Curable polymer composition, cured product and laminate

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 Art

[0002] On the surface of an article such as a thermoplastic resin film typified by a polyethylene terephthalate (PET) film, a hard coat layer may be provided for the purpose of imparting functions such as hardness and matting properties. As the hard coat layer, generally, a curable composition containing a compound having a radically polymerizable group and a photoinitiator, which is cured by radical polymerization, is known. However, in this method, a polymerization termination reaction due to oxygen occurs at the contact interface between the coating film of the curable composition and oxygen, that is, on the coating film surface, so that the curability may decrease or the mechanical properties of the cured product of the curable composition may become insufficient.

[0003] Patent Document 1 describes a curable composition for a hard coat 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

Summary of the Invention

Problems to be Solved by the Invention

[0005] The curable composition described in Patent Document 1 can form a cured product such as a hard coat layer having excellent mechanical properties by using an oligomer-type ultraviolet polymerization initiator, but does not necessarily satisfy the curability. 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 at least one 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, a copolymer according to any one of [1] to [3], which has a unit based on a monomer (x) (excluding the monomer (i)) having an active group that generates radicals upon irradiation with active energy rays. [5] The copolymer according to [4], wherein the monomer (x) has at least one selected from the group consisting of a (meth)acryloyl group, a (meth)acrylamide group, and a vinyl group. [6] The copolymer according to [4] or [5], wherein the active group of the monomer (x) is at least one selected from the group consisting of a benzophenone group, an acetophenone group, a benzoin group, an α-hydroxyketone group (excluding the group (Ia)), an α-aminoketone group, an α-diketone group, an α-diketone dialkyl acetal group, an anthraquinone group, a thioxanthone group, and a phosphine oxide group. [7] The copolymer according to any one of [4] to [6], wherein the total content of the group (Ia) and the active group of the monomer (x) per 1 g of the copolymer is 0.1 to 3.5 mmol / g. [8] A curable polymer composition containing a copolymer (A) according to any one of [1] to [7] and a polyfunctional compound (B) having two or more radically polymerizable groups in one molecule. [9] A cured product of the curable polymer composition according to [8].

[10] A laminate having a base material layer and a layer made of the cured product according to [9].

Advantages of the Invention

[0011] According to the present invention, it is possible 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.

Brief Description of the Drawings

[0012]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Embodiments for Carrying Out the Invention

[0013] Hereinafter, embodiments of the present invention will be described in detail. In the present invention, “(meth)acrylate” is a general term for acrylate or methacrylate. “(Meth)acrylic” is a general term for acrylic and methacrylic. “~” indicating a numerical range means including the numerical values described before and after it as the lower limit value and the upper limit value.

[0014] <Curable Polymer Composition> The curable polymer composition contains a copolymer (A) having an active group that generates radicals upon irradiation with active energy rays (hereinafter, also simply referred to as an active group), and a polyfunctional compound (B) having two or more radical polymerizable groups in one molecule. When the curable polymer composition is irradiated with active energy rays, radicals are generated from the active groups of the copolymer (A), and starting from the generated radicals, the reaction between the radical polymerizable groups of the polyfunctional compound (B) proceeds, and the entire curable polymer composition cures. The curable polymer composition can further contain an organic solvent, if necessary. The curable polymer composition can further contain other components other than the above, if necessary.

[0015] <Copolymer (A)> The copolymer (A) has units based on monomer (i) and units based on monomer (y), and may further have units based on monomer (x). [Monomer (i)] Monomer (i) has a group (Ia) represented by the following formula (Ia) and a radical polymerizable group. It is a compound having. Group (Ia) is an intramolecular cleavage type active group. When the monomer (i) is irradiated with active energy ray light, it easily cleaves to generate radicals, so the initiation efficiency is high, which contributes to the improvement of curability. Specifically, the start of curing can be accelerated, and the amount of light irradiation required to obtain a cured product with a desired hardness can be reduced. Also, if the amount of light irradiation is the same, the hardness of the cured product can be further increased and the scratch resistance can be further improved.

[0016]

Chemical formula

[0017] In formula (Ia), R 2 is a linear or branched alkylene group having 1 to 5 carbon atoms. R 2 is preferably an ethylene group, a propane-1,3-diyl group, a butane-1,3-diyl group, a butane-1,4-diyl group in terms of the synthesis of the copolymer (A) and the reactivity with the polyfunctional compound (B) having a radical polymerizable group, and more preferably an ethylene group. R 3 and R 4 are each independently a linear or branched alkyl group having 1 to 5 carbon atoms. R 3 and R 4 may combine with each other to form a ring. The number of carbon atoms in the ring formed by R 3 and R 4 is preferably 5 to 8, and more preferably 6. R 3 and R 4 or the cyclic group formed by R 3 and R 4 is preferably a methyl group, an ethyl group, a cyclohexyl group in terms of the reactivity with the compound (B) and the ease of availability, more preferably a methyl group, and even more preferably both R 3 and R 4 are methyl groups.

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

[0019]

Chemical formula

[0020] [Monomer (x)] The monomer (x) is a compound (excluding the monomer (i)) having an active group and a radical polymerizable group. In the present specification, the active group means an atomic group including a structure that generates radicals by irradiation with active energy rays (a structure having photopolymerization initiation property). As the structure having photopolymerization initiation property, various known structures can be adopted, and examples include a hydrogen abstraction type, an electron transfer type, and an intramolecular cleavage type. Specific examples of the active group include a benzophenone group, an acetophenone group, a benzoin group, an α-hydroxy ketone group (excluding the above group (Ia)), an α-amino ketone group, an α-diketone group, an α-diketone dialkyl acetal group, an anthraquinone group, a thioxanthone group, and a phosphine oxide group. Among these, a benzophenone group, an acetophenone group, or an α-hydroxy ketone group is preferable in that it is less susceptible to oxygen inhibition during curing and has good surface curability when forming a cured layer.

[0021] Examples of the radical polymerizable group of the monomer (x) include functional groups containing a radical polymerizable unsaturated bond (such as a carbon-carbon double bond), and specific examples include a (meth)acryloyl group, a (meth)acrylamide group, and a vinyl group. As the monomer (x), from the viewpoints of ease of synthesizing the copolymer (A) and ease of adjusting the amount of introduced active groups, a (meth)acrylic acid ester having an active group is preferable. For example, 4-methacryloyloxybenzophenone is preferable.

[0022] [Monomer (y)] The monomer (y) is a compound (excluding the monomer (i)) having at least one selected from the group consisting of an alkyl group having 4 or more carbon atoms, a fluorine atom, and a silicon atom, and a radical polymerizable group. The monomer (y) is a monomer having a low surface energy. If the copolymer (A) has a unit based on the monomer (y), when a coating film of the curable polymer composition is formed, the copolymer (A) tends to segregate to the surface side of the coating film. If the copolymer (A) having an active group segregates to the surface side of the coating film, the polymerization termination reaction by oxygen on the coating film surface can be suppressed, and the curability is enhanced. Thus, for example, it can be cured with a low exposure amount. Also, even a thin film that tends to be easily inhibited by oxygen can be cured well. Further, when the copolymer (A) segregates to the surface side of the coating film, the concentration of the active groups on the surface side of the coating film becomes high. Due to this, the curing rate when irradiated with active energy rays is likely to be uneven between the surface side and the inside of the coating film. For example, when the surface side of the coating film is cured first to form a cured film, and then the inside of the coating film is cured, the cured film on the surface buckles, and unevenness in the form of wrinkles appears. Thereby, a cured layer (uneven layer) having unevenness on the surface is obtained. The curing time until the curing inside the coating film is completed can be adjusted by the amount of radical polymerizable groups, the type and amount of active groups, the irradiation amount of active energy rays, etc. in the curable polymer composition. On the other hand, even when the copolymer (A) segregates to the surface side of the coating film, there may be a case where unevenness hardly occurs on the surface of the cured layer. For example, when the difference in curing rate between the surface side and the inside of the coating film is small, when the cured film is not formed, or when the physical properties are such that the cured film is difficult to buckle, the surface of the cured layer tends to be smooth.

[0023] Examples of the monomer (y) include a monomer (r) having an alkyl group with 4 or more carbon atoms, a monomer (f) having a fluorine atom or a silicon atom, and the like. The alkyl group with 4 or more carbon atoms of the monomer (r) may be linear, branched, or cyclic. The cyclic alkyl group may be monocyclic or polycyclic. From the viewpoint of more effectively segregating the 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) on the surface of the coating film, the number of carbon atoms of the alkyl group with 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 the monomer (r) include compounds having an alkyl group with 4 or more carbon atoms and a radically polymerizable group. From the viewpoints of ease of compound synthesis and ease of adjusting the introduction amount of the alkyl group with 4 or more carbon atoms, an alkyl (meth)acrylate having an alkyl group with 4 or more carbon atoms is preferred. Examples of the monomer (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, isodecyl (meth)acrylate, dodecyl (meth)acrylate, myristyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, tridecyl (meth)acrylate, dicyclopentenyl oxyethyl (meth)acrylate, tricyclodecane (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, and the like. Among these, it is preferable to contain an alkyl (meth)acrylate having a linear alkyl group with 4 or more carbon atoms. As the alkyl (meth)acrylate having a linear alkyl group with 4 or more carbon atoms, those having the number of carbon atoms of the alkyl group within the above-mentioned preferable range are preferred. Considering ease of production and the like, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate, and stearyl (meth)acrylate are more preferred, and stearyl (meth)acrylate is particularly preferred. These (meth)acrylic acid esters may be used alone or in combination of two or more.

[0025] Examples of the monomer (f) include compounds having a fluorine atom or a silicon atom and a radically polymerizable group. The radically polymerizable group is the same as the radically polymerizable group exemplified above in the description of the monomer (x). The monomer (f) is also a component that imparts at least one of water repellency and oil repellency to the cured product and enhances the antifouling property of the cured product. If the copolymer (A) has a unit based on the monomer (f), when a coating film of the curable polymer composition is formed, the copolymer (A) segregates to the surface side of the coating film. As a result, the curability is enhanced, and the concentration of the unit based on the monomer (f) on the surface side of the coating film becomes high, and antifouling property can be efficiently imparted to the surface of the cured product.

[0026] The monomer (f) preferably contains at least one selected from the group consisting of a compound having a fluoroalkyl group and a radically polymerizable group, and a compound having a polydimethylsiloxane chain and a radically polymerizable group. The monomer (f) more preferably contains at least one selected from the group consisting of a (meth)acrylic acid ester having a fluoroalkyl group and a (meth)acrylic acid ester having a polydimethylsiloxane chain.

[0027] As the (meth)acrylic acid ester having a fluoroalkyl group, a (meth)acrylic acid ester having a perfluoroalkyl group is more preferred. The number of carbon atoms of the perfluoroalkyl group is preferably 4 or more. Specific examples of the (meth)acrylate having a polydimethylsiloxane chain include monofunctional (meth)acryloyl group-substituted polydimethylsiloxane with a molecular weight of 500 to 50,000. The molecular weight is preferably 1,000 to 30,000, more preferably 1,500 to 20,000.

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

[0029] Examples of the 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 above in the description of the monomer (x). From the viewpoints of ease of synthesis of the compound and ease of adjustment of the introduction amount of the hydrogen-donating functional group, the monomer (h) is preferably a (meth)acrylate having a hydrogen-donating functional group. Examples of the monomer (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, monobutylhydroxyl fumarate, and monobutyl hydroxyitaconate; amino group- or amide group-containing monomers such as N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-vinylcaprolactam, N-vinylpyrrolidone, N-isopropyl (meth)acrylamide, 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 excellent curing acceleration effect when used in combination with active groups, and 2-hydroxyethyl (meth)acrylate and N,N-diethylaminoethyl (meth)acrylate are more preferred. These compounds may be used alone or in combination of two or more.

[0030] [Monomer (o)] The copolymer (A) may further have units based on monomers (monomer (o)) other than those described above, if necessary. Examples of the monomer (o) include compounds having a radically polymerizable group and not having 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 radically polymerizable group is the same as the radically polymerizable group exemplified above in the description of the monomer (x). Examples of the monomer (o) include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, citraconic acid, and salts thereof; (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate; nitrogen-containing monomers such as (meth)acrylonitrile; styrene-based compounds such as styrene, α-methylstyrene, divinylbenzene, vinyltoluene, vinyl esters such as vinyl propionate, vinyl acetate; phosphorus-containing vinyl-based monomers; vinyl halides such as vinyl chloride, vinylidene chloride; conjugated dienes such as butadiene.

[0031] The copolymer (A) preferably has a plurality of active groups in the molecule. The content of the active groups per gram of the 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 content of the active groups is at least the lower limit value of the above range, the curability is more excellent. In addition, the scratch resistance of the coating film is enhanced. When it is at most the upper limit value of the above range, the storage stability of the curable composition is excellent. When the copolymer (A) has units based on the monomer (i) and does not have units based on the monomer (x), the content of the active groups per gram of the copolymer (A) is the content of the group (Ia) per gram of the copolymer (A). When the copolymer (A) has units based on the monomer (i) and units based on the monomer (x), the content of the active groups per gram of the copolymer (A) is the total content of the group (Ia) and the active groups of the monomer (x) per gram of the copolymer (A).

[0032] Monomer (i) contributes to the improvement of the curability of the curable polymer composition. In addition to the unit based on monomer (i), when having a unit based on monomer (x), uneven wrinkles are likely to be formed on the surface of the cured layer. When unevenness is formed on the cured layer, functions such as matting properties are easily obtained. With respect to the total of group (Ia) and the active group of monomer (x), the content of group (Ia) is preferably 10 mol% or more, more preferably 30 mol% or more. It may be 100 mol%. When it is at or above the above lower limit value, the effect of improving curability is excellent. When copolymer (A) has a unit based on monomer (i) and a unit based on monomer (x), with respect to the total of group (Ia) and the active group of monomer (x), the content of group (Ia) is preferably 90 mol% or less, more preferably 70 mol% or less. When it is at or below the above upper limit value, unevenness is likely to be formed on the surface of the cured layer.

[0033] The content of the hydrogen-donating functional group per 1 g 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, still more preferably 1.0 to 3.0 mmol / g. When the content of the hydrogen-donating functional group is at or above the lower limit value of the above range, the curability is more excellent. When the content of the hydrogen-donating functional group is at or below the upper limit value of the above range, the compatibility between copolymer (A) and the polyfunctional compound (B) is excellent.

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

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

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

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

[0038] The proportion of the units based on the monomer (h) with respect to the total mass of all the units constituting the copolymer (A) is preferably 80% by mass or less, more preferably 1 to 60% by mass, still more preferably 3 to 50% by mass, and particularly preferably in the range of 5 to 40% by mass. If the proportion of the units based on the monomer (h) is within the above range, the curability is more excellent.

[0039] The weight average molecular weight (Mw) of the copolymer (A) is preferably in the range of 1,000 to 500,000, more preferably 2,000 to 100,000, and still more preferably 3,000 to 60,000. When Mw is not less than the lower limit value of the above range, the curability is more excellent. When Mw is not more than the upper limit value of the above range, the coatability of the curable polymer composition is excellent. The Mw of the copolymer (A) is a value in terms of 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 the copolymer (A) is preferably in the range of -30 to 180°C, more preferably 0 to 150°C, and still more preferably 25 to 100°C. When Tg is not less than the lower limit value of the above range, the curability is more excellent. When it is not more than the upper limit value, the compatibility between the copolymer (A) and the polyfunctional compound (B) is excellent. The Tg of the copolymer (A) is determined by Fox's equation.

[0041] The copolymer (A) can be obtained, for example, by polymerizing a monomer component containing the monomer (i) and the monomer (y). The monomer component may further contain any one or more of the monomer (x), the monomer (h), and the monomer (o) as necessary. The polymerization is typically carried out in the presence of a polymerization initiator. During the polymerization, a chain transfer agent may be used in combination as necessary. Examples of the polymerization method include known methods such as solution polymerization, suspension polymerization, bulk polymerization, and emulsion polymerization. Among them, solution polymerization is preferred in terms of simple operation and high productivity.

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

[0043] The difunctional polyfunctional (meth)acrylate is not particularly limited. For example, alkanediol 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, tricyclodecane dimethylol di(meth)acrylate; bisphenol-modified di(meth)acrylates such as bisphenol A ethylene oxide-modified di(meth)acrylate, bisphenol F ethylene oxide-modified di(meth)acrylate; polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, urethane di(meth)acrylate, epoxy di(meth)acrylate, etc. may be mentioned.

[0044] The polyfunctional (meth)acrylate having three or more functional groups is not particularly limited. For example, dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified tri(meth)acrylate of isocyanuric acid, isocyanuric acid-modified tri(meth)acrylate such as ε-caprolactone-modified tris(acryloxyethyl) isocyanurate; urethane acrylates such as pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer. Among these, dipentaerythritol hexa(meth)acrylate is preferred.

[0045] <organic solvent> The organic solvent is used as needed for the purpose of improving the workability when applying the curable polymer composition onto a substrate. Examples of the organic solvent 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 phenetole; 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; halogen solvents such as dichloromethane and chloroform; etc. These organic solvents may be used alone or in combination of two or more. Among these organic solvents, ester solvents, ether solvents, alcohol solvents, and ketone solvents are preferable in terms of easily improving the workability in coating.

[0046] <photoinitiator (C)> The curable polymer composition may further contain one or more photoinitiators (excluding the copolymer (A)). For example, a photopolymerization initiator (C), which is a non-polymer having an active group that generates radicals upon irradiation with active energy rays, can be mentioned. 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, p - t - butyldichloroacetophenone, 2 - chlorothioxanthone, 2 - methylthioxanthone, 2,4 - diethylthioxanthone, 2,2 - diethoxyacetophenone, 2,2 - dimethoxy - 2 - phenylacetophenone, 2,2 - dichloro - 4 - phenoxyacetophenone, phenylglyoxylate, α - hydroxyisobutylphenone, dibenzospirone, 1-(4 - isopropylphenyl)-2 - hydroxy - 2 - methyl - 1 - propanone, 2 - methyl - [4-(methylthio)phenyl]-2 - morpholino - 1 - propanone, tribromophenyl sulfone, tribromomethylphenyl sulfone, and the like. These photopolymerization initiators may be used alone or in combination of two or more.

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

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

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

[0050] The curable polymer composition can be added with a monofunctional (meth)acrylate or (meth)acrylic acid having one radical polymerizable group in one molecule in order to adjust the viscosity and the curing rate by active energy rays. Examples of the monofunctional (meth)acrylate 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, dicyclopentenyl (meth)acrylate, dicyclopentenyl oxyethyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, 7-amino-3,7-dimethyloctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ethyl diethylene glycol (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, lauryl (meth)acrylate, polyurethane mono (meth)acrylate, polyepoxy mono (meth)acrylate, polyester mono (meth)acrylate, and the like.

[0051] <Content> The curable polymer composition may contain a polymerization accelerator such as a compound containing a thiol group, an antistatic agent, a plasticizer, a surfactant, an antioxidant, an ultraviolet absorber, etc., as long as the effects of the present invention are not impaired.

[0052] The content of the copolymer (A) with respect to the non-volatile 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. When it is at or above the lower limit value of the above range, the curability is more excellent. When it is at or below the upper limit value, the coatability is excellent. The non-volatile content of the curable polymer composition is the total mass of components other than the organic solvent. The non-volatile content of the curable polymer composition can be measured by a conventionally known method. For example, it is measured by spreading 1 g of the composition and heating it at 100 °C for 1 hour to volatilize the organic solvent and then measuring the change in weight.

[0053] The content of the active groups derived from the copolymer (A) per 100 g of the non-volatile content of the curable polymer composition is preferably in the range of 0.1 to 20 mmol / 100 g, more preferably 0.5 to 15 mmol / 100 g, still more preferably 1.0 to 12 mmol / 100 g, and particularly preferably 1.5 to 10 mmol / 100 g. When the content of the active groups is not less than the lower limit value of the above range, the curability is more excellent. When it is not more than the upper limit value, the storage stability of the curable composition is excellent.

[0054] The proportion of the polyfunctional compound (B) to the non-volatile 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, still more preferably 80 to 98.5% by mass. When it is within the above range, the curability is more excellent.

[0055] From the viewpoint of improving the operability in the coating operation, the content of the organic solvent per 100 parts by mass of the non-volatile 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 the curable polymer composition contains a photopolymerization initiator (C), the proportion of the photopolymerization initiator (C) to the non-volatile content of the curable polymer composition is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, and still more preferably 1 to 6% by mass. When it is within the above range, the curability is more excellent.

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

[0058] When the curable polymer composition contains an organic solvent, it is preferably preheated and dried before irradiation with active energy rays. By preheating and drying, the organic solvent in the coating film can be effectively removed. When the copolymer (A) segregates to the surface side of the coating film, the concentration of the copolymer (A) on the surface side of the coating film increases by removing the organic solvent. The drying temperature for heating and drying is preferably 30°C or higher and 200°C or lower, more preferably 40°C or higher and 150°C or lower. The drying time is preferably 0.01 minute or longer and 30 minutes or shorter, more preferably 0.1 minute or longer and 10 minutes or shorter.

[0059] Examples of the active energy rays include ultraviolet rays, α-rays, β-rays, γ-rays, etc. Among them, ultraviolet rays are preferred. The irradiation amount of the active energy rays can be appropriately selected according to the active energy rays to be irradiated. When using ultraviolet rays, it is preferably irradiated so that the integrated light quantity of irradiation is 100 mJ / cm 2 or more and 3000 mJ / cm 2 or less, more preferably 200 mJ / cm 2 or more and 2000 mJ / cm 2 or less. Further, as the illuminance, 50 mW / cm 2 or more and 600 mW / cm 2 or less is preferred, 75 mW / cm 2 or more and 450 mW / cm 2 or less is more preferred, and 100 mW / cm 2 or more and 300 mW / cm 2 or less is even more preferred. As the light source, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a electrodeless lamp, a metal halide lamp, or an electron beam by a scanning type or curtain type electron beam accelerator such as a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a low-pressure mercury lamp, 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, it is easy to realize the desired matting property. The thickness of the cured layer is determined by cross-sectional observation with an electron microscope. When the cured layer is an uneven layer having unevenness on the surface, the thickness of the cured layer indicates the maximum thickness of the uneven layer.

[0061] The haze of the cured layer, which is measured by the method described in the examples below, can be adjusted according to the surface shape. When wrinkles are formed on the surface, the haze increases. When the surface is made smooth, the haze decreases. When the active groups derived from the copolymer (A) in the curable polymer composition contain both the group (Ia) and the active groups of the monomer (x), the haze of the cured layer is preferably 0.2% or more, more preferably 0.5% or more, still more preferably 1.0% or more, and particularly preferably 1.2% or more, and the upper limit is, for example, 99%. When the haze is equal to or higher than the above lower limit value, properties such as matting properties and anti-blocking properties due to unevenness are easily obtained. When the active groups derived from the copolymer (A) in the curable polymer composition are only the group (Ia), the haze of the cured layer is preferably less than 10%, more preferably in the range of 0.1 to 5%, and still more preferably in the range of 0.2 to 0.8%. When it is below the above upper limit value, the transparency is more excellent, and the visibility is excellent when used for various applications.

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

[0063] The surface (the surface opposite to the substrate side) of the cured layer of the present laminate may be smooth or may have unevenness. Figs. 1 to 5 are schematic cross-sectional views showing an example of the present laminate in which the cured layer is a concavo-convex layer having concavities and convexities on the surface. The dimensional ratios in Figs. 1 to 5 are for convenience of explanation and are different from the actual ones. The laminate 10 in the example of Fig. 1 has a base material layer 1, a cured layer 2 provided on one surface 1a of the base material layer 1, and a primer layer 3 provided between the base material layer 1 and the cured layer 2. The laminate 10 in the example of Fig. 2 has a base material layer 1, a cured layer 2 provided on one surface 1a of the base material layer 1, and a surface functional layer 4 provided on the surface of the cured layer 2 opposite to the base material layer 1 side. The laminate 10 in the example of Fig. 3 has a base material layer 1, a cured layer 2 provided on one surface 1a of the base material layer 1, a primer layer 3 provided between the base material 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 material layer 1 side. The laminate 10 in the example of Fig. 4 has a base material layer 1, a cured layer 2 provided on one surface 1a of the base material layer 1, a primer layer 3 provided between the base material layer 1 and the cured layer 2, and a back surface functional layer 5 provided on the surface 1b of the base material layer 1 opposite to the cured layer 2 side. The laminate 10 in the example of Fig. 5 has a base material layer 1, a cured layer 2 provided on one surface 1a of the base material layer 1, a primer layer 3 provided between the base material 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 material layer 1 side, and a back surface functional layer 5 provided on the surface 1b of the base material layer 1 opposite to the cured layer 2 side.

[0064] <Base material layer> As the base material layer, known ones can be used, and examples include resin base materials, metal base materials, and paper base materials. Among these, from the viewpoint of processability, resin base materials are preferable. The resin base material may have a single-layer structure or a multi-layer structure of two or more layers, and is not particularly limited. It is preferable to form the resin base material into a multi-layer structure of two or more layers, endow each layer with characteristics, and achieve multi-functionality.

[0065] As the resin substrate, various resin films (sheets) can be used, for example, polyester films, poly(meth)acrylate films, polyolefin films, polycarbonate films, polyimide films, triacetyl cellulose films, polystyrene films, polyvinyl chloride films, polyvinyl alcohol films, nylon films, etc. When this laminate is applied to display applications, polyester films, poly(meth)acrylate films, polyolefin films, polycarbonate films, polyimide films, and triacetyl cellulose films are preferred. Among these, for anti-glare applications, polyester films, poly(meth)acrylate films, and polyolefin films are preferred, and considering transparency, moldability, and versatility, polyester films are more preferred. The polyester film used as the base material layer may be an unstretched film or a stretched film, and a stretched film is preferred. Among them, a uniaxially stretched film stretched in one axial direction or a biaxially stretched film stretched in two axial directions is preferred, and a biaxially stretched film is more preferred from the viewpoint of excellent balance of mechanical properties and flatness.

[0066] The polyester constituting the polyester film that can be used as the base material layer may be a homopolyester or a copolyester. As the homopolyester, those obtained by polycondensing an aromatic dicarboxylic acid and an aliphatic glycol are preferred. Examples of the aromatic dicarboxylic acid include terephthalic acid and 2,6-naphthalenedicarboxylic acid. Examples of the aliphatic glycol include ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethanol. The aromatic dicarboxylic acid and the aliphatic glycol may be used alone or in combination of two or more. Examples of the dicarboxylic acid component of the copolyester include isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, oxycarboxylic acid, etc. Examples of the glycol component include ethylene glycol, diethylene glycol, propylene glycol, butanediol, 4-cyclohexanedimethanol, neopentyl glycol, etc. The dicarboxylic acid component and the glycol component may each be used alone or in combination of two or more. Examples of typical polyesters include polyethylene terephthalate and polyethylene naphthalate.

[0067] As for the polyester film, considering mechanical strength and heat resistance, among them, films formed from polyethylene terephthalate or polyethylene naphthalate are more preferable. Considering ease of production and handleability for applications such as surface protection films, films formed from polyethylene terephthalate are more preferable.

[0068] The poly(meth)acrylate constituting the poly(meth)acrylate film that can be used as the base material layer may be any one having units based on (meth)acrylate, and various acrylic resins can be used. Examples of (meth)acrylate include alkyl (meth)acrylates having an alkyl group with 1 to 4 carbon atoms such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and alkyl (meth)acrylates having an alkyl group with more carbon atoms. Considering transparency, processability, and chemical resistance, it is preferable that the poly(meth)acrylate mainly comprises units based on alkyl (meth)acrylates having an alkyl group with 1 to 4 carbon atoms. More preferably, it mainly comprises at least one selected from the group consisting of units based on methyl (meth)acrylate and units based on ethyl (meth)acrylate. Particularly preferably, it mainly comprises units based on methyl (meth)acrylate. It is also possible to impart properties such as flexibility by incorporating units based on (meth)acrylates other than alkyl (meth)acrylates and units based on other monomers into the poly(meth)acrylate. The proportion of the unit based on the alkyl (meth)acrylate having an alkyl group with 1 to 4 carbon atoms with respect to the total mass of the poly(meth)acrylate is preferably 50% by mass or more, more preferably 80% by mass or more.

[0069] The base material layer can contain particles for the purpose of imparting slipperiness, preventing the occurrence of scratches in each process, and improving anti-blocking properties. The type of the 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, phenol resin, epoxy resin, and benzoguanamine resin. Further, when the base material layer contains a polyester film, precipitated particles obtained by precipitating a part of a metal compound such as a catalyst in the polyester production process can also be used. Among these, silica particles and calcium carbonate particles are preferable in that the effect is easily obtained even in a particularly small amount. The shape of the particles is not particularly limited, and any of spherical, massive, rod-shaped, flat-shaped, etc. can be used. Also, there are no particular restrictions on its hardness, specific gravity, color, etc. These particles may be used in combination of two or more kinds as necessary.

[0070] The average particle diameter of the particles is preferably 10 μm or less, more preferably in the range of 0.01 to 5 μm, and still more preferably 0.01 to 3 μm. If the average particle diameter is 10 μm or less, problems due to a decrease in the transparency of the base material layer are less likely to occur. The average particle diameter of the particles is the value of 50% (mass basis) integration in the equivalent spherical distribution measured by a centrifugal sedimentation type particle size distribution measuring device.

[0071] When the base material layer contains particles, the content of the particles in the base material layer cannot be generally determined because it also depends on the balance with the average particle size. However, with respect to the total mass of the layer containing the particles in the base material layer, 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. If the content of the particles is 5% by mass or less, problems such as particle detachment and a decrease in the transparency of the base material layer are less likely to occur.

[0072] The base material layer can optionally contain additives other than the above-mentioned particles. As the additives, known additives such as ultraviolet absorbers, antioxidants, antistatic agents, heat stabilizers, lubricants, dyes, and pigments can be used.

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

[0074] <Primer layer> The primer layer is provided to impart various functions between the base material layer and the cured layer. Examples of the primer layer include an adhesion improvement layer and an antistatic layer. The primer layer may have a plurality of functions. For example, the adhesion improvement layer may also serve as an antistatic layer.

[0075] In a preferred embodiment, the primer layer is an adhesion improvement layer. If the adhesion between the base material layer and the cured layer is insufficient, the laminate may not be usable depending on the application. By having the adhesion improvement layer, the adhesion between the base material layer and the cured layer is improved, and the laminate can be used for various applications. When the primer layer is an adhesion improvement layer, the primer layer preferably contains either one or both of a compound derived from a resin and a crosslinking agent from the viewpoint of improving the adhesion between the base material 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, it is possible to reduce the adhesion of dust and the like due to peeling static electricity or frictional static electricity to the outermost surface of the laminate, particularly the outermost surface on the side where the cured layer exists with respect to the base material layer. To make the primer layer an antistatic layer, for example, an antistatic agent may be contained in the primer layer.

[0077] As the resin, conventionally known resins can be used. Specific examples of the resin include polyester resins, acrylic resins, urethane resins, polyvinyl resins (such as polyvinyl alcohol, vinyl chloride-vinyl acetate copolymers, etc.). Among them, considering the adhesion performance and coating properties, polyester resins, acrylic resins, and urethane resins are preferred. When the base material layer is a resin film, from the viewpoint of the affinity between the resin of the base material layer and the primer layer, a resin of the same type as the resin of the resin film is preferred. For example, when the base material layer is a polyester film, it is preferable that the primer layer contains a polyester resin. When the base material layer is a poly(meth)acrylate film, it is preferable that the primer layer contains an acrylic resin.

[0078] Examples of the polyester resin include those mainly composed of polyvalent carboxylic acids and polyvalent hydroxy compounds. Examples of the polyvalent carboxylic 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 sulfoisophthalic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, glutaric acid, succinic acid, trimellitic acid, trimesic acid, pyromellitic acid, trimellitic anhydride, phthalic anhydride, monopotassium trimellitate, and their ester-forming derivatives. Examples of the polyhydric hydroxy compound 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 dimethylol ethyl sulfonate, potassium dimethylolpropionate, etc. One or more of these compounds may be appropriately selected from among them, and a polyester resin may be synthesized by a polycondensation reaction according to a conventional method.

[0079] The acrylic resin is a polymer of a polymerizable monomer containing a (meth)acrylic monomer. Examples of the acrylic resin include a homopolymer and copolymer of a (meth)acrylic monomer, a copolymer of a (meth)acrylic monomer and a polymerizable monomer other than the (meth)acrylic monomer, etc. The acrylic resin may be a copolymer of these polymers and other polymers (for example, polyester, polyurethane, etc.). Such copolymers are, for example, block copolymers and graft copolymers. Or, polymers (in some cases, mixtures of polymers) obtained by polymerizing a polymerizable monomer in a solution or dispersion of polyester are also included. Similarly, polymers (in some cases, mixtures of polymers) obtained by polymerizing a polymerizable monomer in a solution or dispersion of polyurethane are also included. Similarly, polymers (in some cases, polymer mixtures) obtained by polymerizing a polymerizable monomer in a solution or dispersion of other polymers are also included.

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

[0081] A urethane resin is a high molecular compound having a urethane bond in the molecule, and typically, it is synthesized by the reaction of a polyol and a polyisocyanate. A chain extender may be used when synthesizing the urethane resin. Examples of the polyol used to obtain the urethane resin include polycarbonate polyol, polyether polyol, polyester polyol, polyolefin polyol, acrylic polyol and the like. These compounds may be used alone or in combination of two or more.

[0082] Polycarbonate polyol is obtained by the reaction (dealcoholization reaction) of a polyhydric alcohol and a carbonate compound. Examples of the polyhydric alcohol 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, 3,3-dimethylolheptane, and the like. Examples of the carbonate compound include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, and the like. Specific examples of the polycarbonate polyol include poly(1,6-hexylene) carbonate, poly(3-methyl-1,5-pentylene) carbonate, and the like.

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

[0084] Examples of the polyester polyol include those obtained by the reaction of a polyvalent carboxylic acid or its acid anhydride and a polyhydric alcohol, and those having a derivative unit of a lactone compound such as polycaprolactone. Examples of the polyvalent carboxylic acid include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, terephthalic acid, isophthalic acid, and the like. Examples of 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, 1,8 - 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, alkyldialkanolamine, lactone diol, and the like.

[0085] As the polyol, considering the adhesion performance, polyester polyol and polycarbonate polyol are preferred, and polyester polyol is particularly preferred.

[0086] Examples of the polyisocyanate used to obtain the urethane resin include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, and tolidine diisocyanate; aliphatic diisocyanates having an aromatic ring 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 alone or in combination of two or more.

[0087] The chain extender is not particularly limited as long as it has two or more active groups that react with isocyanate groups. Generally, a chain extender having two hydroxyl groups or amino groups can be mainly used. Examples of the chain extender having two hydroxyl groups include glycol compounds such as aliphatic glycols such as ethylene glycol, propylene glycol, and butanediol; aromatic glycols such as xylylene glycol and bis(hydroxyethoxy)benzene; and ester glycols such as neopentyl glycol hydroxypivalate. Examples of the chain extender having two amino groups include aromatic diamines such as tolylene diamine, xylylene diamine, diphenylmethane diamine; aliphatic diamines such as ethylenediamine, propylenediamine, hexamethylenediamine, 2,2-dimethyl-1,3-propanediamine, 2-methyl-1,5-pentanediamine, trimethylhexamethylenediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine; and alicyclic diamines such as 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, dicyclohexylmethane diamine, isopropylidene cyclohexyl-4,4'-diamine, 1,4-diaminocyclohexane, 1,3-bisaminomethylcyclohexane, etc.

[0088] The urethane resin is typically used in the form of a dispersion or a solution. As the medium of the dispersion or the solution, a solvent may be used, but water is preferred. Examples of the aqueous dispersion or aqueous solution of the urethane resin include a forced emulsification type using an emulsifier, a self-emulsification type or a water-soluble type in which a hydrophilic group is introduced into the structure of the urethane resin. In particular, a self-emulsification type in which an ionic group is introduced into the structure of the urethane resin to form an ionomer is preferred because of its excellent storage stability of the liquid, water resistance and transparency of the resulting primer layer.

[0089] Examples of the ionic group introduced into the structure of the urethane resin include various groups such as a carboxyl group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a quaternary ammonium base, etc., and a carboxyl group is preferred. The carboxyl group is preferably in the form of a salt neutralized with a neutralizing agent such as ammonia, amine, alkali metals, inorganic alkalis, etc. Particularly preferred neutralizing agents are ammonia, trimethylamine, and triethylamine. The urethane resin having a carboxyl group neutralized with a neutralizing agent can use the carboxyl group from which the neutralizing agent has detached in the drying process after coating as a crosslinking reaction point by a crosslinking agent. Thereby, not only is the stability in the state of the liquid before coating excellent, but it is also possible to further improve the durability, solvent resistance, water resistance, blocking resistance, etc. of the obtained primer layer.

[0090] As a method for introducing a carboxyl group into a urethane resin, various methods can be adopted at each stage of the polymerization reaction. For example, there are a method of using a resin having a carboxyl group as a copolymerization component during prepolymer synthesis, and a method of using a component having a carboxyl group as one component such as a polyol, polyisocyanate, or chain extender. In particular, a method of using a carboxyl group-containing diol and introducing a desired amount of carboxyl groups according to the charged amount of this component is preferred. For example, a carboxyl group-containing diol can be copolymerized with the polyol used in the synthesis of the urethane resin. Examples of the carboxyl group-containing diol include dimethylolpropionic acid, dimethylolbutanoic acid, bis-(2-hydroxyethyl)propionic acid, bis-(2-hydroxyethyl)butanoic acid, and salts in which their carboxyl groups are 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. As the crosslinking agent, known materials can be used. For example, melamine compounds, oxazoline compounds, isocyanate compounds, epoxy compounds, carbodiimide compounds, silane coupling compounds, hydrazide compounds, aziridine compounds, etc. can be mentioned. Among them, 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, and oxazoline compounds and isocyanate compounds are particularly preferred. These crosslinking agents can be used alone or in combination of two or more. In some cases, the adhesion and durability can be further improved and become better by using two or more in combination.

[0092] The melamine compound refers to a compound having a melamine skeleton in the compound. For example, alkylolated melamine derivatives, compounds obtained by reacting an alkylolated melamine derivative with alcohol to be partially or completely etherified, and mixtures thereof can be mentioned. Examples of the alcohol used for etherification include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, isobutanol, etc. The melamine compound may be either a monomer or a multimer of dimer or higher, or a mixture thereof may be used. Furthermore, those obtained by co-condensing urea or the like with a part of melamine can also be used, and it is also possible to use a catalyst to increase the reactivity of the melamine compound. As the melamine compound, considering the reactivity with various compounds, those having a hydroxyl group are preferred.

[0093] The isocyanate compound refers to a compound having an isocyanate or an isocyanate derivative structure represented by blocked isocyanate. Examples of the isocyanate include aromatic isocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, naphthalene diisocyanate; aliphatic isocyanates having an aromatic ring such as α,α,α’,α’-tetramethylxylylene diisocyanate; aliphatic isocyanates such as methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate; alicyclic isocyanates such as cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexyl isocyanate), isopropylidene dicyclohexyl diisocyanate. Also included are polymers and derivatives such as biuret compounds, isocyanurate compounds, uretdione compounds, and carbodiimide-modified products of these isocyanates. These may be used alone or in combination of two or more. Among the above isocyanate compounds, from the viewpoint of avoiding yellowing due to ultraviolet rays, aliphatic isocyanates or alicyclic isocyanates are more preferable than aromatic isocyanates.

[0094] Examples of the blocked isocyanate include those in which the isocyanate groups of the above isocyanate compounds are blocked with blocking agents. Examples of the blocking agents include bisulfites, phenolic compounds such as phenol, cresol, and ethylphenol, alcohol compounds such as propylene glycol monomethyl ether, ethylene glycol, benzyl alcohol, methanol, and ethanol, active methylene compounds such as dimethyl malonate, diethyl malonate, methyl isobutanoyl acetate, 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 alone or in combination of two or more. From the viewpoint that the primer layer is difficult to be destroyed, the isocyanate blocked with an active methylene compound is preferable as the blocked isocyanate.

[0095] The isocyanate compound may be used alone or as a mixture or a conjugate with various polymers. In terms of improving the dispersibility and crosslinkability of the isocyanate compound, it is preferable to use a mixture or a conjugate with a polyester resin or a urethane resin.

[0096] The oxazoline compound is a compound having an oxazoline group in the molecule. As the oxazoline compound, a polymer containing an oxazoline group is preferable. The polymer containing an oxazoline group is obtained by polymerization of an addition polymerizable oxazoline group-containing monomer alone or with other monomers. Examples of the monomer containing an additional crosslinkable oxazoline group 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, 2-isopropenyl-5-ethyl-2-oxazoline, and the like. These may be used alone or in combination of two or more. Among these, 2-isopropenyl-2-oxazoline is industrially easily available and suitable. Other monomers are not particularly limited as long as they are monomers copolymerizable with the monomer containing an additional crosslinkable oxazoline group. For example, (meth)acrylates such as alkyl (meth)acrylates (the alkyl group includes methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group, etc.); unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrenesulfonic acid and its salts (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.); unsaturated nitriles such as acrylonitrile, methacrylonitrile; unsaturated amides such as (meth)acrylamide, N-alkyl (meth)acrylamide, N,N-dialkyl (meth)acrylamide (the alkyl group includes methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group, etc.); vinyl esters such as vinyl acetate, vinyl propionate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether; α-olefins such as ethylene, propylene; halogen-containing α,β-unsaturated monomers such as vinyl chloride, vinylidene chloride, vinyl fluoride; α,β-unsaturated aromatic monomers such as styrene, α-methylstyrene, and the like. These may be used alone or in combination of two or more.

[0097] The amount of oxazoline groups per gram of the oxazoline compound is preferably in the range of 0.5 to 10 mmol / g, more preferably 1 to 9 mmol / g, still 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 adjustment of adhesion becomes easier.

[0098] An epoxy compound is a compound having an epoxy group in the molecule. Examples of epoxy compounds include condensates of epichlorohydrin and compounds having a hydroxyl group or an amino group (such as ethylene glycol, polyethylene glycol, glycerin, polyglycerin, bisphenol A, etc.), and there are polyepoxy compounds, diepoxy compounds, monoepoxy compounds, glycidylamine compounds, etc. 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, trimethylolpropane polyglycidyl ether. Examples of diepoxy compounds include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcin diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether. Examples of monoepoxy compounds include allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether. Examples of glycidylamine compounds include N,N,N’,N’-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylamino)cyclohexane.

[0099] A carbodiimide-based compound is a compound having one or more carbodiimide structures or carbodiimide derivative structures in the molecule. As the carbodiimide compound, a polycarbodiimide compound having two or more carbodiimide structures or carbodiimide derivative structures in the molecule is more preferable for better strength of the primer layer and the like.

[0100] The carbodiimide compound can be synthesized by known techniques. Generally, a condensation reaction of diisocyanate is used. The diisocyanate is not particularly limited, and either an aromatic type or an aliphatic type can be used. Specifically, tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl diisocyanate, dicyclohexylmethane diisocyanate, etc. can be mentioned.

[0101] In order to improve the water solubility and water dispersibility of the polycarbodiimide compound, a surfactant may be added within a range that does not eliminate the effects of the present invention, or a hydrophilic monomer such as a polyalkylene oxide, a quaternary ammonium salt of a dialkylamino alcohol, or a hydroxyalkyl sulfonate may be added.

[0102] The silane coupling compound is an organosilicon compound having an organic functional group and a hydrolyzable group such as an alkoxy group in one molecule. Examples of the silane coupling compound include epoxy group-containing compounds such as 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; vinyl group-containing compounds such as vinyltrimethoxysilane, vinyltriethoxysilane; styryl group-containing compounds such as p-styryltrimethoxysilane, p-styryltriethoxysilane; (meth)acryloyl group-containing compounds such as 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane; amino group-containing compounds such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(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, N-phenyl-3-aminopropyltriethoxysilane; isocyanurate group-containing compounds such as tris(trimethoxysilylpropyl)isocyanurate, tris(triethoxysilylpropyl)isocyanurate; mercapto group-containing compounds such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, etc.

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

[0104] These crosslinking agents react during the drying process or the film-forming process to improve the performance of the primer layer. It is presumed that in the formed primer layer, as compounds derived from the crosslinking agent, unreacted substances of the crosslinking agent, compounds after reaction, or mixtures thereof are present.

[0105] There are no particular restrictions on the antistatic agent to be incorporated into the primer layer, and known antistatic agents can be used. Examples thereof include compounds having an ammonium group, polyether compounds, compounds having a sulfonic acid group, betaine compounds, conductive organic polymers, and the like. As the antistatic agent, a polymer-type antistatic agent is preferable because of its good heat resistance and heat and humidity resistance.

[0106] The compound having an ammonium group is a compound having an ammonium group in the molecule, and examples thereof include ammonium compounds of aliphatic amines, alicyclic amines, and aromatic amines. The compound having an ammonium group is preferably a compound having a polymer-type ammonium group. In the compound having a polymer-type ammonium group, the ammonium group is preferably incorporated into the main chain or side chain of the polymer rather than being a counter ion. Examples of such compounds include those obtained by polymerizing an addition-polymerizable monomer having a precursor group of an ammonium group such as an ammonium group or an amine, and converting the precursor group of the ammonium group into an ammonium group as necessary to obtain a polymer 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 thereof, or copolymerized with other monomers.

[0107] As the compound having an ammonium group, a compound having a pyrrolidinium ring is also preferable in terms of excellent antistatic properties and heat stability. The two substituents bonded to the nitrogen atom of the compound having a pyrrolidinium ring are each independently an alkyl group, a phenyl group, etc., and these alkyl groups and phenyl groups may be substituted with the groups shown below. The substitutable groups are, for example, a hydroxyl group, an amide group, an ester group, an alkoxy group, a phenoxy group, a naphthoxy group, a thioalkoxy, a thiophenoxy group, a cycloalkyl group, a trialkylammonium alkyl group, a cyano group, and a halogen. Further, the two substituents bonded to the nitrogen atom may be chemically bonded, and examples of the group in which the two substituents are chemically bonded include -(CH2) m -(where m is 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. The polymer having a pyrrolidinium ring can be obtained, for example, by subjecting a diallylamine derivative to cyclopolymerization using a radical polymerization catalyst. A compound having a polymerizable carbon-carbon unsaturated bond may be used as a copolymerization component. The polymerization can be carried out by a known method 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 thereto.

[0109] Examples of the anion that becomes the counter ion of the ammonium group of the compound having the ammonium group described above include ions such as halogen ions, sulfonates, phosphates, nitrates, alkyl sulfonates, and carboxylates.

[0110] The number average molecular weight of the compound having an ammonium group is preferably from 1,000 to 500,000, more preferably from 2,000 to 350,000, and still more preferably from 5,000 to 200,000. If the number average molecular weight is 1,000 or more, the strength and heat resistance stability of the coating film are more excellent. If the number average molecular weight is 500,000 or less, the viscosity of the coating liquid for forming the primer layer is low, and the handleability and coatability are good.

[0111] Examples of the polyether compound include polyethylene oxide, polyether ester amide, and an acrylic resin having polyethylene glycol in the side chain.

[0112] In the compound having a sulfonic acid group, the sulfonic acid group may be neutralized with a neutralizing agent to be in the form of a salt. As the compound having a sulfonic acid group, compounds having a plurality of sulfonic acid groups in the molecule, such as polystyrene sulfonic acid and its salts, are preferable.

[0113] As the conductive organic polymer, known materials can be used. For example, polythiophene-based, polyaniline-based, polypyrrole-based, polyacetylene-based, polyphenylene sulfide-based, etc. can be mentioned. Among these, polythiophene-based (polythiophene or polythiophene derivative) is preferable because it can achieve both high transparency and high conductivity, is difficult to be colored, and is easy to exhibit performance by coating. Among the polythiophene-based, a compound obtained by combining poly(3,4-ethylenedioxythiophene) with polystyrene sulfonic acid is particularly preferable from the viewpoint of conductive performance. The conductive organic polymer is preferable in that it exhibits high conductivity, has little humidity dependence, and can be expected to have various applications.

[0114] The primer layer may contain particles for improving blocking and slipperiness. The primer layer may contain additives such as an antifoaming agent, a coatability improver, a thickener, an organic lubricant, an ultraviolet absorber, an antioxidant, a foaming agent, a dye, and a pigment, as necessary, within a range not impairing the gist of the present invention.

[0115] The proportion of the 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 still more preferably 30 to 90% by mass. If the proportion of the resin is within the above range, the adhesion performance and the appearance of the primer layer are more excellent.

[0116] The proportion of the compound derived from the crosslinking agent 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 still more preferably 5 to 40% by mass. If the proportion of the compound derived from the crosslinking agent is within the above range, the adhesion performance and the strength of the primer layer are more excellent.

[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 depends on the type of the antistatic agent and thus cannot be generalized, but is, for example, 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 easy to impart a sufficient antistatic function to the primer layer, and the antistatic performance is likely to be exhibited even after a cured layer is formed on the primer layer.

[0118] The thickness of the primer layer cannot be generally stated because it also depends on the material used for the primer layer and the performance to be exhibited, but is preferably in the range of 0.001 to 10 μm, more preferably 0.01 to 4 μm, and still more preferably 0.02 to 1 μm. The primer layer can be formed by a known method.

[0119] <Surface functional layer> The surface functional layer is provided to impart various functions on the cured layer. Examples of the surface functional layer include an antifouling layer, an antistatic layer, a refractive index adjustment layer (antireflection layer, low reflection layer, etc.), an infrared absorption layer, an ultraviolet absorption layer, and a color correction layer. The antifouling layer is provided to improve the antifouling performance by imparting water repellency and oil repellency to the cured layer. The antistatic layer is provided to reduce the adhesion of dust and the like due to peeling charge or triboelectric charge to the outermost surface of the laminate, particularly the outermost surface on the side where the cured layer exists with respect to the base material layer. The refractive index adjustment layer is provided, for example, to improve the total light transmittance of the laminate.

[0120] The antifouling layer contains an antifouling component. As the antifouling component, known ones such as silicone compounds, fluorine compounds, and long-chain alkyl group-containing compounds can be used. Among these, from the viewpoint of exhibiting stronger antifouling performance, silicone compounds and fluorine compounds are preferable, and from the viewpoint of being less likely to contaminate the object in contact with the antifouling layer, fluorine compounds and long-chain alkyl group-containing compounds are preferable.

[0121] A silicone compound is a compound having a silicone structure in the molecule, and examples thereof include alkylsilicones (dimethylsilicone, diethylsilicone, etc.) and silicones having a phenyl group (phenylsilicone, methylphenylsilicone, etc.). The silicone compound may have various functional groups. Examples of the functional group include an ether group, a hydroxyl group, an amino group, an epoxy group, a carboxylic acid group, a halogen group such as fluorine, a perfluoroalkyl group, a hydrocarbon group such as various alkyl groups and various aromatic groups, etc. As other functional groups, silicone having a vinyl group and hydrogen silicone in which a hydrogen atom is directly bonded to a silicon atom can also be exemplified, and both can be used in combination and used as an addition type (type by addition reaction of a vinyl group and a hydrogen silane) silicone. It is also possible to introduce a double bond such as an acryloyl group and react at the double bond portion.

[0122] As silicone compounds, it is also possible to use modified silicones such as acrylic graft silicone, silicone graft acrylic, amino-modified silicone, perfluoroalkyl-modified silicone, etc. Considering heat resistance and contamination, it is preferable to use a curable silicone resin. As the type of curing, any curing reaction type such as condensation type, addition type, active energy ray curing type, etc. can be used.

[0123] A fluorine compound is a compound containing fluorine atoms in the compound. As the fluorine compound, an organic fluorine compound is preferably used, and examples thereof include a perfluoroalkyl group-containing compound, a polymer of an olefin compound containing fluorine atoms, an aromatic fluorine compound such as fluorobenzene, etc. From the viewpoint of mold release property, a perfluoroalkyl group-containing compound is preferable. A compound containing a long-chain alkyl group as described later can also be used as the fluorine compound.

[0124] Examples of the perfluoroalkyl group-containing compound include perfluoroalkyl (meth)acrylate, perfluoroalkylmethyl (meth)acrylate, 2-perfluoroalkylethyl (meth)acrylate, 3-perfluoroalkylpropyl (meth)acrylate, 3-perfluoroalkyl-1-methylpropyl (meth)acrylate, 3-perfluoroalkyl-2-propenyl (meth)acrylate, etc. perfluoroalkyl group-containing (meth)acrylates and their polymers, perfluoroalkylmethyl vinyl ether, 2-perfluoroalkylethyl vinyl ether, 3-perfluoropropyl vinyl ether, 3-perfluoroalkyl-1-methylpropyl vinyl ether, 3-perfluoroalkyl-2-propenyl vinyl ether, etc. perfluoroalkyl group-containing vinyl ethers and their polymers, etc. Considering heat resistance and contamination, it is preferably a polymer. The polymer may be a polymer of a single compound or a polymer of a plurality of compounds. Further, it may be a polymer with a compound containing a long-chain alkyl compound as described later. From the viewpoint of antifouling property, the number of carbon atoms of the perfluoroalkyl group is preferably 3 to 11.

[0125] A compound containing a long-chain alkyl group refers to a compound having a linear or branched alkyl group (long-chain alkyl group) with usually 6 or more carbon atoms, preferably 8 or more carbon atoms, and more preferably 12 or more carbon atoms. Examples of the long-chain alkyl group include a hexyl group, an octyl group, a decyl group, a lauryl group, an octadecyl group, a behenyl group, and the like. Examples of the compound containing a long-chain alkyl group include various high-molecular compounds containing a long-chain alkyl group, an amine compound containing a long-chain alkyl group, an ether compound containing a long-chain alkyl group, a quaternary ammonium salt containing a long-chain alkyl group, and the like. Considering heat resistance and contamination, the compound containing a long-chain alkyl group is preferably a high-molecular compound. Further, from the viewpoint of effectively obtaining antifouling properties, a high-molecular compound having a long-chain alkyl group in the side chain is more preferable.

[0126] A high-molecular compound having a long-chain alkyl group in the side chain can be obtained, for example, by reacting a high-molecular compound having a reactive group with a compound containing a long-chain alkyl group capable of reacting with the reactive group. Examples of the reactive group include a hydroxyl group, an amino group, a carboxyl group, an acid anhydride, and the like. Examples of the high-molecular compound having these reactive groups include polyvinyl alcohol, polyethyleneimine, polyethyleneamine, a polyester resin containing a reactive group, a poly(meth)acrylic resin containing a reactive group, and the like. Among these, polyvinyl alcohol is preferable in consideration of antifouling properties and ease of handling. Examples of the long-chain alkyl group-containing compound capable of reacting with the above reactive group include long-chain alkyl group-containing isocyanates such as hexyl isocyanate, octyl isocyanate, decyl isocyanate, lauryl isocyanate, octadecyl isocyanate, behenyl isocyanate, etc., long-chain alkyl group-containing acid chlorides such as hexyl chloride, octyl chloride, decyl chloride, lauryl chloride, octadecyl chloride, behenyl chloride, etc., long-chain alkyl group-containing amines, long-chain alkyl group-containing alcohols, and the like. Among these, considering mold release properties and ease of handling, long-chain alkyl group-containing isocyanates are preferred, and octadecyl isocyanate is particularly preferred.

[0127] The polymer compound having a long-chain alkyl group in the side chain can also be obtained as a polymer of long-chain alkyl (meth)acrylate or a copolymer of long-chain alkyl (meth)acrylate and other vinyl group-containing monomers. Examples of the long-chain alkyl (meth)acrylate include hexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, octadecyl (meth)acrylate, behenyl (meth)acrylate, and the like.

[0128] The antifouling layer may further contain, if necessary, in addition to the antifouling component, a resin, a compound derived from a crosslinking agent, an antistatic agent, an antifoaming agent, a coating property improver, a thickener, an ultraviolet absorber, an antioxidant, a foaming agent, a dye, a pigment, and the like. The resin and the compound derived from the crosslinking agent are as described above. From the viewpoints of improving the strength and durability of the layer, the antifouling layer preferably has a crosslinked structure. Examples of the antifouling layer having a crosslinked structure include a layer of a cured product of a composition containing a compound having a plurality of radically polymerizable groups such as an acryloyl group or a crosslinking agent and an antifouling component.

[0129] The proportion of the antifouling component in 100% by mass of the surface functional layer cannot be generally determined as it depends on the antifouling component used. However, when the antifouling component is a silicone compound or a fluorine compound, it 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, and the upper limit may be 100% by mass. When the antifouling component is a compound containing a long-chain alkyl group, it is usually 0.1% by mass or more, preferably 1% by mass or more, and even more preferably 3% by mass or more, and the upper limit may be 100% by mass. If the proportion of the antifouling component is within the above range, the antifouling performance is more excellent.

[0130] The antistatic layer contains an antistatic agent. The antistatic agent is as described above. The antistatic layer may further contain, if necessary, in addition to the antistatic agent, a resin, a compound derived from a crosslinking agent, 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 compound derived from the crosslinking agent are as described above.

[0131] The proportion of the antistatic agent in 100% by mass of the antistatic layer is not general as it depends on the type of the antistatic agent, but is, for example, 0.1 to 100% by mass.

[0132] Examples of the refractive index adjustment layer include a high refractive index layer, a low refractive index layer, and a laminate thereof. As the material constituting the high refractive index layer, known high refractive index materials can be used. For example, aromatic structure-containing compounds such as benzene structure, bisphenol A structure, melamine structure, fluorene structure, etc., and condensed polycyclic aromatic compounds considered to be high refractive index compounds among aromatic structure-containing compounds, such as naphthalene, anthracene, phenanthrene, naphthacene, benzo[a]anthracene, benzo[a]phenanthrene, pyrene, benzo[c]phenanthrene, perylene structure, etc., metal oxides such as zirconium oxide, titanium oxide, zinc oxide, tin oxide, antimony oxide, yttrium oxide, indium oxide, cerium oxide, ATO (antimony tin oxide), ITO (indium tin oxide), etc., metal-containing compounds such as titanium chelate, zirconium chelate and other metal chelate compounds, compounds containing sulfur element, compounds containing halogen element, etc. can be mentioned.

[0133] Since there is a concern that the adhesion may decrease depending on the usage form, it is preferably used in the form of particles. Also, from the viewpoint of coating appearance and the like, its average particle size is preferably 100 nm or less, more preferably 50 nm or less, and even more preferably 25 nm or less.

[0134] As the material constituting the low refractive index layer, known low refractive index materials can be used. For example, resins such as acrylic resin, urethane resin, and compounds in which fluorine atoms are incorporated into the resin (for example, fluororesin, compounds containing fluororesin in the main skeleton, compounds containing perfluoroalkyl groups in the side chain), etc.; inorganic materials such as hollow silica particles, magnesium fluoride, calcium fluoride and other fluorine atom-containing inorganic compounds, and 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 function of the surface functional layer is likely to be exhibited. When the hardened layer is a layer that exhibits various functions due to unevenness, the thickness of the surface functional layer is preferably 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 the surface functional layer is provided, functions such as matting property and anti-blocking property due to the unevenness are less likely to be reduced. The surface functional layer can be formed by a known method.

[0136] <Back surface functional layer> The back surface functional layer is provided to impart various functions to the surface on the side opposite to the hardened layer side of the base material layer. Examples of the back surface functional layer include an adhesive layer, an antistatic layer, a refractive index adjustment layer, and an anti-blocking layer. The adhesive layer is provided to bond the laminate to various adherends. The antistatic layer is provided to prevent the adhesion of surrounding dust, etc. due to peeling static electricity or friction static electricity, and defects caused thereby, to the outermost surface of the laminate, particularly the outermost surface on the side opposite to the hardened layer side of the base material layer. The refractive index adjustment layer is provided, for example, to improve the total light transmittance of the laminate. The anti-blocking layer is provided to reduce the blocking of the laminate.

[0137] As the adhesive for forming the adhesive layer, known ones can be used, and examples include acrylic-based, polyester-based, urethane-based, and rubber-based ones. Among them, considering versatility, acrylic-based is preferable. The antistatic layer and the refractive index adjustment layer are the same as the antistatic layer and the refractive index adjustment layer as the surface functional layer, respectively.

[0138] The thickness of the back surface functional layer cannot be generally stated as it also depends on the material used for the back surface functional layer and the performance to be exhibited. For example, it is 0.001 to 30 μm. When the back surface functional layer is an adhesive layer, it is preferably 0.01 to 30 μm, more preferably 0.1 to 20 μm. When the back surface functional 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 a known method.

Example

[0139] Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded. The measurement method and evaluation method used in the present invention are as follows.

[0140] (1) Weight-average molecular weight (Mw) The weight-average molecular weight of the copolymer was measured by GPC under the following conditions. Equipment: "e2695" manufactured by Waters Column: "TSKgel Super H3000 + H4000 + H6000" manufactured by Tosoh Corporation Detector: Differential refractive index detector (RI detector / built-in) Solvent: Tetrahydrofuran Temperature: 40 °C Flow rate: 0.5 mL / min Injection volume: 10 μL Concentration: 0.2 mass% Calibration sample: Monodisperse polystyrene Calibration method: Polystyrene conversion.

[0141] (2) Total light transmittance and haze A laminate having a cured layer formed on a PET film was used as a measurement target. The total light transmittance and haze were measured at a wavelength of 550 nm using a haze meter "SH7000" manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS Z8722Z (Geometric conditions for irradiation and light reception of transmissive objects) and JIS K7361-1 (Test method for total light transmittance of plastic - transparent materials) and JIS K7136 (Method for determining haze of plastic - transparent materials). Note that the haze of the laminate is the percentage of transmitted light that has deviated by 0.044 rad (2.5°) or more from the incident light due to forward scattering among the transmitted light that enters from the outermost surface on the side where the cured layer exists with respect to the base material layer and passes through the laminate (the ratio of the diffuse transmittance to the total light transmittance).

[0142] (3) Scratch resistance The laminate with a cured layer formed on a PET film was used as the measurement target. In an atmosphere of 23°C and 55% RH, a weight of 200 gf (per an area of 4 cm 2 was placed on steel wool #0000, and the surface of the cured layer of the laminate was rubbed 15 times back and forth with a wear testing machine (manufactured by Toyo Seiki Seisakusho Co., Ltd.), and the scratches were observed visually. Evaluation was carried out according to the following criteria. A: The number of scratches is 0. B: The number of scratches is 1 or more and less than 50. C: The number of scratches is 50 or more and less than 100. D: The number of scratches is 100 or more.

[0143] (4) Levelling property The surface (10 cm × 10 cm) of the cured layer was observed visually, and the number of peeling and bump defects was examined. Evaluation was carried out according to the following criteria. A: The total number of peeling and bump defects is less than 10. B: The total number of peeling and bump defects is 10 or more.

[0144] (5) Curing property The irradiation amount (integrated light amount) until the tack disappeared by finger touch when irradiated with ultraviolet rays at an illuminance of 100 mW / cm 2 was measured. Evaluation was carried out according to the following criteria. A: Cures with an irradiation amount of 100 mJ / cm 2 or less. B: Cures with an irradiation amount exceeding 100 mJ / cm 2 and less than 200 mJ / cm 2 . C: Cures with an irradiation amount of 200 mJ / cm 2 or more and less than 300 mJ / cm 2 . D: Cures with an irradiation amount of 300 mJ / cm 2 or more.

[0145] Copolymers were produced with the compositions shown in Table 1. The raw materials 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 is an ethylene group compound. <Monomer (x)> x - 1: 4 - Methacryloyloxybenzophenone. <Monomer (r)> r - 1: Stearyl methacrylate. r - 2: 2 - Ethylhexyl methacrylate. <Monomer (h)> h - 1: Diethylaminoethyl methacrylate. <Other monomer (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 distilled under reduced pressure, and a fraction with a purity of 99.8% or more was recovered to obtain a distillate of methacrylic anhydride. The distillation under reduced pressure 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 - hydroxy - methylpropanone (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.). To this, 23.1 g (0.15 mol) of the above - mentioned distillate of methacrylic anhydride was added dropwise at room temperature, and the mixture was stirred for 12 hours. The obtained reaction solution was washed three times with 500 mL of ion - exchanged water, and then the organic phase was concentrated to distill off the solvent. 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 By \(^1H\)-NMR analysis, it was confirmed that the obtained compound was 2-[4-(2-hydroxy-2-methyl-1-oxopropyl)phenoxy]ethyl methacrylate. 1 \(^1H\) NMR (300 MHz, chloroform-d): δ 8.06 (d, \(J\) = 9.0 Hz, 2H), 6.96 (d, \(J\) = 9.0 Hz, 2H), 6.13 (d, \(J\) = 0.6 Hz, 1H), 5.59 (s, 1H), 4.50 (d, \(J\) = 5.1 Hz, 2H), 4.29 (dd, \(J\) = 5.5, 4.1 Hz, 3H), 1.94 (dd, \(J\) = 1.6, 1.0 Hz, 3H), 1.61 (s, 6H).

[0147] (Production Example 1: Production of copolymer (A-1)) Into a flask equipped with a stirrer, a condenser, and a thermometer, 70 parts of methyl isobutyl ketone (hereinafter referred to as MIBK) was charged. Next, the inside of the flask was purged with nitrogen and heated to 65 °C. Then, 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 a chain transfer agent (t-1), 1 part by mass of a polymerization initiator (k-1), and 78 parts by mass of MIBK was added dropwise over 2 hours. Further, after 2 hours, to increase the polymerization rate, a mixed solution of 0.5 part by mass of the polymerization initiator (k-1) and 0.6 part by mass of MIBK was added and held for 5 hours. Thereafter, the reaction solution was cooled to 40 °C to obtain a MIBK solution (A-1) of the copolymer. Hereinafter, the solid content in the solution (A-1) is referred to as the copolymer (A-1). The solid content (non-volatile content) of the solution (A-1) was 40% by mass. The weight average molecular weight (\(M_w\)) of the copolymer (A-1) and the content of active groups per gram of the copolymer (A-1) are shown in Table 1.

[0148] (Production Example 2: Production of copolymer (A-2)) 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, a MIBK solution (A-2) of the copolymer was obtained under the same conditions as in Production Example 1. Hereinafter, the solid content in solution (A-2) is 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 1 g of copolymer (A-2) are shown in Table 1.

[0149] (Production Example 3: Production of Copolymer (H-1)) In Production Example 1, except that 50 parts by mass of monomer (i-1) was changed to 50 parts by mass of monomer (x-1) and 3 parts by mass of chain transfer agent (t-1) was changed to 3 parts by mass of chain transfer agent (t-2), a MIBK solution (H-1) of the copolymer was obtained under the same conditions as in Production Example 1. Hereinafter, the solid content in solution (H-1) is referred to as copolymer (H-1). The solid content (non-volatile content) of solution (H-1) was 40% by mass. The weight average molecular weight (Mw) of copolymer (H-1) and the content of active groups per 1 g of copolymer (H-1) are shown in Table 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 so as to be in the ratio (parts by mass) shown in Table 2 in terms of non-volatile content. Thereafter, a mixed solvent of propylene glycol monomethyl ether (hereinafter, PGM) and methyl ethyl ketone (hereinafter, MEK) (PGM:MEK (mass ratio) of 7:3) was added so that the solid content concentration became 40% by mass, and the mixture was stirred until it became uniform to obtain a coating solution (curable polymer composition). The content of active groups per 100 g of non-volatile content in the coating solution is shown in Table 2.

[0152] The materials in Table 2 are as follows. A-1: MIBK solution of the copolymer (A-1) obtained in Production Example 1. A-2: MIBK solution of the copolymer (A-2) obtained in Production Example 2. H-1: MIBK solution of the copolymer (H-1) obtained in Production Example 3. B-1: 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 obtained coating solution was applied to a PET film (T602E50 manufactured by Mitsubishi Chemical Corporation) with a thickness of 50 μm using a bar coater No. 8, and dried for 60 seconds with a hot air dryer heated to 70 °C to volatilize the solvent. Then, it was irradiated with ultraviolet light using a high-pressure mercury lamp in an air atmosphere with an integrated light amount of 250 mJ / cm 2 , and an illuminance of 100 mW / cm 2 to form a cured layer with a thickness of 3 μm. Thus, a laminate in which a layer (cured layer) made of a cured product was laminated on a base material layer made of a PET film was obtained. The irradiation of ultraviolet light was performed using the UV conveyor of an Eye Graphics high-output UV device (model: US5-X1802-X1202). The integrated light amount is the value measured by an illuminometer (Eye ultraviolet integrated illuminometer "UVPF - A1", "PD-365") manufactured by Iwasaki Electric Co., Ltd. when measuring the integrated light amount with a wavelength of 300 to 390 nm. For the obtained laminate, the items shown in Table 2 were measured or evaluated by the above method. The results are shown in Table 2.

[0154]

Table 2

[0155] As shown in the results of Table 2, the curable polymer compositions of Examples 1 and 2 containing the copolymer (A-1) or (A-2) having a unit based on the monomer (i) were superior in curability and provided a cured layer with much better scratch resistance than those of Reference Example 1 and Comparative Example 1. In particular, for the cured layer of Example 1 using the copolymer (A-1) having a unit based on the monomer (i) as the copolymer (A), the surface was almost smooth and the haze was 0.4%. Also, in Example 2 using the copolymer (A-2) having a unit based on the monomer (i) and a unit based on the monomer (x) as the copolymer (A), the surface had wrinkle-like irregularities and the haze was 1.4%.

Explanation of Symbols

[0156] 1... Substrate layer 2... Cured layer 3... Primer layer 4... Surface functional layer 5... Back surface 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 per molecule, and an acrylic resin (P) having neither an active group that generates radicals upon irradiation with active energy rays nor a radical-polymerizable group, wherein the copolymer (A) has a unit based on a monomer (i) which is a compound represented by the following formula (I), and one or more selected from the group consisting of an alkyl group having 4 to 30 carbon atoms, a fluorine atom, and a silicon atom, and a radical-polymerizable group, and has a unit based on a monomer (y) having no active group that generates radicals upon irradiation with active energy rays the content of the active group that generates radicals upon irradiation with active energy rays per 1 g of the copolymer (A) is 0.5 to 2.5 mmol / g, a curable polymer composition in which the unit based on the monomer (y) is 1 to 80% by mass based on the total mass of all units of the copolymer (A). 【Chemical 1】 [wherein, R １ represents a hydrogen atom, a methyl group or an ethyl group, 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, 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, R ３ and R ４ may be bonded 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 (meth)acrylic acid alkyl esters having an alkyl group having 4 to 30 carbon atoms, and compounds having a radical-polymerizable group selected from the group consisting of (meth)acryloyl group, (meth)acrylamide group, and 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 a unit based on the following monomer (x), a unit based on the following monomer (h), and a unit based on the following 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 the monomer (i)). Monomer (h): A monomer having one or more hydrogen-donating functional groups selected from the group consisting of a hydroxyl group, an amino group, a mercapto group, and an amide group and a radical-polymerizable group, and having no active group that generates radicals upon irradiation with active energy rays (excluding the monomer (y)). Monomer (o): A monomer having a radical-polymerizable group and having no active group that generates radicals upon irradiation with active energy rays (excluding the monomer (y) and the monomer (h)).

4. The curable polymer composition according to claim 3, which has a unit based on the monomer (x), and wherein the radical polymerizable group of the monomer (x) is at least one 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, which has a unit based on the monomer (x), and wherein the active group of the monomer (x) is at least one selected from the group consisting of a benzophenone group, an acetophenone group, a benzoin group, an α-hydroxy ketone group (excluding the group (Ia) represented by the following formula (Ia)), an α-amino ketone group, an α-diketone group, an α-diketone dialkyl acetal group, an anthraquinone group, a thioxanthone group, and a phosphine oxide group. 【Chemical 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 a unit based on the monomer (h), and wherein the radical polymerizable group of the monomer (h) is at least one selected from the group consisting of a (meth)acryloyl group, a (meth)acrylamide group, and a vinyl group.

7. The curable polymer composition according to any one of claims 3 to 6, wherein the copolymer (A) has a unit based on the monomer (o), and wherein the monomer (o) is at least one selected from the group consisting of acrylic acid, acrylate, methacrylic acid, methacrylate, crotonic acid, crotonate, itaconic acid, itaconate, fumaric acid, fumarate, maleic acid, maleate, citraconic acid, citraconate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, (meth)acrylonitrile, styrene, α-methylstyrene, divinylbenzene, vinyltoluene, vinyl propionate, vinyl acetate, a phosphorus-containing vinyl compound, vinyl chloride, vinylidene chloride, and butadiene.

8. A cured product of the 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 material layer and a layer comprising the cured product according to claim 8 or 9.

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