Active energy ray-curable composition, cured product, and laminate

Abstract

To provide an active energy ray-curable composition that can form a cured product having excellent wear resistance and substrate adhesion and also less prone to cracking during molding, and a cured product of the composition, and a laminate including the cured product.SOLUTION: An active energy ray-curable composition comprises at least a resin A and a resin B. The resin A is a radical polymerizable double bond equivalent of 501-10000 g / mol. The resin B has a radical polymerizable double bond equivalent of 200-500 g / mol.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an active energy ray-curable composition, a method for curing the active energy ray-curable composition, and a method for curing the active energy ray-curable composition. and a laminate having a layer made of the cured product. [Background technology]

[0002] Surface protection and decoration of resin molding materials for automobile interior and exterior parts, electronic devices, miscellaneous goods, building materials, etc. To prevent this, methods such as hard coating the surface or attaching a film are known. Known decoration methods include insert method, thermal lamination method, and transfer method. In addition, the hard coat layer is generally made of a compound having a radical polymerizable group. and a photopolymerization initiator, and curing the curable composition by radical polymerization. However, when a hard coat layer is used to protect the surface, abrasion resistance is reduced. Although this improves the strength and scratch resistance, it reduces the elongation during molding and is therefore not suitable for decorative applications. In addition, the substrate and hard coat layer must be separated to prevent them from peeling off during processing. Adhesion to the adhesive layer is also an issue.

[0003] Patent document 1 describes an insert film for in-mold labels, and cited document 2 describes a decorative component. Reference 3 describes a hard coating agent for molding, Reference 4 describes a decorative sheet for automobile interiors, and Reference 5 describes a thermal transfer Decorative hard coat is printed directly onto the hard coat layer using a thermal transfer printing method with a photo printer. A film is described. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-288720 [Patent Document 2] Japanese Patent Application Laid-Open No. 2016-180082 [Patent Document 3] Japanese Patent Application Publication No. 2019-189043 [Patent Document 4] Japanese Patent Application Laid-Open No. 2011-110903 Summary of the Invention [Problem to be solved by the invention]

[0005] The hard coat layer described in Patent Document 1 has excellent abrasion resistance, but does not necessarily have good stretchability during molding. It does not satisfy the corrosion resistance, and it is difficult to follow the surface shape of the molding material, and the hard coat layer peels off. In addition, the hard disk described in Patent Document 2 may become detached or cracks may occur. Regarding hard coating agents, they have excellent abrasion resistance, but do not necessarily satisfy the elongation and adhesion to the substrate. The sheet described in Patent Document 3 does not fully satisfy the abrasion resistance of the surface protection layer. Therefore, it is difficult to ensure the elongation of the hard coat film described in Patent Document 4. do. The present invention has excellent abrasion resistance and chemical resistance, and also has low elongation during molding (preventing cracks from occurring). Furthermore, it is possible to form a hard coat layer with excellent adhesion to the substrate. an active energy ray-curable composition, a cured product of the active energy ray-curable composition, and The object is to provide a laminate having a layer made of a cured product. [Means for solving the problem]

[0006] The present invention has the following aspects. That is, the above object of the present invention can be achieved by the following means [1] to

[10] . [1] An active energy ray-curable composition containing resin A and resin B, wherein the radical polymerization of resin A The polymerizable double bond equivalent of Resin B is 501 to 10,000 g / mol, and the radical polymerizable double bond of Resin B is An active energy ray-curable composition having a bond equivalent of 200 to 500 g / mol. [2] The active energy storage device according to [1], wherein the hydroxyl value of the resin A is 5 to 115 mgKOH / g. Lugie radiation curable composition. [3] The hydroxyl value of the resin B is 116 to 270 mgKOH / g [1] or [2] The active energy ray-curable composition according to claim 1. [4] The radical polymerizable double bond equivalent of the nonvolatile component of the active energy ray-curable composition The active energy according to any one of [1] to [3] is 300 to 1000 g / mol. - Linear curable composition. [5] The active energy ray absorbent according to any one of [1] to [4], which contains a leveling agent. Curable composition. [6] The active energy ray ... Curable composition. [7] A cured product of the active energy ray-curable composition according to any one of [1] to [6]. [8] A cured product of [7] that has an elongation of 15% or more in a tensile test at 140°C. [9] A laminate having the cured product according to [7] or [8] on a substrate.

[10] The laminate of [9], which has a transmittance of 80% or less at a wavelength of 360 nm. DETAILED DESCRIPTION OF THE INVENTION

[0007] In this specification, "(meth)acrylic" is a general term for "acrylic" and "methacrylic". "(Meth)acrylate" is a general term for "acrylate" and "methacrylate." "(Meth)acryloyl group" is a general term for "acryloyl group" and "methacryloyl group" , CH2=C(R 1 )-C(=O)-(R1 is a hydrogen atom or a methyl group) Furthermore, "monofunctional" means having one radically polymerizable double bond. The term "functional" means having two or more radically polymerizable double bonds, e.g., "bifunctional" means having two radically polymerizable double bonds.

[0008] <Active energy ray-curable composition> The active energy ray-curable composition of the present invention is an active energy ray-curable composition containing at least resin A and resin B. The resin A is a ray-curable composition, and the radical polymerizable double bond equivalent of the resin A is 501 to 10,000. g / mol, and the radical polymerizable double bond equivalent of Resin B is 200 to 500 g / mol. The resin A and the resin B are combined to form an active energy ray-curable composition. This not only achieves both abrasion resistance and workability during stretching of the cured product, but also improves the workability after coating. It has excellent quick-drying properties in the drying process before hardening with active energy rays, improving workability and , and can exhibit anti-blocking properties.

[0009] <Resin A> The radical polymerizable double bond equivalent weight of resin A is usually 501 to 10,000 g / mol , preferably 510 to 6000 g / mol, more preferably 530 to 2500 g / mol More preferably, it is in the range of 550 to 1200 g / mol. When the cured film (hard coat layer) is formed, it has good extensibility during molding. The radical polymerizable double bond equivalent is determined by, for example, mixing the resin composition with sodium bromide and bromide. The mixture is reacted with a mixed solution of potassium iodide and potassium iodide solution, and the mixture is mixed with starch. The solution can be measured by a specified method using sodium thiosulfate solution as an indicator.

[0010] The hydroxyl value of the resin A is usually 5 to 115 mgKOH / g, preferably 10 to 11 0 mgKOH / g, more preferably 25 to 107 mgKOH / g, and even more preferably 50 By using it in this range, compatibility with Resin B is improved. The hydroxyl value is also improved when the resin composition is subjected to piezo-resistance treatment, for example. It is reacted with excess acetic anhydride in lysine, and the liberated acetic acid is titrated with potassium hydroxide. It can be measured.

[0011] The weight average molecular weight of Resin A should be selected appropriately depending on the application of the curable composition. , preferably 1,000 to 200,000, more preferably 5,000 to 100,000, and further Preferably, it is in the range of 8,000 to 80,000, and particularly preferably in the range of 10,000 to 60,000. By using it in this range, the adhesion to the substrate is improved and the extensibility during molding is also good. In addition, the viscosity of the composition can be easily adjusted to an appropriate range, and the coating properties are excellent. The weight average molecular weight (Mw) of the resin can be determined by gel permeation Determined as a converted value using a polystyrene standard using gel permeation chromatography (GPC). Specific measurement conditions will be shown in the Examples below.

[0012] The content of resin A in the active energy ray curable composition depends on the application and the required properties of the cured film. Although it is difficult to generalize because it changes depending on the amount of non-volatile matter, it is preferable to use a value of 25 to 99%. % by mass, more preferably 35 to 90% by mass, even more preferably 45 to 85% by mass, and particularly preferably The range is preferably 60 to 80 mass %. By using it in this range, wear resistance is ensured. At the same time, it is possible to provide good extensibility during molding and good adhesion to the substrate. In particular, in applications where elongation is important, the content is preferably 60 to 99 mass %, more preferably Preferably, it is in the range of 65 to 90 mass %, and more preferably, it is in the range of 70 to 85 mass %. The nonvolatile content is the total mass of components other than the solvent, such as the organic solvent. The nonvolatile content of the radiation-curable composition can be measured by a conventionally known method. For example, The composition was spread out and heated at 100°C for 1 hour to evaporate the organic solvent. The weight change was measured. It is measured by

[0013] <Resin B> The radical polymerizable double bond equivalent weight of the resin B is usually 200 to 500 g / mol, preferably Preferably, it is 215 to 450 g / mol, more preferably 225 to 400 g / mol, and even more preferably 215 to 450 g / mol. The preferred range is 230 to 370 g / mol. By using the copolymer in this range, the cured product When a cured film (hard coat layer) is formed, the abrasion resistance and chemical resistance are good. do.

[0014] The hydroxyl value of the resin (B) is usually 116 to 270 mgKOH / g, preferably 1 25 to 260 mgKOH / g, more preferably 140 to 250 mgKOH / g, and even more preferably The preferred range is 150 to 245 mgKOH / g. The adhesion to the substrate is good.

[0015] The weight average molecular weight of Resin B should be selected appropriately depending on the application of the curable composition. , preferably 1,000 to 200,000, more preferably 5,000 to 100,000, and further Preferably, it is in the range of 8,000 to 80,000, and particularly preferably in the range of 10,000 to 60,000. By using it within this range, it is possible to improve the abrasion resistance and also to improve the adhesion to the substrate. In addition, the viscosity of the composition can be easily adjusted to an appropriate range, and the coating properties can also be improved. can be done.

[0016] The content of resin B in the active energy ray curable composition depends on the application and the required properties of the cured film. Although it is difficult to generalize because it varies depending on the amount of non-volatile matter, it is preferably 5 to 95% by weight. %, more preferably 1 to 75 mass%, even more preferably 5 to 60 mass%, and particularly preferably The range is 9 to 50% by mass, and most preferably 14 to 35% by mass. As a result, it is possible to provide good abrasion resistance, chemical resistance, and adhesion to the substrate. In particular, in applications where elongation is important, the content is preferably 1 to 40 mass %, more preferably The content is preferably in the range of 3 to 25% by mass, and more preferably in the range of 5 to 20% by mass.

[0017] Resin A and resin B that satisfy the above requirements include (meth)acrylic resins and polyester resins. Among them, radical polymerizable di- and di-polymerizable resins such as urethane resins can be used. The heavy bond equivalent and hydroxyl value can be easily adjusted to form a hard coat layer with appropriate properties. (Meth)acrylic resins are preferred from the viewpoint of ease of application.

[0018] As a method for introducing a radical polymerizable double bond into a (meth)acrylic resin, an epoxy group A method of reacting an acrylic resin having the formula ( Method 1) Adding a compound having a double bond and an epoxy group to an acrylic resin having a carboxyl group Method 2: Reacting acrylic resin with hydroxyl groups with double bonds and carboxyl groups. a method of reacting a compound having a carboxyl group with an acrylic resin having a carboxyl group (Method 3); (Method 4) is a method of reacting a compound having a double bond and a hydroxyl group with a method of reacting an acrylic resin having the above structure with a compound having a double bond and a hydroxyl group (Method 5); A compound having a double bond and an isocyanate group is reacted with an acrylic resin having a hydroxyl group. Method 6) and the like. The above methods may be used in combination. In the following, a monomer having a radical polymerizable double bond is referred to as a vinyl monomer. This sometimes happens.

[0019] In the above-mentioned method 1, the epoxy group used to obtain the acrylic resin having epoxy groups Examples of vinyl monomers having a hydroxyl group include glycidyl (meth)acrylate, 3, 4-Epoxycyclohexyl (meth)acrylate, 3,4-Epoxycyclohexyl methacrylate Among these, the most popular are acrylates, methacrylates, and acrylates, which are particularly good in reactivity and material Considering ease of use, glycidyl (meth)acrylate is preferred, and glycidyl Methacrylates are particularly preferred. These may be used alone or in combination of two or more. It may be combined.

[0020] In addition, examples of the compound having a double bond and a carboxyl group in the method 1 include For example, (meth)acrylic acid, carboxyethyl (meth)acrylate, glycerin di(meth)acrylate, ) acrylate and succinic anhydride adduct, pentaerythritol tri(meth)acrylate adduct of pentaerythritol and succinic anhydride, pentaerythritol tri(meth)acrylate and anhydrous pentane Among these, (meth)acrylic acid, pentaerythritol, and the like are preferred. The adduct of (meth)acrylic acid tri(meth)acrylate and succinic anhydride is preferred. More preferred is acrylic acid, and even more preferred is acrylic acid. The compound may be used alone or in combination of two or more.

[0021] In the above-mentioned method 2, the carboxyl group-containing acrylic resin is obtained by Examples of vinyl monomers having a carboxyl group include (meth)acrylic acid, carboxyl Examples of suitable acrylates include diethyl (meth)acrylate and polybasic acid-modified (meth)acrylate. Among these, (meth)acrylic acid is preferred, and acrylic acid is more preferred. They may be used alone or in combination of two or more.

[0022] In the method 2, examples of the compound having a double bond and an epoxy group include , glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl Among these, glycidyl (meth)acrylate is preferred. These may be used alone or in combination of two or more.

[0023] In the method 3, the hydroxyl group-containing acrylic resin is obtained by Examples of the vinyl monomer include 2-hydroxyethyl (meth)acrylate, 4-hydroxyethyl (meth)acrylate, -Hydroxybutyl (meth)acrylate, hydroxypropyl (meth)acrylate, etc. These may be used alone or in combination of two or more.

[0024] In the method 3, the compound having a double bond and a carboxyl group may be the compound The same compounds as those in Method 1 can be used.

[0025] In the method 4, the acrylic resin having a carboxyl group is the same as that in the method 2. Various types of materials can be used.

[0026] In the method 4, examples of the compound having a double bond and a hydroxyl group include: -Hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate , hydroxypropyl (meth)acrylate, etc. These can be used alone. Alternatively, two or more types may be combined.

[0027] In the above method 5, a compound used to obtain an acrylic resin having an isocyanate group is Examples of vinyl monomers having an isocyanate group include isocyanate ethyl (methyl) p) acrylates, etc.

[0028] In the method 5, the compound having a double bond and a hydroxyl group may be, for example, The same compounds as those listed in Method 4 can be used.

[0029] In the method 6, the acrylic resin having a hydroxyl group is the compound in the method 3. The same thing can be used.

[0030] In the method 6, the compound having a double bond and an isocyanate group is For example, isocyanate ethyl (meth)acrylate etc. are listed. may be used, or two or more of them may be combined.

[0031] Among the above methods, method 1 or method 2 is preferred because it allows the simultaneous introduction of hydroxyl groups. In addition, method 1 is more preferable because the reaction is easier to control. In method 1, the double bond is The epoxy group of the acrylic resin having an epoxy group and the compound having a double bond and a carboxyl group It is introduced by a ring-opening addition reaction with the carboxyl group in the compound.

[0032] When resin A is synthesized by the above-mentioned method 1, the epoxy group in the acrylic resin having the epoxy group is The monomer having an epoxy group is the total amount of the monomers constituting the acrylic resin having an epoxy group. Of these, preferably 1% by weight or more, more preferably 2% by weight or more, and even more preferably 5% by weight or more. The range is preferably 10% by weight or more, and more preferably 10% by weight or more. By using it in this range, the adhesion of the cured film to the substrate and the scratch resistance are improved. Not only has hardness been improved, but stretchability has also been achieved that prevents cracks from occurring due to stress during decorative molding. It can be achieved.

[0033] In addition, when resin A is synthesized by the above-mentioned method 1, a compound having a double bond and a carboxyl group is used. The compound has a double bond and carbonyl group to the epoxy group in the acrylic resin having an epoxy group. The proportion of the compound having a carboxyl group is preferably 10 to 150 mol %, and more preferably Preferably 30 to 130 mol %, more preferably 50 to 120 mol %, particularly preferably The amount used is 100 to 110 mol %, which is the amount that allows the reaction to proceed without excess or deficiency. This makes it possible to effectively introduce a radically polymerizable double bond.

[0034] When resin B is synthesized by the above-mentioned method 1, the epoxy group in the acrylic resin having the epoxy group is The monomer having an epoxy group is the total amount of the monomers constituting the acrylic resin having an epoxy group. Of these, preferably 26% by weight or more, more preferably 30% by weight or more, and even more preferably The range is preferably 35% by weight or more, and more preferably 40% by weight or more. There is no limit to the amount, but it is 99% by weight. By using it in this range, it is possible to prevent damage caused by stress during decorative molding. Not only does it have stretchability that prevents cracks from occurring, but it also improves the scratch resistance and hardness of the cured film. This can be done.

[0035] When resin B is synthesized by the above method 1, a compound having a double bond and a carboxyl group is used. The compound has a double bond and carbonyl group to the epoxy group in the acrylic resin having an epoxy group. The proportion of the compound having a carboxyl group is preferably 10 to 150 mol %, and more preferably Preferably 30 to 130 mol %, more preferably 50 to 120 mol %, particularly preferably The amount used is 100 to 110 mol %, which is the amount that allows the reaction to proceed without excess or deficiency. This makes it possible to effectively introduce a radically polymerizable double bond.

[0036] It is also possible to introduce a hydroxyl group by a method other than Method 1 or Method 2. For example, A method of copolymerizing a compound having a hydroxyl group as a monomer during the production of methacrylic resin. Examples include:

[0037] Examples of the monomer having a hydroxyl group include hydroxyethyl (meth)acrylate, Hydroxypropyl (meth)acrylate, Hydroxybutyl (meth)acrylate, Hydroxyhexyl (meth)acrylate, hydroxyoctyl (meth)acrylate, hydroxydecyl (meth)acrylate, hydroxylauryl (meth)acrylate, etc. Among these, hydroxyalkyl (meth)acrylates are preferred due to their ease of introduction and From the viewpoint of being able to efficiently adjust the hydroxyl value, hydroxyethyl (meth)acrylate is preferred.

[0038] Furthermore, (meth)acrylic resins such as the above-mentioned (meth)acrylic resins having epoxy groups may be used. The fat is a copolymer of (meth)acrylates and other vinyl monomers other than those mentioned above. The polymerization reaction of these raw materials is usually radical polymerization, and The polymerization can be carried out under the following conditions.

[0039] Monomers that can be used in combination as raw materials include methyl (meth)acrylate, ethylenediamine, ethylenediaminetetraacetic acid ... ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl ( (meth)acrylate, phenyl (meth)acrylate, methoxy (poly)ethylene glycol (meth)acrylate, methoxy(poly)propylene glycol (meth)acrylate Methoxy (poly)ethylene glycol (poly)propylene glycol (meth)acrylate acrylate, octoxy(poly)ethylene glycol (meth)acrylate, octoxy(poly)ethylene glycol (meth)acrylate i) Propylene glycol (meth)acrylate, octoxytetramethylene glycol (meth)acrylate, lauroxy(poly)ethylene glycol (meth)acrylate, (Meth)acrylates such as stearoxy (poly)ethylene glycol (meth)acrylate Ethyl (meth)acrylamide, n-butyl (meth)acrylamide, i-butyl ( (meth)acrylamide, t-butyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide (meth)acrylamide, N-hydroxypropyl (meth)acrylamide, N,N-dihydr acrylamides such as hydroxyethyl (meth)acrylamide; styrene, p-chlorostyrene Examples of such monomers include styrene-based monomers such as styrene and p-bromostyrene. It may be used alone or in combination of two or more.

[0040] (Meth)acrylic resins are produced by radical polymerization of the above-mentioned raw vinyl monomers. The radical polymerization reaction can be carried out in an organic solvent in the presence of a radical polymerization initiator. It is preferable to carry out the method using the method described above.

[0041] Examples of organic solvents used in radical polymerization include acetone and methyl ethyl ketone (M Ketone solvents such as EK; ethanol, methanol, isopropyl alcohol (IPA) alcohol solvents such as ethylene glycol dimethyl ether, propylene glycol; Ether solvents such as ethylene glycol monomethyl ether; ethyl acetate, propylene glycol Ester solvents such as methyl ether acetate and 2-ethoxyethyl acetate and aromatic hydrocarbon solvents such as toluene. Alternatively, two or more of them may be used in combination.

[0042] Examples of radical polymerization initiators used in radical polymerization include benzoyl peroxide. organic peroxides such as di-t-butyl peroxide; 2,2'-azobisbutyronitrile , 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4- These lazo compounds include azo compounds such as methoxy-2,4-dimethylvaleronitrile. The radical polymerization initiator may be used alone or in combination of two or more. The polymerization initiator is used in the range of 0.01 to 5 parts by weight per 100 parts by weight of the total of the vinyl monomers used as raw materials. It is preferable to use it in this range.

[0043] In addition, during radical polymerization, the weight average molecular weight of the (meth)acrylic resin can be controlled. For this purpose, a chain transfer agent can be used. Examples of the chain transfer agent include butanethiol. thiol, octanethiol, decanethiol, dodecanethiol, hexadecanethiol, Octadecanethiol, cyclohexyl mercaptan, thiophenol, thioglycol Octyl mercaptopropionate, octyl 2-mercaptopropionate, octyl 3-mercaptopropionate mercaptopropionic acid 2-ethylhexyl ester, thioglycolic acid 2-ethyl Hexyl, butyl-3-mercaptopropionate, mercaptopropyltrimethoxysilane Ran, methyl-3-mercaptopropionate, 2,2-(ethylenedioxy)diethane Thiol, ethanethiol, 4-methylbenzenethiol, 2-mercaptoethyl octanoate ethyl ester, 1,8-dimercapto-3,6-dioxaoctane, decane trithiol , dodecyl mercaptan, diphenyl sulfoxide, dibenzyl sulfide, 2,3-di Methylcapto-1-propanol, mercaptoethanol, thiosalicylic acid, thioglycerin Roll, thioglycolic acid, 3-mercaptopropionic acid, thiomalic acid, mercaptoacetic acid thiol compounds such as mercaptosuccinic acid, 2-mercaptoethanesulfonic acid, etc. These may be used alone or in combination of two or more.

[0044] The amount of chain transfer agent used is 0.1 to 2 parts by weight per 100 parts by weight of the total vinyl monomers used as raw materials. 5 parts by weight is preferable, 0.5 to 20 parts by weight is more preferable, and 1.0 to 15 parts by weight is even more preferable. preferable.

[0045] The reaction time for the radical polymerization is preferably 1 to 20 hours, more preferably 3 to 12 hours. The reaction temperature is preferably 40 to 120°C, more preferably 50 to 100°C.

[0046] When a compound having a double bond and a carboxyl group is reacted with a (meth)acrylic resin, The (meth)acrylic resin obtained as described above is added with a double bond and a carboxyl group. Compounds containing triphenylphosphine, tetrabutylammonium bromide, etc. are added to One or two of the catalysts, such as tetramethylammonium chloride, triethylamine, etc. In the presence of The catalyst is the (meth)acrylic acid ester polymer as the raw material. and a compound having a double bond and a carboxyl group, etc., for a total of 100 parts by weight It is preferable to use it in a proportion of about 0.5 to 3 parts by weight. This may be carried out continuously after the (meth)acrylic resin is produced by polymerization reaction. Once separated, compounds such as compounds with double bonds and carboxyl groups are added. It is also possible.

[0047] <Radical Polymerizable Double Bond Equivalent of Active Energy Ray-Curable Composition> The radical polymerizable double bond equivalent of the nonvolatile component of the active energy ray-curable compound of the present invention is Usually, it is 300 to 1000 g / mol, preferably 330 to 600 g / mol, more preferably Preferably, the range is 400 to 575 g / mol, more preferably 450 to 550 g / mol. By using the composition in this range, when a cured film (hard coat layer) is formed, This allows for both good abrasion resistance and stretchability during molding.

[0048] <Active energy ray-curable compounds other than Resin A and Resin B> Furthermore, when used as an active energy ray curable composition, it is possible to improve the abrasion resistance and hardness of the cured film. In order to improve or adjust the viscosity, an active energy ray curable compound other than the above-mentioned resin is used. However, when an active energy ray curable compound other than a resin is used, After the composition is applied to a substrate or an article and dried, an odor or a sticky feeling may remain. This is because compounds other than resin seep out of the coating after drying, and this is a problem during work. There are concerns that the increased risk to workers may lead to reduced workability and blocking of items. In addition, if unreacted compounds remain in the cured product, bleeding out occurs, and each When there are concerns about equipment or environmental contamination during the manufacturing process, or deterioration of visibility after the coating has hardened Due to these factors, depending on the application, active energy ray curable compounds other than resins may be used. There are times when it is preferable to use less or no material.

[0049] As active energy ray curable compounds other than Resin A and Resin B, conventionally known materials are used. Suitable materials include, for example, (meth)acrylate. The (meth)acrylate is not particularly limited, and may be a monofunctional (meth)acrylate, a bifunctional (meth)acrylate, or the like. The (meth)acrylate may be either a trifunctional or higher functional (meth)acrylate. (Meth)acrylates that are commercially available as curable resin materials can also be used. The related compound may contain other components as long as the object of the present invention is not impaired. Among these, bifunctional or trifunctional or more multifunctional (meta) compounds are particularly excellent in terms of abrasion resistance. Acrylates are preferred, and tri- or higher functional (meth)acrylates are particularly preferred. In addition, (meth)acrylates include epoxy (meth)acrylate, urethane (meth)acrylate, It is also possible to use silicone (meth)acrylate, silicone (meth)acrylate, etc.

[0050] The monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylate, butyl (meth)acrylate, propyl (meth)acrylate, n- Butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate Acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate , lauryl (meth)acrylate, stearyl (meth)acrylate, morpholyl (meth)acrylate meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (Meth)acrylate, Tricyclodecane (meth)acrylate, Polyethylene Glyco- Mono(meth)acrylate, cyclohexyl(meth)acrylate, tetrahydrofuran Furyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentanyl Thenyl (meth)acrylate, isobornyl (meth)acrylate, allyl (meth)acrylate acrylate, 2-ethoxyethyl (meth)acrylate, benzyl (meth)acrylate, Mono(meth)acrylates such as phenoxyethyl (meth)acrylate and phenyl (meth)acrylate ) acrylate, adduct of phthalic anhydride and 2-hydroxyethyl (meth)acrylate and the like mono(meth)acrylate compounds.

[0051] Examples of bifunctional polyfunctional (meth)acrylates include 1,4-butanediol di( meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexa Nonanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, Alkanediol di(meth)acrylate such as tricyclodecanedimethylol di(meth)acrylate Acrylate, bisphenol A ethylene oxide modified di(meth)acrylate, bis Phenol F ethylene oxide modified di(meth)acrylate and other bisphenol modified di(meth)acrylates (Meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene ethylene glycol di(meth)acrylate, urethane di(meth)acrylate, epoxy di( methacrylates, etc.

[0052] Examples of trifunctional or higher polyfunctional (meth)acrylates include dipentaerythritol. Hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, Prolactone-modified dipentaerythritol hexa(meth)acrylate, pentaerythritol Pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, Ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate Trimethylolpropane tri(meth)acrylate, ethylene oxide Iodo-modified dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified Ethylene oxide modified (meth)acrylate such as pentaerythritol tetra(meth)acrylate Acrylate, isocyanuric acid ethylene oxide modified tri(meth)acrylate, ε- Isocyanuric acid modified such as caprolactone-modified tris(acryloxyethyl) isocyanurate Tri(meth)acrylate, Pentaerythritol triacrylate hexamethylene diacrylate Isocyanate urethane prepolymer, pentaerythritol triacrylate toluene Diisocyanate urethane prepolymer, dipentaerythritol pentaacrylate Urethane (meth)acrylates such as hexamethylene diisocyanate urethane prepolymer etc.

[0053] <Leveling agent> A leveling agent is added to the active energy ray curable composition to improve the appearance of the cured product. As the leveling agent, acrylic leveling agents, silicone leveling agents, etc. Among these, one of the objects of the present invention is to From the viewpoint of improving the wear resistance of the coating, silicone-based leveling agents are preferred. Furthermore, it is preferable to prevent bleeding of the leveling agent after forming the hard coat layer during molding or the like. From the viewpoint of preventing outflow, silicone with radical polymerizable functional groups is used. Silicone leveling agents are particularly preferred. Silicone leveling agents impart slip properties to the cured product. This provides high abrasion resistance. The blocking agent reacts with the active energy ray-curable composition and is incorporated into the cured product, It is extremely useful because it can achieve slip resistance, abrasion resistance, and chemical resistance. do.

[0054] The content of the leveling agent in the active energy ray-curable composition relative to the nonvolatile content is Preferably 20% by mass or less, more preferably 0.01 to 10% by mass, and even more preferably 0 0.1 to 5% by weight, particularly preferably 0.2 to 4% by weight, most preferably 0.3 to 3% by weight By using it in this range, not only the appearance of the cured film is improved, but also the abrasion resistance is improved. Improvements can also be achieved.

[0055] <UV absorber> In order to improve the weather resistance of the cured product, an ultraviolet absorber is added to the active energy ray curable composition. From the viewpoint of heat resistance, those with a molecular weight of 500 or more are preferred. The agent is selected from the group consisting of triazines, benzoates, etc., from the viewpoint of good solubility in the composition and improvement in weather resistance. Phenones, benzotriazoles, cyclic iminoesters, salicylate esters, or or derived from a cyanoacrylate compound, and having a maximum absorption wavelength of 24 Among these, ultraviolet absorbers with a wavelength in the range of 0 to 380 nm are particularly preferred. In terms of good adhesion and excellent appearance when used as a hard coat layer, triazine The benzotriazole-based compounds are more preferred, and the triazine-based compounds are even more preferred.

[0056] The triazine-based ultraviolet absorber includes, but is not limited to, the following: 2- [4-([2-hydroxy-3-dodecyloxypropyl]oxy)-2-hydroxypropyl phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2- [4-([2-hydroxy-3-tridecyloxypropyl]oxy)-2-hydroxy phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (T inuvin (registered trademark) 400 (BASF), 2-[4,6-bis( 2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyl) 2-(2,4-dihydroxyphenyl)-2-hydroxypropoxy]phenol) phenyl)-4,6-bis-(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid ester reaction product (Tinuvin® ) 405, manufactured by BASF), 2,4-bis "2-hydroxy-4-butoxyphenyl" - 6-(2,4-dibutoxyphenyl)-1,3-5-triazine (Tinuvin (registered trademark) BASF 460, 2-(4,6-diphenyl-1,3,5-triazine- 2-yl)-5-[(hexyl)oxy]-phenol (Tinuvin® 1 577, BASF), 2-(4,6-diphenyl-1,3,5-triazine-2-yl) 2-(2-ethylhexanoyloxy)ethoxy]-5-[2-(2-ethylhexanoyloxy)ethoxy]-phenol (ADK STAB LA46, manufactured by ADEKA), 2-(2-hydroxy-4-[1-octyl [oxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3 ,5-triazine (Tinuvin (registered trademark) 479, manufactured by BASF), etc. .

[0057] Benzotriazole-based ultraviolet absorbers include, but are not limited to, the following: For example, 2-[2'-hydroxy-5'-(methacryloyloxymethyl)phenyl]-2H -Benzotriazole, 2-[2'-hydroxy-5'-(methacryloyloxyethyl )phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacrylamide (2'-hydroxypropyl)phenyl]-2H-benzotriazole, [5'-(methacryloyloxyhexyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-3'-tert-butyl-5'-(methacryloyloxyethyl) phenyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-tert -butyl-3'-(methacryloyloxyethyl)phenyl]-2H-benzotriazol 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]-5- Chloro-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloyl 2-[2'-hydroxyethyl)phenyl]-5-methoxy-2H-benzotriazole hydroxy-5'-(methacryloyloxyethyl)phenyl]-5-cyano-2H-benzo[b] 2-[2'-hydroxy-5'-(methacryloyloxyethyl)phenyl]phenyl Nyl]-5-tert-butyl-2H-benzotriazole, 2-[2'-hydroxy- 5'-(Methacryloyloxyethyl)phenyl]-5-nitro-2H-benzotriazo Examples include ru.

[0058] The cyclic iminoester-based ultraviolet absorber is not limited to the following, but examples thereof include: For example, 2-methyl-3,1-benzoxazin-4-one, 2-butyl-3,1-benzoxazin-4-one, Xazin-4-one, 2-phenyl-3,1-benzoxazin-4-one, 2-(1- or 2-naphthyl)-3,1-benzoxazin-4-one, 2-(4-biphenyl)- 3,1-Benzoxazin-4-one, 2-p-nitrophenyl-3,1-benzoxazin-4-one 2-m-nitrophenyl-3,1-benzoxazin-4-one, 2- p-Benzoylphenyl-3,1-benzoxazin-4-one, 2-p-methoxyphenyl 2-o-Methoxyphenyl-3,1-benzoxazin-4-one, 2-o-Methoxyphenyl-3,1-benzoxazin-4-one benzoxazin-4-one, 2-cyclohexyl-3,1-benzoxazin-4-one, 2-p-(or m-)phthalimidophenyl-3,1-benzoxazin-4-one, N -phenyl-4-(3,1-benzoxazin-4-one-2-yl)phthalimide, N -benzoyl-4-(3,1-benzoxazin-4-one-2-yl)aniline, N- Benzoyl-N-methyl-4-(3,1-benzoxazin-4-one-2-yl)aniline Phosphorus, 2-(p-(N-methylcarbonyl)phenyl)-3,1-benzoxazine-4 -one, 2,2'-bis(3,1-benzoxazin-4-one), 2,2'-ethylene Bis(3,1-benzoxazin-4-one), 2,2'-tetramethylenebis(3,1 -benzoxazin-4-one), 2,2'-decamethylenebis(3,1-benzoxazin-4-one), 2,2'-p-phenylenebis(3,1-benzoxazin-4-one) 2,2'-m-phenylenebis(3,1-benzoxazin-4-one), 2,2 '-(4,4'-diphenylene)bis(3,1-benzoxazin-4-one), 2,2 '-(2,6- or 1,5-naphthylene)bis(3,1-benzoxazin-4-one) , 2,2'-(2-methyl-p-phenylene)bis(3,1-benzoxazine-4-ol) 2,2'-(2-nitro-p-phenylene)bis(3,1-benzoxazine-4 -one), 2,2'-(2-chloro-p-phenylene)bis(3,1-benzoxazine -4-one), 2,2'-(1,4-cyclohexylene)bis(3,1-benzoxazolidine) 1,3,5-tri(3,1-benzoxazin-4-one-2-yl) Benzene, 1,3,5-tri(3,1-benzoxazin-4-one-2-yl)naphtha 2,4,6-tri(3,1-benzoxazin-4-one-2-yl)naphthalene , 2,8-dimethyl-4H,6H-benzo(1,2-d;5,4-d')bis(1,3) -oxazine-4,6-dione, 2,7-dimethyl-4H,9H-benzo(1,2-d; 4,5-d')bis(1,3)-oxazine-4,9-dione, 2,8-diphenyl- 4H,8H-benzo(1,2-d;5,4-d')bis(1,3)-oxazine-4,6 -dione, 2,7-diphenyl-4H,9H-benzo(1,2-d;4,5-d')bis (1,3)-oxazine-4,6-dione, 6,6'-bis(2-methyl-4H,3,1 -benzoxazin-4-one), 6,6'-bis(2-ethyl-4H,3,1-benzoxazin-4-one), oxazin-4-one), 6,6'-bis(2-phenyl-4H,3,1-benzoxazin-4-one) din-4-one), 6,6'-methylenebis(2-methyl-4H,3,1-benzoxazin-4-one) din-4-one), 6,6'-methylenebis(2-phenyl-4H,3,1-benzoxyl) 6,6'-ethylenebis(2-methyl-4H,3,1-benzoxazinone), sazin-4-one), 6,6'-ethylenebis(2-phenyl-4H,3,1-benzo[ Xazin-4-one), 6,6'-butylenebis(2-methyl-4H,3,1-benzoxazin-4-one) Xazin-4-one), 6,6'-butylenebis(2-phenyl-4H,3,1-benzoxazin-4-one) oxazin-4-one), 6,6'-oxybis(2-methyl-4H,3,1-benzoxazin-4-one) Xazin-4-one), 6,6'-oxybis(2-phenyl-4H,3,1-benzoxazin-4-one) oxazin-4-one), 6,6'-sulfonylbis(2-methyl-4H,3,1-benzoxazin-4-one) oxazin-4-one), 6,6'-sulfonylbis(2-phenyl-4H,3,1-benzyl) benzoxazin-4-one), 6,6'-carbonylbis(2-methyl-4H,3,1- benzoxazin-4-one), 6,6'-carbonylbis(2-phenyl-4H,3, 1-benzoxazin-4-one), 7,7'-methylenebis(2-methyl-4H,3, 1-benzoxazin-4-one), 7,7'-methylenebis(2-phenyl-4H,3 ,1-benzoxazin-4-one), 7,7'-bis(2-methyl-4H,3,1-benzyl) benzoxazin-4-one), 7,7'-ethylenebis(2-methyl-4H,3,1-benzyl) benzoxazin-4-one), 7,7'-oxybis(2-methyl-4H,3,1-benzoxazin-4-one) 7,7'-sulfonylbis(2-methyl-4H,3,1-benzoxazin-4-one), benzoxazin-4-one), 7,7'-carbonylbis(2-methyl-4H,3,1- benzoxazin-4-one), 6,7'-bis(2-methyl-4H,3,1-benzoxazin-4-one) Xazin-4-one), 6,7'-bis(2-phenyl-4H,3,1-benzoxazin-4-one) 6,7'-methylenebis(2-methyl-4H,3,1-benzoxazol-1-one) 6,7'-methylenebis(2-phenyl-4H,3,1-benzoxa- gin-4-one) and the like.

[0059] Benzophenone-based UV absorbers (benzophenone-based compounds), oxybenzophenone-based Examples of ultraviolet absorbers (oxybenzophenone compounds) include 2,4-dihydroxybenzophenone. Dibenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4 -Methoxybenzophenone-5-sulfonic acid (anhydrous and trihydrate), 2-hydroxy-4- Octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2'-dihydroxy-4-methylbenzophenone Toxicbenzophenone (trade name "KEMISORB111", manufactured by Chemipro Chemical Co., Ltd.) , 2,2',4,4'-tetrahydroxybenzophenone (trade name "SEESORB10 6", manufactured by Shipro Chemical Co., Ltd.), 2,2'-dihydroxy-4,4-dimethoxybenzofuran Examples include phenon.

[0060] Examples of salicylate ester-based ultraviolet absorbers (salicylate ester-based compounds) include , phenyl-2-acryloyloxybenzoate, phenyl-2-acryloyloxy -3-methylbenzoate, phenyl-2-acryloyloxy-4-methylbenzoate , phenyl-2-acryloyloxy-5-methylbenzoate, phenyl-2-acryloyloxy-5-methylbenzoate phenyl-2-hydroxybenzoate, Phenyl-2-hydroxy-3-methylbenzoate, Phenyl-2-hydroxy-4-methylbenzoate phenyl 2-hydroxy-5-methylbenzoate, phenyl 2- Hydroxy-3-methoxybenzoate, 2,4-di-tert-butylphenyl-3, 5-di-tert-butyl-4-hydroxybenzoate (Tinuvin®) 120, manufactured by BASF).

[0061] Cyanoacrylate-based ultraviolet absorbers (cyanoacrylate-based compounds) include, for example: , alkyl-2-cyanoacrylate, cycloalkyl-2-cyanoacrylate, alkoxy Alkoxyalkyl-2-cyanoacrylate, alkenyl-2-cyanoacrylate, alkoxyalkyl ... quinyl-2-cyanoacrylate and the like. These compounds may be used alone or in combination of two or more.

[0062] The content of the ultraviolet absorber in the active energy ray-curable composition is, relative to the nonvolatile content, Preferably 20% by mass or less, more preferably 0.01 to 15% by mass, and even more preferably 0 1 to 10% by mass, particularly preferably 0.5 to 8% by mass, most preferably 1 to 5% by mass. By using it within this range, a cured film can be effectively formed and the weather resistance of the cured film can be improved. Improve.

[0063] When used in applications requiring weather resistance, it is preferable that the ultraviolet absorption is good, and the wavelength is 360 The transmittance of the laminate after forming the cured product at 1000 nm is preferably 80% or less, more preferably It is preferably 70% or less, more preferably 60% or less, and particularly preferably 50% or less. The limit depends on the application, but in applications where weather resistance is highly required, a lower limit is preferable, so 0% By using it in this range, it is possible to obtain a product with excellent weather resistance.

[0064] <Light stabilizer> In order to further improve the weather resistance of the cured product, a light stabilizer is added to the active energy ray curable composition. The light stabilizer is not particularly limited as long as it is a hindered amine light stabilizer. Specific examples of light stabilizers include bis(2,2,6,6-tetramethyl-4-piperidinyl) Bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate Bis(1-methoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate , bis(1-ethoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, Bis(1-butoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, Bis(1-butoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate bis(1-pentyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, Bis(1-hexyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate , bis(1-heptyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate Bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate Bis(1-nonyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate Bis(1-decanyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebake bis(1-dodecyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-(4-methan tetrakis(2,2,6,6-pentamethyl-4-pyridinyl)malonate, Peridyl) 1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2, 6,6-Pentamethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate Aminomethyl group-containing compounds such as 1,2,3,4-butanetetracarboxylic acid and 1,2, 2,6,6-Pentamethyl-4-piperidinol and β,β,β,β-tetramethyl-3, 9-(2,4,8,10-tetraoxaspiro[5,5])undecane)diethanol and Condensation product of 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-pentamethyl- 4-Piperidinol and β,β,β,β-tetramethyl-3,9-(2,4,8,10-tetramethyl)- Condensation product of thiazospiro[5,5]undecane with diethanol, decanedicarbon Diester of acid with 2,2,6,6-tetramethyl-1-octoxy-4-piperidinol The reaction product of 1,1-dimethylethyl hydroperoxide with octane (BA SF, product name Tinuvin 123), bis(1,2,2,6,6-pentamethyl-4-piperidine) Lysinyl)-[[3,5-bis(1,1,dimethylethyl)-4-hydroxyphenyl] methyl] (BASF, trade name Tinuvin 144) and other amino ether group-containing compounds are examples. Among these, amino ether group-containing compounds are preferred from the viewpoint of weather resistance of the cured product. , especially bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bi Particularly preferred is (1,1,dimethylethyl)-4-hydroxyphenylmethyl. These compounds may be used alone or in combination of two or more.

[0065] The content of the light stabilizer in the active energy ray-curable composition is preferably or 20% by mass or less, more preferably 0.01 to 15% by mass, and even more preferably 0.1 to 10% by mass, particularly preferably 0.5 to 8% by mass, most preferably 1 to 5% by mass By using the composition in this range, a cured film can be effectively formed and the weather resistance of the cured film can be improved. do.

[0066] <Photopolymerization initiator> A photopolymerization initiator may be added to promote the curing of the curable composition. The molecular weight is preferably 1000 or less. Specific examples include benzoin, benzoin methyl ether, Benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether ethyl ether, benzoin phenyl ether, benzyl diphenyl disulfide, diphenyl Diacetyl, anthraquinone, naphthoquinone, 3,3'-dimethyl-4-methoxy Benzophenone, Benzophenone, p,p'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, pivaloin ethyl ether, benzyl dimethyl ketal, 1,1-dichloroacetophenone, pt-butyl dichloroacetophenone Phenone, 1-hydroxycyclohexyl phenyl ketone, 2-chlorothioxanthone, 2-Methylthioxanthone, 2,4-diethylthioxanthone, 2,2-diethoxyacetone acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-dichloro-4 -Phenoxyacetophenone, phenylglyoxylate, α-hydroxyisobutyl Dibenzosparone, 1-(4-isopropylphenyl)-2-hydroxy-2- Methyl-1-propanone, 2-methyl-[4-(methylthio)phenyl]-2-morpho Lino-1-propanone, Tribromophenyl sulfone, Tribromomethylphenyl sulfone These photopolymerization initiators may be used alone or in combination of two or more. good.

[0067] The content of the photopolymerization initiator in the active energy ray-curable composition is preferably set to a value relative to the nonvolatile content. Preferably, it is 20% by mass or less, more preferably 0.1 to 15% by mass, and even more preferably 0.3% by mass. to 10% by mass, particularly preferably 0.5 to 8% by mass, most preferably 1 to 7% by mass By using the compound in this range, the formation of a cured film can be effectively promoted.

[0068] The active energy ray curable composition may further contain, as necessary, an organic solvent, an antioxidant, a yellowing agent, or the like. Anti-degradants, bluing agents, pigments, dyes, defoamers, thickeners, anti-settling agents, anti-static agents, anti- Various additives such as a clouding agent may also be added.

[0069] In addition, when forming a cured film, the active energy ray curable composition is applied to a substrate. For the purpose of improving workability during application, an organic solvent may be used as needed. Organic solvents include aromatic solvents such as toluene and xylene; methyl ethyl ketone; and acetone. ketone solvents such as methyl isobutyl ketone and cyclohexanone; diethyl ether, isopropyl alcohol; Isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether , diethylene glycol diethyl ether, propylene glycol monomethyl ether, Ether solvents such as anisole and phenetole; ethyl acetate, butyl acetate, isopropyl acetate Ester solvents such as ethylene glycol diacetate; dimethylformamide, di Amide solvents such as ethylformamide and N-methylpyrrolidone; methyl cellosolve, ethyl Cellosolve solvents such as butyl cellosolve; methanol, ethanol, Alcohol-based solvents such as propanol, isopropanol, and butanol; dichloromethane, chloromethane, and the like These organic solvents are not used alone. Of these organic solvents, those that improve workability in coating are Ester solvents, ether solvents, alcohol solvents and ketone solvents are preferred because they are easy to dissolve. Agents are preferred.

[0070] <Cured product (cured film)> The cured product of the active energy ray-curable composition can be obtained by applying the active energy ray-curable composition to a substrate or Apply it to the object to form a coating film, dry it if necessary, and then irradiate the coating film with active energy rays. The method for applying the active energy ray-curable composition is not particularly limited. For example, dip coating, air knife coating, curtain coating, spin coating, Coating method, roller coating method, bar coating method, wire bar coating method, gravure coating method The coating can be carried out by a known method such as spray coating.

[0071] When the active energy ray-curable composition contains an organic solvent, By pre-heating and drying, the organic solvent in the coating film can be removed. The drying temperature for the heat drying is preferably 30 to 200°C, more preferably 50 to 100°C. The drying temperature is more preferably 40 to 150°C, and further preferably 50 to 120°C. A time of 0.01 to 30 minutes is preferred, and 0.1 to 10 minutes is more preferred.

[0072] Examples of active energy rays include ultraviolet rays, electron beams, visible light, infrared rays, and X-rays. Among these, ultraviolet rays and electron beams are preferred from the viewpoint of curing properties and prevention of resin deterioration. The irradiation amount of the active energy ray is more preferably Can be selected as appropriate.

[0073] For example, when ultraviolet light is used, the cumulative light intensity is 20 to 5000 mJ / cm 2 is preferred 100-3000mJ / cm 2 More preferably, 200 to 2000 mJ / cm 2 Gasa It is more preferable that the illuminance is 50 to 600 mW / cm. 2 is preferable, and 75 to 45 0mW / cm 2 More preferably, 100 to 300 mW / cm 2 is more preferable. These include medium pressure mercury lamps, high pressure mercury lamps, ultra-high pressure mercury lamps, electrodeless lamps, and metal halide lamps. , or scanning type, curtain type electron beam acceleration path, high pressure mercury lamp, ultra-high pressure mercury lamp, low A pressure mercury lamp or the like can be used.

[0074] When curing is performed by electron beam irradiation, various electron beam irradiation devices can be used. The irradiation dose (Mrad) of the electron beam is usually 0.5 to 20 Mrad. It is preferred from the viewpoints of curability of the energy ray-curable composition, flexibility of the cured product, prevention of damage to the substrate, etc. Typically 1 to 15 Mrad.

[0075] The thickness of the cured product (cured film) is preferably 0.1 to 20 μm, more preferably 0.2 to 1 When the thickness of the cured product is within the above range, the thickness is preferably in the range of 0.0 μm, and more preferably in the range of 0.3 to 7 μm. If the above-mentioned material is used, it is easy to achieve desired properties such as wear resistance. The thickness of the cured product can be determined by observing the cross section using an electron microscope or the like.

[0076] The elongation of the cured product is preferably measured as an elongation percentage in a tensile test at 140°C as described below. It is preferably 15% or more, more preferably 20% or more, and even more preferably 30% or more. When used in applications where elongation is important, it is preferably 50% or more, more preferably 55% or more. The upper limit is not particularly limited, but it is preferably 2 By keeping it within this range, defects such as cracks during molding can be suppressed. can.

[0077] The abrasion resistance of the cured product is preferably measured as the amount of change in haze in the abrasion test described below. 2.0% or less, more preferably 1.5% or less, even more preferably 1.0% or less, and particularly preferably The content is preferably 0.5% or less, and most preferably 0.3% or less, with the lower limit being 0.0%. By setting the thickness within this range, it is possible to prevent scratches during the processing step and scratches after molding.

[0078] As the chemical resistance of the cured product, the change in haze in the test described below is preferably 1. 0.5% or less, more preferably 1.4% or less, even more preferably 1.2% or less, particularly preferably The range is preferably 1.1% or less, and most preferably 0.7% or less, with the lower limit being 0.0%. By setting the temperature within this range, the chemical resistance after molding becomes excellent.

[0079] <Laminate> The laminate of the present invention (hereinafter also referred to as "the present laminate") comprises a substrate layer and an active energy ray curable film. The laminate further comprises a layer made of a cured product of the curable composition (cured film, hard coat layer). a primer layer provided between the base layer and the cured product, and a cured product of the base layer and a back functional layer provided on the surface opposite to the object side. In addition, as long as the effect of the present invention is not impaired, the cured product may have a layer on the base layer side. The substrate may have a surface functional layer provided on the surface opposite to the substrate.

[0080] (base material layer) As the substrate layer, known substrates can be used, for example, resin substrates, metal substrates, and paper substrates. Among these, resin substrates are preferred from the viewpoint of processability. The resin substrate may have a single layer structure or a multi-layer structure of two or more layers, and is not particularly limited. It is not a multi-layer structure with two or more resin substrates, each with its own characteristics, and is a multi-functional It is preferable to improve the functionality.

[0081] As the resin substrate, various resin films (sheets) can be used, for example, polyester films. Film, poly(meth)acrylate film, polyurethane film, polyolefin film Film, polycarbonate film, polyimide film, triacetyl cellulose film Film, polystyrene film, polyvinyl chloride film, polyvinyl alcohol film , nylon film, etc.

[0082] This laminate is used for surface protection and decoration of resin molding materials for interior and exterior automotive parts and electronic devices. When using polyester film, poly(meth)acrylate film, polyurethane Polyethylene film and polyolefin film are preferable, and polyester film is also preferable in consideration of formability. Preferred are vinyl films, poly(meth)acrylate films and polyurethane films, particularly Among these, polyester films and poly(meth)acrylate films are preferred.

[0083] The polyester film may be a non-stretched film or a stretched film. A stretched film is preferred. Among them, a uniaxially stretched film or a biaxially stretched film is preferred. A biaxially stretched film is preferred, from the viewpoint of excellent balance of mechanical properties and flatness. Therefore, biaxially stretched films are more preferable. Also, easily moldable types with improved moldability are preferable. For example, copolymerization of an isophthalic acid structure or the like into the structure of polyethylene terephthalate is Examples include polyester.

[0084] The base layer is designed to provide slipperiness, prevent scratches during each process, and improve blocking resistance. It is possible to include particles as a coating, and to improve weather resistance, it is possible to include an ultraviolet absorber. If necessary, additives other than the above-mentioned particles and ultraviolet absorbers can be added. The additives may include antioxidants, antistatic agents, heat stabilizers, lubricants, plasticizers, etc. Known additives such as colorants, dyes, and pigments can be used.

[0085] The thickness of the substrate layer is not particularly limited, but is preferably in the form of a film. Preferably 2 to 350 μm, more preferably 5 to 250 μm, and even more preferably 10 to 100 μm range.

[0086] In addition, the base layer is formed of a material having a thickness of 100 μm to 100 μm. Alternatively, corona treatment or plasma treatment may be performed.

[0087] (primer layer) The primer layer provides various functions between the substrate layer and the cured product of the active energy ray-curable composition. Examples of such layers include an adhesion improving layer and an antistatic layer.

[0088] In a preferred embodiment, the primer layer is an adhesion improving layer. If the adhesion is insufficient, the laminate may not be usable depending on the application. By doing so, the adhesion between the base layer and the cured product is improved, and the laminate can be used for various applications. The components constituting the primer layer include, for example, polyester resin, acrylic resin, urethane resin, polyvinyl resin (polyvinyl alcohol, vinyl chloride-vinyl acetate copolymer, etc.) etc.

[0089] <Application> The cured product obtained from the active energy ray-curable composition of the present invention has excellent abrasion resistance, adhesion to substrates, and Since it has excellent stretchability, it can be suitably used as a curable composition for decorative films. For example, it is effective for various components such as interior and exterior building materials, automobiles, home appliances, and information and electronic materials. It is possible to apply [Example]

[0090] The present invention will be described in more detail below with reference to examples, but the present invention does not exceed the gist of the invention. However, the present invention is not limited to the following examples. The values ​​of the conditions and evaluation results are meant as preferable upper or lower limit values ​​in the embodiments of the present invention. The preferred range is the upper or lower limit value described above and the values ​​or actual values ​​in the following examples. The range may be defined by combining the values ​​of the examples. The measurement and evaluation methods used in the present invention are as follows.

[0091] (1) Weight average molecular weight The weight average molecular weight of the copolymer was measured by GPC under the following conditions. Equipment: Waters "e2695" Column: TSKgel Super H3000+H4000+H manufactured by Tosoh Corporation 6000", Detector: Differential refractive index detector (RI detector / built-in), Solvent: tetrahydrofuran, Temperature: 40℃, Flow rate: 0.5mL / min, Injection volume: 10μL, Concentration: 0.2% by mass, Calibration sample: monodisperse polystyrene, Calibration method: Polystyrene equivalent

[0092] (2) Evaluation method for abrasion resistance test The cured surface of the laminate on which the cured product of the active energy ray-curable composition was formed was subjected to a 23°C , 50%RH atmosphere, Gakushin type friction tester (RT-2 manufactured by Daiei Scientific Instruments Co., Ltd.) 00) was used to perform 1000 round trips of Kanakin No. 3 with a 300g weight and R contact arm. The haze value was evaluated before and after the treatment. The haze was measured using a haze meter (manufactured by Murakami Color Research Laboratory Co., Ltd.) and JIS K The haze value after the abrasion test measured in accordance with JIS-7136 (2000) was compared with the haze value before the abrasion test. The haze value obtained by subtracting the haze value of the first sample from the first sample was evaluated as the amount of haze change.

[0093] (3) Evaluation method for chemical resistance test The cured surface of the laminate on which the cured product of the active energy ray-curable composition was formed was subjected to a 23°C , 50%RH atmosphere, Gakushin type friction tester (RT-2 manufactured by Daiei Scientific Instruments Co., Ltd.) 00) and the R contact arm is used to attach a nonwoven fabric (Bencotto (registered trademark) manufactured by Asahi Kasei Corporation) The test piece (M-3II) was soaked in 1 mL of methyl ethyl ketone and then reciprocated 50 times. The haze values ​​before and after treatment were evaluated. The haze was measured using a haze meter (manufactured by Murakami Color Research Laboratory Co., Ltd.) and JIS K The haze value after the abrasion test measured in accordance with JIS-7136 (2000) was compared with the haze value before the abrasion test. The haze value obtained by subtracting the haze value of the first sample from the first sample was evaluated as the amount of haze change.

[0094] (4) Evaluation of elongation (cured product) The laminate on which the cured product of the active energy ray-curable composition was formed was cut into 10 mm widths and Using a Shiron tensile testing machine (IMADA Co., Ltd. "MX2-500N"), the temperature was 140°C. The specimen was stretched at a tensile speed of 40 mm / min and a chuck distance of 40 mm, and the breaking elongation (visually The elongation (the elongation until cracks were observed) was measured and the elongation rate was evaluated. The elongation rate was calculated by dividing the length at which a crack appeared in the cured product by the length before the tensile test. Calculated.

[0095] (5) Measurement of transmittance at 360 nm The laminate on which the cured product of the active energy ray curable composition was formed was measured with a spectrophotometer (Hitachi Using a ratio beam spectrophotometer U-1900 manufactured by High Technologies, measurement mode : Wavelength scan, wavelength: 300-600nm, speed: 400, cell length: 10mm The transmittance at a wavelength of 360 nm was evaluated.

[0096] (6) Adhesion evaluation method The cured product side of the laminate having the cured product of the active energy ray curable composition formed thereon was subjected to a test at 23°C, 50% Under a RH environment, an 18 mm wide tape (Nichiban Cellotape (registered trademark) CT -18) was applied, and the peeled surface was observed after being rapidly peeled off at a peeling angle of 180 degrees. When there was no peeling, it was rated as A, and when there was peeling, it was rated as B. When there was no peeling, it was determined that the adhesion to the substrate was good. It can be judged that this is the case.

[0097] (7) Evaluation of tackiness The active energy ray curable composition is applied to a corona-treated easily moldable polyester film as a substrate. The coating thickness after drying was measured using a bar coater on the corona treated surface of the film (thickness: 100 μm). The coating was applied to a thickness of 5 μm and dried by heating at 80°C for 2 minutes. When touching the surface, if no finger marks were left, it was rated as A, and if finger marks were left, it was rated as B. When the tackiness is not so great, it can be judged that the tackiness is good.

[0098] The compounds used in the examples and comparative examples are as follows. (Meth)acrylic resin (A) A (meth)acrylic resin produced by the method shown below. In a flask equipped with a thermometer, stirrer and reflux condenser, add propylene glycol monomethyl ether. Ether (178 parts by mass), glycidyl methacrylate (20 parts by mass), methyl methacrylate Acrylate (79 parts by weight), ethyl acrylate (1.0 part by weight), and 2,2'-azobis( ... (2,4-dimethylvaleronitrile) (0.6 parts by mass) was added and the mixture was reacted at 65°C for 3 hours. Then, 2,2'-azobis(2,4-dimethylvaleronitrile) (0.3 After adding propylene glycol monomethyl ether (48 parts by mass) and reacting for 3 hours, parts by mass) and p-methoxyphenol (0.5 parts by mass) were added and heated to 100°C. Next, acrylic acid (10 parts by mass) and triphenylphosphine (1.6 parts by mass) were added. By adding acrylic acid and reacting it at 110°C for 6 hours, the amount of radical polymerizable double bonds (acryloyl (Meth)acrylic resin (A) having a group concentration (amount of acryloyl groups introduced) of 615 g / mol The weight average molecular weight was 48,800. The hydroxyl value was 91 mg KOH / g. (Meth)acrylic resin (B-1) A (meth)acrylic resin produced by the method shown below. In a flask equipped with a thermometer, stirrer and reflux condenser, add propylene glycol monomethyl ether. Ether (178 parts by mass), glycidyl methacrylate (40 parts by mass), methyl methacrylate acrylate (59 parts by weight), ethyl acrylate (1.0 part by weight), and 2,2'-azobis( ... (2,4-dimethylvaleronitrile) (0.6 parts by mass) was added and the mixture was reacted at 65°C for 3 hours. Then, 2,2'-azobis(2,4-dimethylvaleronitrile) (0.3 After adding propylene glycol monomethyl ether (48 parts by mass) and reacting for 3 hours, parts by mass) and p-methoxyphenol (0.5 parts by mass) were added and heated to 100°C. Next, acrylic acid (21 parts by mass) and triphenylphosphine (1.6 parts by mass) were added. The amount of double bonds (acryloyl group concentration ... The amount of methyl groups introduced was 365 g / mol, and a (meth)acrylic polymer (B-1) was obtained. The weight average molecular weight was 40,000. The hydroxyl value was 154 mg KOH / g. (Meth)acrylic resin (B-2) A (meth)acrylic resin produced by the method shown below. In a flask equipped with a thermometer, stirrer and reflux condenser, add propylene glycol monomethyl ether. Ether (178 parts by mass), glycidyl methacrylate (66 parts by mass), methyl methacrylate acrylate (33 parts by weight), ethyl acrylate (1.0 part by weight), and 2,2'-azobis( ... (2,4-dimethylvaleronitrile) (1.0 mass part) was added and the mixture was reacted at 65°C for 3 hours. I did. Then, 2,2'-azobis(2,4-dimethylvaleronitrile) (0.5 mass After adding propylene glycol monomethyl ether (48 mass parts) and reacting for 3 hours, Parts by mass) and p-methoxyphenol (0.5 parts by mass) were added and heated to 100°C. Next, acrylic acid (34 parts by mass) and triphenylphosphine (1.6 parts by mass) were added. The amount of double bonds (acryloyl group concentration ... The amount of introduced methyl group was 266 g / mol. Acrylic polymer (B-2) was obtained. The weight average molecular weight (Mw) was 31,800. The base value was 211 mgKOH / g. (Meth)acrylic resin (B-3) In a flask equipped with a thermometer, stirrer and reflux condenser, add propylene glycol monomethyl ether. Ether (157 parts by mass), glycidyl methacrylate (98 parts by mass), methyl methacrylate Acrylate (1.0 part by mass), ethyl acrylate (1.0 part by mass), mercaptopropyl acrylate Trimethoxysilane (1.9 parts by mass), and 2,2'-azobis(2,4-dimethylvalero) Nitrile) (1.0 mass part), γ-trimethoxysilylpropanethiol (Shin-Etsu Chemical Co., Ltd. 1.9 parts by mass of KBM-803 (manufactured by Co., Ltd.) was added, and the mixture was reacted at 65°C for 3 hours. Then, 2,2'-azobis(2,4-dimethylvaleronitrile) (0.5 mass After adding propylene glycol monomethyl ether (138 parts) and reacting for 3 hours, Parts by mass) and p-methoxyphenol (0.45 parts by mass) were added and heated to 100°C. Next, acrylic acid (51 parts by mass) and triphenylphosphine (3.1 parts by mass) were added. The amount of unsaturated double bonds (acryloyl equivalents (acryloyl equivalents)) was increased by adding 110°C and reacting for 6 hours. The amount of acryloyl group introduced is 216 g / mol, and the side chain has a radically polymerizable double bond. The weight average molecular weight (Mw) of the acrylic resin (B-3) was 17,700. The base value was 259 mg KOH / g. (Meth)acrylic resin (C) Methyl methacrylate polymer (weight average) having no radical polymerizable double bonds or hydroxyl groups average molecular weight 8000). (Meth)acrylate: D Dipentaerythritol hexaacrylate (hexafunctional) (Kayala, manufactured by Nippon Kayaku Co., Ltd.) (registered trademark DPHA) Leveling agent: E A silicone-based leveling agent with radical polymerizable functional groups (BYK-UV 3500) UV absorber: F 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)- 4,6-bis(4-phenylphenyl)-1,3,5-triazine (BASF Ti nuvin 479) Light stabilizer: G Bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis( 1,1,dimethylethyl)-4-hydroxyphenyl]methyl] (BASF Tin uvin 144) Photopolymerization initiator: H 1-Hydroxycyclohexyl phenyl ketone (IGM Resins BV) Omnirad 184)

[0099] [Example 1] The coating liquid (active energy ray curable composition) shown in Table 1 below was used as a substrate and subjected to corona treatment. The corona treated surface of the easily molded polyester film (thickness: 100 μm) was coated with a bar coater. The coating was applied using a coating solution so that the coating thickness after drying would be 5 μm, and then heated and dried at 80°C for 2 minutes. After that, it was exposed to a high-pressure mercury lamp in an air atmosphere with an integrated light intensity of 300 mJ / cm 2 , illuminance 200mW / cm 2 (High-power UV device manufactured by Eye Graphics Co., Ltd. (Model: US5-X1802 UV rays are irradiated on the UV conveyor of the -X1202) to form a cured product (cured film) and laminate obtained.

[0100] The resulting laminate was excellent in abrasion resistance, chemical resistance, elongation, and adhesion. The properties are shown in Table 2 below.

[0101] [Examples 2 to 8] The same as in Example 1 except that the coating agent composition was changed to the coating agent composition shown in Table 1. The laminate thus obtained had excellent abrasion resistance, chemical resistance, and The extensibility, adhesion, and tackiness were all good. The properties of the resulting laminate are shown in Table 2 below.

[0102] [Comparative Examples 1 to 7] The same as in Example 1 except that the coating agent composition was changed to the coating agent composition shown in Table 1. The properties of the resulting laminate are shown in Table 2 below. As shown in the figure, the results showed poor properties such as abrasion resistance and elongation. Since the resin does not have a double bond or a hydroxyl group, it is inferior in abrasion resistance and adhesion to the substrate. Since polyfunctional (meth)acrylate was used instead of fat B, the tackiness was poor. Comparative Examples 4 and 5 did not contain Resin B, and therefore the chemical resistance was insufficient. In comparison, Comparative Example 5 does not contain a silicone-based leveling agent having a radical polymerizable functional group. In Comparative Examples 6 and 7, Resin A was not included, and therefore the extensibility was poor. was inferior.

[0103] [Table 1]

[0104] The coating agent in Table 1 was applied with methyl ethyl ketone so that the non-volatile content was 25%. The unit of each value in the table is parts by mass.

[0105] [Table 2]

Claims

1. An active energy ray-curable composition comprising (meth)acrylic resin A and (meth)acrylic resin B, wherein the (meth)acrylic resin A has a radical polymerizable double bond equivalent of 501 to 10,000 g / mol, the (meth)acrylic resin A has a hydroxyl value of 5 to 115 mgKOH / g, the (meth)acrylic resin B has a radical polymerizable double bond equivalent of 200 to 500 g / mol, and the (meth)acrylic resin B has a hydroxyl value of 116 to 270 mgKOH / g.

2. 2. The active energy ray-curable composition according to claim 1, wherein the radical polymerizable double bond equivalent of the nonvolatile matter of the active energy ray-curable composition is 300 to 1000 g / mol.

3. The active energy ray-curable composition according to claim 1 or 2, further comprising a leveling agent.

4. The active energy ray-curable composition according to any one of claims 1 to 3, further comprising an ultraviolet absorber.

5. An active energy ray-curable composition described in any one of claims 1 to 4, wherein the weight average molecular weight of the (meth)acrylic resin A is 1,000 to 200,000.

6. An active energy ray-curable composition according to any one of claims 1 to 5, wherein the weight average molecular weight of the (meth)acrylic resin B is 1,000 to 200,000.

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

8. 8. The cured product according to claim 7, which has an elongation of 15% or more in a tensile test at 140°C.

9. A laminate comprising the cured product according to claim 7 or 8 on a substrate.

10. The laminate according to claim 9, which has a transmittance of 80% or less at a wavelength of 360 nm.

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