CN111278880A - Active energy ray-curable resin composition and coating agent - Google Patents

Active energy ray-curable resin composition and coating agent Download PDF

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CN111278880A
CN111278880A CN201880069383.4A CN201880069383A CN111278880A CN 111278880 A CN111278880 A CN 111278880A CN 201880069383 A CN201880069383 A CN 201880069383A CN 111278880 A CN111278880 A CN 111278880A
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meth
acrylate
active energy
energy ray
curable resin
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酒谷修平
小西敦子
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
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    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
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    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract

An active energy ray-curable resin composition which has excellent storage stability of a coating liquid and can form a coating film having excellent antifouling performance (stain resistance and persistence thereof) and excellent characteristics (appearance, hardness, scratch resistance), comprising: the urethane (meth) acrylate composition [ I ], the fluorine-containing (meth) acrylate compound [ II ] and the polymerization inhibitor [ III ] obtained by reacting the hydroxyl group in the (meth) acrylic adduct (A) of a polyhydric alcohol with the isocyanate group of the polyisocyanate compound (B) are contained in an amount of 800 to 10,000ppm by weight based on the total amount of the urethane (meth) acrylate composition [ I ], the fluorine-containing (meth) acrylate compound [ II ] and the polymerization inhibitor [ III ].

Description

Active energy ray-curable resin composition and coating agent
Technical Field
The present invention relates to an active energy ray-curable resin composition containing a urethane (meth) acrylate composition and a coating agent, and more particularly, to an active energy ray-curable resin composition capable of forming a coating film excellent in antifouling performance (stain resistance and durability thereof) and properties of a cured coating film (appearance, hardness, abrasion resistance) and a coating agent containing the same.
Background
Conventionally, active energy ray-curable resin compositions have been widely used as coating agents, adhesives, anchor coating agents, and the like for various substrates because they are cured by irradiation with active energy rays such as very short-time radiation or ultraviolet rays, and urethane (meth) acrylate compounds and polyfunctional monomers have been used as curing components thereof. In recent years, when an active energy ray-curable resin composition is used as a coating agent, particularly a coating agent for hard coating, it is required to have high surface hardness and scratch resistance instead of glass.
As a hard coating agent having high surface hardness and scratch resistance of the cured coating film, for example, a hard coating agent obtained by adding a fluorine compound to a curing component mainly composed of dipentaerythritol hexaacrylate and an N-substituted acrylamide has been proposed (for example, see patent document 1). The film obtained by applying the hard coating agent onto a laminated film at a film thickness of 11 μm and curing the same exhibits a hardness of about 5H in pencil hardness and scratch resistance without damage even when a 500g load is applied using steel wool and the film is reciprocated 500 times.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2017-141416
Disclosure of Invention
Problems to be solved by the invention
However, the technique disclosed in patent document 1 is excellent in the surface hardness of the cured coating film and the scratch resistance under a load of 500g, but there is no description about the more severe scratch resistance under a load of 1kg, and further improvement is required.
In recent years, when stains such as fingerprints adhere to the surface of displays, monitors, screens of touch-panel-type devices, and electrical products such as mobile phones, the transparency of the screens and the sharpness of the screens are reduced, and the appearance is impaired, and therefore, studies have been made on a method for wiping various stains, a coating agent for preventing the adhesion of stains, and stain-removing properties, and a coating film surface abrasion resistance when a top coating is performed with a coating agent. Further, a fluorine compound is often used for the purpose of exhibiting stain resistance and scratch resistance, and a coating agent containing a fluorine compound is likely to be gelled during storage, and further improvement in storage stability is required.
Under such circumstances, the present invention provides an active energy ray-curable resin composition which has excellent storage stability of a coating liquid, and can form a coating film having excellent antifouling performance (stain resistance and durability thereof) and excellent properties of a cured coating film (appearance, hardness, scratch resistance), and a coating agent using the same.
For solving the problemsScheme(s)
However, the present inventors have made intensive studies in view of the above circumstances, and as a result, have found that a cured coating film having excellent storage stability in a liquid of an active energy ray-curable resin composition and excellent coating film properties such as stain-proofing property and scratch resistance when a cured coating film is formed can be obtained by containing the above polymerization inhibitor in an amount larger than usual in an active energy ray-curable resin composition containing, as a curing component, a urethane (meth) acrylate composition obtained by reacting a (meth) acrylic acid adduct of a polyol with a polyisocyanate compound, a fluorine-containing (meth) acrylate compound, and a polymerization inhibitor.
That is, the invention according to item 1 is an active energy ray-curable resin composition containing: the urethane (meth) acrylate composition [ I ], the fluorine-containing (meth) acrylate compound [ II ] and the polymerization inhibitor [ III ] obtained by reacting the hydroxyl group in the (meth) acrylic adduct (A) of a polyhydric alcohol with the isocyanate group of the polyisocyanate compound (B) are contained in an amount of 800 to 10,000ppm by weight based on the total amount of the urethane (meth) acrylate composition [ I ], the fluorine-containing (meth) acrylate compound [ II ] and the polymerization inhibitor [ III ].
The coating agent according to item 2 is a coating agent containing the active energy ray-curable resin composition according to item 1 above.
In general, in the production of a urethane (meth) acrylate composition, a polymerization inhibitor is charged into the reaction system for the purpose of suppressing the polymerization reaction of the (meth) acryloyl group in the urethanization reaction and improving the storage stability, but the presence of the polymerization inhibitor reduces the curing properties with active energy rays and causes coloring, and therefore, the amount of the polymerization inhibitor to be added is generally considered to be as small as possible. However, in the present invention, it has been unexpectedly found that by using a polymerization inhibitor in an amount larger than that used in the production of a urethane (meth) acrylate composition, a coating film can be formed which is free from the problems of reduction in the curing properties by active energy rays and coloring of the coating liquid and the cured coating film, has excellent storage stability of the coating liquid, and is excellent in antifouling properties (stain resistance and durability thereof), and characteristics (appearance, hardness, abrasion resistance) of the cured coating film.
ADVANTAGEOUS EFFECTS OF INVENTION
The active energy ray-curable resin composition of the present invention contains: the urethane (meth) acrylate composition [ I ], the fluorine-containing (meth) acrylate compound [ II ] and the polymerization inhibitor [ III ] obtained by reacting the hydroxyl group in the (meth) acrylic adduct (A) of a polyhydric alcohol with the isocyanate group of the polyisocyanate compound (B) are contained in an amount of 800 to 10,000ppm by weight based on the total amount of the urethane (meth) acrylate composition [ I ], the fluorine-containing (meth) acrylate compound [ II ] and the polymerization inhibitor [ III ]. Therefore, the coating liquid has excellent storage stability and further has excellent antifouling performance and scratch resistance when a cured coating film is formed. Further, these excellent characteristics are useful for applications of a coating agent for hard coating or a coating agent for optical film in particular.
In the present invention, particularly when the polyol is at least one of dipentaerythritol and pentaerythritol, the storage stability in the coating liquid is further excellent, and further the antifouling property and scratch resistance when a cured coating film is formed are also excellent.
In the present invention, particularly when the fluorine-containing (meth) acrylate compound [ II ] has a siloxane bond, the stain-proofing performance is more excellent.
Further, in the present invention, particularly when the weight average molecular weight of the fluorine-containing (meth) acrylate compound [ II ] is 1,000 to 100,000, the antifouling property is further excellent.
In the present invention, particularly, when the weight average molecular weight of the urethane (meth) acrylate composition [ I ] is 900 to 30,000, the scratch resistance when a cured coating film is formed is more excellent.
Further, when the active energy ray-curable resin composition of the present invention further contains the stainblocker [ IV ], the storage stability in the coating liquid is more excellent.
In addition, when the active energy ray-curable resin composition of the present invention further contains an organic solvent having a boiling point of 80 ℃ or higher, the urethane (meth) acrylate composition [ I ] is more excellent in compatibility with the fluorine-containing (meth) acrylate compound [ II ], and therefore the storage stability in the coating liquid is further more excellent.
Detailed Description
The present invention will be described in detail below.
In the present invention, "(meth) acrylic acid" means acrylic acid or methacrylic acid, "(meth) acryloyl group" means acryloyl group or methacryloyl group, and "(meth) acrylate" means acrylate or methacrylate.
[ active energy ray-curable resin composition ]
The active energy ray-curable resin composition of the present invention contains a urethane (meth) acrylate composition [ I ], a fluorine-containing (meth) acrylate compound [ II ] and a polymerization inhibitor [ III ]. The details thereof will be described below.
< urethane (meth) acrylate composition [ I ] >
The urethane (meth) acrylate composition [ I ] used in the present invention can form a urethane bond by reacting a hydroxyl group in the (meth) acrylic adduct (a) of a polyol with an isocyanate group of the polyisocyanate compound (B). Hereinafter, each component used in the present invention will be described.
[ (meth) acrylic acid adduct (A) of polyol ]
The (meth) acrylic acid adduct (a) of the polyol used in the present invention is obtained by adding (meth) acrylic acid to hydroxyl groups of the polyol, and is a mixture containing a product obtained by adding (meth) acrylic acid to all hydroxyl groups of the polyol, a product obtained by adding (meth) acrylic acid to a part of hydroxyl groups of the polyol, and the like.
The polyol is preferably a trihydric or higher polyol, and a dihydric alcohol may be used. Examples of the alcohol include aliphatic alcohols, alicyclic alcohols, and aromatic alcohols, and among them, aliphatic alcohols are preferable.
Examples of the tri-or higher aliphatic polyhydric alcohol include pentaerythritol, dipentaerythritol, tripentaerythritol, glycerol, trimethylolpropane, trimethylolethane, 1,3, 6-hexanetriol, and adamantanetriol. These may be used alone or in combination of 2 or more. Among them, pentaerythritol and dipentaerythritol are preferable.
Hereinafter, a (meth) acrylic acid adduct of pentaerythritol and dipentaerythritol [ a (meth) acrylic acid adduct of pentaerythritol (a1) and a (meth) acrylic acid adduct of dipentaerythritol (a2) ] will be described as suitable polyols.
[ pentaerythritol (meth) acrylic acid adduct (A1) ]
Usually, the (meth) acrylic acid adduct of pentaerythritol is a mixture containing pentaerythritol tetra (meth) acrylate obtained by adding (meth) acrylic acid to all 4 hydroxyl groups of pentaerythritol, pentaerythritol tri (meth) acrylate monol obtained by adding (meth) acrylic acid to 3 pieces, pentaerythritol di (meth) acrylate diol obtained by adding (meth) acrylic acid to 2 pieces, and pentaerythritol mono (meth) acrylate triol obtained by adding (meth) acrylic acid to only 1 piece.
The (meth) acrylic acid adduct of pentaerythritol (a1) may be obtained by reacting pentaerythritol and (meth) acrylic acid by a known and conventional method.
The hydroxyl value of the (meth) acrylic acid adduct of pentaerythritol (A1) is preferably 50 to 300mgKOH/g, more preferably 70 to 200mgKOH/g, and particularly preferably 100 to 160 mgKOH/g.
If the hydroxyl value is too small, the molecular weight is low, the number of ethylenically unsaturated groups is large, and the content of pentaerythritol tetra (meth) acrylate that does not react with isocyanate groups is large, so that curing shrinkage during curing becomes large, and curling tends to occur easily. When the hydroxyl value is too large, the content of a polyol component such as pentaerythritol di (meth) acrylate diol or pentaerythritol mono (meth) acrylate triol increases, and therefore the molecular weight of the obtained urethane (meth) acrylate tends to increase, the viscosity tends to increase, and handling tends to be difficult.
The hydroxyl value of the (meth) acrylic acid adduct of pentaerythritol (a1) is the hydroxyl value of the entire mixture of the (meth) acrylic acid adduct of pentaerythritol.
In the present invention, the hydroxyl value is a value obtained by the method according to JIS K1557-1.
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) ]
The (meth) acrylic acid adduct of dipentaerythritol is usually a mixture containing dipentaerythritol hexa (meth) acrylate obtained by adding (meth) acrylic acid to 6 hydroxyl groups of dipentaerythritol, 5 dipentaerythritol penta (meth) acrylate monols obtained by adding (meth) acrylic acid, 4 dipentaerythritol tetra (meth) acrylate diols obtained by adding (meth) acrylic acid, 3 dipentaerythritol tri (meth) acrylate triols obtained by adding (meth) acrylic acid, 2 dipentaerythritol di (meth) acrylate tetraols obtained by adding (meth) acrylic acid, and 1 dipentaerythritol (meth) acrylate pentanol obtained by adding (meth) acrylic acid alone.
The (meth) acrylic acid adduct of dipentaerythritol (a2) may be obtained by reacting dipentaerythritol and (meth) acrylic acid by a known and customary method.
The hydroxyl value of the (meth) acrylic acid adduct of dipentaerythritol (A2) is preferably 10 to 120mgKOH/g, more preferably 20 to 80mgKOH/g, particularly preferably 30 to 70mgKOH/g, and particularly preferably 40 to 60 mgKOH/g.
If the hydroxyl value is too small, the molecular weight is low, the number of ethylenically unsaturated groups is large, and the content of dipentaerythritol hexa (meth) acrylate that does not react with isocyanate groups is large, so that curing shrinkage during curing tends to be large, and curling tends to occur easily. When 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, and therefore the molecular weight of the obtained urethane (meth) acrylate increases, and the viscosity increases, and therefore handling tends to be difficult.
The hydroxyl value of the (meth) acrylic acid adduct of dipentaerythritol (a2) is 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) ]
As the polyisocyanate compound (B) which reacts with the hydroxyl group of the (meth) acrylic adduct (a) of the polyol, a known and usual polyisocyanate compound used in the production of a urethane (meth) acrylate composition can be generally used.
Examples of the polyisocyanate compound (B) include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate and naphthalene diisocyanate, aliphatic polyisocyanates such as pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate and lysine triisocyanate, alicyclic polyisocyanates such as hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate and norbornene diisocyanate, trimer compounds and polymer compounds of these polyisocyanates, allophanate polyisocyanates, and the like, Biuret type polyisocyanates, water dispersible polyisocyanates, and the like. These polyisocyanate compounds (B) may be used in 1 kind or in combination of 2 or more kinds.
The polyisocyanate compound (B) may be a reaction product of a polyol such as a low-molecular-weight polyol or a high-molecular-weight polyol, particularly a polyether polyol, a polyester polyol, a polycarbonate polyol, a polyolefin polyol, a polybutadiene polyol, or a (meth) acrylic polyol, with a polyisocyanate compound.
Among these, from the viewpoint of excellent yellowing resistance and versatility, aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate, and alicyclic diisocyanates such as hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, and norbornene diisocyanate are preferable, and isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, and hexamethylene diisocyanate are particularly preferable, and isophorone diisocyanate and hexamethylene diisocyanate are even more preferable.
[ method for producing urethane (meth) acrylate composition [ I ]
As described above, the urethane (meth) acrylate composition [ I ] used in the present invention is obtained by reacting the hydroxyl group in the (meth) acrylic acid adduct (a) of a polyol with the isocyanate group of the polyisocyanate compound (B).
Specifically, the urethane (meth) acrylate composition [ I ] can be obtained by adjusting the molar ratio of the isocyanate groups of the polyisocyanate compound (B) to the functional groups of the hydroxyl groups of the (meth) acrylic adduct of a polyol (a) and, if necessary, reacting the polyisocyanate compound (B) with the (meth) acrylic adduct of a polyol (a) using a catalyst such as dibutyltin dilaurate.
The urethane (meth) acrylate composition of the present invention is a urethane (meth) acrylate composition obtained by reacting an acrylic adduct (a2) of dipentaerythritol having a hydroxyl value of 60mgKOH/g or more as an acrylic adduct (a) of a polyol with at least 1 polyisocyanate compound selected from the group consisting of xylylene diisocyanate, hydrogenated xylylene diisocyanate, and derivatives thereof.
The charged reaction molar ratio of the polyisocyanate compound (B) to the (meth) acrylic acid adduct of polyol (a) [ (B): (A) 1: 2-1: about 5.
In the above reaction molar ratio, when the proportion of the (meth) acrylic acid adduct (a) of the polyol is too large, the content of the low-molecular-weight monomer (obtained by adding (meth) acrylic acid to all hydroxyl groups of the polyol) which does not react with the polyisocyanate compound (B) increases, and curing shrinkage increases, so that curling of the cured coating film tends to increase, and when the proportion of the (meth) acrylic acid adduct (a) of the polyol is too small, the unreacted polyisocyanate compound (B) remains, and the stability and safety of the cured coating film tend to decrease.
The reaction between the (meth) acrylic acid adduct of a polyol (a) and the polyisocyanate compound (B) can be carried out by generally charging the (meth) acrylic acid adduct of a polyol (a) and the polyisocyanate compound (B) into a reactor together or separately.
Among the above-mentioned reactions, a catalyst is also preferably used for the purpose of promoting the reaction, and examples of the catalyst include organic metal compounds such as dibutyltin dilaurate, dibutyltin diacetate, trimethyltin hydroxide, tetra-N-butyltin, zinc bisacetylacetonate, zirconium tris (acetylacetonate) ethylacetoacetate, zirconium tetraacetylacetonate, etc., metal salts such as tin octylate, tin octenoate, zinc caproate, zinc octenoate, zinc stearate, zirconium 2-ethylhexanoate, cobalt naphthenate, stannous chloride, tin chloride, potassium acetate, etc., 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-butylmorpholine, N ' -tetramethyl-1, 3-butanediamine, N-methylmorpholine, etc, Examples of the bismuth-based catalyst include amine-based catalysts such as N-ethylmorpholine, organic bismuth compounds such as bismuth nitrate, bismuth bromide, bismuth iodide and bismuth sulfide, dibutyl bismuth dilaurate and dioctyl bismuth dilaurate, bismuth 2-ethylhexanoate, bismuth naphthenate, bismuth isodecanoate, bismuth neodecanoate, bismuth laurate, bismuth maleate, bismuth stearate, bismuth oleate, bismuth linoleate, bismuth acetate, bismuth bisneodecanoate (bismuthyl bis-neodecanoate), bismuth disilicate and bismuth digallate, and among these, dibutyl tin dilaurate and 1, 8-diazabicyclo [5,4,0] undecene are suitable. These may be used alone or in combination of 2 or more.
< polymerization inhibitor [ III' ]
In the above reaction, it is preferable to further use a polymerization inhibitor [ III' ]. When the polymerization inhibitor [ III' ] is used in the above reaction, it is included in the content of the polymerization inhibitor [ III ] described later.
As the polymerization inhibitor [ III' ], a known and usual polymerization inhibitor used as a polymerization inhibitor can be used. Examples thereof include quinones such as p-benzoquinone, naphthoquinone, toluquinone and 2, 5-diphenyl-p-benzoquinone, and phenols such as hydroquinone, 2, 5-di-t-butylhydroquinone, methylhydroquinone, mono-t-butylhydroquinone, 4-methoxyphenol, 2, 6-di-t-butylcresol and p-t-butylcatechol. Among them, phenols are preferable, and 4-methoxyphenol and 2, 6-di-t-butylcresol are particularly preferable. These may be used alone or in combination of 2 or more.
The content of the polymerization inhibitor [ III' ] in the above reaction is 0.005 to 0.095 parts by weight, preferably 0.01 to 0.08 parts by weight, based on 100 parts by weight of the total of the (meth) acrylic acid adduct (A) of a polyol and the polyisocyanate compound (B). If the content of the polymerization inhibitor [ III' ] is too small, polymerization of acryloyl groups may be caused in the above reaction. Further, the urethane (meth) acrylate composition [ I ] tends to have a reduced liquid stability, and tends to be easily gelled during storage. When the content of the polymerization inhibitor [ III' ] is too large, coloration occurs, and curing tends to be difficult even when the active energy ray is irradiated.
In the above reaction, an organic solvent having no functional group which reacts with an isocyanate group, for example, esters such as ethyl acetate, butyl acetate and 2-methoxy-1-methylethylacetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and aromatic solvents such as toluene and xylene, can be used.
The reaction temperature of the reaction is usually 30 to 90 ℃, preferably 40 to 80 ℃, 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 can be obtained.
The urethane (meth) acrylate composition [ I ] may contain a plurality of urethane (meth) acrylates, and further contain a polyol (meth) acrylic acid adduct (a) which is not reactive with the polyisocyanate compound (B), and further a polymer of the polyol (meth) acrylic acid adduct (a).
The urethane (meth) acrylate composition [ I ] preferably has a weight average molecular weight of 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.
When the weight average molecular weight is too small, the cured coating film tends to be brittle, and when too large, the cured coating film tends to have high viscosity and be difficult to handle.
The weight average molecular weight in the present invention is a weight average molecular weight in terms of a standard polystyrene molecular weight, and the weight average molecular weight is determined by subjecting a column: the measurement was carried out by using 4 ACQUITYAPCXT 450X 1, ACQUITYAPCXT 200X 1, and ACQUITYAPCXT 45X 2 in tandem.
The viscosity of the urethane (meth) acrylate composition [ I ] at 60 ℃ is preferably 500 to 300,000 mPas, particularly preferably 750 to 100,000 mPas, and further preferably 1,000 to 30,000 mPas. When the viscosity is outside the above range, the coatability tends to decrease.
The viscosity measurement method is based on an E-type viscometer.
The content of the 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, further preferably 30% by weight or more, and particularly preferably 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 include a hetero atom such as oxygen, nitrogen, silicon, or sulfur.
The fluorine-containing (meth) acrylate-based compound [ II ] is preferably a compound obtained by bonding an alkyl group of an alkyl (meth) acrylate to a fluorine atom, and examples thereof include DAIKIN INDUSTRIES, "ptoolDAC", "ptool DAC-HP", available from DIC, "MEGAFACE RS-75", "MEGAFACE RS-76", "MEGAFACERS-91C", "DIFENSA TF 3028", "DIFENSA TF 3001", "DIFENSA TF 3000", SUA1900L10 "," SUA1900L6 ", available from Ningkohamu chemical Co., Ltd," UT 395300 "," KY-1203 ", available from Kakko chemical Co., Ltd," VISUAT 3F "," VIAT 4F "," VISUAT 8F "," VISUAT 13F ", available from VISUX-380 AGC", and the like. These fluorine-containing (meth) acrylate compounds [ II ] may be used alone or in combination of 2 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 from the viewpoint of more excellent antifouling performance, and "KY-1203" is particularly 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, particularly preferably 10,000 to 50,000, and further preferably 15,000 to 40,000. When the weight average molecular weight of the fluorine-containing (meth) acrylate compound [ II ] is too small, the scratch resistance and the stain-proofing property tend to be reduced, and when the weight average molecular weight is too large, the compatibility with the urethane (meth) acrylate composition [ I ] and the solvent tends to be reduced.
The content of the fluorine-containing (meth) acrylate compound [ II ] in the active energy ray-curable resin composition of the present invention is usually 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, and particularly preferably 0.1 to 1 part by weight, based on 100 parts by weight of the urethane (meth) acrylate composition [ I ]. When the content of the fluorine-containing (meth) acrylate compound [ II ] is too small, the scratch resistance and the stain-proofing property tend to be lowered, and when the content is too large, the compatibility with the urethane (meth) acrylate composition [ I ] tends to be lowered.
< polymerization inhibitor [ III ]
The active energy ray-curable resin composition of the present invention contains a polymerization inhibitor [ III ] in an amount larger than that of a usual active energy ray-curable resin composition. In general, the active energy ray-curable resin composition does not contain the polymerization inhibitor [ III ] in an amount of the same extent as that usually used for producing the urethane (meth) acrylate composition [ I ] because the active energy ray-curability is lowered and coloring is caused by the inclusion of a large amount of the polymerization inhibitor [ III ]. However, in the present invention, by adding the polymerization inhibitor [ III ] in an amount larger than that used in a usual active energy ray-curable resin composition to the active energy ray-curable resin composition containing the specific urethane (meth) acrylate composition [ I ] and the fluorine-containing (meth) acrylate compound [ II ], the effects of preventing the decrease in the active energy ray-curability and the coloring, improving the liquid stability of the active energy ray-curable resin composition, and suppressing the gelation during storage are exhibited.
The polymerization inhibitor [ III ] used in the present invention may be any known polymerization inhibitor, and specifically, the same compounds as those listed for the polymerization inhibitor [ III' ] can be used. The polymerization inhibitor [ III ] to be added to the active energy ray-curable resin composition is preferably the same compound as the polymerization inhibitor [ III' ] used for producing the urethane (meth) acrylate composition [ I ], and compounds different from each other may be used.
The content of the polymerization inhibitor [ III ] is important to be 800 to 10,000ppm by weight, preferably 1,000 to 8,000ppm, more preferably 1,500 to 7,000ppm, further preferably 2,000 to 6,000ppm, particularly preferably 3,100 to 5,000ppm, based on the total weight of the urethane (meth) acrylate composition [ I ], the fluorine-containing (meth) acrylate compound [ II ] and the polymerization inhibitor [ III ]. If the content of the polymerization inhibitor [ III ] is too small, the liquid stability of the active energy ray-curable resin composition before curing is lowered, and gelation tends to occur during storage. Further, if the content of the polymerization inhibitor [ III ] is too large, it is not easily cured even by irradiation with active energy rays. When the polymerization inhibitor [ III '] is used in the production of the urethane (meth) acrylate composition [ I ], the content of the polymerization inhibitor [ III' ] is also included in the content of the polymerization inhibitor [ III ] of the present invention.
< stainblocker [ IV ] >
In the present invention, it is preferable that the composition further contains an anti-coloring agent [ IV ] in order to prevent coloring of the urethane (meth) acrylate composition [ I ] and to further improve the storage stability of the liquid of the active energy ray-curable resin composition.
Examples of the stain inhibitor [ IV ] include arylphosphine compounds such as triphenylphosphine, silazane compounds such as 1,1,3, 3-tetramethyldisilazane and 1,1,3,3, 3-hexamethyldisilazane, and hydrazine compounds such as phenylhydrazine, benzophenylhydrazine and diacetylhydrazine. These stainblocker may be used alone in 1 kind, or may be used in combination in 2 or more kinds. Among these, the arylphosphine compound is preferable, and triphenylphosphine is particularly preferable, since the coloration of the urethane (meth) acrylate composition [ I ] can be further prevented.
The content of the stain-proofing agent [ IV ] is usually 10 to 10,000ppm, preferably 100 to 5,000ppm, and more preferably 250 to 2,000ppm, on the weight basis, based on the total amount of the urethane (meth) acrylate composition [ I ], the fluorine-containing (meth) acrylate compound [ II ], and the polymerization inhibitor [ III ].
[ other optional Components ]
The active energy ray-curable resin composition of the present invention preferably further contains a photopolymerization initiator. In addition, an ethylenically unsaturated monomer other than urethane (meth) acrylate, an acrylic resin, a surface conditioner, a leveling agent, and the like may be blended within a range not to impair the effects of the present invention, and further, a filler, a dye pigment, an oil, a plasticizer, a wax, a drying agent, a dispersant, a wetting agent, a gelling agent, a stabilizer, an antifoaming agent, a surfactant, a leveling agent, a thixotropy imparting agent, an antioxidant, a flame retardant, an antistatic agent, a filler, a reinforcing agent, a matting agent, a crosslinking agent, silica dispersed in water or a solvent, a zirconium compound, a preservative, and the like may be blended. These may be used alone or in combination of 2 or more.
Examples of the photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzildimethylketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) one, 1-hydroxycyclohexylphenylketone, 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] -phenyl } -2-methyl-propane, and the like, Acetophenones such as 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propanone oligomer; benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenones such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyl-diphenyl sulfide, 3 ', 4,4 ' -tetrakis (t-butylperoxycarbonyl) benzophenone, 2,4, 6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl ] benzylammonium bromide, and (4-benzoylbenzyl) trimethylammonium chloride; thioxanthones such as 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and 2- (3-dimethylamino-2-hydroxy) -3, 4-dimethyl-9H-thioxanthone-9-one methylchloride; acylphosphine oxides such as 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) -2,4, 4-trimethyl-pentylphosphine oxide and bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, and oxime esters such as 1- [4- (phenylthio) phenyl-1, 2-octanedione 2- (O-benzoyloxime) ], and 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -ethanone 1- (O-acetyloxime).
These photopolymerization initiators may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
Among these, acetophenones are preferable, benzildimethylketal, 1-hydroxycyclohexylphenyl ketone, benzoin isopropyl ether, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, and 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1-hydroxycyclohexylphenyl ketone is particularly preferable.
When the 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 further preferably 1 to 10 parts by weight, based on 100 parts by weight of the curing component contained in the active energy ray-curable resin composition.
If the content of the photopolymerization initiator is too small, curing is poor and film formation is not likely to proceed, while if too large, yellowing of the cured coating film is likely to be caused and a problem of coloring is unlikely to occur.
Further, as the auxiliary agent of the photopolymerization initiator, for example, triethanolamine, triisopropanolamine, 4 '-dimethylaminobenzophenone (mikrolone), 4' -diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate (n-butoxy) ester, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2, 4-diethylthioxanthone, 2, 4-diisopropylthioxanthone, and the like may be used in combination.
Examples of the ethylenically unsaturated monomer other than the urethane (meth) acrylate include a monofunctional monomer, a 2-functional monomer, and a 3-or more-functional polyfunctional monomer. These ethylenically unsaturated monomers may be used alone or in combination of 2 or more.
Examples of the monofunctional monomer include styrene monomers such as styrene, vinyltoluene, 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, glycerol mono (meth) acrylate, glycidyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2-methyl-2-ethyl-1, 3-dioxolan-4-yl) -meth (meth) acrylate, cyclospiro-2- (1, 3-dioxolan-4-yl) -methyl (meth) acrylate, N-butoxyethyl (meth) acrylate, N-methyl (N-propyl) acrylate, N-decyl (meth) acrylate, N-2-N-propyl (meth) acrylate, N-2-nonyl, N-2-nonyl, N-ethyl (meth) acrylate, N-2-nonyl, N-ethyl (meth) acrylate, N-nonyl, N-2-ethyl (meth) acrylate, N-4-nonyl, N-octyl (N-ethyl, N-octyl (meth) acrylate, N-ethyl, N-4-nonyl, N-methyl) acrylate, and (N-octyl (meth) acrylate, (meth.
Examples of the 2-functional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butanediol 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, dimethyloldicyclopentane di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, and mixtures thereof, Glycerol 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, isocyanuric acid ethylene oxide-modified diacrylate, and the like.
Examples of the 3-or more-functional monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris (meth) acryloyloxyethoxytrimethylolpropane, glycerol polyglycidyl ether poly (meth) acrylate, 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, propylene oxide-modified pentaerythritol hexa (meth) acrylate, propylene oxide-modified, Ethylene oxide-modified pentaerythritol tri (meth) acrylate, ethylene oxide-modified pentaerythritol tetra (meth) acrylate, ethoxylated 15 glycerol triacrylate, and the like.
Further, as the ethylenically unsaturated monomer other than urethane (meth) acrylate, a michael adduct of (meth) acrylic acid or a 2-acryloyloxyethyl dicarboxylic acid monoester may be used in combination. Examples of the michael adduct of (meth) acrylic acid include (meth) acrylic acid dimer, (meth) acrylic acid trimer, and (meth) acrylic acid tetramer. Examples of the carboxylic acid having a specific substituent as the 2-acryloyloxyethyl dicarboxylic acid monoester include 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, 2-acryloyloxyethyl phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexahydrophthalic acid monoester, and 2-methacryloyloxyethyl hexahydrophthalic acid monoester. Further, other oligoester acrylates and the like can be exemplified.
The content of the ethylenically unsaturated monomer other than the urethane (meth) acrylate is preferably 70% by weight or less, particularly preferably 50% by weight or less, and more preferably 30% by weight or less, of the total curing component contained in the active energy ray-curable resin composition.
The surface conditioner is not particularly limited, and examples thereof include cellulose resins and alkyd resins. The cellulose resin has an effect of improving the surface smoothness of a coating film, and the alkyd resin has an effect of improving the film-forming property during coating.
As the leveling agent, a known and usual leveling agent can be used as long as it has a function of imparting wettability of the coating liquid to the substrate and a function of reducing surface tension, and for example, a silicone-modified resin, a fluorine-modified resin, an alkyl-modified resin, or the like can be used.
The active energy ray-curable resin composition of the present invention can be obtained by mixing the urethane (meth) acrylate composition [ I ], the fluorine-containing (meth) acrylate compound [ II ], the polymerization inhibitor [ III ], and other optional components. The mixing method is not particularly limited, and various methods such as a method of mixing the respective components together, a method of mixing arbitrary components and then mixing the remaining components together or sequentially, and the like can be employed.
Therefore, the obtained active energy ray-curable resin composition of the present invention has excellent storage stability in a coating liquid, and further has excellent abrasion resistance when a cured coating film is formed and excellent antifouling properties after abrasion.
The active energy ray-curable resin composition of the present invention may be applied as it is or may be applied by diluting with an organic solvent. When the dilution is performed, the solid content concentration can be usually set to 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 isobutanol, ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone, aromatics such as toluene and xylene, glycol ethers such as 1-methoxy-2-propanol (also known as propylene glycol monomethyl ether), propylene glycol monomethyl ether acetate and ethyl cellosolve, acetates such as methyl acetate, ethyl acetate and butyl acetate, and diacetone alcohol. These organic solvents may be used alone, or 2 or more of them may be used in combination.
Among these, from the viewpoint of excellent compatibility between the urethane (meth) acrylate composition [ I ] and the fluorine-containing (meth) acrylate [ II ] and excellent stability of the liquid of the active energy ray-curable resin composition, a high boiling point solvent having a boiling point of 80 ℃ or more, particularly 100 ℃ or more, and further 120 to 170 ℃ is preferable, and glycol ethers are more preferable, and 1-methoxy-2-propanol and propylene glycol monomethyl ether acetate are particularly preferable.
When 2 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, an alcohol such as methanol, a combination of a glycol ether such as propylene glycol monomethyl ether and an ester such as butyl acetate, a combination of a ketone such as methyl ethyl ketone and an alcohol such as methanol, or the like can be used.
The active energy ray-curable resin composition of the present invention has a viscosity at 20 ℃ of preferably 5 to 50,000 mPas, particularly preferably 10 to 10,000 mPas, and further preferably 15 to 5,000 mPas. When the viscosity is outside the above range, the coatability tends to decrease.
The viscosity measurement method is based on 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 a top coating agent or an anchor coating agent on various substrates, and is cured by applying the active energy ray-curable resin composition to a substrate (in the case of applying an active energy ray-curable resin composition diluted with an organic solvent, further drying the composition) and then irradiating the composition with an active energy ray.
Examples of the substrate to be coated with the active energy ray-curable resin composition of the present invention include polyolefin resins, polyester resins, polycarbonate resins, acrylonitrile-butadiene-styrene copolymer (ABS), polystyrene resins, acrylic resins, and the like, plastic substrates such as molded articles thereof (films, sheets, cups, and the like), optical films such as polyethylene terephthalate films, triacetyl cellulose films, cycloolefin films, and the like, composite substrates thereof, or composite substrates of the above materials in which glass fibers and inorganic substances are mixed, metals (aluminum, copper, iron, SUS, zinc, magnesium, alloys thereof, and the like), glass, substrates provided with primer layers on these substrates, and the like.
Examples of the method for applying the active energy ray-curable resin composition of the present invention include wet coating methods such as spraying, showering, gravure coating, dipping, roll coating, rotary coating, screen printing, and the like, and the coating method can be applied to a substrate under normal temperature conditions (particularly, a temperature range in which heating is not performed).
In addition, as the drying conditions in the case of applying the active energy ray-curable resin composition diluted with the organic solvent, the temperature may be usually 40 to 120 ℃ (preferably 50 to 100 ℃), and the drying time may be usually 1 to 20 minutes (preferably 2 to 10 minutes).
The active energy ray used for curing the active energy ray-curable resin composition applied to the substrate may be, for example, light such as far ultraviolet ray, near ultraviolet ray, and infrared ray, electromagnetic wave such as X-ray and γ -ray, electron beam, proton beam, and neutron beam, and the like, and from the viewpoint of curing speed, availability of an irradiation apparatus, cost, and the like, ultraviolet ray or electron beam is preferable, and ultraviolet ray is particularly preferable.
When curing is performed by irradiation with an electron beam, curing can be performed without using a photopolymerization initiator.
When curing by ultraviolet irradiation, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless discharge lamp, an LED lamp or the like which emits light in a wavelength region of 150 to 450nm may be used, and the irradiation is usually performed at 30 to 3,000mJ/cm2(preferably 100 to 1,500 mJ/cm)2) Ultraviolet rays of (1).
After the irradiation with ultraviolet rays, if necessary, heating may be performed to complete the curing.
The coating thickness (thickness after curing) is usually 1 to 1,000 μm, preferably 2 to 500 μm, and particularly preferably 3 to 200 μm, in view of allowing light to pass therethrough and allowing the photopolymerization initiator to react uniformly, as an active energy ray-curable coating film.
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 coating or a coating agent for optical films.
As described above, the active energy ray-curable resin composition of the present invention is excellent in liquid storage stability, and further excellent in abrasion resistance when formed into a cured coating film and stain resistance after abrasion, and is useful particularly as a coating agent (further, a coating agent for hard coating, a coating agent for optical film), and further useful as a coating material, ink, or the like.
Examples
The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the following examples as long as the invention does not depart from the gist thereof. In the examples, "part" and "%" are based on weight.
First, the following materials were prepared as the urethane (meth) acrylate composition [ I ].
< production example 1>
[ production of urethane acrylate composition [ I-1]
184.6 parts of isophorone diisocyanate (B-1), and an acrylic acid adduct of pentaerythritol (A1-1) [ hydroxyl value: 815.4 parts of 120mgKOH/g, 0.8 part of 2, 6-di-t-butylcresol as a polymerization inhibitor [ III' -1], and 0.05 part of dibutyltin dilaurate as a reaction catalyst were reacted at 60 ℃ to complete the reaction when the residual isocyanate group was 0.1%, thereby obtaining a urethane acrylate composition [ I-1] (resin component concentration 100%).
The weight-average molecular weight of the resulting urethane acrylate composition [ I-1] was 1,400, and the viscosity at 60 ℃ was 3,000 mPas.
< production example 2>
[ production of urethane acrylate composition [ I-2]
219.1 parts of hydrogenated diphenylmethane diisocyanate (B-2), an acrylic acid adduct of pentaerythritol (a1-1) [ hydroxyl value: 780.9 parts of 120mgKOH/g, 0.4 part of 2, 6-di-t-butylcresol as a polymerization inhibitor [ III' -1], and 0.1 part of dibutyltin dilaurate as a reaction catalyst were reacted at 60 ℃ to complete the reaction at a time when the remaining isocyanate group was 0.1%, thereby obtaining a urethane acrylate composition [ I-2] (resin component concentration 100%).
The weight-average molecular weight of the resulting urethane acrylate composition [ I-2] was 2,200, and the viscosity at 60 ℃ was 5,000 mPas.
< production example 3>
[ production of urethane acrylate composition [ I-3]
66.2 parts of isophorone diisocyanate (B-1), and an acrylic acid adduct of dipentaerythritol (a2-1) [ hydroxyl value: 933.8 parts of 48mgKOH/g, 0.6 parts of 2, 6-di-tert-butylcresol as a polymerization inhibitor [ III' -1], and 0.2 parts of dibutyltin dilaurate as a reaction catalyst were reacted at 50 ℃ to complete the reaction at a time when the residual isocyanate group was 0.3%, thereby obtaining a urethane acrylate composition [ I-3] (resin component concentration 100%).
The weight-average molecular weight of the resulting urethane acrylate composition [ I-3] was 1,700, and the viscosity at 60 ℃ was 1,500 mPas.
< production example 4>
[ production of urethane acrylate composition [ I-4]
Into a 4-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen gas inlet were charged 237.8 parts of a trimer compound of hexamethylene diisocyanate having an isocyanurate skeleton (B-3) (isocyanate group content: 21%), (A2-1) an acrylic acid adduct of dipentaerythritol (hydroxyl value: 639.5 parts of 50mgKOH/g, 122.7 parts of 2-hydroxypropyl acrylate, 0.8 part of 2, 6-di-t-butylcresol as a polymerization inhibitor [ III' -1], and 0.2 part of dibutyltin dilaurate as a reaction catalyst were reacted at 60 ℃ to complete the reaction when the residual isocyanate group was 0.3%, thereby obtaining a urethane acrylate composition [ I-4] (resin component concentration: 100%).
The weight-average molecular weight of the resulting urethane acrylate composition [ I-4] was 3,700, and the viscosity at 60 ℃ was 3,000 mPas.
Then, an active energy ray-curable resin composition was produced using the urethane acrylate compositions [ I-1] to [ I-4 ].
[ production of an 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 in the above manner in 100 parts of 1-methoxy-2-propanol (boiling point 120 ℃ C.), 0.2 parts of "KY-1203" (active ingredient 20%, manufactured by shin-Etsu chemical Co., Ltd., weight average molecular weight (measured value) 27,000) as the fluorine-containing acrylate compound [ II-1] (1 part containing a solvent component) as the active ingredient, 0.3 parts of 2, 6-di-tert-butylcresol as the polymerization inhibitor [ III-1] (2,990 ppm in total of the urethane acrylate composition [ I-1], the fluorine-containing acrylate compound [ II-1] and the polymerization inhibitor [ III-1 ]), and 0.05 parts of "curable energy ray-curable resin composition" as the anti-coloring agent [ IV-1] (manufactured by Fine chemical Co., Ltd.). were further compounded with α parts of a photopolymerization initiator (OmniM 184 "), and" active ray-curable resin composition "containing a photopolymerization initiator" was obtained.
The content of the polymerization inhibitor [ III ] (including the polymerization inhibitor [ III' ] used for producing the urethane acrylate composition) was 3,780ppm based on the total of the urethane acrylate composition [ I ], the fluorine-containing acrylate compound [ II ] and the polymerization inhibitor [ III ].
< example 2>
An active energy ray-curable resin composition and an active energy ray-curable resin composition containing a photopolymerization initiator were obtained in the same manner as in example 1, except that the urethane acrylate composition [ I-2] was used instead of the urethane acrylate composition [ I-1] in example 1.
The content of the polymerization inhibitor [ III ] (including the polymerization inhibitor [ III' used for producing the urethane acrylate composition [ I ]) was 3,380ppm based on the total of the urethane acrylate composition [ I ], the fluorine-containing acrylate compound [ II ] and the polymerization inhibitor [ III ].
< example 3>
An active energy ray-curable resin composition and an active energy ray-curable resin composition containing a photopolymerization initiator were obtained in the same manner as in example 1, except that the amount of the fluorine-containing acrylate compound [ II-1] added in example 1 was changed to 0.05 parts (0.25 parts inclusive of the solvent component) based on the active ingredient.
The content of the polymerization inhibitor [ III ] (including the polymerization inhibitor [ III' used for producing the urethane acrylate composition [ I ]) was 3,790ppm in terms of the total of the urethane acrylate composition [ I ], the fluorine-containing acrylate compound [ II ] and the polymerization inhibitor [ III ].
< example 4>
An active energy ray-curable resin composition and an active energy ray-curable resin composition containing a photopolymerization initiator were obtained in the same manner as in example 1, except that the amount of the fluorine-containing acrylate compound [ II-1] added in example 1 was changed to 1 part (5 parts including a solvent component) based on the active ingredient.
The content of the polymerization inhibitor [ III ] (including the polymerization inhibitor [ III' used for producing the urethane acrylate composition [ I ]) was 3,750ppm based on the total of the urethane acrylate composition [ I ], the fluorine-containing acrylate compound [ II ] and the polymerization inhibitor [ III ].
< example 5>
An active energy ray-curable resin composition and an active energy ray-curable resin composition containing a photopolymerization initiator were obtained in the same manner as in example 1 except that "ptool DAC-HP" (20% of an active ingredient, DAIKIN inustrees, manufactured by ltd., having a weight average molecular weight (measured value) of 2,300) as the fluorine-containing acrylate compound [ II-2], was used in place of the fluorine-containing acrylate compound [ II-1] in example 1 in an amount of 0.2 parts (1 part including a solvent component) of the active ingredient.
The content of the polymerization inhibitor [ III ] (including the polymerization inhibitor [ III' used for producing the urethane acrylate composition [ I ]) was 3,780ppm based on the total of the urethane acrylate composition [ I ], the fluorine-containing acrylate compound [ II ] and the polymerization inhibitor [ III ].
< example 6>
An active energy ray-curable resin composition and an active energy ray-curable resin composition containing a photopolymerization initiator were obtained in the same manner as in example 1 except that "IRX-380" (active ingredient 10%, weight average molecular weight (measured value) 1,300, manufactured by AGC corporation) as the fluorine-containing acrylate compound [ II-3], based on the active ingredient, was used in example 1 in place of the fluorine-containing acrylate compound [ II-1, and 0.2 parts (2 parts including a solvent component) was used.
The content of the polymerization inhibitor [ III ] (including the polymerization inhibitor [ III' used for producing the urethane acrylate composition [ I ]) was 3,780ppm based on the total of the urethane acrylate composition [ I ], the fluorine-containing acrylate compound [ II ] and the polymerization inhibitor [ III ].
< example 7>
An active energy ray-curable resin composition and an active energy ray-curable resin composition containing a photopolymerization initiator were obtained in the same manner as in example 1, except that the amount of the polymerization inhibitor [ III-1] added in example 1 was changed to 0.9 parts.
The content of the polymerization inhibitor [ III ] (including the polymerization inhibitor [ III' used for producing the urethane acrylate composition [ I ]) was 9,690ppm in terms of the total of the urethane acrylate composition [ I ], the fluorine-containing acrylate compound [ II ] and the polymerization inhibitor [ III ].
< example 8>
An active energy ray-curable resin composition and an active energy ray-curable resin composition containing a photopolymerization initiator were obtained 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]2, 6-di-t-butylcresol in example 1.
The content of the polymerization inhibitor [ III ] (including the polymerization inhibitor [ III' used for producing the urethane acrylate composition [ I ]) was 3,780ppm based on the total of the urethane acrylate composition [ I ], the fluorine-containing acrylate compound [ II ] and the polymerization inhibitor [ III ].
< example 9>
An active energy ray-curable resin composition and an active energy ray-curable resin composition containing a photopolymerization initiator were obtained in the same manner as in example 1 except that 100 parts of the urethane acrylate composition [ I-3] and 0.1 part of "CSP" as the stain inhibitor [ IV-1] were used in place of the urethane acrylate composition [ I-1] in example 1.
The content of the polymerization inhibitor [ III ] (including the polymerization inhibitor [ III' used for producing the urethane acrylate composition [ I ]) was 3,580ppm in terms of the total of the urethane acrylate composition [ I ], the fluorine-containing acrylate compound [ II ] and the polymerization inhibitor [ III ].
< example 10>
An active energy ray-curable resin composition and an active energy ray-curable resin composition containing a photopolymerization initiator were obtained in the same manner as in example 9, except that in example 9, the urethane acrylate composition [ I-4] was used in place of the urethane acrylate composition [ I-3 ].
The content of the polymerization inhibitor [ III ] (including the polymerization inhibitor [ III' used for producing the urethane acrylate composition [ I ]) was 3,780ppm based on the total of the urethane acrylate composition [ I ], the fluorine-containing acrylate compound [ II ] and the polymerization inhibitor [ III ].
< example 11>
An active energy ray-curable resin composition and an active energy ray-curable resin composition containing a photopolymerization initiator were obtained in the same manner as in example 9, except that the amount of the fluorine-containing acrylate compound [ II-1] added in example 9 was changed to 0.05 parts (0.25 parts inclusive of the solvent component) based on the active ingredient.
The content of the polymerization inhibitor [ III ] (including the polymerization inhibitor [ III' used for producing the urethane acrylate composition [ I ]) was 3,590ppm in terms of the total of the urethane acrylate composition [ I ], the fluorine-containing acrylate compound [ II ] and the polymerization inhibitor [ III ].
< example 12>
An active energy ray-curable resin composition and an active energy ray-curable resin composition containing a photopolymerization initiator were obtained in the same manner as in example 9, except that the amount of the fluorine-containing acrylate compound [ II-1] added in example 9 was changed to 1 part (5 parts including a solvent component) based on the active ingredient.
The content of the polymerization inhibitor [ III ] (including the polymerization inhibitor [ III' used for producing the urethane acrylate composition [ I ]) was 3,550ppm based on the total of the urethane acrylate composition [ I ], the fluorine-containing acrylate compound [ II ] and the polymerization inhibitor [ III ].
< example 13>
In example 9, an active energy ray-curable resin composition and an active energy ray-curable resin composition containing a photopolymerization initiator were obtained in the same manner as in example 9 except that "ptool DAC-HP" (20% of an active ingredient, DAIKIN inustrees, manufactured by ltd., having a weight average molecular weight (measured value) of 2,300) as the fluorine-containing acrylate compound [ II-2], was used in place of the fluorine-containing acrylate compound [ II-1] in an amount of 0.2 parts (1 part including a solvent component) of the active ingredient.
The content of the polymerization inhibitor [ III ] (including the polymerization inhibitor [ III' used for producing the urethane acrylate composition [ I ]) was 3,580ppm in terms of the total of the urethane acrylate composition [ I ], the fluorine-containing acrylate compound [ II ] and the polymerization inhibitor [ III ].
< example 14>
An active energy ray-curable resin composition and an active energy ray-curable resin composition containing a photopolymerization initiator were obtained in the same manner as in example 9 except that "IRX-380" (active ingredient 10%, weight average molecular weight (measured value) 1,300, manufactured by AGC corporation) as the fluorine-containing acrylate compound [ II-3], based on the active ingredient, was used in example 9 in place of the fluorine-containing acrylate compound [ II-1 in an amount of 0.2 parts (2 parts including a solvent component).
The content of the polymerization inhibitor [ III ] (including the polymerization inhibitor [ III' used for producing the urethane acrylate composition [ I ]) was 3,580ppm in terms of the total of the urethane acrylate composition [ I ], the fluorine-containing acrylate compound [ II ] and the polymerization inhibitor [ III ].
< example 15>
An active energy ray-curable resin composition and an active energy ray-curable resin composition containing a photopolymerization initiator were obtained in the same manner as in example 9, except that the amount of the polymerization inhibitor [ III-1] added in example 9 was changed to 0.9 parts.
The content of the polymerization inhibitor [ III ] (including the polymerization inhibitor [ III' used for producing the urethane acrylate composition [ I ]) was 9,500ppm based on the total of the urethane acrylate composition [ I ], the fluorine-containing acrylate compound [ II ] and the polymerization inhibitor [ III ].
< example 16>
An active energy ray-curable resin composition and an active energy ray-curable resin composition containing a photopolymerization initiator were obtained in the same manner as in example 9, except that 4-methoxyphenol was used as the polymerization inhibitor [ III-2] in place of the polymerization inhibitor [ III-1]2, 6-di-t-butylcresol in example 9.
The content of the polymerization inhibitor [ III ] (including the polymerization inhibitor [ III' used for producing the urethane acrylate composition [ I ]) was 3,580ppm in terms of the total of the urethane acrylate composition [ I ], the fluorine-containing acrylate compound [ II ] and the polymerization inhibitor [ III ].
< example 17>
An active energy ray-curable resin composition and an active energy ray-curable resin composition containing a photopolymerization initiator were obtained in the same manner as in example 9, except that the stainblocker [ IV-1] was not used in example 9.
The content of the polymerization inhibitor [ III ] (including the polymerization inhibitor [ III' used for producing the urethane acrylate composition [ I ]) was 3,580ppm in terms of the total of the urethane acrylate composition [ I ], the fluorine-containing acrylate compound [ II ] and the polymerization inhibitor [ III ].
< comparative example 1>
An active energy ray-curable resin composition and an active energy ray-curable resin composition containing a photopolymerization initiator were obtained in the same manner as in example 1, except that the fluorine-containing acrylate compound [ II-1] was not used in example 1.
The content of the polymerization inhibitor [ III ] (including the polymerization inhibitor [ III' ] used for producing the urethane acrylate composition) was 3,790ppm in terms of the total of the urethane acrylate composition [ I ], the fluorine-containing acrylate compound [ II ] and the polymerization inhibitor [ III ].
< comparative example 2>
An active energy ray-curable resin composition and an active energy ray-curable resin composition containing a photopolymerization initiator were obtained in the same manner as in example 1, except that the polymerization inhibitor [ III-1] was not used in example 1.
The content of the polymerization inhibitor [ III ] (including the polymerization inhibitor [ III' ] used for producing the urethane acrylate composition) was 800ppm based on the total of the urethane acrylate composition [ I ], the fluorine-containing acrylate compound [ II ] and the polymerization inhibitor [ III ].
< comparative example 3>
An active energy ray-curable resin composition and an active energy ray-curable resin composition containing a photopolymerization initiator were obtained in the same manner as in example 9, except that the fluorine-containing acrylate compound [ II-1] was not used in example 9.
The content of the polymerization inhibitor [ III ] (including the polymerization inhibitor [ III' ] used for producing the urethane acrylate composition) was 3,590ppm in terms of the total of the urethane acrylate composition [ I ], the fluorine-containing acrylate compound [ II ] and the polymerization inhibitor [ III ].
< comparative example 4>
An active energy ray-curable resin composition and an active energy ray-curable resin composition containing a photopolymerization initiator were obtained in the same manner as in example 9, except that the polymerization inhibitor [ III-1] was not used in example 9.
The content of the polymerization inhibitor [ III ] (including the polymerization inhibitor [ III' ] used for producing the urethane acrylate composition) was 600ppm based on the total of the urethane acrylate composition [ I ], the fluorine-containing acrylate compound [ II ] and the polymerization inhibitor [ III ].
< comparative example 5>
An active energy ray-curable resin composition and an active energy ray-curable resin composition containing a photopolymerization initiator were obtained in the same manner as in example 9 except that trimethylolpropane triacrylate ("aronex M-309", manufactured by east asian co., ltd., containing 100ppm of a polymerization inhibitor) was used in place of the urethane acrylate composition [ I-3] in example 9.
The content of the polymerization inhibitor [ III ] (including the polymerization inhibitor contained in trimethylolpropane triacrylate) was 3,090ppm based on the total of trimethylolpropane, the fluorine-containing acrylate compound [ II ] and the polymerization inhibitor [ III ].
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 active energy ray-curable resin composition, a spectral colorimeter "SE 6000: manufactured by Nippon Denshoku industries Co., Ltd.) "measurement of the haxan color number (APHA). Further, the active energy ray-curable resin composition was placed in a sealed glass test container, a heat resistance test was performed under heat resistant conditions (storage at 60 ℃ for 4 weeks), and the value of APHA after the heat resistance test was measured. The results are shown in tables 1 to 3 below.
Further, samples for evaluation were produced from the active energy ray-curable resin composition containing the photopolymerization initiator obtained above, and pencil hardness, scratch resistance, stain resistance, water contact angle, and oleic acid contact angle were evaluated. The results are shown in tables 1 to 3 below.
[ method of producing sample for evaluation ]
The active energy ray-curable resin composition containing a photopolymerization initiator obtained in the above was applied to an easy-adhesion layer using a bar coater so that the dried film thickness became 5 μmA PET film (available from Toyo Boseki Co., Ltd., "COSMOSHINEA 4300" having a thickness of 125 μm) was dried at 90 ℃ for 3 minutes, and then subjected to 2-pass ultraviolet irradiation (cumulative irradiation dose of 450 mJ/cm) from a height of 18cm at a belt speed of 5.1 m/min using 1 high-pressure mercury lamp of 80W2) To form a cured coating film.
[ Pencil hardness ]
The cured coating film coated on the easy-to-bond PET film was tested based on JISK5600, and pencil hardness was measured.
[ scratch resistance ]
The cured coating film applied to the easy-adhesion PET film was evaluated by using Steel wool (Nippon Steel wool, ltd., BONSTAR #0000) and reciprocating the cured coating film surface while applying a load of 1kg, and then visually measuring the number of times of reciprocating until the surface was damaged, according to the following criteria.
(evaluation)
○. has no damage even if the reciprocating motion is performed 1,000 times
△. Damage occurred more than 600 times and less than 1,000 times
X. Damage occurred 600 times less
[ antifouling Property (Magic Ink (registered trademark) wiping Property) ]
On the cured coating surface, the coating film was scribed with black Magic Ink in 1 round trip, left to stand for 24 hours, and then the coating film wiped with a waste cloth was observed and evaluated as follows. The wiping properties of the Magic Ink were also evaluated similarly for the coating film after the scratch resistance test (after 1,000 round trips).
(evaluation)
○. clean and wipe off
△. wiping off to some extent but leaving traces
X. not rubbed off
[ contact angles of water and oleic acid ]
The contact angles of water and oleic acid on the surface of the cured coating film were measured with a contact angle measuring apparatus (DropMaster 600, manufactured by Kyowa Kagaku K.K.). The coating films after the scratch resistance test were also evaluated for water and oleic acid contact angles in the same manner.
[ Table 1]
Figure BDA0002464859450000331
[ Table 2]
Figure BDA0002464859450000341
[ Table 3]
Figure BDA0002464859450000351
From the above results, it was found that the storage stability in the coating liquid was excellent in the example in which the composition containing the urethane (meth) acrylate composition [ I ] and the fluorine-containing (meth) acrylate compound [ II ] further contained a predetermined amount of the polymerization inhibitor [ III ]. Further, in the examples, although the polymerization inhibitor [ III ] was contained in an amount larger than that in comparative examples 2 and 4, the antifouling property and scratch resistance were excellent and were not inferior to those of the cured coating films. On the other hand, in comparative examples 1 and 3 which did not contain the fluorine-containing (meth) acrylate compound [ II ], the stain-proofing performance and the scratch resistance were poor, and in comparative examples 2 and 4 which did not further contain the polymerization inhibitor [ III ] except for the production of the urethane (meth) acrylate composition [ I ], the storage stability of the liquid was poor. In addition, in comparative example 5 in which the urethane (meth) acrylate composition [ I ] was not used, the curability was insufficient, and the object of the present invention was not satisfied.
The above embodiments are merely examples and are not to be construed as limiting the present invention. Various modifications which are intended to be obvious to those skilled in the art are intended to be within the scope of the present invention.
Industrial applicability
The active energy ray-curable resin composition of the present invention is excellent in storage stability of a coating liquid, and can form a coating film excellent in antifouling performance (stain resistance and persistence thereof) and characteristics (appearance, hardness, scratch resistance) of a cured coating film, and is useful as a coating agent, particularly a coating agent for hard coating and a coating agent for optical films. Further, the composition is also useful as a paint, an ink, or the like.

Claims (10)

1. An active energy ray-curable resin composition characterized by containing: the urethane (meth) acrylate composition [ I ], the fluorine-containing (meth) acrylate compound [ II ] and the polymerization inhibitor [ III ] obtained by reacting the hydroxyl group in the (meth) acrylic adduct (A) of a polyhydric alcohol with the isocyanate group of the polyisocyanate compound (B) are contained in an amount of 800 to 10000ppm by weight based on the total amount of the urethane (meth) acrylate composition [ I ], the fluorine-containing (meth) acrylate compound [ II ] and the polymerization inhibitor [ III ].
2. The active energy ray-curable resin composition according to claim 1, wherein the polyol is at least one of dipentaerythritol and pentaerythritol.
3. The active energy ray-curable resin composition according to claim 1 or 2, wherein the fluorine-containing (meth) acrylate compound [ II ] has a siloxane bond.
4. The active energy ray-curable resin composition according to any one of claims 1 to 3, wherein the weight average molecular weight of the fluorine-containing (meth) acrylate compound [ II ] is 1000 to 100000.
5. The active energy ray-curable resin composition according to any one of claims 1 to 4, wherein the weight average molecular weight of the urethane (meth) acrylate composition [ I ] is 900 to 30000.
6. The active energy ray-curable resin composition according to any one of claims 1 to 5, further comprising an anti-coloring agent [ IV ].
7. 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 ℃ or higher.
8. 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, wherein the coating agent is used as a hard coating agent.
10. The coating agent according to claim 8, which is used as a coating agent for an optical film.
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