Curable composition, cured product and laminate

Abstract

To provide a laminate capable of broadening the application range of a cured layer such as a substrate and a hard coat layer by providing a primer layer between a cyclic olefin substrate and a hard coat layer, having good interlayer adhesion and having excellent transparency and scratch resistance.SOLUTION: There is provided a laminate having a primer layer containing a polyolefin-based resin on at least one surface of a cyclic olefin substrate and having a cured layer on the primer layer.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a laminate having a cyclic olefin substrate, a primer layer, and a cured layer. [Background technology]

[0002] Liquid crystal display devices, electroluminescent display devices, etc. are becoming larger and thinner. Higher performance than ever before is being demanded. The cyclic olefin substrate, which has excellent moisture-proofing properties, optical isotropy, low birefringence, and heat resistance, is used to protect polarizing plates. It is being investigated for use in optical components such as protective films and retardation films. These films have low surface hardness, and therefore, in order to improve scratch resistance, In 1, a hard coat layer is formed. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-200709 Summary of the Invention [Problem to be solved by the invention]

[0004] However, in the method of Patent Document 1, the type of cyclic olefin substrate and hard coat layer used In some cases, the adhesion between the substrate and the hard coat layer was insufficient.

[0005] The present invention has been made to solve the above problems, and is a method for manufacturing a cyclic olefin substrate and a hard coat. By providing a primer layer between the base and hard coat layers, it is possible to apply a hardened layer such as a substrate or hard coat layer. To provide a laminate which can be used in a wide range, has good adhesion between layers, and is excellent in transparency and scratch resistance. The purpose is to: [Means for solving the problem]

[0006] The present invention has the following aspects. [1] A cyclic olefin substrate containing a polyolefin resin on at least one surface thereof. and a cured layer on the primer layer. [2] The polyolefin resin is a mixture of ethylene and / or propylene and a copolymer having 4 or more carbon atoms. The laminate according to [1] above, which is a copolymer with the above α-olefin. [3] The weight average molecular weight of the polyolefin resin converted using a calibration curve of polystyrene is The laminate of [1] or [2] above, wherein the molecular weight is 5,000 to 500,000. [4] Any of the above [1] to [3], wherein the polyolefin resin contains a reactive group. The laminate according to any one of claims 1 to 3. [5] In the polyolefin resin, a structural unit derived from a monomer having a reactive group.

[0023] According to any one of the above [1] to [4], the content of Laminate of. [6] The compound according to any one of [1] to [5], wherein the reactive group is an acid anhydride group or a carboxyl group. The laminate according to any one of claims 1 to 14. [7] The polyolefin resin contains a polyether structure, The curable composition according to any one of claims 1 to 4. [8] The cured layer contains a compound derived from a (meth)acrylate compound. The laminate according to any one of [1] to [6]. [9] The curable layer contains a compound derived from a resin containing a curable group, [6] The laminate according to any one of the preceding items. [Effects of the Invention]

[0007] According to the present invention, a laminate having good interlayer adhesion, transparency, and scratch resistance is provided. It is possible. DETAILED DESCRIPTION OF THE INVENTION

[0008] Hereinafter, embodiments of the present invention will be described in detail. In the present invention, "(meth)acrylate" refers to the total of acrylates or methacrylates. It is a title. The "~" symbol indicates a range of values, and includes the values ​​before and after it as the lower and upper limits. The numerical ranges disclosed in this specification can be obtained by arbitrarily combining the lower and upper limits. The new numerical range can be created by combining the above.

[0009] <Cyclic olefin substrate> The base material is required to have transparency, mechanical properties, moisture-proof properties, optical isotropy, low birefringence, and heat resistance. The present invention is characterized by the use of a cyclic olefin substrate having excellent properties. Any of those known in the art can be used, and the structure thereof is such that cyclic olefin units form a polymer backbone. It has an alicyclic structure in its molecular structure, which is polymerized alternately or randomly. from olefinic compounds, monocyclic olefins, cyclic conjugated dienes and vinyl alicyclic hydrocarbons Cycloolefin (co)polymer containing at least one compound selected from The material is a polymer or a cycloolefin copolymer. From the viewpoint of mechanical strength, the glass transition temperature is preferably 50 to 250°C, more preferably Preferably, the temperature is 100 to 220°C, more preferably 120 to 200°C, and particularly preferably 150 to 1 The range is 90°C.

[0010] The substrate may be in the form of a film or a substrate, and is suitable for use in optical components such as liquid crystal displays. When used as a material, it can be in the form of a film. Various types of stretched films can be used, such as uniaxial stretched films, and inclined stretched films. In consideration of optical properties, non-stretched or inclined stretched types are preferable. Although there are no particular limitations, in consideration of mechanical strength etc., it is 5 to 5000 μm, preferably 10 to 3 00 μm, and more preferably in the range of 20 to 200 μm.

[0011] In addition, the substrate is subjected to corona treatment or plasma treatment to improve adhesion with the primer layer. may be applied.

[0012] <Primer layer> A ply containing a polyolefin resin is provided on at least one surface of the cyclic olefin substrate. The primer has a cyclic olefin substrate and a layer that provides scratch resistance. It is used to improve adhesion with the hardening layer provided for the purpose of bonding. The material has excellent optical properties and moisture-proofing properties, but on the other hand, it has poor adhesion to topcoats. Unless the selected material is used, it is difficult to achieve adhesion with the hardened layer such as the hard coat layer. Therefore, it is difficult to fully utilize the performance of the hardened layer, and a wide range of materials cannot be used. A design that can adhere to the cyclic olefin substrate and also to various types of cured layers was desired. We considered interposing a primer layer containing a polyolefin-based material. It was found that the inclusion of such a material can significantly improve adhesion.

[0013] The polyolefin resin contained in the primer layer is a variety of polyolefins and modified polyolefins. It is a polyolefin, and is not particularly limited to, for example, a homopolymer of ethylene or propylene. copolymers of ethylene and propylene, copolymers of ethylene and / or propylene with other copolymers Examples of copolymers include copolymers with olefins.

[0014] Examples of copolymers of ethylene and / or propylene with other comonomers include: Ethylene and / or propylene, butene, pentene, hexene, heptene, octene, cyclohexene α-olefin monocompounds with 4 or more carbon atoms, such as cyclopentene, cyclohexene, and norbornene Copolymers of these comonomers and copolymers of two or more of these comonomers are also included.

[0015] The α-olefin comonomer is preferably an α-olefin comonomer having 4 to 20 carbon atoms. Also, α-olefin comonomers and vinyl acetate, acrylic esters or methyl esters are used. Copolymers with comonomers such as acrylate esters, α-olefin comonomers and aromatic Copolymers with comonomers such as vinyl monomers or hydrogenated products thereof, or conjugated diene A lock copolymer or a hydrogenated product thereof can also be used. In consideration of adhesion to the substrate and the cured layer, aliphatic compounds are preferred, and linear compounds are preferred over cyclic compounds. The chain structure is preferable. The number of carbon atoms is preferably 4 to 12, and more preferably 1 to 2. butene having 4 to 8 carbon atoms, more preferably 4 to 6 carbon atoms, and most preferably 4 carbon atoms is.

[0016] Furthermore, chlorinated polyolefins obtained by chlorinating these polyolefins can also be used. The degree of chlorination of the polyolefin is 5% by mass or more, preferably 10% by mass or more. The degree of polymerization is usually 50% by mass or less, preferably 30% by mass or less. Although it is expected to be effective in improving adhesion with various materials, its use is discouraged in light of current environmental issues. It is preferable not to do so.

[0017] The polyolefin resin may be a random copolymer or a block copolymer. It may be straight-chain or branched. , polypropylene, ethylene-propylene copolymer, propylene-butene copolymer, pro Pyrene-hexene copolymer, chlorinated polyethylene, chlorinated polypropylene, chlorinated ethylene propylene-propylene copolymer, chlorinated propylene-butene copolymer, ethylene-vinyl acetate copolymer Polymers, hydrogenated styrene-butadiene-styrene block copolymers (SEBS) and and hydrogenated styrene-isoprene-styrene block copolymer (SEPS). In order to improve adhesion more effectively, the polyolefin resin should be: It is preferable that the material is composed of only polyolefin, for example, a block copolymer with styrene. It is preferable that the polyolefin does not contain any constituent parts other than polyolefins, such as polyolefins (including hydrogenated polyolefins). Among these, it is preferable to contain a propylene structure from the viewpoint of adhesiveness. For example, preferred forms include propylene homopolymers or propylene and other α-olefins. Copolymers with olefins are also preferred, and these may be chlorinated. Substantially chlorine-free propylene homopolymer, ethylene-propylene copolymer, propylene ethylene-butene copolymer, ethylene-propylene-butene copolymer, and more preferably is a propylene-butene copolymer. These may be used alone or in combination of two or more. may be used in combination.

[0018] Ethylene and / or propylene and α-olefin for the entire polyolefin resin In the case of copolymers with comonomers, the ratio of α-olefin to the total polyolefin resin is The proportion of the comonomer is preferably 80 mol % or less, more preferably 1 to 70 mol %. , more preferably 5 to 60 mol %, particularly preferably 10 to 50 mol %, and most preferably The range is 15 to 40 mol %. By using it in the above range, the adhesion to the substrate and the cured layer is improved. It can be raised. In addition, the presence of a propylene structure in polyolefin resins is effective in improving adhesion. It was found that the ratio of propylene to the total polyolefin resin was is preferably 20 mol % or more, more preferably 30 to 99 mol %, and further preferably 4 0 to 95 mol %, particularly preferably 50 to 90 mol %, most preferably 60 to 85 mol % It is a range.

[0019] The melting point of the polyolefin resin is in the range of 30 to 125°C from the viewpoint of adhesion, etc. The temperature is preferably from 50 to 100°C, more preferably from 60 to 90°C.

[0020] The weight average molecular weight (Mw) of the polyolefin resin used in the polyolefin resin is The polypropylene equivalent is preferably 5,000 to 500,000, and more preferably 10,000 to 400,000 is more preferable, and 30,000 to 300,000 is even more preferable. By using it in this range, adhesion to the substrate improves and the viscosity becomes within a moderate range when applying. This makes it easier to adjust the resin dispersion used in the above cases.

[0021] Polyolefin resins can also be analyzed by gel permeation chromatography (GP C) and converted using the calibration curve of each polyolefin. The molecular weight distribution (Mw / Mn), which is the ratio of the molecular weight (Mn), is preferably 10 to 1. It is more preferably 5 to 1, and even more preferably 3 to 1. By using this, the viscosity does not become too high and it becomes easy to handle, and it can be used as a dispersion liquid for coating, etc. When used as a sol, the dispersibility is good. This is carried out by a conventionally known method using a commercially available device, with benzene or the like as a solvent. As shown in the figure.

[0022] The method for producing the polyolefin resin is not particularly limited, and any method may be used. Examples of polymerization include radical polymerization, cationic polymerization, anionic polymerization, and coordination polymerization. Each may be a living polymer.

[0023] In the case of coordination polymerization, for example, a method of polymerization using a Ziegler-Natta catalyst or A preferred method is polymerization using a Glucite catalyst or a Kaminsky catalyst. As an example, a production method using a single-site catalyst can be mentioned. The reason for this is as follows: Generally, single-site catalysts have molecular weight distribution or stereoregularity distribution depending on the ligand design. are sharp.

[0024] Examples of single-site catalysts include metallocene catalysts and Brookhart catalysts. Among them, metallocene catalysts are preferred. Metallocene catalysts include C1 symmetrical, C2 symmetrical, C2V symmetrical or CS symmetrical type is preferred depending on the stereoregularity of the polyolefin to be polymerized. A suitable catalyst should be selected. Preferably, a C1 symmetric or C2 symmetric metallocene catalyst is used. There is.

[0025] The polymerization may be carried out in any form, such as solution polymerization, slurry polymerization, bulk polymerization, or gas phase polymerization. In the case of solution polymerization or slurry polymerization, the solvent may be, for example, toluene and xylene. aromatic hydrocarbons such as hexane, octane, and decane; aliphatic hydrocarbons such as cyclohexane, cyclohexane, and cyclohexane; Alicyclic aliphatic hydrocarbons such as hexane and methylcyclohexane, chloroform and chloroform halogenated hydrocarbons such as benzene, esters such as ethyl acetate and butyl acetate, acetone ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Alcohols such as methanol, ethanol, isopropanol and n-butanol, dibutyl ether Ethers such as ethyl ether and tetrahydrofuran, as well as dimethylformamide and diethyl ether Examples of suitable solvents include polar solvents such as methyl sulfoxide. Preferred are alicyclic hydrocarbons and alicyclic hydrocarbons, and more preferred are toluene, xylene, and hexane. These are hexane, heptane, cyclopentane, and cyclohexane. Alternatively, two or more of them may be used in combination.

[0026] The polyolefin resin preferably has a reactive group from the viewpoint of providing adhesiveness. Examples of the reactive group include a carboxyl group, a dicarboxylic acid anhydride group, a dicarboxylic acid anhydride mono group, and the like. Examples of the alkyl group include an ester group, a hydroxyl group, an amino group, an epoxy group, and an isocyanate group. More preferably, carboxyl groups, dicarboxylic acid anhydride groups and dicarboxylic acid anhydride monoesters The main purpose of the present invention is to have at least one carboxyl group selected from the group consisting of carboxyl groups and terephthalic acid groups. The groups are highly reactive and easily bonded to other compounds. There are many compounds, and copolymerization or graft reaction is used to introduce reactive groups into polyolefin resins. It is also possible to use it as a polar group, which can improve the dispersibility of the coating liquid. It can also contribute to improving adhesion.

[0027] Examples of polyolefin resins containing reactive groups include those which have reactive groups during polymerization. Copolymers of unsaturated compounds with no reactive groups and unsaturated compounds with reactive groups Examples of polymers include those obtained by graft polymerizing a radical polymerizable unsaturated compound having the following structure onto a polyolefin. In terms of ease of adjusting the amount of reactive groups, the latter graft-polymerized polymer The body is more preferable.

[0028] Copolymerization of an unsaturated compound that does not have a reactive group during polymerization with an unsaturated compound that has a reactive group The copolymer is a copolymer of an unsaturated compound having no reactive group and an unsaturated compound having a reactive group. It is a copolymer obtained by copolymerizing the above and has an unsaturated compound having a reactive group inserted into the main chain. For example, an α-olefin such as ethylene, propylene, or butene and an acrylic acid or It is obtained by copolymerizing an α,β-unsaturated carboxylic acid such as maleic anhydride or its anhydride. Specifically, for example, ethylene-acrylic acid copolymer and ethylene-acrylic acid ester These may be used alone or in combination of two or more. The above may be used in combination. The method for producing the copolymer is the same as that described for the polyolefin resin. The above method can be used as well.

[0029] Polymers in which radically polymerizable unsaturated compounds having reactive groups are graft-polymerized onto polyolefins The polymer is a polymerized polyolefin polymerized in advance, to which a radical polymerizable unsaturated compound having a reactive group is added. It is obtained by graft polymerization of an unsaturated compound having a reactive group grafted onto the main chain. For example, polyolefins such as polyethylene or polypropylene are p) Acrylic acid, fumaric acid, maleic acid or its anhydride, itaconic acid or its anhydride Water, Crotonic acid, (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid 2- Hydroxypropyl, (meth)acrylamide, (meth)acrylic acid (dimethylamino) Ethyl (meth)acrylate, glycidyl (meth)acrylate or (2-isocyanato)ethyl (meth)acrylate Among these, the polymers with grafted ethylene, etc. are particularly suitable for ease of introduction. , (meth)acrylic acid, fumaric acid, maleic acid or anhydride thereof is preferred, and the reactive group In consideration of the efficiency of introduction, acid anhydrides are more preferred, and maleic anhydride is even more preferred. These may be used alone or in combination of two or more. The polyolefin used in this reaction to obtain the polymer is a polyolefin having no reactive groups as described above. Polyolefin resins can be used.

[0030] The radical polymerization initiator used in the graft polymerization is appropriately selected from ordinary radical initiators. Examples of the organic peroxides include organic peroxides and azonitriles.

[0031] Examples of organic peroxides include peroxides such as di(t-butylperoxy)cyclohexane. Hydroxyketals, hydroperoxides such as cumene hydroperoxide, di(t-butyl) dialkyl peroxides such as methyl peroxide, diacid peroxides such as benzoyl peroxide, peroxides such as butyl peroxides and t-butylperoxyisopropyl monocarbonate esters and the like.

[0032] Examples of azonitriles include azobisbutyronitrile and azobisisopropylnitrile. Among them, benzoyl peroxide and t-butylperoxyisopropyl Propyl monocarbonate is particularly preferred. These may be used alone or in combination of two or more. The above may be used in combination.

[0033] The ratio of the radical polymerization initiator to the radical polymerizable unsaturated compound having a reactive group is generally Usually, the ratio of radical polymerization initiator to radically polymerizable unsaturated compound having a reactive group is 1:100 or more. The molar ratio is in the range of 2:1, preferably in the range of 1:30 to 1:1.

[0034] Polymers in which radically polymerizable unsaturated compounds having reactive groups are graft-polymerized onto polyolefins The method for producing the combination is not particularly limited, and any method may be used. For example, a method of reacting by heating and stirring in a solvent-free state, a method of reacting by melting, heating and stirring in a solvent-free state, and an extrusion method. For example, the solvent for the production in a solution is The solvents mentioned as solvents used in the production of polyolefin resins can be used in the same manner. can.

[0035] The reaction temperature is usually 50°C or higher, preferably 80 to 250°C, more preferably 90 The reaction time is usually 1 to 20 hours, preferably 2 to 12 hours. do.

[0036] Polymers in which radically polymerizable unsaturated compounds having reactive groups are graft-polymerized onto polyolefins Specific examples of the polymer include maleic anhydride-modified polypropylene and its chlorinated products. , maleic anhydride modified ethylene-propylene copolymer and its chlorinated derivatives, maleic anhydride Modified propylene-butene copolymer and its chlorinated derivatives, acrylic acid modified polypropylene and chlorinated acrylic acid-modified ethylene-propylene copolymers and chlorinated acrylic acid-modified ethylene-propylene copolymers, and acrylic acid-modified ethylene-propylene copolymers and chlorinated acrylic acid-modified ethylene-propylene copolymers. Acrylic acid-modified propylene-butene copolymer, etc. Among these, maleic anhydride is particularly preferred. Acid-modified polypropylene, maleic anhydride-modified ethylene-propylene copolymer, maleic anhydride Maleic anhydride-modified propylene-butene copolymer is preferred, and maleic anhydride-modified propylene-butene copolymer is preferred. These may be used alone or in combination of two or more. It may also be used in combination.

[0037] Polyolefin resins containing reactive groups are measured by GPC and are analyzed using a calibration curve for polystyrene. The converted weight average molecular weight (Mw) is preferably 5,000 to 500,000, 10,000 to 400,000 is more preferable, and 30,000 to 300,000 is even more preferable. Preferably, 50,000 to 250,000 is particularly preferred, and 100,000 to 250,000 is particularly preferred. By using it in the above range, stickiness can be reduced and adhesion to the substrate can be improved. Improved adhesion and a moderate viscosity range make it easier to adjust the resin dispersion when applying. There is a tendency for this to happen.

[0038] Polyolefin resins containing reactive groups were measured by GPC and each polystyrene was analyzed. Molecular weight distribution, which is the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) converted by the molecular weight curve. (Mw / Mn) is preferably 10 to 1, more preferably 5 to 1, and It is more preferable that the viscosity is 1 to 1. By using the above range, the viscosity is not too high and the composition can be easily handled. It is easy to use, and when used as a dispersion for coating, etc., it has good dispersibility. The GPC measurement was carried out using a commercially available equipment with tetrahydrofuran (THF) as a solvent. This is carried out by a conventionally known method using a suitable device, as will be specifically described later.

[0039] The content of reactive groups in polyolefin resins containing reactive groups affects adhesion and liquid From the perspective of improving dispersibility when using a polyolefin resin containing reactive groups, 0. It is preferable that the range of the amount of the hydroxyl group is 0.01 to 5 mmol, that is, 0.01 to 5 mmol / g. It is more preferable that the content is 0.03 to 3 mmol / g, and it is preferable that the content is 0.05 to 2 mmol / g. It is more preferable that the content is 0.1 to 1 mmol / g, and particularly preferable that the content is 0.1 to 1 mmol / g.

[0040] Furthermore, by reacting with the reactive groups contained in polyolefin resins, it can improve adhesion, dispersibility, etc. It is also possible to make the resin have a structure that provides additional performance. For example, a polyether structure can be mentioned. Polyolefin resin having a polyether structure By doing so, it is possible to expect improvement in adhesion and dispersibility in various solvents such as water. For example, when preparing a water dispersion of polyolefin resin, it is usually necessary to use a surfactant. Although it is difficult to do so, using surfactants may result in poor water resistance and chemical resistance, or may cause polio. When olefin resin is used to make paint, surfactants tend to bleed onto the surface of the paint film after application. Therefore, there are cases where the surface appearance deteriorates due to the coating being out of shape. It is desirable to disperse the polymer, and the inclusion of a polyether structure solves this problem. This may lead to.

[0041] The polyether resin for introducing a polyether structure into a polyolefin resin is As long as the effect of the light is not significantly impaired, any suitable material may be used, including synthetic polymers, semi-synthetic polymers, etc. Either synthetic or natural polymers can be used.

[0042] The polyether resin may be, for example, a cyclic alkylene oxide or a cyclic alkylene imine. The polyether resin and the polyolefin resin are bonded by ring-opening polymerization. Although not particularly limited, for example, a cyclic alkyl group in a polyolefin resin containing a reactive group A method for ring-opening polymerization of alkylene oxide, and a polyether polymer obtained by ring-opening polymerization, etc. Reaction of reactive groups such as ol or polyetheramine contained in polyolefin resin Examples of the method include a method of reacting a functional group.

[0043] Polyether polyol is a resin having a polyether structure, which has one or both ends thereof: Examples of the reactive group include compounds having a hydroxyl group. A resin having a terephthalate structure, which has a primary amino group as a reactive group at one or both ends. Also, hydrophilic polyalkylene oxides or polyalkylene compounds can be used. The imine preferably includes polyethylene oxide or polyethyleneimine. .

[0044] Examples of polyetheramines include Jeffamine M series manufactured by Huntsman. , D series, ED series and Surfonamin L series.

[0045] The polyether resin used in the present invention is preferably a polyolefin resin before being bonded to the polyolefin resin. It is preferable that the polymer has one or more reactive groups capable of reacting with the vinyl resin. , for example, a carboxyl group, a dicarboxylic acid anhydride group, a dicarboxylic acid anhydride monoester group hydroxyl group, amino group, epoxy group and isocyanate group. Preferably, the hydroxyl group has at least one of an amino group and a hydroxyl group. It is more preferable that the .alpha.-hydroxybenzoate has the following structure:

[0046] The amino group can be a carboxyl group, an acid anhydride group, a glycidyl group, an isocyanate group, or any other group. It has high reactivity with the reactive groups of polyolefin resins and polyether resins. The amino group may be primary, secondary or tertiary, but more preferably It is a primary amino group.

[0047] The polyether resin may have one or more reactive groups, but more preferably has one reactive group. If there are two or more reactive groups, they can be bonded to polyolefin resins. When the material is mixed with water, a three-dimensional network structure may form, causing gelation.

[0048] However, even if there are multiple reactive groups, if only one reactive group is more reactive than the others, For example, a polyether having multiple hydroxyl groups and one more reactive amino group can be used. The reactive group of the polyolefin resin is a preferable example. This refers to reactivity with

[0049] Examples of polyether resins include polyethylene oxide and polypropylene oxide. copolymers with various polyether structures, such as carbon A polyether block having an alkylene group with a carbon number of 2 and a polyether block having an alkylene group with a carbon number of 3 to 4 Examples include block copolymers with polyether blocks. Two or more types of polyether blocks having ethylene groups are contained in the block copolymer. Among these, polyethylene oxide / polyethylene glycol is preferred from the viewpoint of adhesion and liquid dispersibility. Polypropylene oxide copolymers and polyethylene oxide / polybutylene oxide Copolymers of polyethylene oxide / polypropylene oxide are preferred. In the case of copolymers, there is no particular limitation on the ratio, but polyethylene oxide is preferred. The ratio of side and polypropylene oxide or polybutylene oxide is preferably Preferably, the ratio is 1:100 to 100:1, more preferably 1:50 to 50:1, and even more preferably 1: The range is 10 to 10:1.

[0050] Polyether resins are measured by GPC and compared with polystyrene in terms of adhesion and liquid dispersibility. The weight average molecular weight (Mw) calculated by the weight curve is preferably 200 to 200,000. , 300 to 100,000 is more preferable, 400 to 10,000 is more preferable, and 50 A range of 0 to 5,000 is particularly preferred.

[0051] The proportion of polyether resin contained in polyolefin resin affects adhesion and liquid dispersion. From the viewpoint of the property, the content is preferably 1 to 50% by mass, more preferably 3 to 45% by mass, and even more preferably The content is preferably in the range of 5 to 40 mass %.

[0052] In addition to the polyolefin resin, the primer layer may contain various conventionally known resins. For example, acrylic resin, polyester resin, urethane resin, vinyl Among these, the resins with excellent adhesion to the substrate and the cured layer are In this respect, acrylic resins, polyester resins and urethane resins are preferred, and particularly Considering the adhesion to the cured layer, acrylic resins are preferred.

[0053] Acrylic resins are made from carbon-based materials such as acrylic and methacrylic monomers. These are polymers made from polymerizable monomers with carbon-carbon double bonds. In addition, the polymer may be a copolymer of the polymer with other polymers (e.g., poly(ethylene glycol)). Also included are copolymers with polymers (polyesters, polyurethanes, etc.). For example, block copolymers, gr Alternatively, a carbon RAFT copolymer may be used in a polyester solution or dispersion. Polymers (sometimes called polymers) obtained by polymerizing polymerizable monomers with carbon-carbon double bonds. Similarly, the use of carbon- A polymer (sometimes called a polymer) obtained by polymerizing a polymerizable monomer having a carbon double bond. Similarly, carbon-carbon dimers in other polymer solutions or dispersions are also included. Polymers (sometimes polymer blends) obtained by polymerizing polymerizable monomers with double bonds In addition, to further improve adhesion, hydroxyl groups and amino groups are included. It is also possible to have

[0054] The polymerizable monomer having a carbon-carbon double bond is not particularly limited, but particularly, Typical compounds include, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, Various carboxyl group-containing monomers such as fumaric acid, maleic acid, citraconic acid, and and their salts; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl ( meth)acrylate, 4-hydroxybutyl (meth)acrylate, monobutyl hydroxy Various hydroxyl group-containing monomers such as monobutyl hydroxy itaconate, monobutyl hydroxy itaconate Methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, (Meth)acrylic acid esters; (meth)acrylamide, diacetone acrylamide, N - various nitrogen-containing compounds such as methylol acrylamide or (meth)acrylonitrile, etc. Compounds: γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, etc. various silicon-containing polymerizable monomers such as; phosphorus-containing vinyl monomers; Examples of such conjugated dienes include:

[0055] Polyester resins are mainly composed of polycarboxylic acids such as those shown below. and polyvalent hydroxy compounds. , terephthalic acid, isophthalic acid, orthophthalic acid, phthalic acid, 4,4'-diphenyldibenzoate carboxylic acid, 2,5-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, and 2,6-Naphthalenedicarboxylic acid, 2,7-Naphthalenedicarboxylic acid, 1,4-Cyclohexyl Xanedicarboxylic acid, 2-potassium sulfoterephthalate, 5-sodium sulfoisophthalate Acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, glutaric acid, succinic acid Trimellitic acid, trimesic acid, pyromellitic acid, trimellitic anhydride, pyromellitic anhydride Monopotassium salts of benzoic acid, p-hydroxybenzoic acid, trimellitic acid and their esters As the polyhydroxy compound, ethylene glycol derivatives can be used. 1,2-propylene glycol, 1,3-propylene glycol, 1,3-propane Hexanediol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,5 -Pentanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, p-Xylylene glycol, bisphenol A-ethylene glycol adduct, diethylene Glycol, triethylene glycol, polyethylene glycol, polypropylene glycol -al, polytetramethylene glycol, polytetramethylene oxide glycol, dimethyl Trimethylolpropionic acid, glycerin, trimethylolpropane, dimethylolethyl sulfonate sodium phosphate, potassium dimethylolpropionate, etc. One or more of the compounds are suitably selected from each of the above, and polyester is obtained by a conventional polycondensation reaction. A resin can be synthesized.

[0056] Urethane resin is a polymer compound that has urethane bonds in its molecules. Polyurethane resin is made by the reaction of polyol and isocyanate. , polycarbonate polyols, polyester polyols, polyether polyols Polyolefin polyols and acrylic polyols are examples of such compounds. They may be used alone or in combination of two or more.

[0057] In addition, a conventionally known crosslinking agent can be used in the primer layer to increase its strength. Examples of the compound include oxazoline compounds, epoxy compounds, melamine compounds, isocyanates, and the like. Examples of the compound include methyl methacrylate compounds, carbodiimide compounds, and silane coupling compounds.

[0058] Furthermore, the primer layer may contain particles, defoamers, coating improvers, thickeners, organic compounds, etc., as required. Even if lubricants, antistatic agents, UV absorbers, antioxidants, foaming agents, dyes, pigments, etc. are contained, good.

[0059] The content of the polyolefin resin in the primer layer is preferably 1% by mass or more, more preferably Preferably 30% by mass or more, more preferably 50% by mass or more, particularly preferably 70% by mass or more The most preferred range is 85% by mass or more, and 100% by mass (all components are polyolefins) By using it in the above range, good adhesion to the substrate and the cured layer is obtained. It becomes something like this.

[0060] The primer layer can be formed by applying a coating liquid or by transferring. The preferred method is to apply a coating liquid. When selecting a method for forming the coating liquid by the above method, the solid content of the coating liquid may be appropriately changed depending on the application. However, from the viewpoint of improving the operability in the coating operation, it is preferably 1 to 100%. The range is more preferably 2 to 70%, and even more preferably 3 to 50%.

[0061] When forming the primer layer by coating, it is applied to the substrate to form a coating film, and if necessary, It can be formed by drying or heating. When forming a primer layer by coating, the coating method is not particularly limited. Top coating method, air knife coating method, curtain coating method, spin coating method, roller coating method coating method, bar coating method, wire bar coating method, gravure coating method, spray coating method, etc. The coating can be carried out by a known method.

[0062] When the coating solution for the primer layer contains an organic solvent, the organic solvent in the coating film is effectively removed. It is preferable to carry out a drying process for this purpose, and the drying temperature for the heat drying is preferably 30 to 200 °C, more preferably 40 to 150 °C, and even more preferably 50 to 120 °C. The time is preferably 0.01 to 30 minutes, more preferably 0.1 to 10 minutes.

[0063] The thickness of the primer film is not particularly limited, but is preferably 0.01 to 20 μm, more preferably Preferably, it is 0.1 to 10 μm, more preferably 0.3 to 7 μm, and even more preferably 0.5 to If the thickness of the primer film is within the above range, the desired adhesion is achieved. The thickness of the primer layer can be determined by observing the cross section using an electron microscope or the like.

[0064] <Hardened layer> The hardened layer is provided for the purpose of imparting strength and improving scratch resistance. There are no particular limitations on the type of curing agent, but examples include active energy ray curing and heat curing. More preferred is one that is cured by active energy rays.

[0065] When forming a cured layer by active energy ray curing, a conventionally known active energy ray curable layer is used. For example, a (meth)acrylate compound can be preferably used. It is a material that can be used in various applications. It also uses a resin that contains a curable group that reacts with active energy rays. It is also possible to use resins containing carbon-carbon unsaturated bonds, more specifically (meth)- ) Acrylic resins, urethane resins or polyester resins containing acryloyl groups The curable group is a group that reacts with irradiation of active energy rays. This refers to reactive groups in general, including, for example, ethylenically unsaturated groups and (meth)acryloyl groups. Among these resins with reactive groups, the resin with improved adhesion and the ease of adjusting the reactive groups are In terms of the ease of use, acrylic resins containing (meth)acryloyl groups ((meth) It is preferable that the resin is an acrylic (meth)acrylate. By using this, when a method of forming a hardened layer by applying a coating liquid is selected, the coating property is improved. In the present invention, the primer layer contains an olefin resin. Therefore, depending on the application method, the liquid tends to be repelled. Utilizing resins containing curable groups is a useful method.

[0066] The (meth)acrylate is not particularly limited, and may be a monofunctional (meth)acrylate, a bifunctional (meth)acrylate, or the like. (Meth)acrylate, trifunctional or higher multifunctional (meth)acrylate mixed with one or more types or a commercially available hardening resin material, or a material other than these that is not included in the present embodiment. Other components may be further added to the composition within a range that does not impair the properties of the composition. Among these, from the viewpoint of excellent curability and scratch resistance, multifunctional (meta) compounds with three or more functional groups are preferred. ) acrylates are preferred, and hexa- or higher-functional (meth)acrylates are more preferred.

[0067] Monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, Acrylate, butyl (meth)acrylate, propyl (meth)acrylate, n-butyl butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, Uryl (meth)acrylate, Stearyl (meth)acrylate, Morpholyl (meth)acrylate Acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl ( (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth) Acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate (meth)acrylate, tricyclodecane (meth)acrylate, polyethylene glycol Cyclohexyl (meth)acrylate, tetrahydrofurfuryl dicyclopentanyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl Allyl (meth)acrylate, isobornyl (meth)acrylate, allyl (meth)acrylate acrylate, 2-ethoxyethyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethanol Mono(meth)acrylates such as hydroxyethyl (meth)acrylate and phenyl (meth)acrylate acrylate, adduct of phthalic anhydride and 2-hydroxyethyl (meth)acrylate, etc. Examples thereof include mono(meth)acrylate compounds.

[0068] The difunctional polyfunctional (meth)acrylate is not particularly limited, but examples thereof include For example, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate Acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanedi All di(meth)acrylate, tricyclodecane dimethylol di(meth)acrylate Alkanediol di(meth)acrylates, bisphenol A ethylene oxide modified Di(meth)acrylate, bisphenol F, ethylene oxide modified di(meth)acrylate bisphenol-modified di(meth)acrylates, polyethylene glycol di(meth)acrylates, etc. acrylate, polypropylene glycol di(meth)acrylate, urethane di(meth)acrylate di(meth)acrylate, epoxy di(meth)acrylate, etc.

[0069] The trifunctional or higher polyfunctional (meth)acrylate is not particularly limited, but may be: For example, dipentaerythritol hexa(meth)acrylate, pentaerythritol tetraacetate Pentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethicone Cholesterol propane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate Acrylate, Trimethylolpropane Tri(meth)acrylate, Glycerin Triacrylate Glycerin-containing polyfunctional (meth)acrylates such as ethylene oxide-modified dipentaerythritol, Ethylene oxide modified pentaerythritol hexa(meth)acrylate tetra(meth)acrylate, ethylene oxide modified pentaerythritol tri(meth)acrylate Ethylene oxide modified (meth)acrylates such as methacrylate, ethylene isocyanurate ethylene oxide modified tri(meth)acrylate, ε-caprolactone modified tris(acrylate) isocyanuric acid-modified tri(meth)acrylates such as (hydroxyethyl) isocyanurate, Pentaerythritol triacrylate hexamethylene diisocyanate urethane prepoly mer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer Polymer, Dipentaerythritol Pentaacrylate Hexamethylene Diisocyanate Among these, urethane (meth)acrylates such as urethanprepolymer are also included. Hexafunctional or higher (meth)acrylates are preferred from the viewpoint of hardness and scratch resistance, and urethane is also preferred. In view of adhesion, it is preferable to use poly(meth)acrylate.

[0070] In addition, the formation of the cured layer may be achieved by using active energy ray curable compounds other than (meth)acrylates. For example, styrene, vinyl halide, vinyl acetate, etc. Vinyl compounds, vinylidene halides, 1,3-butadiene, isoprene, chloroprene and other diene compounds.

[0071] As an example of a resin containing a curable group, a resin containing a carbon-carbon unsaturated bond is Here, the carbon-carbon unsaturated bond is a bond between carbon and carbon. It means a carbon-carbon double bond or a carbon-carbon triple bond, and a carbon-carbon double bond is preferred. For example, a (meth)acryloyl group, a (meth)acrylamide group, a vinyl group, an allyl group, Among these, those with excellent curability by active energy rays are Therefore, a (meth)acryloyl group is preferred, and an acryloyl group is particularly preferred. The resin containing a carbon-carbon unsaturated bond may contain only one of the above functional groups, or may contain two of the above functional groups. It may include the above.

[0072] Examples of resins containing carbon-carbon unsaturated bonds include resins containing (meth)acryloyl groups. The acrylic resin is preferably in the form of a polymer, and the method for producing the acrylic resin is Examples of the (meth)acrylates include those containing an epoxy group and other (meth)acrylates. The epoxy group of the polymer obtained by copolymerizing the epoxy group with a hydroxyl group monomer is reacted with an acid or a base. In particular, the method using glycidyl (meth)acrylate is a carbon-carbon method. This is useful because it is easy to control the amount of unsaturated bonds.

[0073] Examples of (meth)acrylates containing an epoxy group include glycidyl (meth)acrylate. Acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxy Cyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, etc. Among these, glycerol is the most popular, considering its good reactivity and ease of use. Glycidyl (meth)acrylate is preferred, and glycidyl methacrylate is particularly preferred.

[0074] Introducing carbon-carbon unsaturated bonds using (meth)acrylates containing epoxy groups In this case, the (meth)acrylate polymer contains an epoxy group. The proportion of acrylate is preferably 10% by mass or more, more preferably 30% by mass or more. More preferably, the range is 50% by mass or more, and particularly preferably 80% by mass or more. The limit is 100% by mass. By using it in this range, the carbon-carbon unsaturation in the resin can be reduced. The amount of bonding can be made sufficient, and the hardness and scratch resistance of the cured layer can be improved. do.

[0075] (Meth)acrylate polymers containing epoxy groups due to carbon-carbon unsaturated bond formation The compounds used for this purpose include acids and bases, but they are not effective in improving the stability of (meth)acrylate polymers. Considering these considerations, acids are preferred, and among these, carboxylic acids are particularly preferred. Among these, by using (meth)acrylic acid, it is possible to introduce double bonds. This is a more preferable form. Considering the reactivity of the acid and the reactivity of the introduced double bond, acrylic acid is the most suitable. Reacting two or more carboxylic acids with an epoxy group to form two or more structures It is also possible.

[0076] The amount of epoxy groups to be reacted is usually 1% by mass or more, preferably 20% by mass or more, and more preferably The range is preferably 50% by mass or more, more preferably 80% by mass or more, and the upper limit is 10 By carrying out the reaction within this range, the carbon-carbon unsaturated bonds in the resin can be reduced. The amount of the cured layer can be made sufficient, and the hardness and scratch resistance of the cured layer can be improved.

[0077] When a (meth)acrylic resin is used as the resin containing a carbon-carbon unsaturated bond In addition to the above-mentioned compounds, various polymerizable (meth)acrylates can also be used. For example, (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate Acrylate, butyl (meth)acrylate, stearyl (meth)acrylate, phenoxy Ethyl (meth)acrylate, ethoxyethyl (meth)acrylate, methoxyethyl ( (meth)acrylate, butoxyethyl (meth)acrylate, benzyl (meth)acrylate acrylate, cyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate alkyl (meth)acrylates such as dicyclopentenyloxyethyl (meth)acrylate Perfluorohexylethyl (meth)acrylate monomer; Perfluorohexylethyl (meth)acrylate, 1H,1H,7H- Dodecafluoroheptyl (meth)acrylate, 1H,1H,9H-hexadecafluoro (Meth)acrylate mono-esters having a fluoroalkyl group, such as nonyl (meth)acrylate mer; N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminoethyl (Meth)acrylate monomers having an amino group, such as methyl (meth)acrylate; 2-Hydroxypropyl (meth)acrylate, 2-Hydroxyethyl (meth)acrylate hydroxyl group-containing (meth)acrylates such as 1,6-hexanediol mono(meth)acrylate, Acrylate monomers; raw materials other than (meth)acrylic acid derivatives include styrene, p-acrylic acid, C12-12, p-methoxystyrene, divinylbenzene, N-vinylpyrrolidone, N- Vinylcaprolactam, acrylonitrile, ethylene glycol divinyl ether, pentaerythritol Taerythritol divinyl ether, 1,6-hexanediol divinyl ether, tri Methylolpropane divinyl ether, ethylene oxide modified hydroquinone divinyl ether ether, ethylene oxide modified bisphenol A divinyl ether, pentaerythritol Dipentaerythritol trivinyl ether, dipentaerythritol hexavinyl ether, ditrimethylol Examples of such hydrocarbon monomers include those having a vinyl group, such as diolpropane polyvinyl ether. .

[0078] The raw material used is not limited to one type, but two or more types may be used in combination to form (meth)acrylic resins. It is also possible to prepare a (meth)acrylic resin by using two or more kinds of the above in combination. I wish.

[0079] The polymerization conditions for producing a (meth)acrylic resin containing a carbon-carbon unsaturated bond are There is no particular limitation, and a known method can be appropriately selected. The reaction to obtain the olefin is a radical polymerization reaction, and the raw materials are polymerized in an organic solvent in the presence of a radical polymerization initiator. By polymerizing the starting monomer, a (meth)acrylic resin can be obtained.

[0080] For example, the organic solvent may be acetone, methyl ethyl ketone, methyl isobutyl ketone, or the like. ethanol, methanol, isopropyl alcohol, isobutanol, etc. Alcohol solvents; ethylene glycol dimethyl ether, propylene glycol monomethyl ether solvents such as diethyl ether; ethyl acetate, propylene glycol monomethyl ether Ester solvents such as acetate and 2-ethoxyethyl acetate; aromatic carbons such as toluene These organic solvents can be used alone or in combination of two or more. It may also be used in combination.

[0081] Radical polymerization initiators include benzoyl peroxide and di-t-butyl peroxide. Organic peroxides, 2,2'-azobisbutyronitrile, 2,2'-azobis(2,4-dimethyl 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) These radical polymerization initiators are azo compounds such as benzotriazole and benzotriazole. Two or more of them may also be used in combination.

[0082] The polymerization temperature is usually 20 to 150°C, preferably 50 to 100°C. The incubation time is usually 1 to 72 hours, preferably 3 to 36 hours.

[0083] The reaction conditions for the above-mentioned epoxy group and carboxylic acid compound are not particularly limited, and may be any known reaction conditions. The reaction method can be appropriately selected. The reaction may be carried out in the absence or presence of a catalyst. The catalyst may be a tertiary amine such as triethylamine or benzyldimethylamine, or a tetramethylamine. Ammonium such as ethylammonium chloride and tetrabutylammonium bromide salts, phosphines such as triphenylphosphine and tributylphosphine, tetrabutylphosphine phosphonium salts such as phosphonium bromide and tetrabutylphosphonium iodide The amount of catalyst used is usually 0.5% by mass or more, preferably 0.5% by mass or more, based on the weight of the polymer. It is preferably 1.0 mass % or more, usually 5.0 mass % or less, and preferably 3.5 mass % or less. is.

[0084] The reaction temperature is usually 20 to 200°C, preferably 50 to 150°C. The incubation time is usually 1 to 72 hours, preferably 3 to 20 hours.

[0085] The weight average molecular weight (Mw) of the resin containing carbon-carbon unsaturated bonds is determined depending on the application of the laminate. It should be selected appropriately depending on the situation, but it is preferably 5,000 to 100,000, more preferably Preferably, it is 7,000 to 70,000, more preferably 9,000 to 50,000, and even more preferably The range is preferably 10,000 to 30,000. By using the above range, the coating liquid The coating property when the (meth)acrylate is used as a laminate is good, and the adhesion property when the (meth)acrylate is used as a laminate is good. The weight average molecular weight (Mw) of acrylic polymers was measured using GPC with polystyrene standards. The specific measurement conditions are as described below.

[0086] From the viewpoint of curing properties, resins containing carbon-carbon unsaturated bonds are The amount is preferably 1.0 to 10 mmol / g, more preferably 2.0 to 8.0 mmol / g. The range of 1.5 to 6.0 mmol / g is more preferable. This improves the scratch resistance of the cured film and the stability of the coating solution. The reaction of the epoxy group with the carboxylic acid is carried out so that the carbon-carbon unsaturated bond such as the aryl group falls within the above range. It is preferable to select

[0087] The hardened layer is formed by the above-mentioned carbon- The resin may contain a resin other than the resin containing a carbon-carbon unsaturated bond. Examples of the resin include acrylate resin, polyester resin, urethane resin, and vinyl resin.

[0088] The hardened layer may be formed by thermal curing, and may be formed by curing a resin having a crosslinking group with a crosslinking agent. There is a thermal reaction method. For example, acrylic polyol, polyester polyol, poly Examples include a method of combining a resin having a polyol structure such as vinyl with an isocyanate. can be.

[0089] The cured layer may contain an ultraviolet absorber to improve weather resistance. From the viewpoint of transparency and compatibility, organic UV absorbers are preferred. The organic ultraviolet absorber is not particularly limited, but examples thereof include: Triazines, benzotriazoles, benzophenones, cyclic iminoesters, salicylic acid Among these, the most popular are those with weather resistance and durability. From the viewpoint of durability, triazines, benzotriazoles, benzophenones, and cyclic imino Ester-based compounds are more preferred, and triazine-based compounds are even more preferred. These compounds may be used alone or in combination of two or more. It is also possible to use one incorporated into a mer.

[0090] Similarly, a light stabilizer may be contained. The light stabilizer is not particularly limited, but examples thereof include: For example, amine-based light stabilizers, phenol-based light stabilizers, phosphorus-based light stabilizers, thioether-based light stabilizers Among these, amine-based light stabilizers, phenol-based light stabilizers, and phosphorus-based light stabilizers are Light stabilizers are preferred, and amine-based light stabilizers are more suitable, considering that they are less likely to yellow. These light stabilizers may be used singly or in combination of two or more. It is also possible to use polymers incorporating these compounds. be.

[0091] It is also preferable that the cured layer further contains a leveling agent to improve the appearance. In particular, the primer layer contains polyolefin resin, which improves the wettability. It is important to use a leveling agent that is acrylic or silicone-based. Leveling agents, fluorine-based leveling agents, etc. Among these, those that improve wettability and From the viewpoint of obtaining a good appearance, acrylic leveling agents are more preferable. The leveling agents may be used alone or in combination of two or more.

[0092] In the case of a layer cured by active energy ray curing, active energy is used to cure the curable compound. It is preferred that the composition contains a compound derived from a photopolymerization initiator that generates radicals upon irradiation with energy rays. As the photopolymerization initiator to be used, conventionally known compounds can be used. However, since it can be dispersed uniformly and easily in the coating solution before curing, Compounds with less than 500 are preferred, with 500 or less being more preferred.

[0093] Examples of the photopolymerization initiator include a photoradical polymerization initiator, a photocationic polymerization initiator, a photocatalytic polymerization initiator, and a photopolymerization initiator. Among these, photo-radical polymerization initiators are preferred. The dicarboxylic polymerization initiators are 1-hydroxycyclohexyl phenyl ketone, 2-hydroxycyclohexyl phenyl ketone, hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl {2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one Pan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy 2-methyl-[4-(methylthio)phenyl]-2-morpholino -1-Propanone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1 -propanone and other alkylphenone compounds, 2,2-dimethoxy-2-phenylacetone, Benzyl ketal compounds such as phenone, benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoylbenzoate, 4-fluoro Benzophenone-type compounds such as phenylbenzophenone; t-butylanthraquinone, 2-ethoxybenzophenone, Anthraquinone compounds such as thiathraquinone; 2-benzyl-2-dimethylamino- 1-(4-morpholinophenyl)-butanone-1, diethylthioxanthone, isopropyl Thioxanthone-type compounds such as thioxanthone; 2,4,6-trimethylbenzoyldifluoro Phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-triphenylphosphine oxide Trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)- Acylphosphine oxide compounds such as phenylphosphine oxide; Examples of such compounds include phenylglyoxylate compounds such as phenylglyoxylic acid methyl ester. Among these, Acetone is the most popular because it cures even with a small amount of active energy ray irradiation. Alkylphenone type compounds or benzil ketal type compounds are preferred, and alkylphenone Among alkylphenone type compounds, α-hydroxyapatite type compounds are more preferred. Alkyl alkylphenone type compounds and α-amino alkylphenone type compounds are preferred, and α-hydro The hydroxyalkylphenone type compounds are more preferred, and among them, 1-hydroxycyclohexyl The most preferred polymerization initiator is xylphenyl ketone. Alternatively, two or more of them may be used in combination.

[0094] The cured layer may contain particles to prevent blocking and improve lubricity. The inorganic particles may be organic particles or inorganic particles, and two or more kinds may be used in combination. Particles surface-modified with a silane coupling agent having a reactive group such as an acrylyl group. Good too.

[0095] The cured layer may contain a polymerization accelerator, an antistatic agent, a polymerizable agent, etc., within the range that does not impair the effects of the present invention. It may also contain a plasticizer, an antioxidant, an infrared absorbing agent, etc.

[0096] Furthermore, when forming the hardened layer, if the coating solution is prepared and applied, workability is improved. For this purpose, it is preferable to use a solvent as needed. Aromatic solvents such as silane; methyl ethyl ketone, acetone, methyl isobutyl ketone, Ketone solvents such as cyclohexanone; diethyl ether, isopropyl ether, tetrahydrofuran Dioxane, ethylene glycol dimethyl ether, ethylene glycol di Ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, phenetole, etc. Ether solvents: ethyl acetate, butyl acetate, isopropyl acetate, ethylene glycol diacetate Ester solvents such as acetate; dimethylformamide, diethylformamide, N-methyl Amide solvents such as methylpyrrolidone; methyl cellosolve, ethyl cellosolve, butyl cellosol Cellosolve solvents such as ethanol, propanol, isopropanol, Alcohol-based solvents such as butanol; halogen-based solvents such as dichloromethane and chloroform; These organic solvents may be used alone or in combination of two or more. Among these organic solvents, ester-based solvents are preferred because they tend to improve workability during application. Preferred are solvents, ether-based solvents, alcohol-based solvents and ketone-based solvents.

[0097] The cured layer is formed by active energy ray curing, and the (meth)acrylate compound is cured. When used as the main material of a compound, the chemicals derived from (meth)acrylate compounds in the cured layer The content of the compound is (when forming by coating a coating liquid, the content of the non-volatile component of the curable composition in the coating liquid) (considered as a volatile component), preferably 1 to 99.9 mass%, more preferably 5 to 99.7 mass% , more preferably 10 to 99 mass %, particularly preferably 20 to 98 mass %, and most preferably The content is in the range of 30 to 97% by mass. By using it in the above range, the hardness of the cured film is improved, and the durability is improved. In particular, when it is desired to increase the hardness of the cured product, it is recommended to use a compound having six or more functional groups (methacrylamide, methacrylate ... p) The acrylate is preferably 10% by mass or more, more preferably 20% by mass or more, and A preferable range is 30% by mass or more. The non-volatile content is the total mass of components other than the solvent, such as the organic solvent. can be measured by a conventionally known method, for example, by spreading 1 g of the composition and measuring It can be calculated from the change in weight when the organic solvent is evaporated by heating for one hour.

[0098] The cured layer is formed by active energy ray curing, and the resin containing the carbon-carbon unsaturated bond is When used as the main material of a curable compound, the cured layer contains carbon-carbon unsaturated bonds. The content of compounds derived from resins used in forming the film is determined based on the hardening properties of the coating liquid. (considered as the non-volatile content of the curable composition), preferably 1 to 99.9 mass%, more preferably 5 up to 99.7% by mass, more preferably 10 to 99% by mass, and particularly preferably 20 to 98% by mass %, and most preferably in the range of 30 to 97 mass %. The hardness is improved and the scratch resistance is good.

[0099] On the other hand, a (meth)acrylate compound and a resin containing a carbon-carbon unsaturated bond are used in combination. When using (meth)acrylate, the content of compounds derived from these compounds in the cured layer is The compound is preferably 1 to 97% by mass, more preferably 5 to 94% by mass, and further preferably 1 to 97% by mass. Preferably 10 to 89 mass%, particularly preferably 20 to 83 mass%, most preferably 30 to The range is 77% by mass, and the resin containing a carbon-carbon unsaturated bond is preferably 1 % by mass, more preferably 5 to 94% by mass, even more preferably 10 to 89% by mass, The range is preferably 15 to 78% by mass, and most preferably 20 to 67% by mass. By using it in this range, the scratch resistance of the cured film is improved and the appearance is improved.

[0100] A compound (photopolymerization initiator) that generates radicals when irradiated with active energy rays in the cured layer The content of the compound derived from the curable composition in the coating liquid is (considering the amount of photopolymerization initiator contained as non-volatile matter of the product), preferably 0.1 mass % or more More preferably, the content is 0.2 to 10% by mass, even more preferably 0.5 to 8% by mass, and particularly preferably 0.2 to 10% by mass. The content is preferably in the range of 1 to 7% by mass, and most preferably in the range of 2 to 6% by mass. This improves the curability and results in a cured film with good scratch resistance.

[0101] The content of the compound derived from the leveling agent in the cured layer (when formed by coating a coating liquid, (considered as the non-volatile content of the curable composition in the coating liquid), and is preferably 10 mass % or less , more preferably 0.001 to 5 mass%, further preferably 0.01 to 4 mass%, particularly preferably The range is preferably 0.05 to 3% by mass, and most preferably 0.1 to 2% by mass. By using it in this condition, it will have a good appearance.

[0102] The solid content concentration of the curable composition as a coating liquid for forming a cured film may vary depending on the application. However, from the viewpoint of improving the operability in the coating operation, it is preferable to use up to 100%, more preferably 5 to 90%, even more preferably 10 to 80%, and particularly preferably is in the range of 20-70%.

[0103] The cured layer is formed by, for example, applying a curable composition (coating liquid) onto a primer layer to form a coating film. After drying as necessary, the coating film is irradiated with active energy rays or heat to cause a curing reaction. It can be formed by When forming a cured film by coating, the coating method is not particularly limited. coating method, air knife coating method, curtain coating method, spin coating method, roller coating method coating, bar coating, wire bar coating, gravure coating, spray coating, and other known methods. It can be applied by a method.

[0104] When the curable composition contains an organic solvent, it is necessary to heat and dry it before irradiating it with active energy rays. By pre-heating and drying, the organic solvent in the coating film can be effectively removed. The drying temperature for the heat drying is preferably 30 to 200°C, more preferably 40 The drying temperature is preferably from 0.01 to 30 minutes. It is preferable, and 0.1 to 10 minutes is more preferable.

[0105] 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 deterioration of the substrate. The amount of irradiation of the active energy ray is more preferably can be selected appropriately.

[0106] For example, when using ultraviolet light, the total cumulative light intensity is 50 to 3,000 mJ / cm². m 2 It is preferable to irradiate so that the radiation intensity is 100 to 2,000 mJ / cm 2 is more preferred 200-1,000mJ / cm 2The illuminance is more preferably 50 to 6 00mW / cm 2 is preferred, and 75 to 450 mW / cm 2 More preferably, 100 to 30 0mW / cm 2 As the light source, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, lamp, electrodeless lamp, metal halide lamp, or scanning or curtain type electron beam acceleration path Electron beams, high pressure mercury lamps, ultra-high pressure mercury lamps, low pressure mercury lamps, etc. can be used.

[0107] The thickness of the cured film is preferably 0.1 to 20 μm, more preferably 0.2 to 10 μm, and even more preferably It is more preferably in the range of 0.3 to 7 μm. If the thickness of the cured film is within the above range, the desired The thickness of the cured film can be measured by cross-sectional observation using an electron microscope, etc. Required.

[0108] <Laminate> Cyclic olefin substrate / primer layer containing polyolefin resin / cured layer stacked in order The haze of the laminated body measured by the method described in the examples below is suitable for various applications. The optimum value varies depending on the material, so it is difficult to generalize, but it is preferably 10% or less, and more preferably 5% or less. , more preferably 2% or less, particularly preferably 1% or less, and most preferably 0.5% or less The lower limit is not particularly limited, but is preferably 0.0%. This makes it possible to use it for a variety of optical applications.

[0109] Cyclic olefin substrate / primer layer containing polyolefin resin / cured layer stacked in order The total light transmittance of the laminated body measured by the method described in the examples below was The optimum value varies depending on the application, but it is preferable to set the value at 80% or more, and more preferably at 80% or more. The range is 5% or more, more preferably 90% or more. There is no particular upper limit, but it is preferred By keeping it in the above range, it has excellent transparency and is suitable for various optical applications. This becomes:

[0110] Cyclic olefin substrate / primer layer containing polyolefin resin / cured layer stacked in order The laminate further includes a surface functional layer having various functions on the hardening layer, or The substrate may have a backside functional layer on the surface opposite to the cured layer side.

[0111] The surface functional layer can be provided on the surface of the hardened layer to impart various functions. Examples of functional layers include an antifouling layer, an antistatic layer, a refractive index adjusting layer (antireflection layer, low reflection layer, etc.), ), an infrared absorbing layer, an ultraviolet absorbing layer, a color correction layer, etc. The surface functional layer can be formed by a known method. It can be formed by

[0112] The back functional layer is provided on the surface of the substrate opposite the cured layer to impart various functions. The backside functional layer includes an adhesive layer, an antistatic layer, a refractive index adjustment layer, an anti-blocking layer, etc. The adhesive layer is provided to bond the laminate to various adherends. The outermost surface of the laminate, especially the outermost surface of the base material layer opposite the cured layer, is subject to peeling electrification and friction. This is provided to prevent the adhesion of dust and other foreign matter due to triboelectric charging and the resulting defects. The refractive index adjusting layer is provided, for example, to improve the total light transmittance of the laminate. The back functional layer is provided to reduce blocking of the laminate. It can be formed by the following method. [Example]

[0113] The present invention will be described in more detail below with reference to examples, but the present invention will not be limited to the gist of the present invention. However, the present invention is not limited to the following examples. The measurement and evaluation methods used in the present invention are as follows.

[0114] (1) Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) (1)-1 Method for measuring molecular weight in polypropylene equivalent 20 mg of sample was placed in a 30 ml vial and dibutylhydroxybenzoate was added as a stabilizer. 20 g of orthodichlorobenzene containing 0.04% by mass of benzene was added. The sample was dissolved in a heated oil bath, and then a polytetrafluoroethylene (PTFE) filter with a pore size of 3 μm was inserted. The sample solution was then hot filtered using a PTFE filter to prepare a polymer solution with a polymer concentration of 0.1% by mass. Made. Next, TSKgel GM H-HT (30 cm x 4 columns) and an RI detector were used. GPC measurements were performed using a Waters GPC150CV equipped with a The measurement conditions were as follows: injection amount of sample solution: 500 μl; column temperature: The temperature was 135°C, the solvent was orthodichlorobenzene, and the flow rate was 1.0 ml / min. When calculating the molecular weight, commercially available monodisperse polystyrene was used as a standard sample. Calibration of retention time and molecular weight from styrene standards and the viscosity equation for polypropylene A curve was constructed and the molecular weight of the polymer was calculated. The viscosity equation used is [η] = K·Mα, and for polystyrene, K = 1.38E -4, α=0.70, and K=1.03E for propylene-α-olefin copolymers. -4, α = 0.78 was used. The molecular weight distribution (Mw / Mn) was calculated.

[0115] (1)-2 Measurement method of molecular weight in polystyrene equivalent (polyolefin resin) 5 mg of sample was placed in a 10 ml vial and butylhydroxytoluene was added as a stabilizer. 5 g of tetrahydrofuran containing 250 ppm of methylcellulose was added and completely dissolved at 50°C. After cooling to room temperature, the mixture was filtered through a filter with a pore size of 0.45 μm to obtain a sample solution with a polymer concentration of 0.1% by mass. A solution was prepared. Next, the columns were TSKgel GMHXL-L (30 cm x 2) with a guard column. Tosoh GPC HLC equipped with TSKguard column HXL-H GPC measurements were carried out using the HPLC-8020. The measurement conditions were as follows: injection of the sample solution; Volume: 50 μl, column temperature: 40°C, solvent: tetrahydrofuran, flow rate 1.0 ml / min was adopted. When calculating the molecular weight, a commercially available monodisperse polystyrene standard sample was measured as a standard sample. A calibration curve was created from the retention time and molecular weight of the standard sample, and calculations were performed. The molecular weight distribution (Mw / Mn) was calculated.

[0116] (1)-3 Method for measuring molecular weight in polystyrene equivalent (other than polyolefin resins) The equipment used was a Waters e2695, and the column was a Tosoh TSKgel. Super H3000+H4000+H6000, differential refractive index detector ( The GPC measurement was carried out using an RI detector (built-in). Injection volume: 10 μL, column temperature: 40°C, solvent: tetrahydrofuran, flow rate: 0 The flow rate was 0.5 mL / min. Other conditions were the same as in (1)-2.

[0117] (2) Measurement method of graft ratio 200 mg of polymer and 4,800 mg of chloroform were placed in a 10 ml sample bottle and left for 50 minutes. The solution was dissolved completely by heating at ℃ for 30 minutes. Next, the dissolved polymer solution was placed in the liquid cell. , using FT-IR460plus manufactured by JASCO Corporation, infrared absorption was measured with 32 accumulations. The spectrum was measured. The graft rate of maleic anhydride was measured by dissolving maleic anhydride in chloroform. The calibration curve was then created and used to calculate the absorption peak of the carbonyl group (1780 cm -1 Nearby maximum peak, 1750-1813 cm -1 ) area, a separate test Based on the quantity curve, the content of the acid component in the polymer was calculated, and this was taken as the graft rate (% by mass).

[0118] (3) Measurement method of glass transition temperature Measurement method according to JIS K 7244, conditions: 1Hz, 2℃ / min.

[0119] (4) Measurement method for total light transmittance and haze The composition of the cyclic olefin substrate / primer layer containing polyolefin resin / cured layer The laminate was used as the measurement object. The total light transmittance and haze were measured according to JIS Z 8722 (Transmitting Object). Geometric conditions of irradiation and reception of light), JIS K 7361-1 (Plastics - All transparent materials Test method for light transmittance) and JIS K 7136 (Haze of plastic transparent materials) The wave length was measured using a haze meter SH7000 manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with the method of calculation. The value was measured at 550 nm. The haze of the laminate is determined by the incident light from the outermost surface of the substrate layer on the side where the cured layer is present. Of the transmitted light that passes through, forward scattering occurs at a distance of 0.044 rad (2.5°) or more from the incident light. It is the percentage of transmitted light that deviates (the ratio of diffuse transmittance to total light transmittance).

[0120] (5) Adhesion evaluation method The composition of the cyclic olefin substrate / primer layer containing polyolefin resin / cured layer The laminate was evaluated. The area of ​​10mm x 10mm on the surface of the cured layer was divided into 11 x 11 Then, a 24mm wide tape (Nichiban Co., Ltd. Cellotape ( After applying the registered trademark CT-24, the peeled surface was peeled off sharply at a 180 degree angle. Observe and grade the peeled area as follows: A if it is less than 5%, B if it is between 5% and 50%, C if it is 50% or more. If it is rated A or B, it may be usable, and it is suitable for applications where adhesion is important, such as optical applications. In this case, an A rating is preferable.

[0121] (6) Evaluation method for scratch resistance of hardened layer Lightly rub the cured layer of the laminate with steel wool #0000. If no scratches are found, If there are any scratches (good scratch resistance), it is rated as A, if there are any light scratches, it is rated as B (acceptable), if there are any obvious scratches or marks, it is rated as B (acceptable), When this was observed, the evaluation was made as C.

[0122] Examples of compounds that may be used to form the primer layer and the cured layer are as follows: (Compound example) Polyolefin resin containing reactive groups: (A) TAFMER™, a propylene-butene copolymer polymerized by a metallocene catalyst, Trademark) XM-7070 (manufactured by Mitsui Chemicals, Inc., melting point 75°C, propylene content 74 mol% , Weight average molecular weight (Mw) 250,000 (polypropylene equivalent), Molecular weight distribution (Mw / 200 kg of Mn2.2 and 5 kg of maleic anhydride were dry blended in a super mixer. did. Then, propylene was extruded using a twin-screw extruder (TEX54αII manufactured by The Japan Steel Works, Ltd.). t-butylperoxyisobutene copolymer was added in an amount of 1 part by mass per 100 parts by mass of the butene copolymer. Propyl monocarbonate (Perbutyl I manufactured by NOF Corporation) was added by a liquid addition pump. While kneading, the cylinder temperature in the kneading section was 200°C and the screw rotation speed was 125 rpm. The mixture was kneaded under the condition of a discharge rate of 80 kg / hour, and pellets of maleic anhydride-modified propylene were obtained. A β-butene copolymer was obtained. The maleic anhydride-modified propylene-butene copolymer thus obtained The content of maleic anhydride groups (graft ratio) was 1.0 mass% (0.1 mmol as maleic anhydride groups). The weight average molecular weight (poly The molecular weight (Mw) (styrene equivalent) was 156,000, and the number average molecular weight (Mn) was 84,000. Ta. The inside of a glass flask equipped with a reflux condenser, thermometer, and stirrer was replaced with nitrogen gas. 50 g of the maleic anhydride-modified propylene-butene copolymer obtained above and Tafmer (registered trademark) Dissolve 50g of XM-7070 in 120g of toluene, add 1.0g of maleic anhydride, -Butyl peroxyisopropyl monocarbonate (Perbutyl I, manufactured by NOF Corporation) 0.5g was added and the reaction was carried out at 110°C for 7 hours. The temperature of the reaction mixture was lowered to 70°C, and 2- Jeffamine M-1000 (Huntsman, methoxy) dissolved in 50 g of propanol 30 g of poly(oxyethylene / oxypropylene)-2-propylamine (polyolefin) 3 parts by weight of a compound having a repeating unit derived from alkylene oxide per 100 parts by weight of fin resin The resulting reaction mixture was heated to 70°C for 1 hour. The mixture was heated and stirred while adding 300 g of water dropwise, and the degree of vacuum in the system was reduced to a polymer concentration of 3 Toluene and 2-propanol were distilled off under reduced pressure until the total weight of the resin was 0%, leaving a milky white aqueous resin dispersion. The dispersed particle diameter (50% particle diameter D50) of the obtained aqueous resin dispersion was 110 nm. It was. The methoxypoly(oxyethylene / oxypropylene)-2-propylamine used was It is a compound with repeating units derived from alkylene oxide, and is dissolved in water at 25°C at a concentration of 10% by weight. When dissolved at a concentration of 1%, the insoluble content is 1% by weight or less. The resin dispersion is a polyolefin modified with a compound having a repeating unit derived from alkylene oxide. It contains a olefin resin. The aqueous resin dispersion obtained above was spray dried using a TR160 spray dryer manufactured by PRIS. Two-fluid nozzle system, spray pressure 0.3MPa, hot air temperature 60℃, coating amount 0.7kg / hr The powder was made by spray drying, and the average particle size was 19 μm, the volatile content was 1.2%, and the weight average Polyolefin resin powder with molecular weight (polystyrene equivalent) (Mw) 200,000 and melting point of 70°C The powder was dissolved in toluene to obtain a polyolefin resin containing 5% reactive groups. A solution (A) was obtained.

[0123] Acrylic resin: (B) Mitsubishi Chemical Corporation BR83 (100% by mass of structural units derived from MMA) Weight average molecular weight (Mw) 40,000 (meth)acrylic polymer

[0124] (Meth)acrylate: C1 Dipentaerythritol hexaacrylate (hexafunctional) (Kayala, manufactured by Nippon Kayaku Co., Ltd.) (registered trademark DPHA) (Meth)acrylate: C2 Urethane (meth)acrylate (hexafunctional) (Mitsubishi Chemical Corporation, Shiko (registered trademark) ) UV-1700B)

[0125] Resins containing carbon-carbon unsaturated bonds: (D) 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. (Meth)acryloyl copolymer (D) with an introduction amount of acryloyl groups of 4.6 mmol / g Got it. The acrylic acid consumption rate of the obtained (meth)acryloyl copolymer (D) was 94%. The weight average molecular weight (Mw) of this solution (solid content 30% by mass) was 17,700.

[0126] Photopolymerization initiator: (E) 1-Hydroxycyclohexyl phenyl ketone (IGM Resins BV) Omnirad 184) Leveling agent: (F) Acrylic leveling agent (BYK BYK-3440)

[0127] The coating liquid for forming the primer layer and the coating liquid for forming the cured layer (curable composition The materials shown in Table 1 are mixed in the proportions (parts by mass) shown in Table 1 in terms of non-volatile content. In the case of the coating liquid for the primer layer, toluene was mixed so that the solid content concentration was 5% by mass. For the coating solution for the hardening layer, adjust the amount of propylene glycol monomethyl ether to solid. The concentration was adjusted to 30% by mass, and the mixture was stirred until homogeneous to obtain each coating solution. Ta.

[0128] [Example 1] The coating solution for the primer layer was applied to a cycloolefin film (Zeon Corporation, manufactured by Zeon Corporation). Drying on NoahFilm (registered trademark) ZF16-050, a resin with a glass transition temperature of 170°C The primer coating solution P1 shown in Table 1 was applied so that the final film thickness was 2 μm. The primer is dried for 180 seconds in a hot air dryer heated to 100°C to volatilize the solvent. A layer was formed. On the primer layer, the hardening layer coating solution HC1 shown in Table 1 was applied so that the film thickness after drying would be 4 μm. The resulting coating was dried for 60 seconds in a hot air dryer heated to 70°C to remove the solvent. was evaporated and exposed to a high-pressure mercury lamp in an air atmosphere with an integrated light intensity of 200 mJ / cm 2 , illuminance 100m W / cm 2 The laminate was irradiated with ultraviolet light at 1000 kJ / cm 2 at 100 kJ / cm 2 to obtain a laminate having a cured layer. The obtained laminate was measured or evaluated for the items shown in Table 2 by the above-mentioned methods. As shown in Figure 2, the adhesion and scratch resistance were good.

[0129] [Examples 2 to 6] In Example 1, the coating liquid compositions for the primer layer and the cured layer were as shown in Table 1. A laminate having a primer layer and a cured layer was produced in the same manner as in Example 1 except for the above changes. The properties of the obtained laminate are shown in Table 2 below.

[0130] [Comparative Example 1] In Example 1, the cycloolefin film was prepared without laminating the primer layer and the cured layer. (ZEON Corporation, ZeonorFilm (registered trademark) ZF16-050) was evaluated. The characteristics are shown in Table 2 below.

[0131] [Comparative Examples 2 to 4] In Example 1, the coating solution for the primer layer was changed to the coating solution composition shown in Table 1, and the cured layer was A laminate having a primer layer was obtained in the same manner as in Example 1, except that no lamination was performed. The properties of the resulting laminate are shown in Table 2 below.

[0132] [Comparative Examples 5 to 8] In Example 1, the primer layer was not provided, and the coating liquid for the cured layer was prepared using the coating liquid composition shown in Table 1. A laminate having a cured layer was obtained by manufacturing in the same manner as in Example 1 except for the above changes. The physical properties are shown in Table 2 below.

[0133] [Table 1]

[0134] [Table 2]

Claims

1. A plastic containing a polyolefin resin is applied to at least one surface of the cyclic olefin substrate. A laminate having a primer layer and a cured layer on the primer layer.

2. The polyolefin resin is a mixture of ethylene and / or propylene and an α-olefin having 4 or more carbon atoms.

2. The laminate according to claim 1, wherein the copolymer is a copolymer with an olefin.

3. The weight average molecular weight of the polyolefin resin converted using a calibration curve of polystyrene is 5.0 3. The laminate according to claim 2, wherein the molecular weight is 0.00 to 500,000.

4. The laminate according to claim 2, wherein the polyolefin resin has a reactive group.

5. The polyolefin resin contains a structural unit derived from a monomer having a reactive group. The laminate according to claim 4, wherein the amount is 0.01 to 5 mmol / g.

6. 6. The laminate according to claim 5, wherein the reactive group is an acid anhydride group or a carboxyl group.

7. The laminate according to claim 2, wherein the polyolefin resin contains a polyether structure.

8. The cured layer according to claim 1, wherein the cured layer contains a compound derived from a (meth)acrylate compound. Laminate.

9. 2. The laminate according to claim 1, wherein the curable layer contains a compound derived from a resin containing a curable group. body.

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