JP7376849B2 - Active energy ray-curable coating composition, cured product, laminate - Google Patents

Description

The present invention relates to an active energy ray-curable coating composition, a cured product, and a laminate.

Active energy ray-curable coating compositions are used in a wide range of fields, including mobile devices such as smartphones and tablets, digital home appliances such as digital cameras and audio devices, and IT-related devices such as radios and modems. . Such a coating agent composition can be applied to a substrate such as an optical film and cured by short-time irradiation with active energy rays such as ultraviolet rays and visible light. On the other hand, since the base material itself is easily deformed and expanded/contracted due to temperature changes, external stress, etc., the coating agent composition is required to have adhesion that can follow the deformation of the base material.

Examples of technologies that address adhesion to substrates include active energy ray-curable compositions containing urethane (meth)acrylates, specific aromatic di(meth)acrylates, and mono(meth)acrylates having a phenyl skeleton. is disclosed (Patent Document 1). However, when trying to increase the adhesion, the coating agent composition becomes softer, resulting in poor workability (lower breaking strength); on the other hand, when trying to increase the breaking strength, cracks occur (breaking elongation decreases). There were cases in which it was not possible to ensure the proper

International publication WO2008/149766

The object of the present invention is to provide an active energy ray-curable coating composition that provides a cured product that has excellent adhesion to a substrate and also has high elongation and strength at break; a cured product of the coating composition; and a cured product of the coating composition. An object of the present invention is to provide a laminate having the following properties.

The present inventors have found that a coating agent composition in which a plurality of specific (meth)acrylate monomers are blended into polyurethane mono(meth)acrylate solves the above problems, and has completed the present invention. That is, the present invention relates to the following active energy ray-curable coating agent composition, cured product, and laminate.

1. Polyurethane mono(meth)acrylate (A) containing diisocyanate (a1), diol (a2), and hydroxyl group-containing mono(meth)acrylate (a3) as reaction components, cyclic (meth)acrylate having an oxygen atom in the ring (B1) ), mono(meth)acrylates (B2) whose glass transition temperature is 50°C or higher when made into a homopolymer (excluding those belonging to component (B1)), and acyclic di(meth)acrylates (C). including,
The ratio of the content of component (A) to the total content of components (B1) and (B2) is (A)/[(B1)+(B2)]=5/95 to It is 80/20,
An active energy ray-curable coating agent composition in which the content of component (C) is less than 10 parts by weight based on a total of 100 parts by weight of components (A), (B1), and (B2).

2. The active energy ray-curable coating composition according to item 1 above, wherein component (a2) is polyester diol and/or polycaprolactone diol.

3. Component (B1) is (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate, cyclic trimethylolpropane formal acrylate, (3-ethyloxetan-3-yl) methyl acrylate and The active energy ray-curable coating composition according to item 1 or 2 above, which is at least one member selected from the group consisting of -ethyloxetan-3-yl)methyl methacrylate.

4. The active energy ray-curable coating composition according to any one of items 1 to 3 above, wherein the component (B2) is an alicyclic mono(meth)acrylate.

5. Active energy ray curing according to any one of the preceding items 1 to 4, wherein the content ratio of the component (B1) and the component (B2) is (B1)/(B2) = 1/5 to 5/1 in terms of solid weight. Mold coating agent composition.

6. The active energy ray-curable coating composition according to any one of items 1 to 5 above, further comprising a thiol (D).

7. A cured product of the active energy ray-curable coating composition according to any one of items 1 to 6 above.

8. A laminate having the cured product of item 7 on at least one side of a base material.

When the active energy ray-curable coating agent composition according to the present invention is made into a cured product, the object of the present invention is to have excellent adhesion to a substrate and also have high elongation at break and high strength at break. The coating agent composition can be applied to, for example, coating agents for polarizing plates, liquid crystal panels of mobile phones, smartphones, personal computers, etc., organic EL panels, and the like.

The active energy ray-curable coating composition of the present invention (hereinafter simply referred to as "coating composition") comprises a specific polyurethane mono(meth)acrylate (A) (hereinafter referred to as component (A)), a ring Cyclic (meth)acrylate (B1) having an oxygen atom (hereinafter referred to as component (B1)), mono(meth)acrylate (B2) having a glass transition temperature of 50°C or higher when made into a homopolymer (however, (excluding those belonging to component (B1)) (hereinafter referred to as component (B2)) and acyclic di(meth)acrylate (C) (hereinafter referred to as component (C)).

Component (A) is a component that has excellent adhesion to the base material. Specifically, diisocyanate (a1) (hereinafter referred to as component (a1)), diol (a2) (hereinafter referred to as component (a2)), and hydroxyl group-containing mono(meth)acrylate (a3) (hereinafter referred to as component (a2)). (referred to as component a3)) is included as a reaction component.

Component (a1) is not particularly limited, and examples thereof include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-xylylene diisocyanate, tetramethylxylylene diisocyanate, 3,3-dimethyldiphenylmethane diisocyanate, Aromatic diisocyanates such as 4,4-diphenylmethane diisocyanate and 1,5-naphthalene diisocyanate; Aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate; dicyclohexylmethane-4,4'-diisocyanate , isophorone diisocyanate, 1,4-cyclohexane diisocyanate, norbornane diisocyanate, cyclohexane-1,4-diylbis(methylene) diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, and other alicyclic diisocyanates. These may be used alone or in combination of two or more. Among these, alicyclic diisocyanates are preferred, and isophorone diisocyanate is more preferred, from the viewpoint of increasing the breaking strength of the cured product.

Component (a2) is a compound having two hydroxyl groups in the molecule, and its type is not particularly limited, and examples thereof include polyether diol, polyester diol, polycarbonate diol, polycaprolactone diol, and the like. These may be used alone or in combination of two or more.

The polyether diol is not particularly limited, and examples thereof include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and copolymers thereof. These may be used alone or in combination of two or more. In addition, commercially available products include, for example, "PEG400", "PEG600", "PEG1000", "PEG2000", "PEG10000" (manufactured by Sanyo Chemical Industries, Ltd.), "ADEKA Polyether Polyol P-1000", "ADEKA Polyether Polyol P-1000", and "ADEKA Polyether Polyol P-1000". Ether Polyol P-2000'', ``ADEKA Polyether Polyol P-3000'' (manufactured by ADEKA Corporation), ``PTMG650'', ``PTMG1000'', ``PTMG1500'', ``PTMG2000'', ``PTMG3000'', (all manufactured by Mitsubishi (manufactured by Chemical Co., Ltd.).

The polyester diol is not particularly limited, and examples include polycondensates of diols and polybasic acids. Diols are not particularly limited, and examples include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and neopentyl. Glycol, pentanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, hexanediol, octanediol, 2,2-diethyl-1,3-propanediol, Aliphatic diols such as 2-ethyl-2-butyl-1,3-propanediol; alicyclic diols such as cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol; Examples include ethylene glycol or propylene glycol adducts. In addition, the polybasic acids are not particularly limited, and include, for example, diacids such as adipic acid, maleic acid, succinic acid, oxalic acid, fumaric acid, malonic acid, glutaric acid, pimelic acid, azelaic acid, sebacic acid, and suberic acid. Basic acids; aromatic polybasic acids such as phthalic anhydride, isophthalic acid, terephthalic acid, 2,6-naphthalene dicarboxylic acid, trimellitic acid, pyromellitic acid; acid anhydrides corresponding to these, their derivatives, and dimer acids; Examples include hydrogenated dimer acids. Note that in the esterification reaction, a known catalyst may be used as necessary, such as a tin compound such as dibutyltin oxide or stannous octylate, or an alkoxy titanium such as tetrabutyl titanate or tetrapropyl titanate. etc. These may be used alone or in combination of two or more. Commercially available products include "Kuraray Polyol P510", "Kuraray Polyol P1010", "Kuraray Polyol P2010", "Kuraray Polyol P3010", "Kuraray Polyol P4010" (manufactured by Kuraray Co., Ltd.), "Adeka New Ace YT" -101'', ``ADEKA New Ace YG-108'', ``ADEKA New Ace Y9-10'', ``ADEKA New Ace NS-2400'' (manufactured by ADEKA Corporation), ``PLACCEL 205'', ``PLACCEL 208'', PLACCEL 210'' (manufactured by Daicel Corporation).

Polycarbonate diols include, for example, products obtained by reacting diols with carbonylating agents. Examples of the diol include those mentioned above. Examples of carbonylating agents include alkylene carbonates such as ethylene carbonate and propylene carbonate; dialkyl carbonates such as dimethyl carbonate, diethyl carbonate and dibutyl carbonate; diphenyl carbonate and phosgene. These diols and carbonylating agents may be used alone or in combination of two or more. In addition, commercially available products include, for example, "Nipporan 963", "Nipporan 964", "Nipporan 981" (manufactured by Tosoh Corporation), "ETERNACOLL (registered trademark)" series (manufactured by Ube Industries, Ltd.), " BENEBiOL (registered trademark) series (manufactured by Mitsubishi Chemical Corporation) and the like.

Polycaprolactone diol is a ring-opening polymer of ε-caprolactone, and diols, alkanolamines, etc. are used during polymerization. Examples of the diol include those mentioned above. Examples of alkanolamines include monoethanolamine, N-methylethanolamine, N-ethylethanolamine, Nn-butylethanolamine, N-(β-aminoethyl)isopropanolamine, N-methyldiethanolamine, and diethanolamine. , N-ethyldiethanolamine, Nn-butyldiethanolamine, triethanolamine and the like. These may be used alone or in combination of two or more. Examples of commercially available products include "Plaxel 210", "Plaxel 210N", "Plaxel 212", "Plaxel L212AL", "Plaxel 220", and "Plaxel 220N" (manufactured by Daicel Corporation).

Among these components (a2), polyester diol and polycaprolactone diol are preferred from the viewpoint of increasing the elongation at break and the strength at break of the cured product.

The physical properties of component (a2) are not particularly limited, and for example, the number average molecular weight (polystyrene equivalent value determined by gel permeation chromatography method, hereinafter the same) is usually about 400 to 5000, preferably 500 to 2000. That's about it. Furthermore, the average number of hydroxyl groups per molecule of component (a2) is not particularly limited, and is usually about 1 to 3, preferably about 1 to 2. Note that the average number of hydroxyl groups means the average number of hydroxyl groups present in one molecule of component (a2).

The molar amount of component (a2) to be used is not particularly limited, but from the viewpoint of increasing the elongation at break of the cured product, it is preferably 0.8 to 1 mole per mole of component (a1). Further, from the same point of view, 0.9 to 1 mol is more preferable.

Component (a3) is not particularly limited, and examples thereof include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxy Hydroxyl group-containing alicyclic mono(meth)acrylates such as butyl (meth)acrylate and 6-hydroxyhexyl acrylate; ) acrylates; hydroxyl group-containing aromatic (meth)acrylates such as 2-hydroxy-3-phenyloxypropyl (meth)acrylate; polyalkylene glycol mono(meth)acrylates such as polyethylene glycol mono(meth)acrylate and polypropylene glycol mono(meth)acrylate; ) acrylate, etc. These may be used alone or in combination of two or more. Among these, hydroxyl group-containing aliphatic (meth)acrylates are preferred, and 2-hydroxyethyl (meth)acrylate is more preferred.

The molar amount of component (a3) to be used is not particularly limited, but is preferably from 0.05 to 1 mole per mole of component (a1) from the viewpoint of increasing the elongation at break and the strength at break of the cured product. Further, from the same point of view, 0.2 to 0.7 mol is more preferable.

Component (A) is not particularly limited, and can be produced by various known methods. For example, component (a1) and component (a2) are reacted to form a urethane prepolymer (hereinafter, component (A')). ) and then reacting component (A') and component (a3). The reaction conditions are not particularly limited, but usually the temperature is about 60 to 90°C and the time is about 0.5 to 3 hours.

Note that the production of component (A) may be carried out in the absence of a solvent, but it can also be carried out in the presence of components (B1) and (B2), which will be described later.

Other physical properties of component (A) are not particularly limited, but the weight average molecular weight is preferably about 2,000 to 40,000, more preferably about 5,000 to 20,000. In addition, the weight average molecular weight here is a value measured by the GPC method (polystyrene equivalent value by gel permeation chromatography method).

The component (B1) is a cyclic (meth)acrylate having an oxygen atom in the ring, and is a component for good adhesion to the base material. Component (B1) is not particularly limited, and examples include (meth)acrylates having an oxetane ring, such as (3-ethyloxetan-3-yl)methyl acrylate and (3-ethyloxetan-3-yl)methyl methacrylate; (2-Methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate, (2-oxo-1,3-dioxolan-4-yl)methyl methacrylate, 4-(meth)acryloyloxymethyl-2 -(Meth)acrylates having a dioxolane ring such as cyclohexyl-1,3-dioxolane; (meth)acrylates having a dioxane ring such as cyclic trimethylolpropane formal acrylate, 1,3-dioxane-5,5-dimethanol diacrylate, etc. etc. These may be used alone or in combination of two or more. Among them, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate, (3-ethyloxetan-3-yl) methyl acrylate, (3- Ethyloxetan-3-yl)methyl methacrylate is preferred.

In addition, commercially available products of component (B1) include "MEDOL-10" ((2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.), " Viscoat #200” (cyclic trimethylolpropane formal acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.), (3-ethyloxetan-3-yl)methyl acrylate (trade name: “OXE-30”, Osaka Organic Chemical Industry Co., Ltd.) ), (3-ethyloxetan-3-yl)methyl methacrylate (trade name: "OXE-10", manufactured by Osaka Organic Chemical Industry Co., Ltd.), and the like.

Component (B2) is a mono(meth)acrylate having a glass transition temperature of 50°C or higher when made into a homopolymer, does not belong to component (B1), and when the coating composition is cured. , is a component that makes the optical member hard to some extent and makes it easier to process (gives good processability).

"Glass transition temperature when made into a homopolymer" refers to the glass transition temperature (Tg) of a polymer produced by polymerizing only the monomer alone. For example, "POLYMER HANDBOOK FOURTH EDITION" by Wiley-Interscience. (2003) describes specific numerical values. In the present invention, the values described in the product information on the homepages and catalogs of chemical manufacturers were adopted. When the glass transition temperature is 50° C. or higher, the breaking strength of the cured product becomes high. From the same point of view, the glass transition temperature is preferably 70°C or higher, more preferably 90°C or higher. Further, from the viewpoint of increasing the elongation at break of the cured product, the glass transition temperature is preferably 150°C or lower, more preferably 100°C or lower.

Component (B2) includes, for example, aliphatic mono(meth)acrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, s-butyl methacrylate, and t-butyl methacrylate; isobornyl acrylate; Isobornyl methacrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, 3,3,5-trimethylcyclohexyl acrylate, 3,3,5-trimethylcyclohexyl methacrylate, 4-t-butylcyclohexyl methacrylate, cyclooctyl methacrylate, dicyclopentanyl acrylate, di Alicyclic mono(meth)acrylates such as cyclopentenyl acrylate, dicyclopentanyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, 1-adamantyl acrylate, 3,5-dimethyladamantyl acrylate, 1-adamantyl methacrylate; Examples include aromatic mono(meth)acrylates such as phenyl acrylate, phenyl methacrylate, benzyl methacrylate, 2-phenoxyethyl methacrylate, and 2-naphthyl acrylate, and acryloylmorpholine. These may be used alone or in combination of two or more. Among them, alicyclic mono(meth)acrylates are preferred, and isobornyl acrylate, isobornyl methacrylate, and dicyclopentanyl acrylate are more preferred, since the cured product becomes hard to some extent and makes it easier to process optical members.

The content of component (A), component (B1), and component (B2) is the solid weight (the same applies hereinafter), and the total content of component (A), component (B1), and component (B2). Expressed as a ratio to the amount, (A)/[(B1)+(B2)]=5/95 to 80/20. When the ratio is less than 5/95, the cured product tends to become brittle and have low elongation at break and low breaking strength, and when it exceeds 80/20, the cured product tends to become flexible and have low breaking strength. . From the same point of view, the ratio is preferably (A)/[(B1)+(B2)]=20/80 to 70/30, more preferably 40/60 to 60/40.

In addition, from the viewpoint of adhesion to the substrate, the content ratio of component (B1) and component (B2) is preferably (B1)/(B2)=1/5 to 5/1, and 1/5 to 5/1 in terms of solid content weight. More preferably 2 to 2/1.

Component (C) is an acyclic di(meth)acrylate and is a component that increases the breaking strength. Component (C) is not particularly limited, and examples include butanediol di(meth)acrylate, pentanediol di(meth)acrylate, hexanediol di(meth)acrylate, heptanediol di(meth)acrylate, octanediol di(meth)acrylate, and octanediol di(meth)acrylate. Alkanediol di(meth)acrylates such as meth)acrylates; Monoalkylene glycol di(meth)acrylates such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate; diethylene glycol di(meth)acrylates; (meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene Examples include polyalkylene glycol di(meth)acrylate such as glycol di(meth)acrylate; ethoxylated polypropylene glycol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, and the like. These may be used alone or in combination of two or more. Among them, alkylene glycol di(meth)acrylate is preferred, and dipropylene glycol di(meth)acrylate and tripropylene glycol di(meth)acrylate are more preferred, from the viewpoint of increasing the elongation at break and the strength at break of the cured product.

The content of component (C) is less than 10 parts by weight based on a total of 100 parts by weight of components (A), (B1), and (B2). With the above content, the elongation at break and the strength at break of the cured product tend to be high. From the same point of view, the content of component (C) is preferably 0.5 to 8 parts by weight, more preferably 1 to 5 parts by weight.

The coating agent composition of the present invention may further contain thiol (D) (hereinafter referred to as component (D)).

Component (D) is not particularly limited, and various known components can be used, including monofunctional thiols, polyfunctional thiols, and the like.

The monofunctional thiol is not particularly limited, and examples thereof include 1-nonanethiol, t-nonanethiol, 1-dodecanethiol mercaptan, t-dodecanethiol, and the like.

The polyfunctional thiol is not particularly limited and includes, for example, 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1, 7-heptanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, triazinedithiol, tetraethylene glycol bis(3-mercaptopropionate), 3-mercaptomethyl-3,5,5-trimethylcyclohexylthiol, Bifunctional thiols such as 1,3-bis(mercaptomethyl)cyclohexane, 1,4-bis(3-mercaptobutyryloxy)butane, and tetraethylene glycol-bis(3-mercaptopropionate); triazinetrithiol, 1 , 2,3-propane trithiol, trimethylolpropane tris(3-mercaptopropionate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4, Trifunctional thiols such as 6-(1H,3H,5H)-trione; tetrafunctional thiols such as pentaerythritol tetrakis thioglucolate, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), etc. etc. These may be used alone or in combination of two or more. Among them, polyfunctional thiols are preferred, and trifunctional thiols and/or tetrafunctional thiols are more preferred.

The content of component (D) is not particularly limited, but from the viewpoint of ensuring high breaking elongation and breaking strength of the cured product, the content of component (A), component (B1), and component (B2) is determined by solid weight. The amount is about 0.1 to 5 parts by weight per 100 parts by weight in total. From the same point of view, the amount is preferably about 0.5 to 2 parts by weight.

The coating composition of the present invention includes an inorganic filler, a silane coupling agent, a colloidal silica, a surface conditioner, a surfactant, a light absorber, an antioxidant, a light stabilizer, a leveling agent, an antifoaming agent, and a light enhancer. Additives such as sensitizers, slip agents, wetting agents, rust preventives, pigments, and pigment dispersions may also be included. The content of these additives is not particularly limited, but is 0.00 parts by weight based on the total of 100 parts by weight of component (A), component (B1), component (B2), and component (C). It is 1 to 7 parts by weight or less.

The coating agent composition of the present invention is obtained by mixing component (A), component (B1), component (B2), component (C), and optionally component (D) and additives. There are no particular limitations on the mixing temperature, the mixing method of each component, and the order of addition.

Further, for the purpose of adjusting the viscosity of the coating composition, an organic solvent may be added as necessary. The organic solvent is not particularly limited, and examples include ethyl acetate, butyl acetate, toluene, xylene, methanol, ethanol, propanol, butanol, acetone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, ethyl cellosolve, propylene glycol monomethyl ether, and diacetone. Examples include alcohol. These can be used alone or in combination of two or more.

The coating composition of the present invention contains a photopolymerization initiator upon irradiation with active energy rays. The photopolymerization initiator is not particularly limited, and includes, for example, photopolymerization initiators such as benzoin compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, thioxanthone compounds, and oxime ester compounds, and photosensitizers such as amines and quinones. More specifically, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1- one, 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-propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-(dimethylamino )-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, bis(2,4 ,6-trimethylbenzoyl)-phenylphosphine oxide, bis(η ⁵ -2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl) Titanium, 1,2-octanedione 1-[4-(phenylthio)-2-(o-benzoyloxime)], ethanone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3- yl]-1-(o-acetyloxime) and the like. These may be used alone or in combination of two or more.

The content of the photopolymerization initiator is not particularly limited, but from the viewpoint of curability of the curable coating agent composition, the total content of the (A) component, (B1) component, (B2) component, and (C) component is 100%. The amount is usually about 0.5 to 10 parts by weight, preferably about 0.5 to 7 parts by weight, and more preferably about 1 to 4 parts by weight.

The cured product of the present invention is obtained by curing the coating composition.

The cured product of the present invention is not particularly limited, and can be obtained, for example, by applying the coating composition of the present invention to a substrate and irradiating it with active energy rays.

The base material is not particularly limited, and examples thereof include polyethylene terephthalate film (PET film), cycloolefin polymer film (COP film), polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, and vinyl chloride. Copolymer film, polyethylene naphthalate film, polybutylene terephthalate film, polyurethane film, ethylene vinyl acetate film, ionomer resin film, ethylene-(meth)acrylic acid copolymer film, ethylene-(meth)acrylic acid ester copolymer Plastic films such as film, polystyrene film, polycarbonate film, polyimide film, and fluororesin film; metal, wood, paper, glass, slate, and the like. Note that the base material may be either light-peelable or heavy-peelable, and may be untreated or plasma-treated.

The coating method is not particularly limited, and examples thereof include an applicator, a bar coater, a roll coater, a knife coater, a gravure coater, and the like. The coating amount of the active energy ray-curable coating composition is not particularly limited, and it is usually coated so that the film thickness after curing is about 10 to 500 μm.

The active energy rays are not particularly limited, and examples include light rays such as ultraviolet rays, infrared rays, and visible rays, electron beams, X-rays, α-rays, β-rays, γ-rays, and neutron beams. In the present invention, light is preferred, and ultraviolet light is more preferred.

The ultraviolet light source is not particularly limited, and examples thereof include xenon lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, chemical lamps, electrodeless lamps, LED lamps, and the like. Further, the cumulative amount of ultraviolet light is not particularly limited, and is usually about 100 to 3000 mJ/cm ² . Further, after irradiating with ultraviolet rays, heating may be performed as necessary for the purpose of complete curing.

The laminate of the present invention has the cured product of the present invention on at least one side of the base material. The base material, curing method, etc. are the same as described above.

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In each example, all parts and percentages are based on weight unless otherwise specified.

Production Example 1 (Production of (A-1))
A polyester polyol (a reaction product of adipic acid/phthalic acid and 1,6-hexanediol, trade name: ``ADEKA New Ace YG-108'', After charging 78 parts (manufactured by Adeka Co., Ltd.) and 19 parts of isophorone diisocyanate, the temperature inside the system was raised to 70°C, and 0.1 part of tin 2-ethylhexanoate was added. The mixture was stirred at 80°C for 90 minutes. Three parts of 2-hydroxyethyl acrylate were then added to this solution. After 30 minutes, 0.1 part of tin 2-ethylhexanoate was added, and after another 30 minutes, 0.1 part of tin 2-ethylhexanoate was added. Stirring was continued for an additional 2 hours at 80°C. It was confirmed in the IR spectrum that the absorption of the isocyanate group at 2270 cm ^-1 had disappeared, and (A-1) was obtained.

Production Examples 2-3, Comparative Production Example 2
With the compositions shown in Table 1, they were synthesized in the same manner as in Production Example 1 to obtain (A-2) to (A-3) and (E-2), respectively.

Comparative Production Example 1 (Production of (E-1))
After charging 78 parts of YG-108 and 12 parts of isophorone diisocyanate into a reaction apparatus equipped with a stirrer, a cooler, a dropping funnel, and a thermometer, the system temperature was raised to 40°C, and 2-ethyl 0.1 part of tin hexanoate was added. After stirring at 80° C. for 1.5 hours, it was confirmed by IR spectrum that the absorption of isocyanate groups at 2270 cm ⁻¹ had disappeared, and component (E-1) was obtained.

The abbreviations shown in Table 1 mean the following compounds.

<Diisocyanate>
・IPDI: Isophorone diisocyanate <diol>
・YG108: Polyester diol (reaction product of adipic acid/phthalic acid and 1,6-hexanediol, product name: "ADEKA New Ace YG-108", manufactured by ADEKA Co., Ltd.)
・L212AL: Polycaprolactone diol (product name: "Plaxel L212AL", manufactured by Daicel Corporation)
<Hydroxy group-containing (meth)acrylate>
・HEA: 2-hydroxyethyl acrylate

Example 1
50 parts of component (A-1), component (B1), (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate (trade name: "MEDOL-10"), Osaka Organic 25 parts of isobornyl acrylate (manufactured by Kagaku Kogyo Co., Ltd.), 25 parts of isobornyl acrylate as the (B2) component, tripropylene glycol diacrylate (trade name: "Viscoat #310P", Osaka Organic Chemical Industry Co., Ltd. as the (C) component) ) and 1 part of 2-hydroxy-2-methylpropiophenone (trade name: "Lunacure 100", manufactured by DKSH Japan Co., Ltd.) as a photopolymerization initiator, and mixed at room temperature. A line-curable coating composition was obtained.

Examples 2 to 17, Comparative Examples 1 to 9
One part of 2-hydroxy-2-methylpropiophenone (trade name: "Lunacure 100", manufactured by DKSH Japan Co., Ltd.) as a photopolymerization initiator was mixed with the composition shown in Table 2, and an active energy ray-curable coating agent was prepared. Each composition was obtained.

<Preparation of laminate>
Each active energy ray-curable coating composition was applied to the surface of a commercially available polyethylene terephthalate film (trade name: "Cosmoshine A4100", manufactured by Toyobo Co., Ltd.) using an applicator so that the thickness of the cured film was 25 μm. I worked on it. Thereafter, a laminate was produced by irradiating ultraviolet rays using a 200W mercury lamp so that the cumulative light amount was 750 mJ/cm ² .

<Elongation at break/Strength at break>
A test piece was prepared by cutting each laminate into a piece having a width of 1 cm and a length of 10 cm. The test piece was set in a tensile testing machine (equipment name: "RTM-500", manufactured by Orientec Co., Ltd.) with a distance between chucks of 50 mm, and the test piece was pulled at a tensile speed of 20 mm/min to obtain a stress-strain curve. . The stress at which the test piece broke was defined as breaking strength (unit: MPa), and the amount of strain at break was evaluated as breaking elongation (unit: %). A sample having a breaking strength of 1.0 MPa or more and a breaking elongation of 100% or more were considered good. The results are shown in Table 2 (the same applies below).

<Adhesion>
A grid adhesion test was conducted in accordance with JIS K 5600-5-6.
Cellophane tape (trade name "LP-24", manufactured by Nichiban Co., Ltd.) was pressed from above with a finger to make it adhere to the cured layer side of the laminate, and then peeled off. Out of 100 squares, if the cured layer has not peeled off in all squares, it is 100/100, if it has peeled off in all squares, it is 0/100, and count the squares where the hardened layer has not peeled off. Ta.

*1: Content of (C) and photopolymerization initiator: Shown in parts based on 100 parts by weight of components (A), (B1), and (B2) in total.

The abbreviations shown in Table 2 mean the following compounds.
<Urethane (meth)acrylate>
・A-1, A-2, A-3: Urethane mono(meth)acrylate of Production Examples 1 to 3 ・E-1: Urethane without (meth)acryloyl group of Comparative Production Example 1 ・E-2: Urethane di(meth)acrylate <cyclic (meth)acrylate> of Comparative Production Example 2
・MEDOL-10: (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate (trade name: "MEDOL-10", manufactured by Osaka Organic Chemical Industry Co., Ltd.)
・OXE-10: (3-ethyloxetan-3-yl) methyl methacrylate (trade name: "OXE-10", manufactured by Osaka Organic Chemical Industry Co., Ltd.)
<Mono(meth)acrylate>
・IBOA: Isobornyl acrylate, product name: "Light acrylate IB-XA", manufactured by Kyoeisha Chemical Co., Ltd. (Tg = 94°C)
・FA-513AS: dicyclopentanyl acrylate, product name: "Fancryl FA-513AS", manufactured by Hitachi Chemical Co., Ltd. (Tg = 120°C)
・IBOMA: Isobornyl methacrylate, product name: "Light Ester IB-X", manufactured by Kyoeisha Chemical Co., Ltd. (Tg = 180°C)
・CHA: Cyclohexyl acrylate, Product type: “Viscoat #155”, manufactured by Osaka Organic Chemical Industry Co., Ltd. (Tg = 15°C)
・2EHA: 2-ethylhexyl acrylate, manufactured by Mitsubishi Chemical Corporation (Tg = -70°C)
<Poly(meth)acrylate>
・V#310HP: Tripropylene glycol diacrylate, trade name: "Viscoat #310P", manufactured by Osaka Organic Chemical Industry Co., Ltd. ・DPGDA: Dipropylene glycol diacrylate ・M305: Mixture of pentaerythritol triacrylate/pentaerythritol tetraacrylate , Product name: "Aronix M-305" (weight ratio of pentaerythritol triacrylate content: 55-63%), manufactured by Toagosei Co., Ltd. <thiol>
・PE1: Pentaerythritol tetrakis (3-mercaptobutyrate), product name: "Karens MT PE1", manufactured by Showa Denko K.K.

Claims (8)

Polyurethane mono(meth)acrylate (A) containing diisocyanate (a1), diol (a2), and hydroxyl group-containing mono(meth)acrylate (a3) as reaction components, cyclic (meth)acrylate having an oxygen atom in the ring (B1) ), mono(meth)acrylates (B2) whose glass transition temperature is 50°C or higher when made into a homopolymer (excluding those belonging to component (B1)), and acyclic di(meth)acrylates (C). including,
The ratio of the content of component (A) to the total content of components (B1) and (B2) is (A)/[(B1)+(B2)]=5/95 to It is 80/20,
An active energy ray-curable coating agent composition in which the content of component (C) is less than 10 parts by weight based on a total of 100 parts by weight of components (A), (B1), and (B2). The active energy ray-curable coating composition according to claim 1, wherein component (a2) is polyester diol and/or polycaprolactone diol. Component (B1) is (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate, cyclic trimethylolpropane formal acrylate, (3-ethyloxetan-3-yl) methyl acrylate and The active energy ray-curable coating composition according to claim 1 or 2, which is at least one selected from the group consisting of -ethyloxetan-3-yl)methyl methacrylate. The active energy ray-curable coating composition according to any one of claims 1 to 3, wherein component (B2) is an alicyclic mono(meth)acrylate. The active energy ray according to any one of claims 1 to 4, wherein the content ratio of the component (B1) and the component (B2) is (B1)/(B2) = 1/5 to 5/1 in terms of solid weight. Curable coating composition. The active energy ray-curable coating composition according to any one of claims 1 to 5, further comprising a thiol (D). A cured product of the active energy ray-curable coating composition according to any one of claims 1 to 6. A laminate comprising the cured product according to claim 7 on at least one side of a base material.