Active energy ray-curable composition, cured product, laminate, article, and method for producing laminate

Abstract

The invention relates to an active energy ray-curable composition, a cured product, a laminate, an article, and a method for producing the laminate. Provided is an active energy ray-curable composition capable of forming a cured product having excellent adhesion to a substrate and high hardness. An active energy ray-curable composition containing a monofunctional monomer (A), a bifunctional (meth) acrylate compound (B), and a trifunctional or higher polyfunctional monomer (C), the monofunctional monomer (A) having a hydroxyl group or an amide bond, the bifunctional (meth) acrylate compound (B) having a molecular weight of 230 or less, the content of the monofunctional monomer (A) being 1-20 mass%, and the content of the trifunctional or higher polyfunctional monomer (C) being 1-20 mass%. The content of the bifunctional (meth) acrylate compound (B) is 40-98% by mass, and the content of the polyfunctional monomer (C) is 1-40% by mass.

Description

Technical Field

[0001] The present invention relates to an active energy ray-curable composition, a cured product, a laminate, an article, and a method for producing a laminate. Background Art

[0002] Plastic films made of PMMA, TAC, PET, COP, etc. are used in polarizing plates mounted on optical displays. Generally, in order to suppress scratches on the surface of the polarizing plate formed of a plastic film, a hard coating layer formed of an active energy ray-curable composition is provided on the surface of the polarizing plate to form a laminate.

[0003] Among the above, acrylic films such as PMMA are useful because of their high transparency and low moisture permeability and hygroscopicity, but they have a problem of low adhesion to a coating layer formed of an active energy ray-curable composition.

[0004] In view of the above-mentioned problems, as a method for improving the adhesion between the plastic film and the hard coating layer, a method for hydrophilizing the surface of the plastic film by performing pretreatment such as primer treatment and corona treatment has been proposed. According to this method, the adhesion between the plastic film and the hard coating layer can be improved, but there are problems such as an increase in the number of steps, a decrease in the yield rate, and an increase in cost due to the coating and drying of the primer layer. Therefore, an active energy ray-curable composition that can be closely attached to the plastic film without pretreatment is sought.

[0005] For example, Patent Document 1 discloses a resin composition for forming a hard coat layer, which comprises a multifunctional urethane (meth)acrylate resin and a specific monofunctional (meth)acrylate monomer having at least a hydroxyl group or an aromatic group. In the resin composition for forming a hard coat layer, the plastic film and the hard coat layer are made to adhere to each other by drying the composition at a high temperature (at 100° C. for 90 seconds).

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Publication No. 2015-152763 Summary of the invention

[0009] Problem that the invention aims to solve

[0010] However, the conventional active energy ray-curable composition described in Patent Document 1 needs to be dried at a relatively high temperature when forming a hard layer, which causes pipeline contamination due to volatilization of the monofunctional monomer and poor appearance of the coating film.

[0011] The present invention has been made in view of such circumstances, and its object is to provide: an active energy ray-curable composition that can form a cured product having excellent adhesion to a substrate and high hardness without subjecting the substrate to pretreatment such as primer treatment and corona treatment, a cured product formed using the active energy ray-curable composition, a laminate having the cured product, an article having the laminate, and a method for producing the laminate.

[0012] Solutions for solving problems

[0013] The present inventors have conducted intensive studies to solve the above-mentioned problems and have found that by mixing a monofunctional monomer (A) having a hydroxyl group or an amide bond with a bifunctional (meth)acrylate compound (B) having a specific molecular weight and a trifunctional or higher polyfunctional monomer (C) in specific proportions, the adhesion to the substrate and the hardness of the cured product can be improved, thereby completing the present invention.

[0014] That is, the present invention has the following aspects.

[0015] [1] An active energy ray-curable composition comprising:

[0016] A monofunctional monomer (A), a bifunctional (meth)acrylate compound (B) and a trifunctional or higher polyfunctional monomer (C),

[0017] The monofunctional monomer (A) has a hydroxyl group or an amide bond,

[0018] The molecular weight of the bifunctional (meth)acrylate compound (B) is 230 or less,

[0019] The content of the monofunctional monomer (A) is 1 to 20% by mass based on 100% by mass of the total of the monofunctional monomer (A), the bifunctional (meth)acrylate compound (B) and the polyfunctional monomer (C).

[0020] The content of the bifunctional (meth)acrylate compound (B) is 40 to 98% by mass relative to 100% by mass of the total of the monofunctional monomer (A), the bifunctional (meth)acrylate compound (B) and the polyfunctional monomer (C).

[0021] The content of the polyfunctional monomer (C) is 1 to 40% by mass based on 100% by mass of the total of the monofunctional monomer (A), the bifunctional (meth)acrylate compound (B) and the polyfunctional monomer (C).

[0022] [2] The active energy ray-curable composition according to [1], wherein the monofunctional monomer (A) is a monofunctional (meth)acrylate compound having a hydroxyl group or an amide bond.

[0023] [3] The active energy ray-curable composition according to [1] or [2], wherein the trifunctional or higher polyfunctional monomer (C) is a trifunctional or higher polyfunctional (meth)acrylate compound.

[0024] [4] The active energy ray-curable composition according to any one of [1] to [3], further comprising a photopolymerization initiator (D).

[0025] [5] A cured product, which is a cured product of the active energy ray-curable composition according to any one of [1] to [4].

[0026] [6] A laminate having the cured product described in [5] on one or both sides of a substrate.

[0027] [7] The laminate according to [6], wherein the substrate is an acrylic substrate.

[0028] [8] The laminate according to [6], wherein the substrate is a polymethyl methacrylate substrate having a Tg of 100° C. or higher, and the substrate is in direct contact with the cured product.

[0029] [9] An article comprising the laminate according to any one of [6] to [8].

[0030]

[10] A method for producing a laminate, comprising the following steps: a coating step of coating an active energy ray-curable composition on one or both surfaces of a substrate to form a coating film; a drying step of drying the coating film at a temperature of 90° C. or less; and a curing step of irradiating the dried coating film with active energy rays to form a cured product, thereby producing a laminate having a substrate and a cured product.

[0031] The active energy ray-curable composition comprises: a monofunctional monomer (A), a bifunctional (meth)acrylate compound (B), a trifunctional or higher-functional polyfunctional monomer (C), and an organic solvent (E).

[0032] The monofunctional monomer (A) has a hydroxyl group or an amide bond,

[0033] The molecular weight of the bifunctional (meth)acrylate compound (B) is 230 or less,

[0034] The content of the monofunctional monomer (A) is 1 to 20% by mass based on 100% by mass of the total of the monofunctional monomer (A), the bifunctional (meth)acrylate compound (B) and the polyfunctional monomer (C).

[0035] The content of the bifunctional (meth)acrylate compound (B) is 40 to 98% by mass relative to 100% by mass of the total of the monofunctional monomer (A), the bifunctional (meth)acrylate compound (B) and the polyfunctional monomer (C).

[0036] The content of the polyfunctional monomer (C) is 1 to 40% by mass based on 100% by mass of the total of the monofunctional monomer (A), the bifunctional (meth)acrylate compound (B) and the polyfunctional monomer (C).

[0037] Effects of the Invention

[0038] According to the present invention, there can be provided: an active energy ray-curable composition that can form a cured product having excellent adhesion to a substrate and high hardness without subjecting the substrate to pretreatment such as primer treatment and corona treatment, a cured product formed using the active energy ray-curable composition, a laminate having the cured product, an article having the laminate, and a method for producing the laminate. DETAILED DESCRIPTION

[0039] (Active energy ray-curable composition)

[0040] The active energy ray-curable composition of the present embodiment contains: a monofunctional monomer (A) having a hydroxyl group or an amide bond (hereinafter also referred to as "component (A)"); a bifunctional (meth)acrylate compound (B) (hereinafter also referred to as "component (B)"); and a trifunctional or higher-functional polyfunctional monomer (C) (hereinafter also referred to as "component (C)").

[0041] In the present specification, "(meth)acrylate" means one or both of acrylate and methacrylate, and "(meth)acryloyl" means one or both of acryloyl and methacryloyl.

[0042] <Component (A): Monofunctional monomer (A) having a hydroxyl group or an amide bond>

[0043] Specific examples of the component (A) include a monofunctional (meth)acrylate compound having a hydroxyl group or an amide bond, and a monofunctional vinyl compound having a hydroxyl group or an amide bond.

[0044] The molecular weight of the component (A) is preferably 200 or less, more preferably 180 or less, and even more preferably 160 or less.

[0045] When the molecular weight of the component (A) is at most the above preferred upper limit value, the adhesion between a cured product formed from the active energy ray-curable composition containing the component (A) and a substrate will be further improved.

[0046] The lower limit of the molecular weight of the component (A) is not particularly limited, but is, for example, preferably 80 or more, more preferably 90 or more, and even more preferably 95 or more.

[0047] For example, the molecular weight of the component (A) is preferably 80 or more and 200 or less, more preferably 90 or more and 180 or less, and further preferably 95 or more and 160 or less.

[0048] As (A) component, among the above, a monofunctional (meth)acrylate compound having a hydroxyl group or an amide bond is preferred.

[0049] Examples of the (meth)acrylate compound having a hydroxyl group or an amide bond include a (meth)acrylate compound (A1) having a hydroxyl group (hereinafter also referred to as “component (A1)”), a (meth)acrylate compound (A2) having an amide bond (hereinafter also referred to as “component (A2)”), and a (meth)acrylate compound (A3) having a hydroxyl group and an amide bond (hereinafter also referred to as “component (A3)”).

[0050] <<Component (A1): (meth)acrylate compound (A1) having a hydroxyl group>>

[0051] The component (A1) is a (meth)acrylate compound having at least one hydroxyl group. The number of hydroxyl groups in the component (A1) is not particularly limited, but is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1.

[0052] The (meth)acrylate compound in the component (A1) may have a substituent other than a hydroxyl group.

[0053] Component (A1) specifically includes hydroxyalkyl (meth)acrylates. The alkylene group of the hydroxyalkyl (meth)acrylate preferably has 1 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms.

[0054] The (meth)acrylate hydroxyalkyl ester may also be a (poly)oxyalkylene modified body having a (poly)oxyethylene chain, (poly)oxypropylene chain, (poly)oxytetramethylene chain or the like introduced into the molecular structure; a (poly)lactone modified body having a (poly)lactone structure introduced into the molecular structure, etc.

[0055] More specifically, as the component (A1), there may be mentioned hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and the like.

[0056] Among them, as the component (A1), 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate are preferred, and 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, and 2-hydroxybutyl methacrylate are more preferred.

[0057] The component (A1) may be used alone or in combination of two or more.

[0058] <<Component (A2): (meth)acrylate compound (A2) having an amide bond>>

[0059] The component (A2) is a (meth)acrylate compound having at least one amide bond. The number of amide bonds in the component (A2) is not particularly limited, but is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1.

[0060] (A2) Component may be any of (meth)acrylamide, N-1-substituted (meth)acrylamide compound, and N,N-2-substituted (meth)acrylamide compound.

[0061] Component (A2) specifically includes (meth)acrylamide; N-1-substituted (meth)acrylamide compounds such as N-isopropyl (meth)acrylamide, N-(1,1-dimethyl-3-oxobutyl)acrylamide, N-hydroxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, N-(2-hydroxymethyl)acrylamide, and N-(2-hydroxyethyl)acrylamide; N-(meth)acrylamide; N-2 substituted (meth)acrylamide compounds such as methylmorpholine, N-(meth)acryloylpiperidone, N-(meth)acryloylpiperidine, N-(meth)acryloylpyrrolidine, N-(meth)acryloyl-4-piperidone, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-diisopropyl(meth)acrylamide, N,N-methylenebis(meth)acrylamide, and N,N-dimethylaminopropyl(meth)acrylamide.

[0062] Among the above, the component (A2) is preferably a compound represented by the following general formula (A2-a) or (A2-b).

[0063]

[0064] [where Ra 1 is a hydrogen atom or a methyl group, Ra 2 and Ra 3 Each independently is a hydrogen atom or an alkyl group, wherein the alkyl group includes -CH 2 -In the case of -CH 2 - is optionally replaced by -CO- or -O-.]

[0065] Ra in the above general formula (A2-a) 1 It is a hydrogen atom or a methyl group, and is preferably a hydrogen atom.

[0066] As Ra in the above general formula (A2-a) 2 and Ra 3 The alkyl group in is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, further preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.

[0067] Specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group are preferable, and a methyl group and an ethyl group are more preferable.

[0068]

[0069] [Wherein, Rb 1 is a hydrogen atom or a methyl group, Rb 2 ~Rb 4 Each independently is a hydrogen atom or an alkyl group, wherein the alkyl group includes -CH 2 -In the case of -CH 2 - part may be substituted with -CO- or -O-. 1 is an alkylene group.]

[0070] Rb in the above general formula (A2-b) 1 It is a hydrogen atom or a methyl group, and is preferably a hydrogen atom.

[0071] As Rb in the above general formula (A2-b) 2 ~Rb 4 The alkyl group in is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, further preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.

[0072] Specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group are preferred, a methyl group and an ethyl group are more preferred, and a methyl group is further preferred.

[0073] As Lb in the above general formula (A2-b) 1 The alkylene group in the group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and still more preferably an alkylene group having 1 to 4 carbon atoms.

[0074] Examples of the linear alkylene group having 1 to 4 carbon atoms include methylene, ethylene [-(CH 2 ) 2 -], trimethylene [-(CH 2 ) 3 -], and tetramethylene [-(CH 2 ) 4 -].

[0075] Examples of the branched alkylene group having 2 to 4 carbon atoms include -CH(CH 3 )-、-CH(CH 2 CH 3 )-、-C(CH 3 ) 2 -、-C(CH 3 )(CH 2 CH 3 )-alkylmethylene; -CH 2 CH(CH 3 )-、-CH(CH 3 )CH 2 -、-CH(CH 3 )CH(CH 3 )-、-C(CH 3 ) 2 CH 2 -、-CH(CH 2 CH 3 )CH 2 -alkylethylene; -CH(CH 3 )CH 2 CH 2 -、-CH 2 CH(CH 3 )CH 2 - etc. alkyl trimethylene etc. alkyl alkylene etc.

[0076] As Lb in the above general formula (A2-b) 1 Among the above, a linear alkylene group having 1 to 4 carbon atoms is preferred, and a trimethylene group [-(CH 2 ) 3 -].

[0077] As the component (A2), among the above, N,N-dimethylacrylamide, N,N-diethylacrylamide, and N-[3-(dimethylamino)propyl]acrylamide are preferred.

[0078] (A2) The component may be used alone or in combination of two or more.

[0079] <<Component (A3): (meth)acrylate compound (A3) having a hydroxyl group and an amide bond>>

[0080] The component (A3) is a (meth)acrylate compound having at least one hydroxyl group and at least one amide bond. The number of hydroxyl groups in the component (A3) is not particularly limited, but is preferably 1 to 3, more preferably 1 or 2, and further preferably 1. The number of amide bonds in the component (A3) is not particularly limited, but is preferably 1 to 3, more preferably 1 or 2, and further preferably 1.

[0081] Component (A3) includes compounds in which at least one hydrogen atom of the alkyl group contained in component (A2) is substituted with a hydroxyl group, and specifically, N-(2-hydroxyethyl)acrylamide and the like are mentioned.

[0082] The component (A3) may be used alone or in combination of two or more.

[0083] As the component (A), among those mentioned above, it is preferred that the component (A1) or the component (A2) is contained.

[0084] (A) The component may be used alone or in combination of two or more.

[0085] The content of the component (A) is 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more, based on 100% by mass of the total of the components (A), (B) and (C).

[0086] The content of the component (A) is 20% by mass or less, preferably 18% by mass or less, more preferably 16% by mass or less, and further preferably 15% by mass or less, based on 100% by mass of the total of the components (A), (B) and (C).

[0087] The content of (A) component is more than 1% by mass relative to the total 100% by mass of (A) component, (B) component and (C) component, thereby improving the adhesion with the substrate. In addition, by making the content of (A) component more than the above-mentioned preferred lower limit, thereby further improving the adhesion with the substrate. The content of (A) component is less than 20% by mass relative to the total 100% by mass of (A) component, (B) component and (C) component, thereby improving the hardness of the cured product. In addition, by making the content of (A) component be below the above-mentioned preferred upper limit, thereby further improving the hardness of the cured product.

[0088] For example, the content of component (A) is preferably 2% by mass or more and 18% by mass or less, more preferably 3% by mass or more and 16% by mass or less, and further preferably 5% by mass or more and 15% by mass or less, relative to 100% by mass of the total of components (A), (B) and (C).

[0089] <Component (B): Bifunctional (meth)acrylate compound (B)>

[0090] (B) Component is a bifunctional (meth)acrylate compound having two (meth)acryloyl groups and a molecular weight of 230 or less.

[0091] The molecular weight of the component (B) is 230 or less, preferably 220 or less, more preferably 210 or less, and further preferably 200 or less.

[0092] When the molecular weight of the component (B) is at most 230, the adhesion to the substrate is improved. When the molecular weight of the component (B) is at most the preferred upper limit value described above, the adhesion to the substrate is further improved.

[0093] The lower limit of the molecular weight of the component (B) is not particularly limited, but is, for example, preferably 170 or more, more preferably 180 or more, and even more preferably 190 or more.

[0094] For example, the molecular weight of the component (B) is preferably 170 or more and 220 or less, more preferably 180 or more and 210 or less, and further preferably 190 or more and 200 or less.

[0095] Specific examples of the component (B) include 1,4-butanediol di(meth)acrylate, ethylene glycol dimethacrylate, glycerol diacrylate, and 1,6-hexanediol diacrylate.

[0096] As the component (B), among the above, from the viewpoint of improving the adhesion to the substrate, a bifunctional methacrylate compound is preferred, and specifically, ethylene glycol dimethacrylate and 1,4-butanediol dimethacrylate are preferred.

[0097] (B) The component may be used alone or in combination of two or more.

[0098] The content of the component (B) is 40% by mass or more, preferably 47% by mass or more, more preferably 50% by mass or more, and further preferably 53% by mass or more, based on 100% by mass of the total of the components (A), (B) and (C).

[0099] The content of the component (B) is 98% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, and further preferably 60% by mass or less, based on 100% by mass of the total of the components (A), (B) and (C).

[0100] The content of the component (B) is 40% by mass or more relative to the total 100% by mass of the component (A), the component (B) and the component (C), thereby improving the adhesion to the substrate. In addition, by making the content of the component (B) be above the above-mentioned preferred lower limit, thereby further improving the adhesion to the substrate.

[0101] The hardness of the cured product is improved by making the content of the component (B) less than 98% by mass relative to the total 100% by mass of the components (A), (B) and (C). In addition, the hardness of the cured product is further improved by making the content of the component (B) less than the above-mentioned preferred upper limit.

[0102] For example, the content of the component (B) is preferably 47% by mass or more and 80% by mass or less, more preferably 50% by mass or more and 70% by mass or less, and further preferably 53% by mass or more and 60% by mass or less, relative to 100% by mass of the total of the components (A), (B) and (C).

[0103] <Component (C): trifunctional or higher polyfunctional monomer (C)>

[0104] (C) As a component, a trifunctional or higher-functional polyfunctional (meth)acrylate compound is mentioned.

[0105] Specific examples of the trifunctional or higher polyfunctional (meth)acrylate compound include trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, di(trimethylolpropane) tri(meth)acrylate, di(trimethylolpropane) tetra(meth)acrylate, tri(2-(meth)acryloyloxyethyl)isocyanurate, glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, and polypentaerythritol poly(meth)acrylate.

[0106] (C) The component may be used alone or in combination of two or more.

[0107] The content of the component (C) is 1% by mass or more, preferably 10% by mass or more, more preferably 28% by mass or more, and further preferably 30% by mass or more, based on 100% by mass of the total of the components (A), (B) and (C).

[0108] The content of the component (C) is 40% by mass or less, preferably 39% by mass or less, based on 100% by mass of the total of the components (A), (B), and (C).

[0109] The hardness of the cured product is improved by making the content of the component (C) 1% by mass or more relative to the total 100% by mass of the components (A), (B) and (C). In addition, the hardness of the cured product is further improved by making the content of the component (C) above the above-mentioned preferred lower limit.

[0110] The content of the component (C) is 40% by mass or less relative to the total 100% by mass of the component (A), the component (B) and the component (C), thereby improving the adhesion to the substrate. In addition, by making the content of the component (C) below the above-mentioned preferred upper limit, thereby further improving the adhesion to the substrate.

[0111] For example, the content of the component (C) is preferably 10% by mass or more and 40% by mass or less, more preferably 28% by mass or more and 40% by mass or less, and further preferably 30% by mass or more and 39% by mass or less, relative to 100% by mass of the total of the components (A), (B) and (C).

[0112] <Optional ingredients>

[0113] The active energy ray-curable composition of the present embodiment may contain any component other than the above-mentioned (A) to (C) components.

[0114] As optional components, there can be mentioned additives such as a photopolymerization initiator (D) (hereinafter also referred to as "component (D)"), an organic solvent (E) (hereinafter also referred to as "component (E)"), a photosensitizer, an inhibitor, a defoaming agent, a leveling agent and the like surface conditioning agents, a viscosity modifier, a light stabilizer, a weather stabilizer, a heat stabilizer, an ultraviolet absorber, an antioxidant, an organic pigment, an inorganic pigment, a pigment dispersant, and organic beads; and inorganic fillers such as alumina, titanium oxide, zirconium oxide, and antimony pentoxide.

[0115] Each optional component may be used alone or in combination of two or more.

[0116] 《Component (D): Photopolymerization initiator (D)》

[0117] The active energy ray-curable composition of the present embodiment preferably contains the component (D).

[0118] As the component (D), various known substances can be used, and for example, an α-cleavage type or hydrogen abstraction type photopolymerization initiator can be used.

[0119] Examples of the α-cleavage type photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethane-1-one, diphenyl(2,4,6-trimethoxybenzoyl)phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone.

[0120] Examples of the hydrogen abstraction type photopolymerization initiator include benzophenone, o-benzoylbenzoyl methyl-4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, 4-methyldiphenyl sulfide, and the like. Benzophenone compounds such as ketone; thioxanthone compounds such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone; xanthone compounds such as xanthone, 2-isopropylxanthone, 2,4-dimethylxanthone, 2,4-diethylxanthone, 2,4-dichloroxanthone; polymers having a benzophenone skeleton such as polybutylene glycol bis(4-benzoylphenoxy)acetate, etc.

[0121] Examples of commercially available products of the component (D) include "Omnirad-1173", "Omnirad-184", "Omnirad-127", "Omnirad-2959", "Omnirad-369", "Omnirad-379", "Omnirad-907", "Omnirad-4265", "Omnirad-1000", "Omnirad-651", "Omnirad-TPO", "Omnirad-819", and "Omnirad-20 22", "Omnirad-2100", "Omnirad-754", "Omnirad-784", "Omnirad-500", "Omnirad-81" (manufactured by IGM), "KAYACURE-DETX", "KAYACURE-MBP", "KAYACURE-DMBI", "KAYACURE-EPA", "KAYACURE-OA" (manufactured by Nippon Kayaku Co., Ltd.), "VICURE-10", "VICURE-55" (manufactured by Stouffer Chemical), "Trigonal P1" (manufactured by Akzo), "Sandoray 1000" (manufactured by Sandoz), "DEAP" (manufactured by Upjohn), "Quantacure-PDO", "Quantacure-ITX", "Quantacure-EPD" (manufactured by Ward Blenkinsop), "Runtecure-1104", "Runtecure-1108" (manufactured by Runtec), etc.

[0122] (D) The component may be used alone or in combination of two or more.

[0123] The content of the component (D) is preferably 1 part by mass or more and 15 parts by mass or less, more preferably 2 parts by mass or more and 10 parts by mass or less, and even more preferably 4 parts by mass or more and 8 parts by mass or less, based on 100 parts by mass of the total of the components (A), (B) and (C).

[0124] 《Ingredient (E): Organic solvent (E)》

[0125] The component (E) is useful for appropriately adjusting the solution viscosity of the active energy ray-curable composition of the present embodiment. In particular, by including the component (E), it becomes easy to adjust the film thickness during thin film coating.

[0126] As the (E) component, for example, there can be mentioned aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, isopropanol, tert-butanol; esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and glycol ethers such as propylene glycol monomethyl ether.

[0127] (E) The component may be used alone or in combination of two or more.

[0128] The content of the component (E) is suitably used so that the solid content concentration of the active energy ray-curable composition of the present embodiment becomes 30 to 70%, for example.

[0129] The active energy ray-curable composition of the present embodiment described above has a monofunctional monomer (A) having a hydroxyl group or an amide bond and capable of improving adhesion to a substrate, and a trifunctional or higher polyfunctional monomer (C) having a large number of crosslinking sites and capable of improving the hardness of a cured product, and also has a bifunctional (meth)acrylate compound (B) having a moderately low molecular weight, improving adhesion to a substrate, having a crosslinking site, and capable of improving the hardness of a cured product. Furthermore, the active energy ray-curable composition of the present embodiment appropriately controls the contents of the three.

[0130] Therefore, according to the active energy ray-curable composition of the present embodiment, a cured product having excellent adhesion to a substrate and high hardness can be formed without subjecting the substrate to pretreatment such as primer treatment or corona treatment.

[0131] (cured material)

[0132] The cured product of the present embodiment is formed from the active energy ray-curable composition of the above-mentioned embodiment.

[0133] The cured product of the present embodiment can be produced by irradiating the active energy ray-curable composition of the above-mentioned embodiment with active energy rays.

[0134] Since the cured product of the present embodiment uses the active energy ray-curable composition of the above-described embodiment, it has excellent adhesion to a substrate and has high hardness.

[0135] (Laminated body)

[0136] The laminated body of the present embodiment has a cured product (cured film) formed from the active energy ray-curable composition of the above-mentioned embodiment on one side or both sides of a substrate.

[0137] The substrate may be in the form of a film or a sheet, and its thickness is not particularly limited. For example, the thickness of the substrate is preferably 10 μm to 5 mm, and more preferably 10 to 60 μm.

[0138] As the material of the substrate, a resin with high transparency is preferred, for example, acrylic resins such as polymethyl methacrylate are preferred; cyclic olefin resins; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyolefin resins such as polypropylene, polyethylene, and polymethyl-1-pentene; cellulose resins such as cellulose acetate (diacetate, triacetate, etc.), cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate, cellulose acetate phthalate, and cellulose nitrate; vinyl chloride resins such as polyvinyl chloride and polyvinylidene chloride; polyvinyl alcohol; ethylene-vinyl acetate copolymer; polystyrene; polyamide; polycarbonate; polysulfone; polyethersulfone; polyetheretherketone; polyimide, polyetherimide, and polyimide polyimide resins; norbornene resins (for example, "Zeonor" manufactured by ZEON CORPORATION), modified norbornene resins (for example, "Arton" manufactured by JSR Corporation), etc.

[0139] Furthermore, a substrate formed of two or more of these resins bonded together may be used.

[0140] Since the cured product of the above-described embodiment has high adhesion to the substrate, it is possible to produce a laminated body with a substrate that has been considered difficult to adhere to a hard coat layer in the past.

[0141] Therefore, as the substrate of the laminated body of the present embodiment, an acrylic substrate is preferred, and a polymethyl methacrylate substrate having a Tg of 100° C. or higher is more preferred.

[0142] The cured product of the above-described embodiment can obtain good adhesion to a substrate even without performing pretreatment on the substrate.

[0143] Therefore, the laminate of the present embodiment preferably has the substrate in direct contact with the aforementioned cured product. That is, it is preferred that the substrate is not pre-treated in advance. As the pre-treatment, it can be cited: surface roughening treatment based on sandblasting, solvent treatment, etc., electrical treatment (corona discharge treatment, atmospheric pressure plasma treatment), chromic acid treatment, flame treatment, hot air treatment, ozone, ultraviolet, electron beam irradiation treatment, oxidation treatment and the like.

[0144] In addition, for the purpose of further improving the adhesiveness, the substrate may be pre-treated in advance.

[0145] The laminate of this embodiment may further include an inorganic layer. When the laminate includes an inorganic layer, the substrate, the cured product, and the inorganic layer are stacked in this order.

[0146] The inorganic layer refers to a layer formed of an inorganic compound, and generally has functions such as antireflection and scratch resistance.

[0147] Examples of the inorganic compound include metal oxides, composite oxides, metal nitrides, metal fluorides, composite fluorides, silicon oxides, silicon nitrides, and mixtures thereof.

[0148] Examples of the metal include lithium, sodium, magnesium, aluminum, titanium, yttrium, indium, tin, zirconium, niobium, cerium, hafnium, and tantalum.

[0149] When the aforementioned inorganic layer is used as the anti-reflection film layer, the aforementioned anti-reflection film layer can be a single layer, but can also have a low refractive index layer and a high refractive index layer. In addition, the low refractive index layer and the high refractive index layer can each be 1 layer, or can be multilayer. It should be noted that the lamination sequence of the low refractive index layer and the high refractive index layer is not particularly limited either.

[0150] Examples of the inorganic compound used in the high refractive index layer include lanthanum titanate, zirconium oxide, titanium oxide, tantalum oxide, niobium oxide, hafnium oxide, cerium oxide, yttrium oxide, and mixtures thereof.

[0151] Examples of the inorganic compound used in the low refractive index layer include silicon oxide, silicon nitride, magnesium fluoride, aluminum fluoride, and mixtures thereof.

[0152] The inorganic layer is obtained by forming a film on the surface of the cured product. The method for forming the inorganic layer is not particularly limited, and a known film forming method can be used as appropriate, but it is preferably formed by physical vapor deposition (PVD) or chemical vapor deposition (CVD).

[0153] As for the film forming method, it is more preferable to use the physical vapor deposition (PVD) described above from the viewpoint of consistency and simplification of the film forming process, and examples thereof include vacuum vapor deposition, ion plating, sputtering and the like.

[0154] As the vacuum deposition, for example, a resistance heating method, a high-frequency induction heating method, an electron beam heating method, or the like can be used.

[0155] The sputtering may be DC sputtering, RF sputtering, magnetron sputtering, or ion beam sputtering. In addition, it may be a parallel flat target method or an opposed target method. In addition, as the gas introduced into the vacuum chamber, for example, argon, krypton, oxygen, nitrogen, etc. can be cited, and they can be used alone or in combination of two or more.

[0156] The film thickness of the inorganic layer can be appropriately adjusted according to the target function. When the anti-reflection function is the target, the range of 10nm to 5000nm is preferred. From the perspective of the film strength and productivity of the inorganic layer, the range of 100nm to 2000nm is more preferred, and the range of 250nm to 1000nm is particularly preferred.

[0157] (Method for producing laminated body)

[0158] In the method for producing a laminate of the present embodiment, a cured product can be brought into close contact with a substrate without depending on the temperature during drying, and therefore, the method is particularly useful for a production method using an organic solvent (E).

[0159] The method for manufacturing a laminate of the present embodiment using an organic solvent (E) comprises the following steps: a coating step of coating the active energy ray-curable composition of the above-mentioned embodiment on one side or both sides of a substrate to form a coating film; a drying step of drying the aforementioned coating film at a temperature below 90° C.; and a curing step of irradiating the dried aforementioned coating film with active energy rays to form a cured product, thereby manufacturing a laminate having a substrate and a cured product.

[0160] [Coating process]

[0161] The coating step is a step of coating the active energy ray-curable composition of the above-described embodiment on one or both surfaces of a substrate to form a coating film.

[0162] Examples of a method for coating the active energy ray-curable composition containing an organic solvent (E) include die coating, microgravure coating, gravure coating, roll coating, comma coating, air knife coating, kiss coating, spray coating, dip coating, spin coating, brush coating, solid coating by screen printing, wire bar coating, flow coating, and the like.

[0163] [Drying process]

[0164] The drying step is a step of drying the coating film at a temperature of 90° C. or lower to evaporate the organic solvent (E).

[0165] In the method for producing a laminated body of the present embodiment, since the active energy ray-curable composition of the above-mentioned embodiment is used, the cured product can be brought into close contact with the substrate even without drying at a high temperature.

[0166] Therefore, the method for producing the laminate of the present embodiment has little concern about poor appearance and volatilization of monomers. In addition, changes in the physical properties of the cured product due to aggregation during drying can be suppressed.

[0167] The drying temperature is 90°C or lower, preferably 80°C or lower, and more preferably 70°C or lower.

[0168] The drying temperature is preferably 40° C. or higher, more preferably 45° C. or higher, and further preferably 50° C. or higher.

[0169] For example, the drying temperature is preferably 40°C to 90°C, more preferably 45°C to 80°C, and further preferably 50°C to 70°C.

[0170] The drying time is preferably 10 seconds to 5 minutes, more preferably 15 seconds to 1 minute, and further preferably 20 seconds to 40 seconds.

[0171] [Curing process]

[0172] The coating step is a step of irradiating the dried coating film with active energy rays to form a cured product, thereby producing a laminate having a substrate and a cured product (cured film).

[0173] The active energy rays are ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays.

[0174] When ultraviolet rays are used as active energy rays, devices for irradiating the ultraviolet rays include, for example, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, electrodeless lamps (melting lamps), chemical lamps, black light lamps, mercury-xenon lamps, short arc lamps, helium-cadmium lasers, argon lasers, sunlight, LED lamps, etc.

[0175] The film thickness of the cured product is preferably 1 to 30 μm, more preferably 2 to 15 μm, and even more preferably 3 to 10 μm, from the viewpoint of achieving sufficient hardness and suppressing curling due to curing shrinkage.

[0176] When no organic solvent (E) is used in the method for manufacturing a laminate of the present embodiment, the method for manufacturing a laminate of the present embodiment comprises the following steps: a coating step of coating the active energy ray-curable composition of the above-mentioned embodiment on one side or both sides of a substrate to form a coating film; and a curing step of irradiating the above-mentioned coating film with active energy rays to form a cured product, thereby manufacturing a laminate having a substrate and a cured product.

[0177] The details of the method for producing the laminate are as described above except that the drying step is not included.

[0178] (thing)

[0179] The article of the present embodiment is an article having the laminate of the above-described embodiment, and specific examples thereof include an optical display, an optical protective film, and a prism sheet.

[0180] Example

[0181] Next, the present invention will be described in further detail with reference to examples, but the present invention is not limited to the following examples.

[0182] [Manufacturing of Laminated Body]

[0183] (Examples 1 to 11, Comparative Examples 1 to 9)

[0184] The components shown in Tables 1 to 3 were mixed to prepare active energy ray-curable compositions of Examples 1 to 11 and Comparative Examples 1 to 9.

[0185] The active energy ray-curable composition of each example was applied to a PMMA substrate (Tg = 120°C) having a thickness of 40 μm using a bar coater. The substrate was then heated at 60°C for 30 seconds to dry the solvent. The substrate was then irradiated with an ultraviolet irradiation device (manufactured by EYE GRAPHICS, high pressure mercury lamp) at a light intensity of 150 mJ / cm 2 The irradiation was performed to form a cured product (cured film) having a film thickness of 5 μm on the PMMA substrate, thereby producing a laminated body.

[0186] (Example 12)

[0187] The components shown in Table 2 were mixed to prepare an active energy ray-curable composition of Example 12.

[0188] The active energy ray-curable composition of Example 12 was applied to a 40 μm thick PMMA substrate (Tg=120°C) using a bar coater. Then, in a nitrogen atmosphere, an ultraviolet irradiation device (manufactured by EYE GRAPHICS, high pressure mercury lamp) was used to irradiate the substrate at a light intensity of 150 mJ / cm 2 The irradiation was performed to form a cured product (cured film) having a film thickness of 5 μm on the PMMA substrate, thereby producing a laminate.

[0189] [Determination of coating haze]

[0190] The haze value of the cured product surface of the laminate produced using the active energy ray-curable composition of each example was measured in accordance with JIS K7136. The results are shown in Tables 1 to 3.

[0191] [Evaluation of Adhesion]

[0192] ·Fitness test based on Cellotape peeling

[0193] On the cured surface of the laminate manufactured using the active energy ray-curable composition of each example, 11 vertical and horizontal slits were introduced at intervals of 1 mm to make 100 grids. Next, the operation of making a cellophane tape ("Cellotape (registered trademark) CT-18" manufactured by NICHIBAN Co., Ltd.) adhere to its surface and then quickly peel it off at one go was repeated twice. The adhesion was evaluated based on the ratio of the residual area that was not peeled off and remained according to the following criteria. A rating of B or above was judged to be qualified. The results are shown in Tables 1 to 3 as "Adhesion".

[0194] A: The residual area ratio is 100%.

[0195] B: The residual area ratio is 95% or more and less than 100%.

[0196] C: The residual area ratio is 10% or more and less than 95%.

[0197] D: The residual area ratio is less than 10%.

[0198] [Evaluation of pencil hardness]

[0199] Pencil test

[0200] The surface of the cured product of the laminate produced using the active energy ray-curable composition of each example was measured for pencil hardness under a load of 500 g in accordance with JIS K5600-5-4 (1999). Five measurements were made for each hardness, and the hardness measured four or more times without damage was taken as the surface hardness of the cured product.

[0201] The pencil hardness is 2H, H, F, HB, and B in descending order of hardness. A value of H or higher is considered acceptable. The results are shown in Tables 1 to 3 as "pencil hardness".

[0202] [Table 1]

[0203]

[0204] [Table 2]

[0205]

[0206] [Table 3]

[0207]

[0208] The numerical values ​​of the components (A) to (C), the monofunctional monomer, and the bifunctional monomer in Tables 1 to 3 are the blending amounts (mass %) of the respective components relative to the total amount of the components.

[0209] The numerical values ​​of the components (D) and (E) are the blending amounts (parts by mass) relative to 100 parts by mass of the total amount of the components (A) to (C), the monofunctional monomer, and the bifunctional monomer.

[0210] The abbreviations in Tables 1 to 3 have the following meanings.

[0211] A-1: 4-Hydroxybutyl acrylate ("4-HBA" manufactured by Osaka Organic Chemical Industry Co., Ltd.)

[0212] A-2: 2-Hydroxyethyl methacrylate ("LIGHT ESTER HOA (N)" manufactured by Kyoeisha Chemical Co., Ltd.)

[0213] A-3: 2-Hydroxybutyl methacrylate ("LIGHT ESTER HOB (N)" manufactured by Kyoeisha Chemical Co., Ltd.)

[0214] A-4: N,N-dimethylacrylamide ("DMAA" manufactured by KJ Chemical Co., Ltd.)

[0215] A-5: N,N-diethylacrylamide ("DEAA" manufactured by KJ Chemical Co., Ltd.)

[0216] A-6: N-[3-(Dimethylamino)propyl]acrylamide ("DMAPAA" manufactured by KJ Chemical Co., Ltd.)

[0217] a-1: Isobornyl acrylate ("IBXA" manufactured by Osaka Organic Chemical Industry Co., Ltd.)

[0218] a-2: Phenoxyethyl acrylate ("LIGHT ACRYLATE PO-A" manufactured by Kyoeisha Chemical Co., Ltd.)

[0219] a-3: benzyl acrylate ("MIRAMER M1182" manufactured by MIWON)

[0220] B-1: Ethylene glycol dimethacrylate ("MIRAMER M221" manufactured by MIWON)

[0221] B-2: 1,4-Butanediol dimethacrylate ("LIGHT ESTER 1,4BG" manufactured by Kyoeisha Chemical Co., Ltd.)

[0222] b-1: 1,6-Hexanediol dimethacrylate ("LIGHT ESTER 1,6HX" manufactured by Kyoeisha Chemical Co., Ltd.)

[0223] b-2: 1,6-Hexanediol diacrylate ("MIRAMER M200" manufactured by MIWON)

[0224] C-1: Pentaerythritol tetraacrylate ("ARONIX M-450" manufactured by Toagosei Co., Ltd.)

[0225] D-1: 1-benzoylcyclohexanol ("Runtecure 1104" manufactured by IGM)

[0226] E-1: Methyl Ethyl Ketone

[0227] E-2: Propylene glycol monomethyl ether

[0228] As shown in Tables 1 to 3, it was confirmed that the cured products formed using the active energy ray-curable compositions of Examples had higher adhesion to the substrate and higher hardness than the cured products formed using the active energy ray-curable compositions of Comparative Examples.

[0229] The cured products formed using the active energy ray-curable compositions of Examples also had low coating haze values ​​and good transparency.

Claims

1. An active energy ray-curable composition comprising: A monofunctional monomer (A), a bifunctional (meth)acrylate compound (B) and a trifunctional or higher polyfunctional monomer (C), The monofunctional monomer (A) has a hydroxyl group or an amide bond, The molecular weight of the bifunctional (meth)acrylate compound (B) is 230 or less, The content of the monofunctional monomer (A) is 1 to 20% by mass based on 100% by mass of the total of the monofunctional monomer (A), the bifunctional (meth)acrylate compound (B) and the polyfunctional monomer (C). The content of the bifunctional (meth)acrylate compound (B) is 40 to 98% by mass based on 100% by mass of the total of the monofunctional monomer (A), the bifunctional (meth)acrylate compound (B) and the polyfunctional monomer (C). The content of the polyfunctional monomer (C) is 1 to 40% by mass based on 100% by mass of the total of the monofunctional monomer (A), the bifunctional (meth)acrylate compound (B), and the polyfunctional monomer (C).

2. The active energy ray-curable composition according to claim 1, wherein The monofunctional monomer (A) is a monofunctional (meth)acrylate compound having a hydroxyl group or an amide bond.

3. The active energy ray-curable composition according to claim 1 or 2, wherein The trifunctional or higher polyfunctional monomer (C) is a trifunctional or higher polyfunctional (meth)acrylate compound. 4 . The active energy ray-curable composition according to claim 1 , further comprising a photopolymerization initiator (D). 5 . A cured product, which is a cured product of the active energy ray-curable composition according to claim 1 or 2 . 6 . A laminate comprising the cured product according to claim 5 on one or both sides of a substrate.

7. The laminate according to claim 6, wherein: The substrate is an acrylic substrate.

8. The laminate according to claim 6, wherein: The substrate is a polymethyl methacrylate substrate having a Tg of 100° C. or higher, and the substrate is in direct contact with the cured product. 9 . An article comprising the laminate according to claim 6 .

10. A method for producing a laminate, comprising the following steps: a coating step of coating an active energy ray-curable composition on one side or both sides of a substrate to form a coating film; a drying step of drying the coating film at a temperature of 90° C. or less; and a curing step of irradiating the dried coating film with active energy rays to form a cured product, thereby producing a laminate having a substrate and a cured product. The active energy ray-curable composition comprises: a monofunctional monomer (A), a bifunctional (meth)acrylate compound (B), a trifunctional or higher-functional polyfunctional monomer (C), and an organic solvent (E). The monofunctional monomer (A) has a hydroxyl group or an amide bond, The molecular weight of the bifunctional (meth)acrylate compound (B) is 230 or less, The content of the monofunctional monomer (A) is 1 to 20% by mass based on 100% by mass of the total of the monofunctional monomer (A), the bifunctional (meth)acrylate compound (B) and the polyfunctional monomer (C). The content of the bifunctional (meth)acrylate compound (B) is 40 to 98% by mass based on 100% by mass of the total of the monofunctional monomer (A), the bifunctional (meth)acrylate compound (B) and the polyfunctional monomer (C). The content of the polyfunctional monomer (C) is 1 to 40% by mass based on 100% by mass of the total of the monofunctional monomer (A), the bifunctional (meth)acrylate compound (B), and the polyfunctional monomer (C).

Images