Hardened composites, hardened materials, laminates

Abstract

To provide a curable polymer composition having excellent curability.SOLUTION: There is provided a curable polymer composition which comprises: a copolymer (A) having a monomer unit of the formula (I) and one or more selected from an alkyl group having 4 to 30 carbon atoms, F and Si, a radical polymerizable group and a monomer (y) unit having no active group which generates a radical by irradiation with active energy ray, in which the content of the active group which generates a radical by irradiation with active energy ray is 0.5 to 2.5 mmol / g, the monomer (y) unit is 1 to 80 mass%; a multifunctional compound (B) having two or more radical polymerizable groups in one molecule; and an acrylic resin (P) having neither an active group which generates a radical by irradiation with active energy ray nor a radical polymerizable group.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a copolymer, a curable polymer composition containing the copolymer, a cured product of the curable polymer composition, and a laminate having a layer made of the cured product. [Background technology]

[0002] A hard coat layer may be applied to the surface of articles such as thermoplastic resin films, typified by polyethylene terephthalate (PET) film, for the purpose of imparting functions such as hardness and matte finish. As a hard coat layer, a curable composition containing a compound having a radical polymerizable group and a photopolymerization initiator is generally known to be cured by radical polymerization. However, with this method, a polymerization termination reaction by oxygen occurs at the contact interface between the coating film of the curable composition and oxygen, i.e., at the coating film surface, which can lead to reduced curability or insufficient mechanical properties of the cured product of the curable composition.

[0003] Patent Document 1 describes a curable composition for hard coatings containing an ultraviolet-curable substance (A) having 5 to 7 functional groups, a urethane acrylate oligomer (B) having 2 to 3 functional groups, and an ultraviolet polymerization initiator (C) which is an oligomer (homopolymer). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2003-292828 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] The curable composition described in Patent Document 1 can form cured products such as hard coat layers with excellent mechanical properties by using an oligomer-type ultraviolet polymerization initiator, but it does not necessarily satisfy the curability requirement. An object of the present invention is to provide a polymer capable of improving curability, a curable polymer composition containing the polymer, a cured product of the curable polymer composition, and a laminate having a layer made of the cured product.

Means for Solving the Problems

[0006] The present invention has the following aspects. [1] A copolymer having a unit based on a monomer (i) having a radical polymerizable group and a group (Ia) represented by the following formula (Ia), and a unit based on a monomer (y) (excluding the monomer (i)) having one or more selected from the group consisting of an alkyl group having 4 or more carbon atoms, a fluorine atom, and a silicon atom.

[0007]

Chemical formula

[0008] [In the formula, R 2 represents a linear or branched alkylene group having 1 to 5 carbon atoms, and R 3 , R 4 each independently represent a linear or branched alkyl group having 1 to 5 carbon atoms, and R 3 and R 4 may be bonded to each other to form a ring.] [2] The copolymer according to [1], wherein the monomer (i) is a compound represented by the following formula (I).

[0009]

Chemical formula

[0010] [In the formula, R 1 represents a hydrogen atom, a methyl group or an ethyl group. R 2 , R 3 , R 4 are the same as those in the formula (Ia).] [3] The copolymer according to [1] or [2], wherein the content of the group (Ia) per 1 g of the copolymer is 0.1 to 3.5 mmol / g. [4], further comprising units based on monomer (x) (excluding monomer (i)) having an active group that generates radicals upon irradiation with active energy rays, any copolymer of [1] to [3]. [5] A copolymer of [4] wherein the monomer (x) is one or more selected from the group consisting of a (meth)acryloyl group, a (meth)acrylamide group, and a vinyl group. [6] A copolymer of [4] or [5] wherein the active group of monomer (x) is one or more selected from the group consisting of a benzophenone group, an acetophenone group, a benzoin group, an α-hydroxyketone group (excluding group (Ia)), an α-aminoketone group, an α-diketone group, an α-diketone dialkylacetal group, anthraquinone group, a thioxanthone group, and a phosphine oxide group. [7] A copolymer according to any of [4] to [6], wherein the total content of the group (Ia) and the active group of the monomer (x) per gram of the copolymer is 0.1 to 3.5 mmol / g. A curable polymer composition comprising a copolymer (A) of any of [1] to [7] and a polyfunctional compound (B) having two or more radical polymerizable groups in one molecule. A cured product of the curable polymer composition of [9][8].

[10] A laminate having a base layer and a layer made of the cured product of [9]. [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a polymer that can improve curability, a curable polymer composition containing the polymer, a cured product of the curable polymer composition, and a laminate having a layer made of the cured product. [Brief explanation of the drawing]

[0012] [Figure 1] This is a schematic cross-sectional view showing an example of the laminate of the present invention. [Figure 2] This is a schematic cross-sectional view showing another example of the laminate of the present invention. [Figure 3] This is a schematic cross-sectional view showing another example of the laminate of the present invention. [Figure 4]This is a schematic cross-sectional view showing another example of the laminate of the present invention. [Figure 5] This is a schematic cross-sectional view showing another example of the laminate of the present invention. [Modes for carrying out the invention]

[0013] The embodiments of the present invention will be described in detail below. In this invention, "(meth)acrylate" is a general term for acrylate or methacrylate. "(meth)acrylic" is a general term for acrylic and methacrylic. The "~" symbol indicating a numerical range means that the numbers before and after it are included as the lower and upper limits, respectively.

[0014] <Curable polymer composition> The curable polymer composition comprises a copolymer (A) having an active group (hereinafter also simply referred to as an active group) that generates radicals upon irradiation with active energy rays, and a polyfunctional compound (B) having two or more radical polymerizable groups in one molecule. When a curable polymer composition is irradiated with active energy rays, radicals are generated from the active groups of copolymer (A). These generated radicals initiate a reaction between the radical polymerizable groups of the polyfunctional compound (B), causing the entire curable polymer composition to harden. The curable polymer composition may further contain an organic solvent, if necessary. The curable polymer composition may further contain other components not mentioned above, as needed.

[0015] <Copolymer (A)> The copolymer (A) may have units based on monomer (i), units based on monomer (y), and may also have units based on monomer (x). [Monomer(i)] Monomer (i) is a compound having a group (Ia) represented by the following formula (Ia) and a radical polymerizable group. The group (Ia) is an intramolecular cleavage type active group. Monomer (i) readily cleaves and generates radicals when irradiated with active energy light, resulting in high initiation efficiency and improved curability. Specifically, curing can be initiated more quickly, and the amount of light irradiation required to obtain a cured product with the desired hardness can be reduced. Furthermore, with the same amount of light irradiation, the hardness of the cured product can be increased, and scratch resistance can be further improved.

[0016] [ka]

[0017] In equation (Ia), R 2 R is a linear or branched alkylene group having 1 to 5 carbon atoms. 2 In terms of the synthesis of copolymer (A) and reactivity with polyfunctional compound (B) having a radical polymerization group, ethylene groups, propane-1,3-diyl groups, butane-1,3-diyl groups, and butane-1,4-diyl groups are preferred, with ethylene groups being more preferred. R 3 , R 4 Each of these is independently a linear or branched alkyl group having 1 to 5 carbon atoms. 3 and R 4 They may be joined to each other to form a ring. 3 and R 4 The number of carbon atoms in the ring formed is preferably 5 to 8, and more preferably 6. R 3 , R 4 or R 3 and R 4 The cyclic group formed is preferably a methyl group, an ethyl group, or a cyclohexyl group, with a methyl group being more preferred, and R 3 , R 4 It is even more preferable that all of them are methyl groups.

[0018] Examples of radical polymerizable groups of monomer (i) include functional groups containing radical polymerizable unsaturated bonds (such as carbon-carbon double bonds), with specific examples including (meth)acryloyl groups, (meth)acrylamide groups, and vinyl groups. As monomer (i), a compound represented by the following formula (I) is preferred in terms of ease of synthesis of monomer (i), ease of synthesis of copolymer (A), and curability of the cured product. In formula (I), R 1 R represents a hydrogen atom, a methyl group, or an ethyl group. Of these, a hydrogen atom or a methyl group is preferred, and a methyl group is particularly preferred. 2 , R 3 , R 4 This is the same as equation (Ia) above.

[0019] [ka]

[0020] [monomer(x)] Monomer (x) is a compound (excluding monomer (i)) that has both an active group and a radical polymerizable group. In this specification, an active group refers to an atomic group containing a structure that generates radicals upon irradiation with active energy rays (a structure having photopolymerization initiation properties). Various known structures can be used as the photopolymerization initiation properties, such as hydrogen abstraction type, electron transfer type, and intramolecular cleavage type. Specific examples of active groups include benzophenone group, acetophenone group, benzoin group, α-hydroxyketone group (excluding group (Ia)), α-aminoketone group, α-diketone group, α-diketone dialkylacetal group, anthraquinone group, thioxanthone group, and phosphine oxide group. Among these, benzophenone groups, acetophenone groups, or α-hydroxyketone groups are preferred because they are less susceptible to oxygen inhibition during curing and provide good surface hardening properties when forming a cured layer.

[0021] Examples of radical polymerizable groups of monomer (x) include functional groups containing radical polymerizable unsaturated bonds (such as carbon-carbon double bonds), with specific examples including (meth)acryloyl groups, (meth)acrylamide groups, and vinyl groups. As the monomer (x), (meth)acrylic acid esters having an active group are preferred from the viewpoint of ease of synthesis of copolymer (A) and ease of adjusting the amount of active group introduced. For example, 4-methacryloyloxybenzophenone is preferred.

[0022] [monomer (y)] Monomer (y) is a compound (excluding monomer (i)) having one or more elements selected from the group consisting of alkyl groups with 4 or more carbon atoms, fluorine atoms, and silicon atoms, and a radical polymerizable group. Monomer (y) is a monomer with low surface energy, and if copolymer (A) has units based on monomer (y), then when a coating film of a curable polymer composition is formed, copolymer (A) tends to segregate to the surface side of the coating film. If copolymer (A) with active groups segregates to the surface side of the coating film, the polymerization termination reaction by oxygen at the coating film surface can be suppressed, and curability is improved. Therefore, curing can be achieved, for example, with low exposure. Furthermore, even thin films that tend to be susceptible to oxygen inhibition can be cured well. Furthermore, when copolymer (A) segregates to the surface side of the coating film, the concentration of active groups on the surface side of the coating film increases. As a result, the curing rate when irradiated with active energy rays tends to be uneven between the surface and the interior of the coating film. For example, if the surface of the coating hardens first, forming a cured film, and then the interior of the coating hardens, the surface cured film buckles, causing wrinkle-like irregularities to appear. This results in a cured layer with irregularities on the surface (irregular layer). The curing time until the interior of the coating hardens can be adjusted by the amount of radical polymerizable groups in the curable polymer composition, the type and amount of active groups, the irradiation dose of active energy rays, etc. On the other hand, even if copolymer (A) segregates to the surface side of the coating film, it is not easy for irregularities to occur on the surface of the cured layer. For example, if the difference in curing speed between the surface and the interior of the coating film is small and the cured film is not formed, or if the cured film has properties that make it resistant to buckling, the surface of the cured layer tends to be smooth.

[0023] Examples of monomers (y) include monomers (r) having an alkyl group with 4 or more carbon atoms, and monomers (f) having a fluorine atom or a silicon atom. The alkyl group having 4 or more carbon atoms in monomer (r) may be linear, branched, or cyclic. The cyclic alkyl group may be monocyclic or polycyclic. From the viewpoint of more effectively segregating copolymer (A) on the surface of the coating film, the alkyl group is preferably linear. From the viewpoint of more effectively segregating the copolymer (A) onto the surface of the coating film, the number of carbon atoms in the alkyl group having 4 or more carbon atoms is preferably in the range of 4 to 30, more preferably in the range of 6 to 20, and even more preferably in the range of 12 to 18.

[0024] Examples of monomers (r) include compounds having an alkyl group with 4 or more carbon atoms and a radical polymerizable group. From the viewpoint of ease of compound synthesis and ease of adjusting the amount of alkyl group with 4 or more carbon atoms introduced, alkyl (meth)acrylate esters having an alkyl group with 4 or more carbon atoms are preferred. Examples of monomers (r) include butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, and isodecyl (meth)acrylate. Examples include dodecyl (meth)acrylate, myristyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, tridecyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tricyclodecane (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, etc. Among these, it is preferable to include alkyl (meth)acrylate esters having a linear alkyl group with 4 or more carbon atoms. As alkyl (meth)acrylate esters having a linear alkyl group with 4 or more carbon atoms, those with the number of carbon atoms in the alkyl group within the above preferred range are preferred, and considering ease of manufacture, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate, and stearyl (meth)acrylate are more preferred, with stearyl (meth)acrylate being particularly preferred. These (meth)acrylic acid esters may be used individually or in combination of two or more.

[0025] Examples of monomer (f) include compounds having a fluorine atom or a silicon atom and a radical polymerizable group. The radical polymerizable group is the same as the radical polymerizable group exemplified earlier in the description of monomer (x). Monomer (f) is also a component that imparts at least one of water-repellent and oil-repellent properties to the cured product, thereby enhancing its stain resistance. If copolymer (A) has units based on monomer (f), when a coating film of the curable polymer composition is formed, copolymer (A) segregates to the surface side of the coating film. As a result, curability is enhanced, and the concentration of units based on monomer (f) on the surface side of the coating film increases, allowing for efficient imparting of stain resistance to the surface of the cured product.

[0026] The monomer (f) preferably contains one or more compounds selected from the group consisting of compounds having a fluoroalkyl group and a radical polymerizable group, and compounds having a polydimethylsiloxane chain and a radical polymerizable group. The monomer (f) more preferably comprises one or more selected from the group consisting of (meth)acrylic acid esters having a fluoroalkyl group and (meth)acrylic acid esters having a polydimethylsiloxane chain.

[0027] Among (meth)acrylic acid esters having a fluoroalkyl group, (meth)acrylic acid esters having a perfluoroalkyl group are more preferred. The number of carbon atoms in the perfluoroalkyl group is preferably 4 or more. Specific examples of (meth)acrylic acid esters having a polydimethylsiloxane chain include polydimethylsiloxanes with one-terminated (meth)acryloyl group having a molecular weight of 500 to 50,000. The molecular weight is preferably 1,000 to 30,000, and more preferably 1,500 to 20,000.

[0028] [Monomer(h)] The copolymer (A) may optionally further have one or more units based on a monomer (h) having a hydrogen-donating functional group. In particular, when monomer (x) has a hydrogen abstraction type active group, curing is accelerated when copolymer (A) contains units based on monomer (h). The hydrogen-donating functional group is preferably one or more selected from the group consisting of hydroxyl groups, amino groups, mercapto groups, and amide groups. Among these, hydroxyl groups, amino groups, or amide groups are particularly preferred from the viewpoint of efficiently promoting the curing reaction.

[0029] Examples of monomer (h) include compounds having a hydrogen-donating functional group and a radical polymerizable group. The radical polymerizable group is the same as the radical polymerizable group exemplified earlier in the description of monomer (x). From the viewpoint of ease of compound synthesis and ease of adjusting the amount of hydrogen-donating functional group introduced, (meth)acrylic acid esters having hydrogen-donating functional groups are preferred as monomer (h). Examples of monomers (h) include hydroxyl group-containing monomers such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, monobutyl hydrochlor fumarate, monobutyl hydroxyitaconate, etc.; N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-vinylcaprolactam, N-vinylpyrrolidone, N-isopropyl (meth)acrylamide Examples include amino group or amide group-containing monomers such as N,N-dimethylaminoethyl (meth)acrylate, 2-[(butylamino)carbonyl]oxy]ethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylamide, N,N-diethylaminopropyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, (meth)acryloylmorpholine, and vinylacetamide. Among these, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, N,N-dimethylacrylamide, N,N-dimethylaminoethyl (meth)acrylate, and N,N-diethylaminoethyl (meth)acrylate are preferred in terms of their excellent curing-accelerating effect when used in combination with an active group, and 2-hydroxyethyl (meth)acrylate and N,N-diethylaminoethyl (meth)acrylate are more preferred. These compounds may be used individually or in combination of two or more.

[0030] [monomer(o)] Copolymer (A) may optionally further have units based on other monomers (monomer (o)). Examples of monomer (o) include compounds having a radical polymerizable group and lacking an active group, an alkyl group having 4 or more carbon atoms, a fluorine atom, a silicon atom, and a hydrogen-donating functional group. The radical polymerizable group is the same as the radical polymerizable group exemplified earlier in the description of monomer (x). Examples of monomers (o) include carboxyl group-containing monomers and their salts such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, and citraconic acid; (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate; nitrogen-containing monomers such as (meth)acrylonitrile; styrene compounds such as styrene, α-methylstyrene, divinylbenzene, and vinyltoluene; vinyl esters such as vinyl propionate and vinyl acetate; phosphorus-containing vinyl monomers; vinyl halides such as vinyl chloride and pyridene chloride; and conjugated dienes such as butadiene.

[0031] The copolymer (A) preferably has multiple active groups in its molecule. The active group content per gram of copolymer (A) is preferably in the range of 0.1 to 3.5 mmol / g, more preferably 0.5 to 2.5 mmol / g, and even more preferably 0.8 to 2.0 mmol / g. When the active group content is above the lower limit of the above range, the curability is better. In addition, the scratch resistance of the coating film is improved. When it is below the upper limit of the above range, the storage stability of the curable composition is excellent. If copolymer (A) has units based on monomer (i) and does not have units based on monomer (x), the content of active groups per gram of copolymer (A) is the content of group (Ia) per gram of copolymer (A). If copolymer (A) has units based on monomer (i) and units based on monomer (x), the content of active groups per gram of copolymer (A) is the total content of active groups of group (Ia) and monomer (x) per gram of copolymer (A).

[0032] Monomer (i) contributes to improving the curability of the curable polymer composition. When units based on monomer (x) are present in addition to units based on monomer (i), wrinkle-like irregularities are more easily formed on the surface of the cured layer. Forming these irregularities in the cured layer makes it easier to obtain functional properties such as matte finish. The content of group (Ia) relative to the total of the active groups of group (Ia) and monomer (x) is preferably 10 mol% or more, more preferably 30 mol% or more. It may also be 100 mol%. When it is above the lower limit of the above value, the effect of improving curability is excellent. When copolymer (A) has units based on monomer (i) and units based on monomer (x), the content of group (Ia) relative to the total of the active groups of group (Ia) and monomer (x) is preferably 90 mol% or less, more preferably 70 mol% or less. If it is below the above upper limit, irregularities are likely to form on the surface of the cured layer.

[0033] The content of hydrogen-donating functional groups per gram of copolymer (A) is preferably in the range of 0.1 to 3.5 mmol / g, more preferably 0.8 to 3.2 mmol / g, and even more preferably 1.0 to 3.0 mmol / g. Curability is better when the content of hydrogen-donating functional groups is above the lower limit of the above range. Compatibility between copolymer (A) and polyfunctional compound (B) is excellent when the content of hydrogen-donating functional groups is below the upper limit of the above range.

[0034] The ratio of units based on monomer (i) to the total mass of all units constituting copolymer (A) is preferably in the range of 1 to 90% by mass, more preferably 10 to 80% by mass, even more preferably 20 to 70% by mass, and particularly preferably 30 to 60% by mass. If the ratio of units based on monomer (i) is above the lower limit of the above range, the curability is better. If the ratio of units based on monomer (i) is below the upper limit of the above range, the storage stability of the curable composition is better. When copolymer (A) has units based on monomer (i) and units based on monomer (x), the ratio of the total mass of units based on monomer (i) and units based on monomer (x) to the total mass of all units constituting copolymer (A) is preferably in the range of 1 to 90% by mass, more preferably 10 to 80% by mass, even more preferably 20 to 70% by mass, and particularly preferably 30 to 60% by mass. If the total ratio is above the lower limit of the above range, the curability is better. If the total ratio is below the upper limit of the above range, the storage stability of the curable composition is better.

[0035] The ratio of monomer (y)-based units to the total mass of all units constituting copolymer (A) is preferably in the range of 1 to 80% by mass, more preferably 5 to 60% by mass, and even more preferably 8 to 50% by mass. When the ratio of monomer (y)-based units is above the lower limit of the above range, the curability is better. When the ratio of monomer (y)-based units is below the upper limit of the above range, the compatibility between copolymer (A) and polyfunctional compound (B) is excellent.

[0036] The ratio of monomer (r)-based units to the total mass of all units constituting copolymer (A) is preferably 80% by mass or less, more preferably 1 to 70% by mass, even more preferably 5 to 60% by mass, and particularly preferably 8 to 50% by mass. When the ratio of monomer (r)-based units is above the lower limit of the above range, the curability is better. When the ratio of monomer (r)-based units is below the upper limit of the above range, the compatibility between copolymer (A) and polyfunctional compound (B) is excellent.

[0037] The ratio of units based on monomer (f) to the total mass of all units constituting copolymer (A) is preferably 80% by mass or less, more preferably 1 to 70% by mass, and even more preferably 5 to 60% by mass. When the ratio of units based on monomer (f) is above the lower limit of the above range, curability and antifouling properties are better. When the ratio of units based on monomer (f) is below the upper limit of the above range, the compatibility between copolymer (A) and polyfunctional compound (B) is better.

[0038] The ratio of monomer (h)-based units to the total mass of all units constituting copolymer (A) is preferably 80% by mass or less, more preferably 1 to 60% by mass, even more preferably 3 to 50% by mass, and particularly preferably 5 to 40% by mass. If the ratio of monomer (h)-based units is within the above range, the curability is better.

[0039] The weight-average molecular weight (Mw) of copolymer (A) is preferably in the range of 1,000 to 500,000, more preferably 2,000 to 100,000, and even more preferably 3,000 to 60,000. When Mw is above the lower limit of the above range, the curability is better. When Mw is below the upper limit of the above range, the coatability of the curable polymer composition is better. The Mw of copolymer (A) is a value equivalent to standard polystyrene, measured by gel permeation chromatography (GPC). The detailed measurement conditions are as described in the examples below.

[0040] The glass transition temperature (Tg) of copolymer (A) is preferably in the range of -30 to 180°C, more preferably 0 to 150°C, and even more preferably 25 to 100°C. If the Tg is above the lower limit of the above range, the curability is better. If it is below the upper limit, the compatibility between copolymer (A) and polyfunctional compound (B) is excellent. The Tg of copolymer (A) can be determined by Fox's formula.

[0041] Copolymer (A) is obtained, for example, by polymerizing a monomer component containing monomer (i) and monomer (y). The monomer component may optionally further contain one or more of monomers (x), monomer (h), and monomer (o). Polymerization is typically carried out in the presence of a polymerization initiator. A chain transfer agent may also be used during polymerization, if necessary. Known polymerization methods include solution polymerization, suspension polymerization, bulk polymerization, and emulsion polymerization. Among these, solution polymerization is preferred because it is easy to operate and highly productive.

[0042] <Polyfunctional compound (B)> The polyfunctional compound (B) can be any compound having two or more radical polymerizable groups in one molecule, and various known compounds can be used. Polyfunctional (meth)acrylates are preferred. Polyfunctional compound (B) may be used alone or in combination of two or more.

[0043] While not particularly limited, examples of difunctional and polyfunctional (meth)acrylates include alkane diol di(meth)acrylates such as 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and tricyclodecanedimethylol di(meth)acrylate; bisphenol-modified di(meth)acrylates such as bisphenol A ethylene oxide-modified di(meth)acrylate and bisphenol F ethylene oxide-modified di(meth)acrylate; polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, urethane di(meth)acrylate, and epoxy di(meth)acrylate.

[0044] Polyfunctional (meth)acrylates with three or more functions are not particularly limited, but examples include dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, isocyanuric acid-modified tri(meth)acrylate such as ethylene oxide-modified isocyanurate tri(meth)acrylate and ε-caprolactone-modified tris(acrooxyethyl) isocyanurate, urethane acrylates such as pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, and dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer. Among these, dipentaerythritol hexa(meth)acrylate is preferred.

[0045] <Organic solvents> Organic solvents are used as needed to improve the workability when applying the curable polymer composition onto a substrate. Examples of organic solvents include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, and phenethole; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and ethylene glycol diacetate; amide solvents such as dimethylformamide, diethylformamide, and N-methylpyrrolidone; cellosolve solvents such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol; and halogen solvents such as dichloromethane and chloroform. These organic solvents may be used individually or in combination of two or more. Among these organic solvents, ester-based solvents, ether-based solvents, alcohol-based solvents, and ketone-based solvents are preferred because they easily improve workability during application.

[0046] <Photopolymerization initiator (C)> The curable polymer composition may further contain one or more photopolymerization initiators (excluding copolymer (A)). For example, a photopolymerization initiator (C) is a nonpolymer having an active group that generates radicals upon irradiation with active energy rays. The molecular weight of the photopolymerization initiator (C) is preferably 1000 or less. Specific examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin phenyl ether, benzyl diphenyl disulfide, dibenzyl, diacetyl, anthraquinone, naphthoquinone, 3,3'-dimethyl-4-methoxybenzophenone, benzophenone, p,p'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, pivaloin ethyl ether, benzyl dimethyl ketal, 1,1-dichloroacetophenone, pt-butyl dichloroacetophenone Examples include phenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-dichloro-4-phenoxyacetophenone, phenylglyoxylate, α-hydroxyisobutylphenone, dibenzosparone, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-propanone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, tribromophenylsulfone, and tribromomethylphenylsulfone. These photopolymerization initiators may be used individually or in combination of two or more.

[0047] <Acrylic resin (P)> The curable polymer composition may further contain one or more acrylic resins (P) that do not have either active groups or radical polymerizable groups, for the purpose of improving adhesion to the substrate layer, processability, and the appearance of the cured product. Acrylic resin (P) is a polymer of polymerizable monomers, including (meth)acrylic monomers. Examples of the acrylic resin (P) include a homopolymer or copolymer of (meth)acrylic monomers, and a copolymer of (meth)acrylic monomers and polymerizable monomers other than (meth)acrylic monomers. In particular, copolymers or homopolymers of (meth)acrylic monomers are preferred, in which the content of units based on (meth)acrylic monomers is 50% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more, relative to the total mass of all units constituting the acrylic resin (P). These are available commercially (for example, the Dianal series manufactured by Mitsubishi Chemical Corporation).

[0048] <Other ingredients> The curable polymer composition may further contain a leveling agent to improve the appearance of the cured product. Examples of leveling agents include acrylic leveling agents, silicone leveling agents, and fluorine leveling agents. These leveling agents may be used individually or in combination of two or more types.

[0049] The curable polymer composition may further contain particles with an average primary particle diameter of 0.01 μm or more and 10 μm or less in order to further improve the matte finish due to the uneven layer. The particles may be organic or inorganic, and two or more types may be used in combination. The inorganic particles may be particles whose surface has been modified with a silane coupling agent having a reactive group such as a (meth)acryloyl group. Surface-modified particles can be obtained, for example, by reacting a silane coupling agent with inorganic particles at 25°C to 120°C for about 1 to 24 hours in the presence of an acid, a base, or a silane coupling reaction catalyst such as aluminum acetylacetone.

[0050] The curable polymer composition may be modified by adding monofunctional (meth)acrylates or (meth)acrylic acids having one radical polymerizable group per molecule to adjust viscosity and curing rate using active energy rays. The aforementioned monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl acrylate, hexyl acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, benzyl (meth)acrylate, cresol (meth)acrylate, and dicyclopentenyl (meth)acrylate. Examples include phosphates, dicyclopentenyloxyethyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, 7-amino-3,7-dimethyloctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ethyldiethylene glycol (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, lauryl (meth)acrylate, polyurethane mono(meth)acrylate, polyepoxy mono(meth)acrylate, polyester mono(meth)acrylate, etc.

[0051] <Content> The curable polymer composition may contain polymerization accelerators such as compounds containing thiol groups, antistatic agents, plasticizers, surfactants, antioxidants, ultraviolet absorbers, etc., to the extent that it does not impair the effects of the present invention.

[0052] The content of copolymer (A) relative to the nonvolatile content of the curable polymer composition is preferably in the range of 0.5 to 50% by mass, more preferably 1 to 20% by mass, and even more preferably 1.5 to 5% by mass. If the content is above the lower limit of the above range, the curability is better. If it is below the upper limit, the coating properties are better. The non-volatile content of a curable polymer composition is the total mass of components other than the organic solvent. The non-volatile content of a curable polymer composition can be measured by conventionally known methods, for example, by spreading 1 g of the composition and heating it at 100°C for 1 hour to evaporate the organic solvent, and measuring the change in weight.

[0053] The content of active groups derived from copolymer (A) per 100g of nonvolatile content of the curable polymer composition is preferably in the range of 0.1 to 20 mmol / 100g, more preferably 0.5 to 15 mmol / 100g, even more preferably 1.0 to 12 mmol / 100g, and particularly preferably 1.5 to 10 mmol / 100g. Curability is better when the content of active groups is above the lower limit of the above range. Storage stability of the curable composition is better when it is below the upper limit.

[0054] The ratio of the polyfunctional compound (B) to the nonvolatile content of the curable polymer composition is preferably in the range of 50 to 99.5% by mass, more preferably 70 to 99% by mass, and even more preferably 80 to 98.5% by mass. Curability is better when the ratio is within the above range.

[0055] From the viewpoint of improving operability in coating operations, the content of the organic solvent per 100 parts by mass of the nonvolatile content of the curable polymer composition is preferably 10 parts by mass or more and 1900 parts by mass or less, and more preferably 40 parts by mass or more and 400 parts by mass or less.

[0056] When a photopolymerization initiator (C) is included in a curable polymer composition, the ratio of the photopolymerization initiator (C) to the nonvolatile content of the curable polymer composition is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1 to 6% by mass. Curability is better when the ratio is within the above range.

[0057] <Cured product> A cured product of a curable polymer composition can be formed by applying the curable polymer composition to a substrate or the surface of an article to form a coating film, drying it as necessary, and then irradiating the coating film with active energy rays. The method of applying the curable polymer composition is not particularly limited. For example, it can be applied by known methods such as dip coating, air knife coating, curtain coating, spin coating, roller coating, bar coating, wire bar coating, gravure coating, and spray coating.

[0058] If the curable polymer composition contains an organic solvent, it is preferable to preheat and dry it before irradiating it with active energy rays. Preheating and drying effectively removes the organic solvent from the coating film. If copolymer (A) segregates to the surface side of the coating film, removing the organic solvent increases the concentration of copolymer (A) on the surface side of the coating film. The drying temperature for heat drying is preferably 30°C to 200°C, and more preferably 40°C to 150°C. The drying time is preferably 0.01 minutes to 30 minutes, and more preferably 0.1 minutes to 10 minutes.

[0059] Examples of active energy rays include ultraviolet rays, alpha rays, beta rays, and gamma rays. Of these, ultraviolet rays are preferred. The irradiation dose of the active energy rays can be appropriately selected depending on the active energy rays being irradiated. When using ultraviolet light, the cumulative light intensity of the irradiation is 100 mJ / cm². 2 More than 3000mJ / cm 2 It is preferable to irradiate at the following rate: 200 mJ / cm² 2 More than 2000mJ / cm 2 The following is preferable. Also, the illuminance should be 50 mW / cm². 2 More than 600mW / cm 2 The following is preferred: 75 mW / cm² 2 More than 450mW / cm 2 The following is more preferable: 100 mW / cm² 2 More than 300mW / cm 2 The following are even more preferable. As light sources, high-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, electrodeless lamps, metal halide lamps, or electron beams using scanning or curtain-type electron beam accelerating circuits, etc., can be used.

[0060] The thickness of the cured layer is preferably in the range of 0.1 to 20 μm, more preferably 0.2 to 10 μm, and even more preferably 0.3 to 5 μm. If the thickness of the cured product is within the above range, the desired matte finish is easily achieved. The thickness of the hardened layer is determined by cross-sectional observation using an electron microscope. If the hardened layer is an uneven layer with irregularities on its surface, the thickness of the hardened layer indicates the maximum thickness of the uneven layer.

[0061] The haze of the hardened layer, as measured by the method described in the examples below, can be adjusted by the surface shape. Creating wrinkle-like irregularities on the surface increases the haze. Making the surface smooth decreases the haze. When the active groups derived from copolymer (A) in the curable polymer composition include both the active groups of group (Ia) and monomer (x), the haze of the cured layer is preferably 0.2% or more, more preferably 0.5% or more, even more preferably 1.0% or more, and particularly preferably 1.2% or more, with an upper limit of, for example, 99%. If the haze is above the above lower limit, properties such as matte finish and antiblocking due to unevenness are easily obtained. When the active group derived from copolymer (A) in the curable polymer composition is only group (Ia), the haze of the cured layer is preferably less than 10%, more preferably 0.1 to 5%, and even more preferably 0.2 to 0.8%. Below the above upper limit, the transparency is better, resulting in superior visibility when used in various applications.

[0062] <Laminate> The laminate of the present invention (hereinafter also referred to as "the laminate") comprises a base layer and a layer made of a cured product of a curable polymer composition (hereinafter also referred to as "cured layer"). Preferably, the laminate further comprises one or more layers selected from the group consisting of a primer layer provided between the base layer and the cured layer, a surface functional layer provided on the side of the cured layer opposite to the base layer, and a back functional layer provided on the side of the base layer opposite to the cured layer. This laminate is suitable as a hard coat film used, for example, as a protective film for articles.

[0063] The surface of the cured layer of this laminate (the side opposite to the substrate) may be smooth or it may have irregularities. Figures 1-5 are schematic cross-sectional views showing an example of this laminate where the hardened layer is an uneven layer with surface irregularities. The dimensional ratios in Figures 1-5 are for illustrative purposes only and do not represent the actual dimensions. The laminate 10 in the example of Figure 1 comprises a base layer 1, a cured layer 2 provided on one surface 1a of the base layer 1, and a primer layer 3 provided between the base layer 1 and the cured layer 2. The laminate 10 in the example shown in Figure 2 comprises a base layer 1, a cured layer 2 provided on one surface 1a of the base layer 1, and a surface functional layer 4 provided on the surface of the cured layer 2 opposite to the base layer 1 side. The laminate 10 in the example shown in Figure 3 comprises a base layer 1, a cured layer 2 provided on one surface 1a of the base layer 1, a primer layer 3 provided between the base layer 1 and the cured layer 2, and a surface functional layer 4 provided on the surface of the cured layer 2 opposite to the base layer 1 side. The laminate 10 in the example of Figure 4 comprises a base layer 1, a cured layer 2 provided on one surface 1a of the base layer 1, a primer layer 3 provided between the base layer 1 and the cured layer 2, and a back surface functional layer 5 provided on the surface 1b of the base layer 1 opposite to the cured layer 2 side. The laminate 10 in the example of Figure 5 comprises a base layer 1, a cured layer 2 provided on one surface 1a of the base layer 1, a primer layer 3 provided between the base layer 1 and the cured layer 2, a surface functional layer 4 provided on the surface of the cured layer 2 opposite to the base layer 1 side, and a back surface functional layer 5 provided on the surface 1b of the base layer 1 opposite to the cured layer 2 side.

[0064] <Base material layer> As the base layer, known materials can be used, such as resin base materials, metal base materials, and paper base materials. Among these, resin base materials are preferred from the viewpoint of processability. The resin substrate may be a single layer or a multilayer structure of two or more layers, and is not particularly limited. It is preferable to have a multilayer structure of two or more layers in the resin substrate, giving each layer its own characteristics to achieve multifunctionality.

[0065] Various resin films (sheets) can be used as the resin substrate, including, for example, polyester film, poly(meth)acrylate film, polyolefin film, polycarbonate film, polyimide film, triacetylcellulose film, polystyrene film, polyvinyl chloride film, polyvinyl alcohol film, nylon film, etc. When this laminate is developed for display applications, polyester film, poly(meth)acrylate film, polyolefin film, polycarbonate film, polyimide film, and triacetylcellulose film are preferred. Among these, polyester film, poly(meth)acrylate film, and polyolefin film are preferred for anti-glare applications, and polyester film is even more preferred when considering transparency, moldability, and versatility. The polyester film may be an unstretched film or a stretched film, with the stretched film being preferred. Among these, a uniaxially stretched film or a biaxially stretched film is preferred, and the biaxially stretched film is more preferred from the viewpoint of superior balance of mechanical properties and flatness.

[0066] The polyester constituting the polyester film that can be used as the base layer may be either homopolyester or copolymer polyester. Preferably, the homopolyester is obtained by polycondensation of an aromatic dicarboxylic acid and an aliphatic glycol. Examples of aromatic dicarboxylic acids include terephthalic acid and 2,6-naphthalenedicarboxylic acid. Examples of aliphatic glycols include ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethanol. The aromatic dicarboxylic acid and aliphatic glycol may be used individually or in combination of two or more. Examples of dicarboxylic acid components in copolymerized polyesters include isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, and oxycarboxylic acid. Examples of glycol components include ethylene glycol, diethylene glycol, propylene glycol, butanediol, 4-cyclohexanedimethanol, and neopentyl glycol. Dicarboxylic acid components and glycol components may be used individually or in combination of two or more. Typical examples of polyesters include polyethylene terephthalate and polyethylene naphthalate.

[0067] Among the polyester films, those made from polyethylene terephthalate or polyethylene naphthalate are more preferable when considering mechanical strength and heat resistance, and those made from polyethylene terephthalate are even more preferable when considering ease of manufacture and handling for applications such as surface protection films.

[0068] The poly(meth)acrylate constituting the poly(meth)acrylate film that can be used as a base layer can be any poly(meth)acrylate having units based on (meth)acrylate, and various acrylic resins can be used. Examples of (meth)acrylates include alkyl(meth)acrylates having alkyl groups with 1 to 4 carbon atoms, such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, and butyl(meth)acrylate, as well as alkyl(meth)acrylates having alkyl groups with more carbon atoms. When considering transparency, processability, and chemical resistance, poly(meth)acrylate is preferably composed mainly of units based on alkyl(meth)acrylate having an alkyl group with 1 to 4 carbon atoms, more preferably of at least one selected from the group consisting of units based on methyl(meth)acrylate and units based on ethyl(meth)acrylate, and particularly preferably of units based on methyl(meth)acrylate as the main component. It is also possible to impart properties such as flexibility to poly(meth)acrylate by incorporating units based on (meth)acrylates other than alkyl(meth)acrylates, or units based on other monomers. The ratio of units based on alkyl(meth)acrylate having an alkyl group with 1 to 4 carbon atoms to the total mass of poly(meth)acrylate is preferably 50% by mass or more, more preferably 80% by mass or more.

[0069] The base layer may contain particles for the purpose of providing slipperiness, preventing scratches during each process, and improving blocking resistance. The type of particles can be appropriately selected according to the purpose and is not particularly limited. Specific examples include inorganic particles such as silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, aluminum oxide, zirconium oxide, and titanium oxide, and organic particles such as acrylic resin, styrene resin, urea resin, phenolic resin, epoxy resin, and benzoguanamine resin. Furthermore, if the base layer includes a polyester film, precipitated particles obtained by precipitating a portion of a metal compound such as a catalyst during the polyester manufacturing process can also be used. Among these, silica particles and calcium carbonate particles are particularly preferred because they are easily effective even in small amounts. The shape of the particles is not particularly limited; they can be spherical, lumpy, rod-shaped, flattened, or any other shape. Furthermore, there are no particular restrictions on their hardness, specific gravity, color, etc. These particles may be used in combination of two or more types, as needed.

[0070] The average particle size is preferably 10 μm or less, more preferably 0.01 to 5 μm, and even more preferably in the range of 0.01 to 3 μm. If the average particle size is 10 μm or less, problems due to a decrease in the transparency of the substrate layer are less likely to occur. The average particle size is the 50% cumulative (mass-based) value of the equivalent spherical distribution measured by a centrifugal sedimentation particle size distribution analyzer.

[0071] When the substrate layer contains particles, the particle content in the substrate layer cannot be generalized as it depends on the average particle size, but it is preferably 5% by mass or less, more preferably in the range of 0.0003 to 3% by mass, and even more preferably in the range of 0.0005 to 1% by mass, relative to the total mass of the particle-containing layer in the substrate layer. If the particle content is 5% by mass or less, problems such as particle shedding and a decrease in the transparency of the substrate layer are less likely to occur.

[0072] The substrate layer may contain additives other than the particles mentioned above, as needed. Known additives such as UV absorbers, antioxidants, antistatic agents, heat stabilizers, lubricants, dyes, and pigments can be used.

[0073] The thickness of the substrate layer is not particularly limited as long as it is within the range in which film formation is possible, but is preferably in the range of 2 to 350 μm, more preferably 5 to 250 μm, and even more preferably 10 to 100 μm.

[0074] <Primer layer> The primer layer is provided between the substrate layer and the cured layer to impart various functions. Examples of primer layers include adhesion-enhancing layers and antistatic layers. The primer layer may have multiple functions. For example, the adhesion-enhancing layer may also serve as an antistatic layer.

[0075] In a preferred embodiment, the primer layer is an adhesion-enhancing layer. If the adhesion between the substrate layer and the cured layer is insufficient, the laminate may not be usable in some applications. By having an adhesion-enhancing layer, the adhesion between the substrate layer and the cured layer is improved, and the laminate can be used in a variety of applications. When the primer layer is an adhesion-enhancing layer, it is preferable that the primer layer contains either or both a resin and a crosslinking agent-derived compound, from the viewpoint of improving adhesion between the substrate layer and the cured layer.

[0076] In another preferred embodiment, the primer layer is an antistatic layer. If the primer layer is an antistatic layer, the adhesion of dust and other particles due to peeling charge and triboelectric charge to the outermost surface of the laminate, particularly the outermost surface on the side where the cured layer is present relative to the substrate layer, can be reduced. To make the primer layer an antistatic layer, for example, an antistatic agent can be added to the primer layer.

[0077] Conventional resins can be used as the resin. Specific examples of resins include polyester resins, acrylic resins, urethane resins, and polyvinyl resins (polyvinyl alcohol, vinyl chloride-vinyl acetate copolymer, etc.). Among these, polyester resins, acrylic resins, and urethane resins are preferred considering adhesion performance and coating properties. When the base layer is a resin film, the resin of the base layer is preferably the same type as the resin of the resin film, from the viewpoint of affinity between the primer layer and the base layer. For example, when the base layer is a polyester film, the primer layer preferably contains polyester resin. When the base layer is a poly(meth)acrylate film, the primer layer preferably contains acrylic resin.

[0078] Polyester resins include those whose main components consist of polycarboxylic acids and polyhydroxy compounds. Examples of polycarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 4,4'-diphenyldicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-potassium sulfoterephthalic acid, 5-sodium sulfisoisophthalic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, glutaric acid, succinic acid, trimellitic acid, trimesic acid, pyromellitic acid, trimellitic anhydride, phthalic anhydride, monopotassium salt of trimellitic acid, and their ester-forming derivatives. Examples of polyvalent hydroxy compounds include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-propanediol, 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, polytetramethylene glycol, polytetramethylene oxide glycol, dimethylolpropionic acid, glycerin, trimethylolpropane, sodium dimethylolethylsulfonate, potassium dimethylolpropionate, and the like. From these compounds, one or more can be appropriately selected, and a polyester resin can be synthesized by a conventional polycondensation reaction.

[0079] Acrylic resin is a polymer of polymerizable monomers, including (meth)acrylic monomers. Examples of acrylic resins include homopolymers and copolymers of (meth)acrylic monomers, and copolymers of (meth)acrylic monomers and polymerizable monomers other than (meth)acrylic monomers. Acrylic resins may be copolymers of these polymers with other polymers (e.g., polyester, polyurethane, etc.). Such copolymers are, for example, block copolymers and graft copolymers. Alternatively, polymers (and possibly mixtures of polymers) obtained by polymerizing polymerizable monomers in a solution or dispersion of polyester are also included. Similarly, polymers (and possibly mixtures of polymers) obtained by polymerizing polymerizable monomers in a solution or dispersion of polyurethane are also included. Similarly, polymers (and possibly mixtures of polymers) obtained by polymerizing polymerizable monomers in a solution or dispersion of other polymers are also included.

[0080] The polymerizable monomers mentioned above are not particularly limited, but some representative compounds include, for example, carboxyl group-containing monomers and their salts such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, and citraconic acid; hydroxyl group-containing monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, monobutyl hydroxyl fumarate, and monobutyl hydroxyitaconate; methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and 2-ethyl Examples include alkyl(meth)acrylates such as hexyl(meth)acrylate and lauryl(meth)acrylate; nitrogen-containing monomers such as (meth)acrylamide, diacetone acrylamide, N-methylolacrylamide, and (meth)acrylonitrile; styrene compounds such as styrene, α-methylstyrene, divinylbenzene, and vinyltoluene; vinyl esters such as vinyl propionate and vinyl acetate; silicon-containing monomers such as γ-methacryloxypropyltrimethoxysilane and vinyltrimethoxysilane; phosphorus-containing vinyl monomers; vinyl halides such as vinyl chloride and pyridene chloride; and conjugated dienes such as butadiene.

[0081] Urethane resin is a polymer compound that contains urethane bonds within its molecule, and is typically synthesized by the reaction of polyols and polyisocyanates. Chain extenders may be used when synthesizing urethane resin. Examples of polyols used to obtain urethane resin include polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, and acrylic polyols. These compounds may be used individually or in combination of two or more.

[0082] Polycarbonate polyols are obtained by the reaction (de-alcoholization reaction) of a polyhydric alcohol with a carbonate compound. Examples of polyhydric alcohols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, and 3,3-dimethylolheptane. Examples of carbonate compounds include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and ethylene carbonate. Specific examples of polycarbonate polyols include poly(1,6-hexylene) carbonate and poly(3-methyl-1,5-pentylene) carbonate.

[0083] Examples of polyether polyols include polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polytetramethylene ether glycol, and polyhexamethylene ether glycol.

[0084] Examples of polyester polyols include those obtained by the reaction of a polycarboxylic acid or its acid anhydride with a polyhydric alcohol, and those having derivative units of lactone compounds such as polycaprolactone. Examples of polycarboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, terephthalic acid, and isophthalic acid. Polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-methyl-2-propyl-1,3-propanediol, 1 Examples include ,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-butyl-2-hexyl-1,3-propanediol, cyclohexanediol, bishydroxymethylcyclohexane, dimethanolbenzene, bishydroxyethoxybenzene, alkyldialkanolamines, lactonediols, etc.

[0085] Considering adhesion performance, polyester polyols and polycarbonate polyols are preferred as polyols, with polyester polyols being particularly preferred.

[0086] Examples of polyisocyanates used to obtain urethane resins include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylenediphenyl diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, and tolidine diisocyanate; aliphatic diisocyanates having aromatic rings such as α,α,α',α'-tetramethylxylylene diisocyanate; aliphatic diisocyanates such as methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, and hexamethylene diisocyanate; and alicyclic diisocyanates such as cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and isopropylidene dicyclohexyl diisocyanate. These may be used individually or in combination of two or more.

[0087] There are no particular restrictions on the chain extender as long as it has two or more active groups that react with isocyanate groups, and generally, chain extenders having two hydroxyl groups or amino groups can be mainly used. Examples of chain extenders having two hydroxyl groups include glycol compounds such as aliphatic glycols like ethylene glycol, propylene glycol, and butanediol, aromatic glycols like xylylene glycol and bishydroxyethoxybenzene, and ester glycols like neopentyl glycol hydroxypivalate. Examples of chain extenders having two amino groups include aromatic diamines such as tolylenediamine, xylylenediamine, and diphenylmethanediamine; aliphatic diamines such as ethylenediamine, propylenediamine, hexanediamine, 2,2-dimethyl-1,3-propanediamine, 2-methyl-1,5-pentanediamine, trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, and 1,10-decanediamine; and alicyclic diamines such as 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, dicyclohexylmethanediamine, isopropylthincyclohexyl-4,4'-diamine, 1,4-diaminocyclohexane, and 1,3-bisaminomethylcyclohexane.

[0088] Urethane resins are typically used in the form of dispersions or solutions. The medium for the dispersion or solution may be a solvent, but water is preferred. Aqueous dispersions or aqueous solutions of urethane resins include forced emulsification types using emulsifiers, self-emulsifying types with hydrophilic groups introduced into the structure of the urethane resin, and water-soluble types. In particular, self-emulsifying types, in which ionic groups are introduced into the structure of the urethane resin to form ionomers, are preferred because they offer excellent storage stability of the liquid and superior water resistance and transparency of the resulting primer layer.

[0089] Various ionic groups can be introduced into the structure of urethane resin, including carboxyl groups, sulfonic acid groups, phosphate groups, phosphonic acid groups, and quaternary ammonium bases, but carboxyl groups are preferred. The carboxyl groups are preferably in the form of salts neutralized with neutralizing agents such as ammonia, amines, alkali metals, and inorganic alkalis. Particularly preferred neutralizing agents are ammonia, trimethylamine, and triethylamine. In urethane resins having carboxyl groups neutralized with a neutralizing agent, the carboxyl groups from which the neutralizing agent has been removed during the drying process after coating can be used as crosslinking reaction sites by a crosslinking agent. This results in excellent stability in the liquid state before coating, and further improves the durability, solvent resistance, water resistance, and blocking resistance of the resulting primer layer.

[0090] Various methods can be used to introduce carboxyl groups into urethane resins at each stage of the polymerization reaction. For example, one method involves using a resin containing carboxyl groups as a copolymer component during prepolymer synthesis, or using a component containing carboxyl groups as one of the components of a polyol, polyisocyanate, or chain extender. In particular, a method using a carboxyl group-containing diol and introducing a desired amount of carboxyl groups by adjusting the amount of this component added is preferred. For example, a carboxyl group-containing diol can be copolymerized with a polyol used in the synthesis of urethane resins. Examples of carboxyl group-containing diols include dimethylolpropionic acid, dimethylolbutanoic acid, bis-(2-hydroxyethyl)propionic acid, bis-(2-hydroxyethyl)butanoic acid, and salts of these in which the carboxyl groups have been neutralized with a neutralizing agent.

[0091] The primer layer preferably contains a compound derived from a crosslinking agent in order to strengthen the primer layer and improve performance such as adhesion. Known materials can be used as crosslinking agents, including, for example, melamine compounds, oxazoline compounds, isocyanate compounds, epoxy compounds, carbodiimide compounds, silane coupling compounds, hydrazide compounds, and aziridine compounds. Among these, melamine compounds, isocyanate compounds, epoxy compounds, oxazoline compounds, carbodiimide compounds, and silane coupling compounds are preferred. From the viewpoint of further improving adhesion and durability, melamine compounds, oxazoline compounds, isocyanate compounds, and epoxy compounds are more preferred, with oxazoline compounds and isocyanate compounds being particularly preferred. These crosslinking agents may be used individually or in combination of two or more. Using two or more in combination may further improve adhesion and durability.

[0092] Melamine compounds are compounds that have a melamine skeleton within them. Examples include alkylolated melamine derivatives, compounds obtained by reacting alkylolated melamine derivatives with alcohol to partially or completely etherify them, and mixtures thereof. Examples of alcohols used for etherification include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, and isobutanol. Melamine compounds may be monomers, polymers of two or more units, or mixtures thereof. Furthermore, compounds in which urea or the like is co-condensed with a portion of the melamine can also be used, and catalysts can be used to increase the reactivity of the melamine compound. As for melamine compounds, those having a hydroxyl group are preferred, considering their reactivity with various other compounds.

[0093] Isocyanate compounds are compounds that have an isocyanate derivative structure, such as isocyanates or blocked isocyanates. Examples of isocyanates include aromatic isocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylenediphenyl diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate; aliphatic isocyanates having aromatic rings such as α,α,α',α'-tetramethylxylylene diisocyanate; aliphatic isocyanates such as methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, and hexamethylene diisocyanate; and alicyclic isocyanates such as cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, methylenebis(4-cyclohexyl isocyanate), and isopropylidene dicyclohexyl diisocyanate. Furthermore, polymers and derivatives of these isocyanates, such as biuretized, isocyanurateized, uretdioneized, and carbodiimide-modified compounds, can also be mentioned. These may be used individually or in combination of two or more. Among the above isocyanate compounds, aliphatic isocyanates or alicyclic isocyanates are more preferred than aromatic isocyanates from the viewpoint of avoiding yellowing due to ultraviolet light.

[0094] Examples of blocked isocyanates include isocyanate compounds in which the isocyanate group is blocked by a blocking agent. Examples of blocking agents include phenolic compounds such as bisulfites, phenol, cresol, and ethylphenol; alcoholic compounds such as propylene glycol monomethyl ether, ethylene glycol, benzyl alcohol, methanol, and ethanol; active methylene compounds such as dimethyl malonate, diethyl malonate, methyl isobutanoylacetate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone; mercaptan compounds such as butyl mercaptan and dodecyl mercaptan; lactam compounds such as ε-caprolactam and δ-valerolactam; amine compounds such as diphenylaniline, aniline, and ethyleneimine; acid amide compounds such as acetanilide and acetic acid amide; and oxime compounds such as formaldehyde, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime. These may be used individually or in combination of two or more. As the blocked isocyanate, isocyanates blocked by an active methylene compound are preferred from the viewpoint of preventing damage to the primer layer.

[0095] Isocyanate compounds may be used individually or as mixtures or binders with various polymers. It is preferable to use mixtures or binders with polyester resins or urethane resins to improve the dispersibility and crosslinking properties of isocyanate compounds.

[0096] Oxazoline compounds are compounds that have an oxazoline group in their molecule. As the oxazoline compound, polymers containing an oxazoline group are preferred. Polymers containing an oxazoline group can be obtained by polymerization of an addition-polymerizable oxazoline group-containing monomer alone or with other monomers. Examples of addition-polymerizable oxazoline group-containing monomers include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, and 2-isopropenyl-5-ethyl-2-oxazoline. These may be used individually or in combination of two or more. Among these, 2-isopropenyl-2-oxazoline is preferred because it is readily available industrially. Other monomers are not particularly limited as long as they are copolymerizable with addition-polymerizable oxazoline group-containing monomers, for example (meth)acrylates such as alkyl (meth)acrylates (alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl, and cyclohexyl groups); unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrenesulfonic acid and their salts (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.); unsaturated nitriles such as acrylonitrile and methacrylonitrile; (meth)acrylates Examples include unsaturated amides such as lylamide, N-alkyl(meth)acrylamide, N,N-dialkyl(meth)acrylamide (alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl, and cyclohexyl groups); vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; α-olefins such as ethylene and propylene; halogen-containing α,β-unsaturated monomers such as vinyl chloride, vinylidene chloride, and vinyl fluoride; and α,β-unsaturated aromatic monomers such as styrene and α-methylstyrene. These may be used individually or in combination of two or more.

[0097] The amount of oxazoline groups per gram of oxazoline compound is preferably in the range of 0.5 to 10 mmol / g, more preferably 1 to 9 mmol / g, even more preferably 3 to 8 mmol / g, and particularly preferably 4 to 6 mmol / g. If the amount of oxazoline groups is within the above range, the durability of the coating film is improved and the adhesion can be easily adjusted.

[0098] Epoxy compounds are compounds that contain an epoxy group within their molecule. Examples of epoxy compounds include condensates of epichlorohydrin with compounds having a hydroxyl group or an amino group (such as ethylene glycol, polyethylene glycol, glycerin, polyglycerin, and bisphenol A), and include polyepoxy compounds, diepoxy compounds, monoepoxy compounds, and glycidylamine compounds. Examples of polyepoxy compounds include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris(2-hydroxyethyl) isocyanate, glycerol polyglycidyl ether, and trimethylolpropane polyglycidyl ether. Examples of diepoxy compounds include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcinol diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and polytetramethylene glycol diglycidyl ether. Examples of monoepoxy compounds include allyl glycidyl ether, 2-ethylhexyl glycidyl ether, and phenyl glycidyl ether. Examples of glycidylamine compounds include N,N,N',N'-tetraglycidyl-m-xylylenediamine and 1,3-bis(N,N-diglycidylamino)cyclohexane.

[0099] Carbodiimide compounds are compounds that have one or more carbodiimide structures or carbodiimide derivative structures within their molecule. As for carbodiimide compounds, polycarbodiimide compounds having two or more carbodiimide structures or carbodiimide derivative structures within the molecule are more preferred for better primer layer strength and other reasons.

[0100] Carbodiimide compounds can be synthesized using known techniques, and generally, diisocyanate condensation reactions are employed. The diisocyanate is not particularly limited and can be either aromatic or aliphatic. Specifically, examples include tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl diisocyanate, and dicyclohexylmethane diisocyanate.

[0101] To improve the water solubility and water dispersibility of polycarbodiimide compounds, surfactants may be added, or hydrophilic monomers such as polyalkylene oxides, quaternary ammonium salts of dialkylamino alcohols, and hydroxyalkyl sulfonates may be added, to the extent that the effects of the present invention are not lost.

[0102] Silane coupling compounds are organosilicon compounds that contain both an organic functional group and a hydrolyzable group such as an alkoxy group within a single molecule. Examples of silane coupling compounds include epoxy group-containing compounds such as 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; vinyl group-containing compounds such as vinyltrimethoxysilane and vinyltriethoxysilane; styryl group-containing compounds such as p-styryltrimethoxysilane and p-styryltriethoxysilane; (meth)acryloyl group-containing compounds such as 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane and 3-(meth)acryloxypropylmethyldiethoxysilane; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-2- Examples include amino group-containing compounds such as (aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltriethoxysilane; isocyanurate group-containing compounds such as tris(trimethoxysilylpropyl)isocyanurate and tris(triethoxysilylpropyl)isocyanurate; and mercapto group-containing compounds such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropylmethyldiethoxysilane.

[0103] Among the above compounds, epoxy group-containing silane coupling compounds, double bond-containing silane coupling compounds such as vinyl groups and (meth)acrylic groups, and amino group-containing silane coupling compounds are more preferred from the viewpoint of the strength of the primer layer.

[0104] Furthermore, these crosslinking agents react during the drying and film formation processes, improving the performance of the primer layer. It can be inferred that the formed primer layer contains compounds derived from the crosslinking agents, such as unreacted crosslinking agents, reacted compounds, or mixtures thereof.

[0105] There are no particular restrictions on the antistatic agent to be included in the primer layer, and known antistatic agents can be used, such as compounds having an ammonium group, polyether compounds, compounds having a sulfonic acid group, betaine compounds, conductive organic polymers, etc. As an antistatic agent, polymer-type antistatic agents are preferred due to their good heat resistance and resistance to humid heat.

[0106] Compounds containing an ammonium group are compounds that have an ammonium group in their molecule, and examples include ammonium compounds of aliphatic amines, alicyclic amines, and aromatic amines. The compound having an ammonium group is preferably a compound having a high molecular weight type ammonium group. In polymeric compounds having ammonium groups, it is preferable that the ammonium groups are incorporated into the main chain or side chains of the polymer rather than as counterions. Examples of such compounds include those obtained by polymerizing an addition polymerizable monomer having an ammonium group or a precursor group of an ammonium group, such as an amine, and, if necessary, converting the precursor group of the ammonium group into an ammonium group to obtain a polymeric compound having an ammonium group. The addition polymerizable monomer containing an ammonium group or a precursor group of an ammonium group may be polymerized alone, copolymerized with two or more types, or copolymerized with other monomers.

[0107] Among compounds containing an ammonium group, compounds containing a pyrrolidinium ring are also preferred due to their excellent antistatic properties and heat stability. The two substituents bonded to the nitrogen atom of a compound having a pyrrolidinium ring are, independently, an alkyl group, a phenyl group, etc., and these alkyl and phenyl groups may be substituted with the following groups. Substitutable groups include, for example, a hydroxyl group, an amide group, an ester group, an alkoxy group, a phenoxy group, a naphthoxy group, a thioalkoxy group, a thiophenoxy group, a cycloalkyl group, a trialkylammonium alkyl group, a cyano group, and a halogen. Furthermore, the two substituents bonded to the nitrogen atom may be chemically bonded, and an example of a group formed by the chemical bonding of two substituents is -(CH2) m Examples include -(m=an integer from 2 to 5), -CH(CH3)CH(CH3)-, -CH=CH-CH=CH-, -CH=CH-CH=N-, -CH=CH-N=C-, -CH2OCH2-, -(CH2)2O(CH2)2-, etc.

[0108] The compound having a pyrrolidinium ring is preferably a polymer having a pyrrolidinium ring. Polymers having a pyrrolidinium ring can be obtained, for example, by cyclopolymerizing a diallylamine derivative using a radical polymerization catalyst. A compound having a polymerizable carbon-carbon unsaturated bond with the diallylamine derivative may also be used as a copolymer component. Polymerization can be carried out by known methods using a polymerization initiator such as hydrogen peroxide, benzoyl peroxide, or tertiary butyl peroxide in a polar solvent (water, methanol, ethanol, isopropanol, formamide, dimethylformamide, dioxane, acetonitrile, etc.), but is not limited to these methods.

[0109] Examples of anions that act as counterions to the ammonium group in the aforementioned compounds containing an ammonium group include halogen ions, sulfonates, phosphates, nitrates, alkyl sulfonates, and carboxylates.

[0110] The number-average molecular weight of the compound having an ammonium group is preferably 1,000 to 500,000, more preferably 2,000 to 350,000, and even more preferably 5,000 to 200,000. If the number-average molecular weight is 1,000 or more, the strength and heat stability of the coating film are better. If the number-average molecular weight is 500,000 or less, the viscosity of the coating liquid for forming the primer layer is low, resulting in good handling and application properties.

[0111] Examples of polyether compounds include polyethylene oxide, polyether ester amide, and acrylic resins having polyethylene glycol as a side chain.

[0112] In compounds having a sulfonic acid group, the sulfonic acid group may be neutralized with a neutralizing agent to form a salt. Preferred compounds having a sulfonic acid group include polystyrene sulfonic acid and its salts, which have multiple sulfonic acid groups in their molecule.

[0113] As conductive organic polymers, known materials can be used, such as polythiophene-based, polyaniline-based, polypyrrole-based, polyacetylene-based, and polyphenylene sulfide-based polymers. Among these, polythiophene-based polymers (polythiophene or polythiophene derivatives) are preferred because they offer both high transparency and high conductivity, are less prone to discoloration, and exhibit good performance through coating. Among polythiophene-based polymers, compounds obtained by combining poly(3,4-ethylenedioxythiophene) with polystyrene sulfonic acid are particularly preferred from the viewpoint of conductive performance. Conductive organic polymers are preferable because they exhibit high conductivity, have low humidity dependence, and are expected to have a wide range of applications.

[0114] The primer layer may contain particles for blocking or improving lubricity. The primer layer may, as necessary, contain additives such as defoaming agents, coating properties improvers, thickeners, organic lubricants, ultraviolet absorbers, antioxidants, foaming agents, dyes, and pigments, to the extent that it does not impair the spirit of the present invention.

[0115] The proportion of resin in 100% by mass of the primer layer is, for example, 5% by mass or more, preferably 10 to 99% by mass, more preferably 20 to 95% by mass, and even more preferably 30 to 90% by mass. When the proportion of resin is within the above range, the adhesion performance and appearance of the primer layer are better.

[0116] The proportion of crosslinking agent-derived compounds in 100% by mass of the primer layer is, for example, 80% by mass or less, preferably 0.5 to 65% by mass, more preferably 3 to 50% by mass, and even more preferably 5 to 40% by mass. When the proportion of crosslinking agent-derived compounds is within the above range, the adhesion performance and strength of the primer layer are better.

[0117] When the primer layer is an antistatic layer containing an antistatic agent, the proportion of the antistatic agent in 100% by mass of the primer layer is not general and depends on the type of antistatic agent, but is, for example, in the range of 80% by mass or less, preferably 0.5 to 70% by mass, and more preferably 1 to 50% by mass. If the proportion of the antistatic agent is within the above range, it is easier to impart sufficient antistatic function to the primer layer, and the antistatic performance is more likely to be exhibited even after the cured layer is formed on the primer layer.

[0118] The thickness of the primer layer cannot be generalized as it depends on the material used for the primer layer and the performance to be achieved, but it is preferably in the range of 0.001 to 10 μm, more preferably 0.01 to 4 μm, and even more preferably 0.02 to 1 μm. The primer layer can be formed by known methods.

[0119] <Surface functional layer> The surface functional layer is provided on top of the hardened layer to impart various functions. Examples of surface functional layers include anti-fouling layers, anti-static layers, refractive index adjusting layers (anti-reflective layers, low-reflection layers, etc.), infrared absorption layers, ultraviolet absorption layers, and color correction layers. The antifouling layer is provided to improve the antifouling performance by imparting water-repellent and oil-repellent properties to the hardened layer. The antistatic layer is provided to reduce the adhesion of dust and other particles due to peeling charge and triboelectric charge to the outermost surface of the laminate, particularly the outermost surface on the side where the hardened layer is present relative to the base layer. The refractive index adjusting layer is provided, for example, to improve the total light transmittance of the laminate.

[0120] The anti-fouling layer contains anti-fouling components. As antifouling components, known substances such as silicone compounds, fluorine compounds, and long-chain alkyl group-containing compounds can be used. Of these, silicone compounds and fluorine compounds are preferred from the viewpoint of exhibiting stronger antifouling performance, and fluorine compounds and long-chain alkyl group-containing compounds are preferred from the viewpoint of being less likely to contaminate the surface that the antifouling layer comes into contact with.

[0121] Silicone compounds are compounds that have a silicone structure within their molecules, and examples include alkyl silicones (dimethyl silicone, diethyl silicone, etc.) and silicones having a phenyl group (phenyl silicone, methylphenyl silicone, etc.). Silicone compounds may have various functional groups. Examples of functional groups include ether groups, hydroxyl groups, amino groups, epoxy groups, carboxylic acid groups, halogen groups such as fluorine, perfluoroalkyl groups, hydrocarbon groups such as various alkyl groups and various aromatic groups. Other examples of functional groups include silicones having vinyl groups and hydrogen silicones in which hydrogen atoms are directly bonded to silicon atoms. It is also possible to use both in combination as addition-type silicones (types resulting from the addition reaction of vinyl groups and hydrogensilane). Furthermore, it is possible to introduce double bonds such as acryloyl groups and allow the reaction to occur at the double bond site.

[0122] Modified silicones such as acrylic grafted silicone, silicone grafted acrylic, amino-modified silicone, and perfluoroalkyl-modified silicone can also be used as the silicone compound. Considering heat resistance and stain resistance, it is preferable to use a curable silicone resin. Any curing reaction type can be used, including condensation type, addition type, and active energy ray curing type.

[0123] Fluorine compounds are compounds that contain fluorine atoms. Organic fluorine compounds are preferably used as fluorine compounds, and examples include perfluoroalkyl group compounds, polymers of olefin compounds containing fluorine atoms, and aromatic fluorine compounds such as fluorobenzene. Perfluoroalkyl group compounds are preferred from the viewpoint of mold release properties. Compounds containing long-chain alkyl groups, as described later, can also be used as fluorine compounds.

[0124] Examples of perfluoroalkyl group-containing compounds include perfluoroalkyl group-containing (meth)acrylates and their polymers, such as perfluoroalkyl (meth)acrylate, perfluoroalkyl methyl (meth)acrylate, 2-perfluoroalkyl ethyl (meth)acrylate, 3-perfluoroalkyl propyl (meth)acrylate, 3-perfluoroalkyl-1-methylpropyl (meth)acrylate, and 3-perfluoroalkyl-2-propenyl (meth)acrylate; and perfluoroalkyl group-containing vinyl ethers and their polymers, such as perfluoroalkyl methyl vinyl ether, 2-perfluoroalkyl ethyl vinyl ether, 3-perfluoropropyl vinyl ether, 3-perfluoroalkyl-1-methylpropyl vinyl ether, and 3-perfluoroalkyl-2-propenyl vinyl ether. Polymers are preferable considering heat resistance and stain resistance. Polymers may be polymers of a single compound or polymers of multiple compounds. Furthermore, polymers with compounds containing long-chain alkyl compounds, as described later, may also be used. From the viewpoint of stain resistance, the number of carbon atoms in the perfluoroalkyl group is preferably 3 to 11.

[0125] Long-chain alkyl group-containing compounds are compounds having a linear or branched alkyl group (long-chain alkyl group) with typically 6 or more carbon atoms, preferably 8 or more, and more preferably 12 or more. Examples of long-chain alkyl groups include hexyl group, octyl group, decyl group, lauryl group, octadecyl group, and behenyl group. Examples of long-chain alkyl group-containing compounds include various long-chain alkyl group-containing polymer compounds, long-chain alkyl group-containing amine compounds, long-chain alkyl group-containing ether compounds, and long-chain alkyl group-containing quaternary ammonium salts. Long-chain alkyl group-containing compounds are preferably polymer compounds, considering heat resistance and stain resistance. Furthermore, from the viewpoint of effectively obtaining antifouling properties, polymer compounds with long-chain alkyl groups in their side chains are even more preferable.

[0126] Polymer compounds having long-chain alkyl groups as side chains can be obtained, for example, by reacting a polymer compound having a reactive group with a long-chain alkyl group-containing compound that can react with the reactive group. Examples of the reactive groups mentioned above include hydroxyl groups, amino groups, carboxyl groups, and acid anhydrides. Examples of polymer compounds having these reactive groups include polyvinyl alcohol, polyethyleneimine, polyethyleneamine, reactive group-containing polyester resin, and reactive group-containing poly(meth)acrylic resin. Among these, polyvinyl alcohol is preferred considering its stain resistance and ease of handling. Examples of long-chain alkyl group-containing compounds that can react with the above-mentioned reactive groups include long-chain alkyl group-containing isocyanates such as hexyl isocyanate, octyl isocyanate, decyl isocyanate, lauryl isocyanate, octadecyl isocyanate, and behenyl isocyanate; long-chain alkyl group-containing acid chlorides such as hexyl chloride, octyl chloride, decyl chloride, lauryl chloride, octadecyl chloride, and behenyl chloride; long-chain alkyl group-containing amines; and long-chain alkyl group-containing alcohols. Among these, long-chain alkyl group-containing isocyanates are preferred, and octadecyl isocyanate is particularly preferred, considering release properties and ease of handling.

[0127] Polymeric compounds having long-chain alkyl groups as side chains can also be obtained as polymers of long-chain alkyl (meth)acrylates, or as copolymers of long-chain alkyl (meth)acrylates with other vinyl group-containing monomers. Examples of long-chain alkyl (meth)acrylates include hexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, octadecyl (meth)acrylate, and behenyl (meth)acrylate.

[0128] The antifouling layer may, if necessary, further contain, in addition to the antifouling component, resins, compounds derived from crosslinking agents, antistatic agents, defoaming agents, coating properties improvers, thickeners, ultraviolet absorbers, antioxidants, foaming agents, dyes, pigments, etc. The resins and compounds derived from crosslinking agents are as described above. From the viewpoint of improving the strength and durability of the layer, the antifouling layer preferably has a crosslinked structure. An example of an antifouling layer having a crosslinked structure is a layer of cured product of a composition containing a compound or crosslinking agent having multiple radical polymerizable groups such as acryloyl groups and an antifouling component.

[0129] The proportion of antifouling components in 100% by mass of the surface functional layer cannot be stated definitively as it depends on the antifouling components used. However, if the antifouling components are silicone compounds or fluorine compounds, the proportion is usually 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.2% by mass or more, with an upper limit of 100% by mass. If the antifouling components are long-chain alkyl group-containing compounds, the proportion is usually 0.1% by mass or more, preferably 1% by mass or more, and even more preferably 3% by mass or more, with an upper limit of 100% by mass. If the proportion of antifouling components is within the above ranges, the antifouling performance will be superior.

[0130] The antistatic layer contains an antistatic agent. The antistatic agent is as described above. The antistatic layer may, if necessary, further contain, in addition to an antistatic agent, a resin, a crosslinking agent-derived compound, an antifoaming agent, a coating property improver, a thickener, an antifouling agent, an ultraviolet absorber, an antioxidant, a foaming agent, a dye, a pigment, etc. The resin and the crosslinking agent-derived compound are as described above.

[0131] The proportion of antistatic agent in 100% by mass of the antistatic layer varies depending on the type of antistatic agent, but it is typically between 0.1% and 100% by mass.

[0132] Examples of refractive index adjustment layers include high refractive index layers, low refractive index layers, and laminates thereof. As materials constituting the high refractive index layer, known high refractive index materials can be used, for example, aromatic structure-containing compounds such as benzene structures, bisphenol A structures, melamine structures, and fluorene structures; condensed polycyclic aromatic compounds such as naphthalene, anthracene, phenanthrene, naphthalene, benzo[a]anthracene, benzo[a]phenanthrene, pyrene, benzo[c]phenanthrene, and perylene structures, which are considered high refractive index compounds among aromatic structure-containing compounds; metal oxides such as zirconium oxide, titanium oxide, zinc oxide, tin oxide, antimony oxide, yttrium oxide, indium oxide, cerium oxide, ATO (antimony-tin oxide), and ITO (indium-tin oxide); metal chelate compounds such as titanium chelate and zirconium chelate; compounds containing sulfur elements; compounds containing halogen elements.

[0133] Because metal oxides may have reduced adhesion depending on the application, it is preferable to use them in granular form. Furthermore, from the viewpoint of the appearance of the coating, the average particle size is preferably in the range of 100 nm or less, more preferably 50 nm or less, and even more preferably 25 nm or less.

[0134] As materials constituting the low refractive index layer, known low refractive index materials can be used, such as resins such as acrylic resins, urethane resins, and compounds in which fluorine atoms are incorporated into the resin (e.g., fluororesins, compounds containing fluororesin in the main skeleton, compounds containing perfluoroalkyl groups in the side chains); and inorganic materials such as hollow silica particles, magnesium fluoride, calcium fluoride, and other fluorine atom-containing inorganic compounds, as well as their hollow particles and nanoporous particles.

[0135] The thickness of the surface functional layer is preferably in the range of 0.001 to 30 μm, more preferably 0.005 to 20 μm, even more preferably 0.01 to 10 μm, particularly preferably 0.02 to 5 μm, and most preferably 0.03 to 3 μm. If the thickness of the surface functional layer is within the above range, the functionality provided by the surface functional layer is easily expressed. When the hardened layer is a layer that exhibits various functions due to its uneven surface, it is preferable that the thickness of the surface functional layer be smaller than the height of the unevenness on the surface of the uneven layer. If the thickness of the surface functional layer is smaller than the height of the unevenness, even if a surface functional layer is provided, the functions such as matte finish and anti-blocking properties due to the unevenness are less likely to be reduced. The surface functional layer can be formed by known methods.

[0136] <Reverse side functional layer> The functional layer on the back surface is provided to impart various functions to the side of the base layer opposite to the hardened layer side. Examples of functional layers on the back surface include adhesive layers, antistatic layers, refractive index adjusting layers, and antiblocking layers. The adhesive layer is provided to bond the laminate to various adherends. The antistatic layer is provided to prevent the adhesion of surrounding dust and other debris due to peeling charge or triboelectric charge, and the resulting defects, on the outermost surface of the laminate, particularly the outermost surface opposite the hardened layer side of the base layer. The refractive index adjustment layer is provided, for example, to improve the total light transmittance of the laminate. The antiblocking layer is provided to reduce blocking of the laminate.

[0137] As the adhesive for forming the adhesive layer, known adhesives can be used, including acrylic, polyester, urethane, and rubber-based adhesives. Among these, acrylic adhesives are preferred considering their versatility. The antistatic layer and refractive index adjusting layer are the same as the antistatic layer and refractive index adjusting layer as surface functional layers, respectively.

[0138] The thickness of the functional backing layer cannot be generalized as it depends on the material used for the functional backing layer and the performance to be achieved, but for example, it is 0.001 to 30 μm. If the functional backing layer is an adhesive layer, it is preferably 0.01 to 30 μm, more preferably 0.1 to 20 μm. If the functional backing layer is an antistatic layer, it is preferably 0.001 to 10 μm, more preferably 0.01 to 5 μm. The back surface functional layer can be formed by known methods. [Examples]

[0139] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the essence of the invention. The measurement and evaluation methods used in this invention are as follows.

[0140] (1) Weight average molecular weight (Mw) The weight-average molecular weight of the copolymer was measured using GPC under the following conditions. Equipment: Waters "e2695", Column: "TSKgel Super H3000+H4000+H6000" manufactured by Tosoh Corporation. 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.

[0141] (2) Total light transmittance and haze The measurement target was a laminate in which a cured layer was formed on a PET film. Total light transmittance and haze were measured at a wavelength of 550 nm using a haze meter "SH7000" manufactured by Nippon Denshoku Industries, in accordance with JIS Z8722Z (Geometric conditions for irradiation and reception of light-transmitting objects), JIS K7361-1 (Plastics - Test method for total light transmittance of transparent materials), and JIS K7136 (Plastics - Method for determining haze of transparent materials). The haze of a laminate is the percentage of transmitted light that is diverged by 0.044 rad (2.5°) or more from the incident light due to forward scattering, out of the transmitted light that passes through the laminate from the outermost surface on the side where the hardened layer is present relative to the substrate layer (the ratio of diffuse transmittance to total transmittance).

[0142] (3) Scratch resistance The laminate, in which a cured layer was formed on a PET film, was used as the measurement target. Under an atmosphere of 23°C and 55% RH, 200 gf (over an area of ​​4 cm²) was applied to steel wool #0000. 2 A weight (of a certain magnitude) was placed on the surface of the hardened layer of the laminate, and the surface was rubbed back and forth 15 times using a JSPS abrasion testing machine (manufactured by Toyo Seiki Seisakusho Co., Ltd.). Scratches were observed visually. The following criteria were used for evaluation. A: Number of wounds: 0. B: The number of scars is 1 or more, but less than 50. C: The number of scars is 50 or more, but less than 100. D: The number of scars is 100 or more.

[0143] (4) Leveling properties The surface of the hardened layer (10cm x 10cm) was visually inspected, and the number of defects such as blemishes and bumps was examined. The evaluation was performed according to the following criteria. A: The total number of defects and flaws is less than 10. B: The total number of defects and flaws in the product is 10 or more.

[0144] (5) Curability Illuminance 100mW / cm 2 The amount of ultraviolet light required to eliminate tackiness by touch (cumulative light dose) was measured. The following criteria were used for evaluation. A: 100 mJ / cm 2 It hardens with the following irradiation doses. B: 100 mJ / cm 2 Super, 200mJ / cm 2 It hardens with an irradiation dose of less than [amount missing]. C: 200 mJ / cm 2 More than 300mJ / cm 2 It hardens with an irradiation dose of less than [amount missing]. D: 300 mJ / cm 2 It hardens with the above irradiation dose.

[0145] Copolymers were prepared using the compositions shown in Table 1. The raw materials listed in the table are as follows: <Monomer(i)> i-1: 2-[4-(2-hydroxy-2-methyl-1-oxopropyl)phenoxy]ethyl methacrylate obtained in Synthesis Example 1 below: In formula (I), R1 , R 3 , R 4 is a methyl group, R 2 A compound in which the group is an ethylene group. <Monomer(x)> x-1:4-methacryloyloxybenzophenone <Monomer(r)> r-1: Stearyl methacrylate. r-2: 2-ethylhexyl methacrylate. <Monomer (h)> h-1: Diethylaminoethyl methacrylate. <Other monomers (o)> o-1: Methyl methacrylate. <Chain transfer agent (t)> t-1:n-dodecyl mercaptan t-2:3-mercaptopropyltrimethoxysilane <Polymerization initiator (k)> k-1: 2,2'-Azobis(2,4-dimethylvaleronitrile)

[0146] (Synthesis Example 1: Synthesis of monomer (i-1)) Methacrylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was subjected to vacuum distillation, and the fraction with a purity of 99.8% or higher was recovered to obtain the methacrylic anhydride distillate. Vacuum distillation was carried out by gradually raising the temperature from room temperature to 90°C at a pressure of 30 Pa. Separately, 22.4 g (0.1 mol) of 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxymethylpropanone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 30.4 g (0.3 mol) of triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 500 mL of methylene chloride (manufactured by Tokyo Chemical Industry Co., Ltd.). 23.1 g (0.15 mol) of the distillate of the above methacrylic anhydride was added dropwise at room temperature, and the mixture was stirred for 12 hours. The resulting reaction mixture was washed three times with 500 mL of deionized water, the organic phase was concentrated, and the solvent was removed by distillation. The residue was purified by column chromatography (ethyl acetate / hexane = 10 / 90 (volume ratio)) to obtain 21.6 g of the target compound (yield 74%). 1 ¹H-NMR analysis confirmed that the obtained compound was 2-[4-(2-hydroxy-2-methyl-1-oxopropyl)phenoxy]ethyl methacrylate. 1 H NMR (300MHz, chloroform-d): δ8.06(d,J=9.0Hz,2H),6.96(d,J=9.0Hz,2H),6.13(d,J=0.6Hz,1H),5.5 9(s,1H),4.50(d,J=5.1Hz,2H),4.29(dd,J=5.5,4.1Hz,3H),1.94(dd,J=1.6,1.0Hz,3H),1.61(s,6H).

[0147] (Manufacturing Example 1: Manufacturing of copolymer (A-1)) 70 parts of methyl isobutyl ketone (hereinafter referred to as MIBK) were placed in a flask equipped with a stirrer, condenser, and thermometer. Then, the flask was purged with nitrogen and the temperature was raised to 65°C. A mixed solution of 50 parts by mass of monomer (i-1), 20 parts by mass of monomer (r-1), 30 parts by mass of monomer (o-1), 3 parts by mass of chain transfer agent (t-1), 1 part by mass of polymerization initiator (k-1), and 78 parts by mass of MIBK was added dropwise over 2 hours. After another 2 hours, to increase the polymerization rate, a mixed solution of 0.5 parts by mass of polymerization initiator (k-1) and 0.6 parts by mass of MIBK was added and held for 5 hours. After that, the reaction solution was cooled to 40°C to obtain the copolymer MIBK solution (A-1). Hereinafter, the solid content in solution (A-1) will be referred to as copolymer (A-1). The solid content (non-volatile content) of solution (A-1) was 40% by mass. Table 1 shows the weight-average molecular weight (Mw) of copolymer (A-1) and the active group content per gram of copolymer (A-1).

[0148] (Manufacturing Example 2: Manufacturing of Copolymer (A-2)) In Production Example 1, a copolymer MIBK solution (A-2) was obtained under the same conditions as in Production Example 1, except that the composition of the mixed solution was changed to 25 parts by mass of monomer (i-1), 25 parts by mass of monomer (x-1), 10 parts by mass of monomer (r-1), 30 parts by mass of monomer (r-2), 10 parts by mass of monomer (h-1), 0.8 parts by mass of polymerization initiator (k-1), and 78 parts by mass of MIBK. Hereinafter, the solid content in solution (A-2) will be referred to as copolymer (A-2). The solid content (non-volatile content) of solution (A-2) was 40% by mass. The weight-average molecular weight (Mw) of copolymer (A-2) and the content of active groups per gram of copolymer (A-2) are shown in Table 1.

[0149] (Manufacturing Example 3: Manufacturing of copolymer (H-1)) In Production Example 1, a copolymer MIBK solution (H-1) was obtained under the same conditions as in Production Example 1, except that 50 parts by mass of monomer (i-1) was replaced with 50 parts by mass of monomer (x-1) and 3 parts by mass of chain transfer agent (t-1) was replaced with 3 parts by mass of chain transfer agent (t-2). Hereinafter, the solid content in solution (H-1) will be referred to as copolymer (H-1). The solid content (non-volatile content) of solution (H-1) was 40% by mass. Table 1 shows the weight-average molecular weight (Mw) of copolymer (H-1) and the content of active groups per gram of copolymer (H-1).

[0150] [Table 1]

[0151] (Examples 1 and 2, Reference Example 1, Comparative Example 1: Production of coating solution (curable polymer composition)) Each material shown in Table 2 was mixed in the proportions (parts by mass) shown in Table 2, calculated on a non-volatile content basis. Then, a mixed solvent of propylene glycol monomethyl ether (hereinafter referred to as PGM) and methyl ethyl ketone (hereinafter referred to as MEK) (PGM:MEK (mass ratio) of 7:3) was added to a solid content concentration of 40% by mass, and the mixture was stirred until homogeneous to obtain a coating solution (curable polymer composition). Table 2 shows the content of active groups per 100g of non-volatile matter in the coating solution.

[0152] The materials listed in Table 2 are as follows: A-1: MIBK solution of copolymer (A-1) obtained in Production Example 1. A-2: MIBK solution of copolymer (A-2) obtained in Production Example 2. H-1: MIBK solution of copolymer (H-1) obtained in Production Example 3. B-1: A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.). B-2: Pentaerythritol triacrylate ("Viscoat V#300" manufactured by Osaka Organic Chemical Industry Co., Ltd.). P-1: Acrylic resin (Dianal BR-80, manufactured by Mitsubishi Chemical Corporation). C-1: Benzophenone.

[0153] The resulting coating solution was applied to a 50 μm thick PET film (Mitsubishi Chemical Corporation's "T602E50") using a bar coater No. 8, dried for 60 seconds in a hot air dryer heated to 70°C to evaporate the solvent, and then exposed to air under a high-pressure mercury lamp with an integrated light intensity of 250 mJ / cm². 2 , illuminance 100mW / cm 2 A cured layer with a thickness of 3 μm was formed by irradiating it with ultraviolet light. This resulted in a laminate in which a layer of cured material (cured layer) was laminated on a substrate layer made of PET film. Ultraviolet irradiation was performed using the UV conveyor of the iGraphics high-power UV device (model: US5-X1802-X1202). The integrated light intensity was measured using an illuminance meter manufactured by Iwasaki Electric Co., Ltd. (i-UV integrated illuminance meter "UVPF-A1" and "PD-365") at wavelengths of 300-390 nm. The obtained laminate was measured or evaluated using the method described above, according to the items shown in Table 2. The results are shown in Table 2.

[0154] [Table 2]

[0155] As shown in the results in Table 2, the curable polymer compositions of Examples 1 and 2, which include copolymers (A-1) or (A-2) having units based on monomer (i), exhibited superior curability compared to Reference Example 1 and Comparative Example 1, resulting in cured layers with superior scratch resistance. In particular, the cured layer of Example 1, in which copolymer (A) was a copolymer (A-1) having units based on monomer (i), had a nearly smooth surface and a haze of 0.4%. Furthermore, in Example 2, which used copolymer (A-2) having units based on monomer (i) and units based on monomer (x) as copolymer (A), the surface had wrinkle-like irregularities and a haze of 1.4%. [Explanation of Symbols]

[0156] 1...Base material layer 2…hardened layer 3…Primer layer 4…Surface functional layer 5…Reverse functional layer 10…Laminate

Claims

1. A curable polymer composition comprising a copolymer (A), a polyfunctional compound (B) having two or more radical polymerizable groups in one molecule, and an acrylic resin (P) that does not have either an active group that generates radicals upon irradiation with active energy rays or a radical polymerizable group, The copolymer (A) comprises a unit based on monomer (i), which is a compound represented by the following formula (I), and a unit based on monomer (y), which has one or more elements selected from the group consisting of alkyl groups having 4 to 30 carbon atoms, fluorine atoms, and silicon atoms, and a radical polymerizable group, and does not have an active group that generates radicals upon irradiation with active energy rays. The copolymer (A) contains 0.5 to 2.5 mmol / g of active groups that generate radicals upon irradiation with active energy rays per gram. A curable polymer composition in which the units based on the monomer (y) are 1 to 80% by mass of the total mass of all units of the copolymer (A). 【Chemistry 1】 [In the formula, R １ R represents a hydrogen atom, a methyl group, or an ethyl group. ２ R represents an alkylene group having 1 to 2 carbon atoms or a linear or branched alkylene group having 3 to 5 carbon atoms. ３ , R ４ Each independently represents an alkyl group having 1 to 2 carbon atoms or a linear or branched alkyl group having 3 to 5 carbon atoms, R ３ and R ４ They may be joined to each other to form a ring.

2. The curable polymer composition according to claim 1, wherein the monomer (y) is one or more selected from the group consisting of alkyl (meth)acrylates having an alkyl group having 4 to 30 carbon atoms, and compounds having a radical polymerizable group selected from the group consisting of a (meth)acryloyl group, a (meth)acrylamide group, and a vinyl group, and a fluorine atom or a silicon atom.

3. The curable polymer composition according to claim 1 or 2, wherein the copolymer (A) further has one or more units selected from the group consisting of units based on the monomer (x), units based on the monomer (h), and units based on the monomer (o). Monomer (x): A monomer having an active group that generates radicals upon irradiation with active energy rays and a radical polymerizable group (excluding monomer (i)). Monomer (h): A monomer having one or more hydrogen-donating functional groups selected from the group consisting of hydroxyl groups, amino groups, mercapto groups, and amide groups, and a radical polymerizable group, and not having an active group that generates radicals upon irradiation with active energy rays (excluding monomer (y)). Monomer (o): A monomer having a radical polymerizable group and not having an active group that generates radicals upon irradiation with active energy rays (excluding monomer (y) and monomer (h)).

4. The curable polymer composition according to claim 3, having a unit based on the monomer (x), wherein the radical polymerizable group of the monomer (x) is one or more selected from the group consisting of a (meth)acryloyl group, a (meth)acrylamide group, and a vinyl group.

5. The curable polymer composition according to claim 3 or 4, having a unit based on the monomer (x), wherein the active group of the monomer (x) is one or more selected from the group consisting of a benzophenone group, an acetophenone group, a benzoin group, an α-hydroxyketone group (excluding the group represented by formula (Ia) below), an α-aminoketone group, an α-diketone group, an α-diketone dialkyl acetal group, anthraquinone group, a thioxanthone group, and a phosphine oxide group. 【Chemistry 2】 [In the formula, R ２ represents an alkylene group having 1 to 2 carbon atoms or a linear or branched alkylene group having 3 to 5 carbon atoms, and R ３ , R ４ each independently represents an alkyl group having 1 to 2 carbon atoms or a linear or branched alkyl group having 3 to 5 carbon atoms, and R ３ and R ４ may combine with each other to form a ring.]

6. The curable polymer composition according to any one of claims 3 to 5, wherein the copolymer (A) has units based on the monomer (h), and the radical polymerizable group of the monomer (h) is one or more selected from the group consisting of (meth)acryloyl group, (meth)acrylamide group, and vinyl group.

7. The curable polymer composition according to any one of claims 3 to 6, wherein the copolymer (A) has units based on the monomer (o), and the monomer (o) is one or more selected from the group consisting of acrylic acid, acrylic acid salt, methacrylic acid, methacrylic acid salt, crotonic acid, crotonic acid salt, itaconic acid, itaconic acid salt, fumaric acid, fumarate, maleic acid, maleate, citraconic acid, citraconic acid salt, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, (meth)acrylonitrile, styrene, α-methylstyrene, divinylbenzene, vinyltoluene, vinyl propionate, vinyl acetate, phosphorus-containing vinyl compounds, vinyl chloride, pyridene chloride, and butadiene.

8. A cured product of a curable polymer composition according to any one of claims 1 to 7.

9. The cured product according to claim 8, wherein the copolymer (A) is unevenly distributed on the surface of the cured product.

10. A laminate having a base layer and a layer made of the cured product described in claim 8 or 9.