc. can be mixed, and fillers, dyes, oils, plasticizers, etc. , waxes, desiccants, dispersants, wetting agents, gelling agents, stabilizers, antifoaming agents, surfactants, leveling agents, thixotropic imparting agents, antioxidants, flame retardants, antistatic agents, fillers, reinforcing agents, polishing agents, crosslinking agents, silica, water. It is also possible to mix dispersed or solvent-dispersed silica, zirconium compounds, preservatives, etc. These may be used individually or in combination of two or more types.

Examples of the photopolymerization initiator include diethoxyacetphenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, and 4-(2-hydroxyethoxy)phenyl-(2). -hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1 -one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]-phenyl}-2-methyl-propane, 2-methyl-1-[4- (methylthio)phenyl]-2-morpholinopropane 1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2-hydroxy-2-methyl-1- Acetophenones such as [4-(1-methylvinyl)phenyl]propanone oligomer; Benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzoins Phenone, o-benzoylmethyl benzoate, 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]benzenemetanaminium bromide, (4-benzoyl Benzophenones such as benzyl)trimethylammonium chloride; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro- Thioxanthone such as 4-propoxythioxanthone, 2-(3-dimethylamino-2-hydroxy)-3,4-dimethyl-9H-thioxanthone 9-one mesocrolide; 2,4,6 -Trimethylbenzoyl-diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide Acylphosphine oxides such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-( Oxime esters, such as 2-methylbenzoyl)-9H-carbazol-3-yl]-, and 1-(O-acetyloxime), are mentioned.

In addition, only one type of these photopolymerization initiators may be used individually, and two or more types may be used together.

Among these, acetophenones are preferable, and more preferable are benzyldimethyl ketal, 1-hydroxycyclohexylphenyl ketone, benzoin isopropyl ether, and 4-(2-hydroxyethoxy)phenyl-(2-hyde). Roxy-2-propyl) ketone and 2-hydroxy-2-methyl-1-phenylpropan-1-one, and particularly preferably 1-hydroxycyclohexylphenyl ketone.

When a photopolymerization initiator is contained, the content is preferably 0.1 to 20 parts by weight, particularly preferably 0.5 to 10 parts by weight, and even more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the curing component contained in the active energy ray-curable resin composition. is 1 to 10 parts by weight.

If the content of the photopolymerization initiator is too small, curing tends to be poor and film formation is difficult to achieve, and if it is too large, it tends to cause yellowing of the cured coating film and causes coloring problems.

In addition, as an adjuvant for the photopolymerization initiator, for example, triethanol amine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (mihyracetone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethyl. Benzoic acid, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid (n-butoxy)ethyl, 4-dimethylaminobenzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, 2,4-diethylthioxanthone, It is also possible to use 2,4-diisopropylthioxanthone together.

Examples of ethylenically unsaturated monomers other than the urethane (meth)acrylate include monofunctional monomers, difunctional monomers, trifunctional or more polyfunctional monomers, etc. These ethylenically unsaturated monomers can be used individually or in combination of two or more types.

Examples of such monofunctional monomers include styrene-based monomers such as styrene, vinyl toluene, chlorostyrene, and α-methylstyrene, methyl (meth)acrylate, ethyl (meth)acrylate, acrylonitrile, and 2-methyl. Toxyethyl (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, dicyclo Pentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolane-4-yl)- Methyl (meth)acrylate, cyclohexane spiro-2-(1,3-dioxolan-4-yl)-methyl (meth)acrylate, 3-ethyl-3-oxetanylmethyl (meth)acrylate, γ －Butylolactone (meth)acrylate, n-butyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate ) Acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, n-stearyl (meth)acrylate, benzyl (meth)acrylate, phenolethylene oxide modified (n=2) (meth)acrylate Phthalic acid, such as late, nonylphenolpropylene oxide modified (n=2.5) (meth)acrylate, 2-(meth)acryloyloxyethyl acid phosphate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, etc. Derivatives of half (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofurpril (meth)acrylate, carbitol (meth)acrylate, benzyl (meth)acrylate, butoxyethyl (meth)acrylate , (meth)acrylate monomers such as aryl (meth)acrylate, (meth)acryloylmorholine, polyoxyethylene secondary alkyl ether acrylate, 2-hydroxyethyl acrylamide, N-methylol ( Meta)acrylamide, N-vinylpyrrolidone, 2-vinylpyridine, vinyl acetate, etc. are mentioned.

Examples of such bifunctional monomers include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and propylene. Glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide Modified bisphenol A type di(meth)acrylate, propylene oxide modified bisphenol A type di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, ethoxylated cyclohexanedimethanol di(meth)acrylate, dimethylol Dicyclopentane di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate Acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl ether di(meth)acrylate, hydroxypivaric acid modification Neopentyl glycol di(meth)acrylate, isocyanuric acid ethylene oxide modified diacrylate, etc. are mentioned.

Examples of such trifunctional or higher monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, Dipentaerythritol hexa(meth)acrylate, tri(meth)acryloyloxyethoxy trimethylolpropane, glycerin polyglycidyl ether poly(meth)acrylate, isocyanuric acid ethylene oxide modified triacrylate, caprolactone modified Dipentaerythritol penta(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, caprolactone modified pentaerythritol tri(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate, ethylene oxide modified Dipentaerythritol penta(meth)acrylate, ethylene oxide modified dipentaerythritol hexa(meth)acrylate, ethylene oxide modified pentaerythritol tri(meth)acrylate, ethylene oxide modified pentaerythritol tetra(meth)acrylate, ethoxylated 15 Glycerin triacrylate, etc. can be mentioned.

Additionally, as ethylenically unsaturated monomers other than urethane (meth)acrylate, Michael's adduct of (meth)acrylic acid or 2-acryloyloxyethyldicarboxylic acid monoester can also be used in combination. Examples of such Michael adducts of (meth)acrylic acid include (meth)acrylic acid dimer, (meth)acrylic acid trimer, and (meth)acrylic acid tetramer. The 2-acryloyloxyethyl dicarboxylic acid monoester is a carboxylic acid having a specific substituent, for example, 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, 2 －Acryloyloxyethylphthalic acid monoester, 2-methacryloyloxyethylphthalic acid monoester, 2-acryloyloxyethylhexahydrophthalic acid monoester, 2-methacryloyloxyethylhexahydrophthalic acid monoester, etc. I can hear it. Additionally, oligo ester acrylates and the like can be mentioned.

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

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

As the labeling agent, any known general labeling agent can be used as long as it has the effect of imparting wettability to the base material of the coating liquid and reducing the surface tension. For example, silicone-modified resin, fluorine-modified resin, alkyl-modified resin, etc. You can use it.

The active energy ray-curable resin composition of the present invention is prepared by mixing the urethane (meth)acrylate-based composition [I], the fluorine-containing (meth)acrylate-based compound [II], the polymerization inhibitor [III], and other optional components. You can get it. In addition, the mixing method is not particularly limited, and various methods are adopted, such as a method of mixing each component in batches or a method of mixing arbitrary components and then mixing the remaining components in batches or sequentially. can do.

The active energy ray-curable resin composition of the present invention obtained in this way is excellent in storage stability in a coating solution, and is also excellent in scratch resistance when used as a cured coating film and antifouling property after scratching.

In addition, the active energy ray-curable resin composition of the present invention may be applied as is, or may be diluted with an organic solvent and applied. In the case of dilution, the solid content concentration can 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, toluene, and xylene. aromatics, 1-methoxy-2-propanol (aka propylene glycol monomethyl ether), glycol ethers such as propylene glycol monomethyl ether acetate and ethyl cellosolve, acetic acids such as methyl acetate, ethyl acetate, and butyl acetate. Esters, diacetone alcohol, etc. can be mentioned. These above-mentioned organic solvents may be used individually, or two or more types may be used together.

In addition, among these, the urethane (meth)acrylate-based composition [I] and the fluorine-containing (meth)acrylate [II] have excellent compatibility, and the active energy ray-curable resin composition has excellent liquid stability, so the boiling point is 80. A solvent with a high boiling point of ℃ or higher, especially 100 ℃ or higher, and 120 to 170 ℃ is preferable, more preferably glycol ethers, particularly preferably 1-methoxy-2-propanol and propylene glycol monomethyl ether. It is acetate.

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

The viscosity of the active energy ray-curable resin composition of the present invention at 20°C is preferably 5 to 50,000 mPa·s, particularly preferably 10 to 10,000 mPa·s, and still more preferably 15 to 5,000 mPa·s. . When the viscosity is outside the above range, coatability tends to decrease.

Additionally, the viscosity is measured using an E-type viscometer.

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 an overcoat or anchor coat agent, on various substrates. After coating such an active energy ray-curable resin composition on a substrate (organic When an active energy ray-curable resin composition diluted with a solvent is applied, it is dried again) and then cured by irradiating an active energy ray.

Substrates to which the active energy ray-curable resin composition of the present invention is applied include, for example, polyolefin resin, polyester resin, polycarbonate resin, acrylonitrile-butadiene-styrene copolymer (ABS), and polystyrene resin. Resin, acrylic resin, etc., plastic substrates such as these molded products (films, sheets, cups, etc.), optical films such as polyethylene terephthalate film, triacetylcellulose film, and cycloolefin film, composite substrates thereof, or glass fibers, etc. Examples include composite substrates of the above materials mixed with inorganic substances, metals (aluminium, copper, iron, SUS, zinc, magnesium, alloys thereof, etc.), glass, or substrates in which a primer layer is provided on these substrates.

Examples of the coating method of the active energy ray-curable resin composition of the present invention include wet coating methods such as spraying, showering, gravure, dipping, roll, spin, and screen printing, and are usually applied at room temperature (especially without heating). It may be applied to the substrate under the conditions of (temperature range).

In addition, as drying conditions when applying the active energy ray-curable resin composition diluted with the organic solvent, the temperature is usually 40 to 120 ° C. (preferably 50 to 100 ° C.), and the drying time is usually 1 to 20 ° C. A minute (preferably 2 to 10 minutes) is sufficient.

Examples of active energy rays used when curing the active energy ray curable resin composition coated on the substrate include rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, electromagnetic waves such as X-rays and γ-rays, Electron beams, proton beams, neutron beams, etc. can be used, but ultraviolet rays or electron beams, especially ultraviolet rays, are preferable due to curing speed, availability of irradiation equipment, price, etc.

Additionally, when curing is performed by irradiation of an electron beam, curing can be achieved without using a photopolymerization initiator.

When curing by irradiation of ultraviolet rays, use high-pressure mercury lamps, ultra-high pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, LED lamps, etc. that emit light in the 150-450 nm wavelength range, Usually, irradiation of ultraviolet rays of 30 to 3,000 mJ/cm2 (preferably 100 to 1,500 mJ/cm2) is sufficient.

After irradiation with ultraviolet rays, heating may be performed as needed to ensure complete curing.

The coating film thickness (film thickness after curing) is usually 1 to 1,000 μm, preferably 2 to 500 μm, from the viewpoint of transmitting light so that the photopolymerization initiator reacts uniformly as an active energy ray-curable coating film. Preferably it is 3 to 200㎛.

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

In this way, the active energy ray-curable resin composition of the present invention is excellent in liquid storage stability, and is also excellent in scratch resistance when used as a cured coating film and antifouling property after scratching, and is especially useful as a coating agent (also as a coating agent for hard coats and optical films). It is useful as a coating agent, and is also useful as a paint, ink, etc.

(Example)

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples as long as it does not exceed the gist of the present invention. In addition, in the examples, “part” and “%” mean weight basis.

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

＜Manufacturing Example 1＞

[Manufacture of urethane acrylate-based composition [I-1]]

In a four-neck flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet, 184.6 parts of isophorone diisocyanate (B-1) and acrylic acid adduct of pentaerythritol (A1-1) [hydroxyl value: 120 mgKOH/g] Add 815.4 parts of 2,6-di-t-butylcresol as a polymerization inhibitor [III'-1], 0.8 parts of 2,6-di-t-butylcresol, and 0.05 parts of dibutyltin dilaurate as a reaction catalyst, and react at 60°C to obtain a residual isocyanate group of 0.1%. The reaction was terminated at the point where urethane acrylate-based composition [I-1] was obtained (resin concentration 100%).

The weight average molecular weight of the obtained urethane acrylate-based composition [I-1] was 1,400, and the viscosity at 60°C was 3,000 mPa·s.

＜Manufacture Example 2＞

[Manufacture of urethane acrylate-based composition [I-2]]

In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet, 219.1 parts of hydrogenated diphenylmethane diisocyanate (B-2) and acrylic acid adduct of pentaerythritol (A1-1) [hydroxyl value: 120 mgKOH] /g] 780.9 parts, 0.4 parts of 2, 6-di-t-butylcresol as a polymerization inhibitor [III'-1], and 0.1 part of dibutyltindilaurate as a reaction catalyst were added and reacted at 60°C. The reaction was terminated when the concentration reached 0.1%, and a urethane acrylate-based composition [I-2] was obtained (resin concentration 100%).

The weight average molecular weight of the obtained urethane acrylate-based composition [I-2] was 2,200, and the viscosity at 60°C was 5,000 mPa·s.

＜Manufacture Example 3＞

[Manufacture of urethane acrylate composition [I-3]]

In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet, 66.2 parts of isophorone diisocyanate (B-1) and acrylic acid adduct of dipentaerythritol (A2-1) [hydroxyl value: 48 mgKOH/g. 〕933.8 parts, 0.6 parts of 2,6-di-t-butylcresol as a polymerization inhibitor [III'-1], and 0.2 parts of dibutyltindilaurate as a reaction catalyst were added, reacted at 50°C, and the remaining isocyanate group was 0.3. When the % reached, the reaction was terminated to obtain a urethane acrylate-based composition [I-3] (resin concentration 100%).

The weight average molecular weight of the obtained urethane acrylate-based composition [I-3] was 1,700, and the viscosity at 60°C was 1,500 mPa·s.

＜Manufacture Example 4＞

[Manufacture of urethane acrylate composition [I-4]]

In a four-neck flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet, 237.8 parts of the trimer compound (B-3) of hexamethylene diisocyanate having an isocyanurate skeleton [isocyanate group content 21%] and D Acrylic acid adduct of pentaerythritol (A2-1) [hydroxyl value: 50 mgKOH/g] 639.5 parts, 2-hydroxypropyl acrylate 122.7 parts, 2,6-di-t- as polymerization inhibitor [III'-1] 0.8 parts of butyl cresol and 0.2 parts of dibutyltin dilaurate as a reaction catalyst were added and reacted at 60°C. The reaction was terminated when the residual isocyanate group reached 0.3%, and a urethane acrylate-based composition [I-4] was obtained (water). stake concentration 100%).

The weight average molecular weight of the obtained urethane acrylate-based composition [I-4] was 3,700, and the viscosity at 60°C was 3,000 mPa·s.

Next, an active energy ray-curable resin composition was manufactured using the urethane acrylate-based compositions [I-1] to [I-4].

[Manufacture of active energy ray curable resin composition]

<Example 1>

While stirring the 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 composition [II-1] 0.2 parts of “KY-1203” (active ingredient 20%, manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight (actual value) 27,000) as an active ingredient (1 part including solvent ingredient), as a polymerization inhibitor [III-1] 0.3 parts of 2,6-di-t-butylcresol (2,990 for the total of urethane acrylate composition [I-1], fluorine-containing acrylate compound [II-1], and polymerization inhibitor [III-1]) ppm), 0.05 part of “CSP” (manufactured by Seiko Chemical Company Limited) was blended as a discoloration inhibitor [IV-1], and an active energy ray curable resin composition was obtained. Additionally, 4 parts of an α-hydroxyalkylphenone-based photopolymerization initiator (“Omnirad 184” manufactured by IGM) was blended as a photopolymerization initiator to obtain an active energy ray-curable resin composition containing the photopolymerization initiator.

In the above, the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III'] used in the production of the urethane acrylate-based composition) is the urethane acrylate-based composition [I], the fluorine-containing acrylate-based compound [II], and The total of polymerization inhibitor [III] was 3,780 ppm.

<Example 2>

An active energy ray-curable resin composition and a photopolymerization initiator were prepared in the same manner as in Example 1, except that the urethane acrylate-based composition [I-2] was used instead of the urethane acrylate-based composition [I-1] in Example 1. A containing 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-based composition [I]) is the urethane acrylate-based composition [I] and the fluorine-containing acrylate-based compound. The total of [II] and polymerization inhibitor [III] was 3,380 ppm.

<Example 3>

Active energy ray curability was determined in the same manner as in Example 1, except that the mixing amount of the fluorine-containing acrylate compound [II-1] was changed from the active ingredient to 0.05 parts (0.25 parts including the solvent ingredient). 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-based composition [I]) is the urethane acrylate-based composition [I] and the fluorine-containing acrylate-based compound. The total of [II] and polymerization inhibitor [III] was 3,790 ppm.

<Example 4>

An active energy ray-curable resin composition was prepared in the same manner as in Example 1, except that the mixing amount of the fluorine-containing acrylate compound [II-1] was changed from 1 part of the active ingredient to 1 part (5 parts including the solvent ingredient). 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-based composition [I]) is the urethane acrylate-based composition [I] and the fluorine-containing acrylate-based compound. The total of [II] and polymerization inhibitor [III] was 3,750 ppm.

<Example 5>

In Example 1, instead of the fluorine-containing acrylate-based compound [II-1], “Optol DAC-HP” (active ingredient 20%, manufactured by Daikin Kogyo, weight average) was used as the fluorine-containing acrylate-based compound [II-2]. An active energy ray curable product containing an active energy ray curable resin composition and a photopolymerization initiator in the same manner as in Example 1, except that 0.2 parts (1 part including solvent component) of molecular weight (actual value) 2,300) was used as the active ingredient. 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-based composition [I]) is the content of the urethane acrylate-based composition [I] and the fluorine-containing acrylate-based composition. The total of compound [II] and polymerization inhibitor [III] was 3,780 ppm.

<Example 6>

In Example 1, instead of the fluorine-containing acrylate-based compound [II-1], “IRX-380” (active ingredient 10%, manufactured by AGC, weight average molecular weight (actual measurement) was used as the fluorine-containing acrylate-based compound [II-3] Value) 1,300) An active energy ray curable resin composition containing an active energy ray curable resin composition and a photopolymerization initiator was prepared in the same manner as in Example 1, except that 0.2 parts (2 parts including solvent component) were used as the active ingredient. got it

In the above, the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III'] used in the production of the urethane acrylate-based composition [I]) is the content of the urethane acrylate-based composition [I] and the fluorine-containing acrylate-based composition. The total of compound [II] and polymerization inhibitor [III] was 3,780 ppm.

<Example 7>

An active energy ray curable resin composition containing an active energy ray curable resin composition and a photopolymerization initiator was obtained in the same manner as in Example 1, except that the mixing amount of the polymerization inhibitor [III-1] was changed to 0.9 parts. .

In the above, the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III'] used in the production of the urethane acrylate-based composition [I]) is the urethane acrylate-based composition [I] and the fluorine-containing acrylate-based compound. The total of [II] and polymerization inhibitor [III] was 9,690 ppm.

<Example 8>

Same as Example 1 except that 4-methoxyphenol was used as the polymerization inhibitor [III-2] in place of 2,6-di-t-butylcresol as the polymerization inhibitor [III-1] in Example 1. Thus, 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 [III'] used in the production of the urethane acrylate-based composition [I]) is the urethane acrylate-based composition [I] and the fluorine-containing acrylate-based compound. The total of [II] and polymerization inhibitor [III] was 3,780 ppm.

<Example 9>

In Example 1, the urethane acrylate composition [I-1] was replaced with 100 parts of the urethane acrylate composition [I-3], and 0.1 part of “CSP” was used as the discoloration inhibitor [IV-1]. 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 [III'] used in the production of the urethane acrylate-based composition [I]) is the urethane acrylate-based composition [I] and the fluorine-containing acrylate-based compound. The total of [II] and polymerization inhibitor [III] was 3,580 ppm.

<Example 10>

An active energy ray-curable resin composition and a photopolymerization initiator were prepared in the same manner as in Example 9, except that the urethane acrylate-based composition [I-4] was used instead of the urethane acrylate-based composition [I-3] in Example 9. A containing 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-based composition [I]) is the urethane acrylate-based composition [I] and the fluorine-containing acrylate-based compound. The total of [II] and polymerization inhibitor [III] was 3,780 ppm.

<Example 11>

An active energy ray curable resin was prepared in the same manner as in Example 9, except that the mixing amount of the fluorine-containing acrylate compound [II-1] was changed from the active ingredient to 0.05 parts (0.25 parts including the solvent ingredient). An active energy ray-curable resin composition containing the 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-based composition [I]) is the urethane acrylate-based composition [I] and the fluorine-containing acrylate-based compound. The total of [II] and polymerization inhibitor [III] was 3,590 ppm.

<Example 12>

An active energy ray curable resin was prepared in the same manner as in Example 9, except that the mixing amount of the fluorine-containing acrylate compound [II-1] was changed from 1 part of the active ingredient (5 parts including the solvent ingredient). An active energy ray-curable resin composition containing the 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-based composition [I]) is the urethane acrylate-based composition [I] and the fluorine-containing acrylate-based compound. The total of [II] and polymerization inhibitor [III] was 3,550 ppm.

<Example 13>

In Example 9, instead of the fluorine-containing acrylate-based compound [II-1], “Optol DAC-HP” (active ingredient 20%, manufactured by Daikin Kogyo, weight average) was used as the fluorine-containing acrylate-based compound [II-2]. An active energy ray curable resin containing an active energy ray curable resin composition and a photopolymerization initiator was prepared in the same manner as in Example 9, except that 0.2 parts (1 part including the solvent component) of the active ingredient (molecular weight (actual value) 2,300) was used. The 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-based composition [I]) is the urethane acrylate-based composition [I] and the fluorine-containing acrylate-based compound. The total of [II] and polymerization inhibitor [III] was 3,580 ppm.

<Example 14>

In Example 9, instead of the fluorine-containing acrylate-based compound [II-1], “IRX-380” (active ingredient 10%, manufactured by AGC, weight average molecular weight (actual measurement) was used as the fluorine-containing acrylate-based compound [II-3] An active energy ray curable resin composition containing an active energy ray curable resin composition and a photopolymerization initiator was obtained in the same manner as in Example 9, except that 0.2 parts (2 parts including solvent component) were used as active ingredients (value) 1,300). .

In the above, the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III'] used in the production of the urethane acrylate-based composition [I]) is the urethane acrylate-based composition [I] and the fluorine-containing acrylate-based compound. The total of [II] and polymerization inhibitor [III] was 3,580 ppm.

<Example 15>

In Example 9, an active energy ray curable resin composition containing an active energy ray curable resin composition and a photopolymerization initiator was prepared in the same manner as in Example 9, except that the compounding amount of the polymerization inhibitor [III-1] was changed to 0.9 parts. got it

In the above, the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III'] used in the production of the urethane acrylate-based composition [I]) is the urethane acrylate-based composition [I] and the fluorine-containing acrylate-based compound. The total of [II] and polymerization inhibitor [III] was 9,500 ppm.

<Example 16>

Same as Example 9, except that 4-methoxyphenol was used as the polymerization inhibitor [III-2] instead of 2,6-di-t-butyl cresol as the polymerization inhibitor [III-1]. Thus, 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 [III'] used in the production of the urethane acrylate-based composition [I]) is the urethane acrylate-based composition [I] and the fluorine-containing acrylate-based compound. The total of [II] and polymerization inhibitor [III] was 3,580 ppm.

<Example 17>

An active energy ray curable resin composition containing an active energy ray curable resin composition and a photopolymerization initiator was obtained in the same manner as in Example 9 except that the discoloration inhibitor [IV-1] was not used in Example 9.

In the above, the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III'] used in the production of the urethane acrylate-based composition [I]) is the urethane acrylate-based composition [I] and the fluorine-containing acrylate-based compound. The total of [II] and polymerization inhibitor [III] was 3,580 ppm.

<Comparative 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 same manner as in Example 1, except that the fluorine-containing acrylate compound [II-1] was not used. .

In the above, the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III'] used in the production of the urethane acrylate-based composition) is the urethane acrylate-based composition [I] and the fluorine-containing acrylate-based compound [II]. and polymerization inhibitor [III], the total was 3,790 ppm.

<Comparative Example 2>

An active energy ray curable resin composition containing an active energy ray curable resin composition and a photopolymerization initiator was obtained in the same manner as in Example 1 except that the polymerization inhibitor [III-1] was not used.

In the above, the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III'] used in the production of the urethane acrylate-based composition) is the urethane acrylate-based composition [I] and the fluorine-containing acrylate-based compound [II]. and polymerization inhibitor [III], the total was 800 ppm.

<Comparative Example 3>

An active energy ray curable resin composition containing an active energy ray curable resin composition and a photopolymerization initiator was obtained in the same manner as in Example 9, except that the fluorine-containing acrylate compound [II-1] was not used. .

In the above, the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III'] used in the production of the urethane acrylate-based composition) is the urethane acrylate-based composition [I] and the fluorine-containing acrylate-based compound [II]. and polymerization inhibitor [III], the total was 3,590 ppm.

<Comparative Example 4>

An active energy ray curable resin composition containing an active energy ray curable resin composition and a photopolymerization initiator was obtained in the same manner as in Example 9 except that the polymerization inhibitor [III-1] was not used in Example 9.

In the above, the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III'] used in the production of the urethane acrylate-based composition) is the urethane acrylate-based composition [I] and the fluorine-containing acrylate-based compound [II]. and polymerization inhibitor [III], the total was 600 ppm.

<Comparative Example 5>

In Example 9, except that trimethylolpropane triacrylate (“Aronics M-309” manufactured by Toagosei Co., Ltd., containing 100 ppm of polymerization inhibitor) was used instead of the urethane acrylate-based composition [I-3]. In the same manner as in Example 9, 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 that of trimethylol propane, fluorine-containing acrylate compound [II], and polymerization inhibitor [III]. For the total, it was 3,090 ppm.

The liquid storage stability of the active energy ray-curable resin composition obtained above was evaluated by the following method.

[Liquid storage stability]

For the above active energy ray-curable resin composition, Hazen color number (APHA) was measured using a spectroscopic colorimeter "SE6000: manufactured by Nippon Denshoku Industries Co., Ltd." Additionally, the active energy ray-curable resin composition was placed in a sealed glass test container and subjected to a heat resistance test under heat resistance conditions (stored in a 60°C environment for 4 weeks), and the APHA value after the heat resistance test was measured. The results are shown in Tables 1 to 3 below.

In addition, samples for evaluation were prepared from the active energy ray-curable resin composition containing the photopolymerization initiator obtained above, and pencil hardness, scratch resistance, antifouling property, water contact angle, and oleic acid contact angle were evaluated. The results are shown in Tables 1 to 3 below.

[Method for producing samples for evaluation]

The activated energy ray-curable resin composition containing the photopolymerization initiator obtained above was applied to a back-adhesive PET film (Cosmoshine A4300, manufactured by Toyobo Company Limited, thickness 125 μm) using a bar coater, and the film thickness after drying was measured. Coat to a thickness of 5㎛, dry at 90°C for 3 minutes, and then irradiate with ultraviolet rays in two passes using an 80W high-pressure mercury lamp, 1st lamp, from a height of 18cm at a conveyor speed of 5.1m/min (accumulated irradiation dose of 450mJ/㎠). was carried out to form a cured coating film.

［Pencil hardness]

The cured film coated on the easily adhesive PET film was tested in accordance with JIS K 5600 to measure pencil hardness.

[Scratch resistance]

With respect to the cured film applied on the easy-adhesive PET film, the surface of the cured film was moved back and forth while applying a load of 1 kg using steel wool (Bonestar #0000, manufactured by Nippon Steel Wool Company Limited), and then the surface was inspected with the naked eye for scratches. The number of round trips until this occurred was measured and evaluated based on the following criteria.

(evaluation)

○···No flaws even after 1,000 round trips

△···Flaws occurred more than 600 times but less than 1,000 times.

×···Flaw occurred in less than 600 cycles

[Antifouling property (Magic Ink (registered trademark) Wiping property)]

On the surface of the cured film, a line was drawn in one round with black magic ink, left for 24 hours, and then wiped off with a rag (waste). The film was observed and evaluated as follows. In addition, the magic ink wiping properties were similarly evaluated for the coating film after the above scratch resistance test (after 1,000 round trips).

(evaluation)

○···Can be wiped cleanly

△···Can be wiped off to some extent, but traces remain.

×···Cannot be wiped off

[Contact angle of water and oleic acid]

The contact angle of water and oleic acid with respect to the cured film surface was measured with a contact angle measuring device (DropMaster600, manufactured by Kyowa Interface Science Company Limited). In addition, the water and oleic acid contact angles were similarly evaluated for the coating film after the above-mentioned scratch resistance test.

As can be seen from the above results, in the composition containing the urethane (meth)acrylate-based composition [I] and the fluorine-containing (meth)acrylate-based compound [II], a predetermined amount of a polymerization inhibitor [III] is again contained. In the example, the storage stability in the coating liquid was excellent. In addition, although Examples contained more polymerization inhibitor [III] than Comparative Examples 2 and 4, they were excellent in antifouling performance and scratch resistance when used as a cured coating film. On the other hand, in Comparative Examples 1 and 3, which do not contain the fluorine-containing (meth)acrylate-based compound [II], the antifouling performance and scratch resistance are poor, and other than the production of the urethane (meth)acrylate-based composition [I], In Comparative Examples 2 and 4, in which the polymerization inhibitor [III] was not added, the storage stability of the liquid was poor. Moreover, in Comparative Example 5 in which the urethane (meth)acrylate-based composition [I] was not used, the curability was insufficient and the purpose of the present invention was not satisfied.

Although the above examples show specific forms of the present invention, the examples are merely examples and are not to be construed as limiting. Various modifications apparent to those skilled in the art are intended to be within the scope of the present invention.

The active energy ray-curable resin composition of the present invention is excellent in the storage stability of the coating solution, and can form a coating film with excellent antifouling performance (fouling resistance and durability) and cured coating film properties (appearance, hardness, scratch resistance). It is useful as a coating agent, especially a coating agent for hard coats or a coating agent for optical films. It is also useful as a paint, ink, etc.

Claims (10)

Urethane (meth)acrylate-based composition [I], a fluorine-containing (meth)acrylate-based composition [II], in which the hydroxyl group in the (meth)acrylic acid adduct of polyhydric alcohol (A) reacts with the isocyanate group of the polyisocyanate-based compound (B) ], however, in the fluorine-containing (meth)acrylate compound [II], a cyclopolysiloxane structure is bonded to both ends of the poly(perfluoroalkylene ether) chain through a divalent linking group, and the cyclopolysiloxane structure is It does not contain a fluorine compound having a structure in which a (meth)acryloyl group is bonded through a divalent linking group, and contains a polymerization inhibitor [III],
The (meth)acrylic acid adduct (A) of the polyhydric alcohol is the (meth)acrylic acid adduct (A2) of dipentaerythritol with a hydroxyl value of 40 to 60 mgKOH/g,
The content of the polymerization inhibitor [III] is 800 to 800 by weight relative to the total of the urethane (meth)acrylate-based composition [I], the fluorine-containing (meth)acrylate-based compound [II] and the polymerization inhibitor [III]. An active energy ray-curable resin composition characterized by 10,000 ppm. In claim 1,
An active energy ray-curable resin composition, wherein the fluorine-containing (meth)acrylate-based compound [II] has a siloxane bond. In claim 1 or 2,
An active energy ray-curable resin composition, wherein the weight average molecular weight of the fluorine-containing (meth)acrylate compound [II] is 1,000 to 100,000. In claim 1 or 2,
An active energy ray-curable resin composition, wherein the urethane (meth)acrylate-based composition [I] has a weight average molecular weight of 900 to 30,000. In claim 1 or 2,
An active energy ray-curable resin composition characterized by further containing a discoloration inhibitor [IV]. In claim 1 or 2,
An active energy ray-curable resin composition, characterized in that it further contains 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 claim 1 or 2. In claim 7,
A coating agent characterized in that it is used as a coating agent for hard coats. In claim 7,
A coating agent characterized in that it is used as a coating agent for optical films.
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