JP6405647B2 - Polymerizable resin, active energy ray-curable composition and article. - Google Patents

Description

  The present invention relates to a polymerizable resin that can be imparted to the cured coating film of the composition with excellent slipperiness and scratch resistance by being added to the active energy ray-curable composition. The present invention also relates to an active energy ray-curable composition using the polymerizable resin, and an article having a cured coating film of the composition.

  The surface layer of the polarizing plate that is the outermost surface of the liquid crystal display is coated with antiglare and antireflection properties such as AG, AG / LR, and clear / LR. Since the coating film obtained by these coatings is the outermost layer, scratch resistance is required. As a method for improving the scratch resistance, a method of forming a cross-linked film obtained using a polyfunctional monomer such as polyfunctional (meth) acrylate on the surface of a substrate and a hard coat agent are known. Examples of a method for forming a cross-linked film for improving scratch resistance on the substrate surface include, for example, a method of adding a silicone-based or fluorine-based leveling agent, inorganic compound particles such as silicon dioxide and aluminum oxide, carbon, or a polyurethane resin, A method of adding synthetic resin particles such as polystyrene resin and acrylic resin has been proposed.

  As a specific example of the hard coat agent, for example, an active energy ray-curable composition containing a silicone compound having a radical polymerizable unsaturated group in a molecule is known (see Patent Document 1). However, with the active energy ray-curable composition disclosed in Patent Document 1, it is difficult to obtain a coating film having sufficient scratch resistance. In particular, when having an LR layer such as AG / LR and Clear / LR, the LR layer has a very thin film thickness of about 0.1 μm, so that it is easy to cause scratches due to external force and can improve the scratch resistance. There is a strong need for sex compositions.

JP 2004-182765 A

  The problem to be solved by the present invention is to add excellent slipperiness and scratch resistance to a very thin coating film having a film thickness of about 0.1 μm by adding it to the active energy ray-curable composition. It is providing the polymerizable resin which can be performed. Another object of the present invention is to provide an active energy ray-curable composition using the polymerizable resin and an article having a cured coating film of the composition.

  As a result of intensive studies to solve the above problems, the present inventors have obtained a polymerizable resin formed by polymerization of a polymerizable unsaturated monomer, and have a silicone chain at one end of the resin. Have been found that can be used as an additive that can improve the scratch resistance, the active energy ray-curable composition containing this resin can impart excellent scratch resistance to the surface of the cured coating film, etc. The present invention has been completed.

  That is, the present invention is a polymerizable resin having a structure obtained by polymerizing a polymerizable unsaturated monomer, the polymerizable resin has a structure containing a silicone chain at one end of the structure, Provided is a polymerizable resin characterized in that the molecular weight of the silicone chain is 2,000 to 20,000, and the content of the silicone chain is 30 to 70% by mass based on the mass of the polymerizable resin It is.

  The present invention also includes an active energy ray comprising the polymerizable resin and an active energy ray-curable resin (D) or an active energy ray-curable monomer (E) other than the polymerizable resin. A curable composition is provided.

  Furthermore, this invention provides the article | item characterized by having the cured coating film of the said active energy ray curable composition.

  By adding the polymerizable resin of the present invention to the active energy ray-curable composition, the surface of the cured coating film is imparted with a slip property and excellent scratch resistance is obtained. Moreover, since this scratch resistance can be exhibited even in a cured coating film that has been subjected to saponification treatment (strong alkali treatment), it is also useful as a material for a hard coat material of a TAC film used for a polarizing plate of a liquid crystal display. .

FIG. 1 is an IR spectrum chart of the polymerizable resin (1) obtained in Example 1. 2 is a chart (overall view) of the ¹ H-NMR spectrum of the polymerizable resin (1) obtained in Example 1. FIG. FIG. 3 is a chart (25 times enlarged view) of the ¹ H-NMR spectrum of the polymerizable resin (1) obtained in Example 1. 4 is a chart (overall view) of ¹³ C-NMR spectrum of the polymerizable resin (1) obtained in Example 1. FIG. FIG. 5 is a chart (25 times enlarged view) of the ¹³ C-NMR spectrum of the polymerizable resin (1) obtained in Example 1. FIG. 6 is a GPC chart of the polymerizable resin (1) obtained in Example 1.

  The polymerizable resin of the present invention is a polymerizable resin having a structure obtained by polymerizing a polymerizable unsaturated monomer, and the polymerizable resin has a structure including a silicone chain at one end of the structure. The molecular weight of the silicone chain is 2,000 to 20,000, and the silicone chain content is 30 to 70% by mass based on the mass of the polymerizable resin. One end may have a single silicone chain or a plurality of silicone chains, but in the present invention, one end has a single (single) silicone chain and is resistant to abrasion. This is preferable because a cured coating film having good properties can be obtained.

  Moreover, the equivalent of the polymerizable unsaturated group (y) in the polymerizable resin of the present invention is 200 to 3,500 g / eq. Because a cured coating film having excellent wear resistance is obtained. The range of 300 to 2,000 g / eq. Is more preferable, 350-1500 g / eq. Is more preferable, 400-1,000 g / eq. The range of is particularly preferable.

  The molecular weight of the silicone chain needs to be 2,000 to 20,000. By having a silicone chain of such molecular weight, the slipperiness of the silicone chain can be suitably expressed, and as a result, the coating film Excellent friction resistance can be imparted by reducing the surface friction. The molecular weight of the silicone chain is preferably 4,000 to 12,000 because a cured coating film excellent in slipperiness can be obtained and a polymerizable resin excellent in compatibility with solvents and other polymerizable resins can be obtained. A molecular weight of 5,000 to 10,000 is more preferred.

  In the polymerizable resin of the present invention, the content of the silicone chain needs to be 30 to 70% by mass based on the mass of the polymerizable resin. If the silicone chain content is less than 30% by mass, it is not preferable because it is difficult to impart sufficient slipperiness to the coating film. When the content of the silicone chain exceeds 70% by mass, the compatibility between the obtained polymerizable resin and other resins is lowered, and as a result, unevenness occurs on the surface of the coating film, and the scratch resistance is inferior. Absent. As for the content rate of a silicone chain | strand, 35-65 mass% is more preferable.

The polymerizable resin of the present invention is, for example, a compound having a functional group having a radical generating ability at one end of a silicone chain having a molecular weight of 2,000 to 20,000 and a reactive functional group (b1). Polymer (P) containing a structure derived from the polymerizable unsaturated monomer (B) by charging the polymerizable unsaturated monomer (B) into the reaction system and generating radicals from the compound (A). And (1) to obtain
The reaction system containing the polymer (P) has a functional group (c1) and a polymerizable unsaturated group (c2) having reactivity with the reactive functional group (b1) of the polymer (P). It can be suitably obtained by a production method comprising the step (2) of charging the compound (C) and reacting the reactive functional group (b1) with the reactive functional group (c1).

  Examples of the functional group having the ability to generate radicals in the compound (A) include an organic group having a halogen atom, an organic group having an alkyl tellurium group, an organic group having a dithioester group, an organic group having a peroxide group, and an azo group. And an organic group having a group. Here, when the polymerizable unsaturated monomer (B) is polymerized to the compound (A) by living radical polymerization, an organic group having a halogen atom as the functional group having the radical generating ability, an alkyl tellurium group An organic group having a halogen atom can be used, particularly an organic group having a halogen atom due to the ease of synthesis, the ease of polymerization control, and the diversity of applicable polymerizable unsaturated monomers. It is preferable to use it.

  Examples of the organic group having a halogen atom include a 2-bromo-2-methylpropionyloxy group, a 2-bromo-propionyloxy group, a parachlorosulfonylbenzoyloxy group, and the like.

  In order to introduce the organic group having a halogen atom into one end of a compound containing a silicone chain having a molecular weight of 2,000 to 20,000, for example, by reaction at one end of a silicone chain having a molecular weight of 2,000 to 20,000. Examples include a method of reacting a compound (a1) having a functional group capable of forming a bond with a compound (a2) having a functional group capable of forming a bond by reacting with the functional group and an organic group having a halogen atom. It is done. Specifically, examples of the functional group at one end of the compound (a1) include a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group, and a carboxylic anhydride group. A specific example of the compound (a1) having one of these functional groups at one end is preferably a compound represented by the following formula (a1-1).

（式中Ｘは反応により結合を形成し得る官能基である、Ｒ_１〜Ｒ_５はそれぞれ独立に炭素原子数１〜１８のアルキル基又はフェニル基である。Ｒ_６は２価の有機基又は単結合である。ｎは２５〜３００である。）

(Wherein X is a functional group capable of forming a bond by reaction, R _{1 to} R ₅ are each independently an alkyl group having 1 to 18 carbon atoms or a phenyl group. R ₆ is a divalent organic group or (It is a single bond. N is 25 to 300.)

R _{1 to} R ₄ are preferably methyl groups. R ₅ is preferably an alkyl group having 6 or less carbon atoms.

Here, examples of R ₆ include an alkylene ether group in which an alkylene group having 1 or more carbon atoms such as a methylene group, a propylene group, or an isopropylidene group, and two or more alkylene groups are connected by an ether bond. .

  On the other hand, examples of the functional group that the compound (a2) has and that can form a bond by reacting with the functional group that the compound (a1) has at one end include the following.

  For example, when the functional group that the compound (a1) has is a hydroxyl group, the functional group other than the organic group having a halogen atom that the compound (a2) has is an isocyanate group, a carboxylic acid halide group, or a carboxylic acid anhydride group. preferable. As another method, first, a carboxyl group is generated by reacting a hydroxyl group of the compound (a1) with an acid anhydride, and the compound having an epoxy group and an organic group having a halogen atom with respect to the carboxyl group. It is also possible to introduce an organic group having a halogen atom at one end of the compound (a1) by further reacting as a compound (a2).

  When the functional group that the compound (a1) has is an isocyanate group, the functional group other than the organic group having a halogen atom that the compound (a2) has is preferably a hydroxyl group. Moreover, when the functional group which the said compound (a1) has is an epoxy group, carboxyl groups are preferable as functional groups other than the organic group which has the halogen atom which the said compound (a2) has.

  When the functional group that the compound (a1) has is a carboxyl group, the functional group other than the organic group having a halogen atom that the compound (a2) has is preferably an epoxy group. Moreover, when the functional group which the said compound (a1) has is a carboxylic anhydride group, the functional group other than the organic group which has a halogen atom which the said compound (a2) has is preferably a hydroxyl group.

  Among the combinations of the functional group that the compound (a1) has and the functional group other than the organic group having a halogen atom that the compound (a2) has, the functional group that the compound (a1) has is a hydroxyl group, A combination in which the functional group other than the organic group having a halogen atom in the compound (a2) is a carboxylic acid halide group is preferable from the viewpoint of easy reaction. The following conditions are mentioned as reaction conditions in the case of this combination.

  As a specific method for introducing the organic group having a halogen atom into one end of a silicone chain, the functional group at one end of the compound (a1) is a hydroxyl group, and the compound (a2) is a carboxylic acid having a halogen group. In this case, the compound having a functional group having a polymerization initiating ability at one end of a compound containing a silicone chain having a molecular weight of 2,000 to 20,000 in the main chain is obtained by carrying out the reaction under dehydrating esterification conditions (A ) Can be obtained. In addition, when the functional group at one end of the compound (a1) is a hydroxyl group and the compound (a2) is a halide of a carboxylic acid having a halogen group, (a1) and ( By reacting with a2), the compound (A) having a functional group having a polymerization initiating ability can be obtained. In this reaction, a basic catalyst can be used as necessary.

  When the functional group at one end of the compound (a1) is an isocyanate group and the compound (a2) has a halogen group and a hydroxyl group as a functional group capable of reacting with the isocyanate group, a catalyst such as tin octylate is used. A compound having a functional group having a polymerization initiating ability can be obtained by reacting (a1) and (a2) in the presence.

  Further, when the functional group at one end of the compound (a1) is an epoxy group and the compound (a2) has a halogen group and a carboxyl group as a functional group capable of reacting with the epoxy group, triphenylphosphine or tertiary amine In the presence of such a basic catalyst, a compound having a functional group having a polymerization initiating ability can be obtained by reacting (a1) and (a2).

  Specific examples of the compound (A) containing a silicone chain having a molecular weight of 2,000 to 20,000 in the main chain used in the present invention and having a functional group having a radical generating ability at one end of the main chain include, for example, Examples include compounds represented by the following formulas.

（ｎは２７〜２７０である。）

(N is 27-270.)

  Next, the polymerizable unsaturated monomer (B) having a reactive functional group (b1) will be described. Examples of the functional group (b1) of the monomer (B) include a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group, and a carboxylic anhydride group. Further, the polymerizable unsaturated group possessed by the monomer (B) is preferably a carbon-carbon unsaturated double bond having radical polymerizability, and more specifically, a vinyl group, a (meth) acryloyl group, a maleimide. A (meth) acryloyl group is more preferable from the viewpoint of easy polymerization.

  In the present invention, “(meth) acrylate” refers to one or both of methacrylate and acrylate, and “(meth) acryloyl group” refers to one or both of methacryloyl group and acryloyl group. “Acrylic acid” refers to one or both of methacrylic acid and acrylic acid.

  Specific examples of the monomer (B) include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. , 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, N- (2-hydroxyethyl) (meth) acrylamide, glycerin mono (meth) acrylate, polyethylene glycol mono (meth) acrylate , Polypropylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, lactone modification having a hydroxyl group at the terminal ( ) Unsaturated monomers having a hydroxyl group such as acrylate; 2- (meth) acryloyloxyethyl isocyanate, 2- (2- (meth) acryloyloxyethoxy) ethyl isocyanate, 1,1-bis ((meth) acryloyloxy) Isocyanate group-containing unsaturated monomers such as methyl) ethyl isocyanate; epoxy group-containing unsaturated monomers such as glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether; (meth) acrylic acid, 2- (meth) acryloyloxyethyl Carboxyl group-containing unsaturated monomers such as succinic acid, 2- (meth) acryloyloxyethylphthalic acid, maleic acid and itaconic acid; carboxylic acid anhydrides having unsaturated double bonds such as maleic anhydride and itaconic anhydride Etc. These monomers (B) can be used alone or in combination of two or more.

  In addition to the compound (A) and the monomer (B), in the production of the polymer (P), which is an intermediate of the polymerizable resin of the present invention, other polymerizations that can be copolymerized therewith. An unsaturated monomer may be used. Examples of such other polymerizable unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n -Pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate , Dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylates such as (meth) acrylate having a polyoxyalkylene chain; styrene, α-methylstyrene, p-methylstyrene , - aromatic vinyl such as methoxystyrene; maleimide, methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, maleimide such as cyclohexyl maleimide.

  Examples of the method for producing the polymer (P) used in the present invention include a method in which the monomer (B) is living radically polymerized using the compound (A) as a radical polymerization initiator. In general, in living radical polymerization, a dormant species whose active polymerization end is protected by an atom or an atomic group reversibly generates a radical and reacts with a monomer, whereby a polymer having a very narrow molecular weight distribution can be obtained. Examples of such living radical polymerization include atom transfer radical polymerization (ATRP), reversible addition-cleavage radical polymerization (RAFT), radical polymerization via nitroxide (NMP), radical polymerization using organic tellurium (TERP), etc. Is mentioned. It is preferable to produce the copolymer (P) by this living radical polymerization because a copolymer having a very narrow molecular weight distribution can be obtained. There is no particular restriction as to which of these methods is used, but the ATRP is preferable from the viewpoint of ease of control. ATRP is polymerized using an organic halide or a sulfonyl halide compound as an initiator, and a metal complex composed of a transition metal compound and a ligand as a catalyst.

The transition metal compound used in the ATRP is represented by M ^{n +} X ⁿ . Transition metal M ^{n +} is Cu ⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ , Ru ²⁺ , Ru ³⁺ , Cr ²⁺ , Cr ³⁺ , Mo ⁰ , Mo ⁺ , Mo ²⁺ , Mo ³⁺ , W ²⁺ , W ³⁺ , Rh ³⁺ , Rh ⁴⁺ , Co ⁺ , Co ²⁺ , Re ²⁺ , Re ³⁺ , Ni ⁰ , Ni ⁺ , Mn ³⁺ , Mn ⁴⁺ , V ²⁺ , V ³⁺ , Zn ⁺ , Zn ²⁺ , Au ⁺ , Au ²⁺ , Ag ⁺ And Ag ²⁺ . X is a halogen atom, an alkoxyl group having 1 to 6 carbon atoms, (SO ₄ ) _1/2 , (PO ₄ ) _1/3 , (HPO ₄ ) _1/2 , (H ₂ PO ₄ ), triflate , Hexafluorophosphate, methane sulfonate, aryl sulfonate (preferably benzene sulfonate or toluene sulfonate), SeR ₁ , CN and R ₂ COO. Here, R ¹ represents aryl, a linear or branched alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), and R 2 is a hydrogen atom or halogen 1 to 5 times. It represents a linear or branched alkyl group having 1 to 6 carbon atoms (preferably a methyl group) which may be substituted (preferably with fluorine or chlorine 1 to 3 times). Further, n represents a formal charge on the metal and is an integer of 0 to 7.

  The transition metal complex is preferably a group 7, 8, 9, 10, or 11 transition metal complex, a complex of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron or divalent nickel. Is more preferable.

  Examples of the compound having a ligand capable of coordinating with a transition metal include a ligand containing at least one nitrogen atom, oxygen atom, phosphorus atom or sulfur atom capable of coordinating with a transition metal via a σ bond. A compound having two or more carbon atoms capable of coordinating with a transition metal via a π bond, a compound having a ligand capable of coordinating with a transition metal via a μ bond or η bond Is mentioned.

  Specific examples of the compound having a ligand include, for example, when the central metal is copper, 2,2′-bipyridyl and its derivative, 1,10-phenanthroline and its derivative, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexa And a complex with a ligand such as polyamine such as methyltris (2-aminoethyl) amine. Examples of the divalent ruthenium complex include dichlorotris (triphenylphosphine) ruthenium, dichlorotris (tributylphosphine) ruthenium, dichloro (cyclooctadiene) ruthenium, dichlorobenzeneruthenium, dichlorop-cymenruthenium, dichloro (norbornadiene) ruthenium, Examples include cis-dichlorobis (2,2′-bipyridine) ruthenium, dichlorotris (1,10-phenanthroline) ruthenium, and carbonylchlorohydridotris (triphenylphosphine) ruthenium. Furthermore, examples of the divalent iron complex include a bistriphenylphosphine complex and a triazacyclononane complex.

  In the production of the polymer (P), it is preferable to use a solvent. Examples of the solvent used include ester solvents such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; ether solvents such as diisopropyl ether, dimethoxyethane, and diethylene glycol dimethyl ether; halogen solvents such as dichloromethane and dichloroethane; toluene, Aromatic solvents such as xylene; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohol solvents such as methanol, ethanol, and isopropanol; aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide. Moreover, said solvent can be used individually or can also be used together 2 or more types.

  Further, the polymerization temperature in the production of the polymer (P) is preferably in the range of room temperature to 100 ° C.

  In order to obtain the polymerizable resin of the present invention, a part or all of the reactive groups of the polymer (P) produced by the above method has reactivity with respect to the functional group (b1). A polymerizable unsaturated group is introduced into the polymer (P) using the compound (C) having a functional group (c1) and a polymerizable unsaturated group (c2). Examples of the functional group (c1) of the compound (C) include a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group, and a carboxylic anhydride group. When the reactive functional group (b1) of the monomer (B) is a hydroxyl group, an isocyanate group, a carboxyl group, a carboxylic acid halide group, a carboxylic anhydride group, or an epoxy group is included as the functional group (c1). When the reactive functional group (b1) is an isocyanate group, the functional group (c1) includes a hydroxyl group, and when the reactive functional group (b1) is an epoxy group, the functional group (c1) ) Include a carboxyl group and a hydroxyl group. When the reactive functional group (b1) is a carboxyl group, the functional group (c1) includes an epoxy group and a hydroxyl group. These may be a combination of a plurality of functional groups. Further, among these combinations, the reactive functional group (b1) is a hydroxyl group and the functional group (c1) is an isocyanate group, the reactive functional group (b1) is an epoxy group, and the functional group (c1) is A combination of carboxyl groups is preferred.

  The polymerizable unsaturated group possessed by the monomer (C) is preferably a carbon-carbon unsaturated double bond having radical polymerizability, and more specifically, a vinyl group, (meth) acryloyl group, maleimide. Groups and the like. Among these, when the fluorine-containing polymerizable polymer of the present invention is added to the active energy ray curable composition, the active energy ray curable resin (D) and the active energy ray curable monomer (E) described later are added. (Meth) acryloyl group is preferable and allyloyl group is more preferable.

  Specific examples of the compound (C) include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4 -Hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, N- (2-hydroxyethyl) (meth) acrylamide, glycerin mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene Glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, lactone modified with a hydroxyl group at the terminal ( ) Unsaturated monomers having a hydroxyl group such as acrylate; 2- (meth) acryloyloxyethyl isocyanate, 2- (2- (meth) acryloyloxyethoxy) ethyl isocyanate, 1,1-bis ((meth) acryloyloxy) Unsaturated monomers having an isocyanate group such as methyl) ethyl isocyanate; unsaturated monomers having an epoxy group such as glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether; (meth) acrylic acid, 2- (meth) acryloyl Carboxyl group-containing unsaturated monomers such as oxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, maleic acid and itaconic acid; carboxylic acids having unsaturated double bonds such as maleic anhydride and itaconic anhydride An anhydride etc. are mentioned. Moreover, 2-hydroxy-3-acryloyloxypropyl methacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate etc. can also be used as what has a several polymerizable unsaturated group. These compounds (C) can be used alone or in combination of two or more.

  Among the specific examples of the compound (C), 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate are preferable. Hydroxybutyl acrylate, 1,4-cyclohexanedimethanol monoacrylate, N- (2-hydroxyethyl) acrylamide, 2-acryloyloxyethyl isocyanate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate 4-hydroxybutyl acrylate glycidyl ether Acrylic acid is preferred.

  The method of reacting the compound (C) with the polymer (P) may be performed under the condition that the polymerizable unsaturated group of the compound (C) or the like does not polymerize. For example, the temperature condition is 30 to 120 ° C. It is preferable to adjust the reaction to the range. This reaction is preferably carried out in the presence of a catalyst or a polymerization inhibitor, and if necessary in the presence of an organic solvent.

  For example, when the reactive functional group (b1) is a hydroxyl group and the functional group (c1) is an isocyanate group, p-methoxyphenol, hydroquinone, 2,6-di-t-butyl is used as a polymerization inhibitor. Using 4-methylphenol or the like, and using dibutyltin dilaurate, dibutyltin diacetate, tin octylate, zinc octylate, etc. as the urethanization reaction catalyst, the reaction temperature is 40 to 120 ° C., particularly 60 to 90 ° C. The method of making it preferable is. When the reactive functional group (b1) is an epoxy group and the functional group (c1) is a carboxyl group, or the reactive functional group (b1) is a carboxyl group, the functional group When (c1) is an epoxy group, p-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methylphenol or the like is used as a polymerization inhibitor, and triethylamine or the like is used as an esterification reaction catalyst. Using tertiary amines, quaternary ammoniums such as tetramethylammonium chloride, tertiary phosphines such as triphenylphosphine, quaternary phosphoniums such as tetrabutylphosphonium chloride, etc., reaction temperature 80 to 130 ° C. In particular, the reaction is preferably performed at 100 to 120 ° C.

  The organic solvent used in the above reaction is preferably ketones, esters, amides, sulfoxides, ethers, hydrocarbons, specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, Examples include propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene and the like. These may be appropriately selected in consideration of the boiling point and compatibility.

  Since the polymerizable resin of the present invention obtained as described above can prevent gelation during production and has excellent antifouling properties, its number average molecular weight (Mn) is in the range of 3,000 to 70,000. It is preferable that it is in the range of 6,000 to 50,000, more preferably 7,000 to 30,000. The weight average molecular weight (Mw) is preferably in the range of 3,000 to 100,000, more preferably in the range of 7,000 to 75,000, and in the range of 8,000 to 50,000. Further preferred. Further, the dispersity (Mw / Mn) of the polymerizable resin of the present invention is preferably 1.0 to 1.6, more preferably 1.0 to 1.5, and most preferably 1.0 to 1.4.

  Here, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are values converted to polystyrene based on gel permeation chromatography (hereinafter abbreviated as “GPC”) measurement. The measurement conditions for GPC are as follows.

[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HHR-H” (6.0 mm ID × 4 cm) manufactured by Tosoh Corporation + “TSK-GEL GMHHR-N” (7.8 mm ID × 30 cm) + Tosoh Corporation manufactured by Tosoh Corporation “TSK-GEL GMHHR-N” (7.8 mm ID × 30 cm) manufactured by Tosoh Corporation “TSK-GEL GMHHR-N” (7.8 mm ID × 30 cm) + “TSK− manufactured by Tosoh Corporation” GEL GMHHR-N "(7.8 mm ID x 30 cm)
Detector: ELSD ("ELSD2000" manufactured by Oltech Japan Co., Ltd.)
Data processing: “GPC-8020 Model II data analysis version 4.30” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min Sample: A 1.0% by mass tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (5 μl).
Standard sample: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II Data Analysis Version 4.30”.

(Monodispersed polystyrene)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
“F-288” manufactured by Tosoh Corporation
“F-550” manufactured by Tosoh Corporation

  The polymerizable resin of the present invention can be used as a main component of the active energy ray-curable composition itself, but has an extremely excellent surface modification performance, so it is added to the active energy ray-curable composition. By using it as a surface modifier (surfactant), excellent scratch resistance can be imparted to the cured coating film.

  The active energy ray-curable composition of the present invention is obtained by adding the polymerizable resin of the present invention. The main component thereof is an active energy ray-curable resin (D) other than the polymerizable resin of the present invention. Or the active energy ray-curable monomer (E) is contained. In the active energy ray-curable composition of the present invention, the active energy ray-curable resin (D) and the active energy ray-curable monomer (E) may be used alone or in combination. It doesn't matter. In addition, the polymerizable resin of the present invention is preferably used as a fluorosurfactant in the active energy ray-curable composition.

  The active energy ray-curable resin (D) is a urethane (meth) acrylate resin, an unsaturated polyester resin, an epoxy (meth) acrylate resin, a polyester (meth) acrylate resin, an acrylic (meth) acrylate resin, or a resin having a maleimide group. In the present invention, a urethane (meth) acrylate resin is particularly preferable from the viewpoint of transparency and low shrinkage.

  The urethane (meth) acrylate resin used here is a resin having a urethane bond and a (meth) acryloyl group obtained by reacting an aliphatic polyisocyanate compound or an aromatic polyisocyanate compound with a (meth) acrylate compound having a hydroxyl group. Is mentioned.

  Examples of the aliphatic polyisocyanate compound include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl- 1,5-pentane diisocyanate, dodecamethylene diisocyanate, 2-methylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, hydrogenated diphenylmethane diisocyanate , Hydrogenated tolylene diisocyanate, hydrogenated xylile Examples include diisocyanate, hydrogenated tetramethylxylylene diisocyanate, cyclohexyl diisocyanate, and the aromatic polyisocyanate compound includes tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, Examples include toridine diisocyanate and p-phenylene diisocyanate.

  On the other hand, examples of the acrylate compound having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1, Monovalent dihydric alcohols such as 5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, and hydroxypivalate neopentyl glycol mono (meth) acrylate ( Meth) acrylate; trimethylolpropane di (meth) acrylate, ethoxylated trimethylolpropane (meth) acrylate, propoxylated trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate Mono- or di (meth) acrylates of trivalent alcohols such as relate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, or hydroxyl groups obtained by modifying some of these alcoholic hydroxyl groups with ε-caprolactone Mono- and di (meth) acrylates having a monofunctional hydroxyl group and tri- or more functional (meth) acryloyl such as pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. A compound having a group, or a polyfunctional (meth) acrylate having a hydroxyl group obtained by modifying the compound with ε-caprolactone; dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, poly (Meth) acrylate compounds having an oxyalkylene chain such as propylene glycol mono (meth) acrylate and polyethylene glycol mono (meth) acrylate; polyethylene glycol-polypropylene glycol mono (meth) acrylate, polyoxybutylene-polyoxypropylene mono (meth) (Meth) acrylate compounds having a block structure oxyalkylene chain such as acrylate; random structures such as poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate and poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate And (meth) acrylate compounds having an oxyalkylene chain.

  The reaction between the aliphatic polyisocyanate compound or the aromatic polyisocyanate compound and the acrylate compound having a hydroxyl group can be performed by a conventional method in the presence of a urethanization catalyst. Specific examples of urethanization catalysts that can be used here include amines such as pyridine, pyrrole, triethylamine, diethylamine, and dibutylamine, phosphines such as triphenylphosphine and triethylphosphine, dibutyltin dilaurate, octyltin trilaurate, and octyl. Examples thereof include organotin compounds such as tin diacetate, dibutyltin diacetate, and tin octylate, and organometallic compounds such as zinc octylate.

  Among these urethane acrylate resins, those obtained by reacting an aliphatic polyisocyanate compound with a (meth) acrylate compound having a hydroxyl group are excellent in transparency of the cured coating film and have good sensitivity to active energy rays. It is preferable from the viewpoint of excellent curability.

  Next, the unsaturated polyester resin is a curable resin obtained by polycondensation of α, β-unsaturated dibasic acid or acid anhydride thereof, aromatic saturated dibasic acid or acid anhydride thereof, and glycols. The α, β-unsaturated dibasic acid or its acid anhydride includes maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid, and esters thereof. As aromatic saturated dibasic acid or acid anhydride thereof, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, halogenated phthalic anhydride and these Examples include esters. Examples of the aliphatic or alicyclic saturated dibasic acid include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride, and esters thereof. As glycols, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpropane-1,3-diol, neopentyl glycol, triethylene glycol, Examples include tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, 2,2-di- (4-hydroxypropoxydiphenyl) propane, and others. In addition, oxides such as ethylene oxide and propylene oxide can be used in the same manner.

  Next, as an epoxy (meth) acrylate resin, (meth) acrylic acid is reacted with an epoxy group of an epoxy resin such as a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, or a cresol novolak type epoxy resin. Can be obtained.

  The resin having a maleimide group includes a bifunctional maleimide urethane compound obtained by urethanizing N-hydroxyethylmaleimide and isophorone diisocyanate, and a bifunctional maleimide ester compound obtained by esterifying maleimide acetic acid and polytetramethylene glycol. Examples thereof include tetrafunctional maleimide ester compounds obtained by esterification of maleimidocaproic acid and a tetraethylene oxide adduct of pentaerythritol, and polyfunctional maleimide ester compounds obtained by esterification of maleimide acetic acid and a polyhydric alcohol compound. These active energy ray-curable resins (D) can be used alone or in combination of two or more.

  Examples of the active energy ray-curable monomer (E) include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and a number average molecular weight in the range of 150 to 1,000. Polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di having a number average molecular weight in the range of 150 to 1000 (Meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol (Meth) acrylate, hydroxypivalate ester neopentyl glycol di (meth) acrylate, bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol Hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dicyclopentenyl (meth) acrylate, methyl (meth) acrylate, Propyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meta Aliphatic alkyl (meth) acrylates such as acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, glycerol (meth) acrylate, 2-hydroxyethyl (meth) acrylate , 3-chloro-2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, allyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2- (diethylamino) ethyl (meth) acrylate, 2- (dimethyl Amino) ethyl (meth) acrylate, γ- (meth) acryloxypropyltrimethoxysilane, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxydi Lopylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydipropylene glycolicol (meth) acrylate, phenoxypolypropylene glycol (meth) acrylate, Polybutadiene (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polyethylene glycol-polybutylene glycol (meth) acrylate, polystyrylethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopenta Nyl (meth) acrylate, dicyclopentenyl (meth) acryl , Isobornyl (meth) acrylate, methoxylated cyclodecatriene (meth) acrylate, phenyl (meth) acrylate; maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-hexyl Maleimide, N-octylmaleimide, N-dodecylmaleimide, N-stearylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, 2-maleimidoethyl-ethylcarbonate, 2-maleimidoethyl-propylcarbonate, N-ethyl- (2- Maleimidoethyl) carbamate, N, N-hexamethylene bismaleimide, polypropylene glycol-bis (3-maleimidopropyl) ether, bis (2-maleimidoethyl) carbonate, 1,4-di And maleimides such as maleimide cyclohexane.

  Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra ( A trifunctional or higher polyfunctional (meth) acrylate such as (meth) acrylate is preferred. These active energy ray-curable monomers (D) can be used alone or in combination of two or more.

  In the active energy ray-curable composition of the present invention, the polymerizable resin of the present invention is used in a total amount of 100 parts by mass of the active energy ray-curable resin (D) and the active energy ray-curable monomer (E). On the other hand, the range of 0.001-20 mass parts is preferable, the range of 0.1-15 mass parts is more preferable, and the range of 0.1-10 mass parts is further more preferable. If the use amount of the polymerizable resin of the present invention is within this range, leveling property, water / oil repellency and antifouling property can be made sufficient, and the hardness and transparency after curing of the composition are also sufficient. Can be. In addition, since the ratio of the polymerizable resin of the present invention in the surface layer portion of the coating film changes depending on the film thickness when the active energy ray-curable composition of the present invention is used as a coating film, The amount of the polymerizable resin of the present invention is set to be low, and in the case of a thin film, the amount of the polymerizable resin of the present invention is set to be high so that the polymerizable resin of the present invention is uniformly present on the coating film surface. It is preferable because high scratch resistance can be expected.

  The polymerizable resin or active energy ray-curable composition of the present invention can be formed into a cured coating film by irradiating active energy rays after application to a substrate. The active energy rays refer to ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When a cured coating film is formed by irradiating ultraviolet rays as active energy rays, a photopolymerization initiator (F) may be added to the polymerizable resin or active energy ray curable composition to improve curability. preferable. Further, if necessary, a photosensitizer can be further added to improve curability. On the other hand, when ionizing radiation such as electron beam, α-ray, β-ray, and γ-ray is used, it cures quickly without using a photopolymerization initiator or photosensitizer. F) or a photosensitizer need not be added.

  Examples of the photopolymerization initiator (F) include intramolecular cleavage type photopolymerization initiators and hydrogen abstraction type photopolymerization initiators. Examples of the intramolecular cleavage type photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy. 2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thio) Acetophenone-based compounds such as methylphenyl) propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone; benzoins such as benzoin, benzoin methyl ether and benzoin isopropyl ether; 4,6-trimethylbenzoindiphenylphos In'okishido, bis (2,4,6-trimethylbenzoyl) - acyl phosphine oxide-based compounds such as triphenylphosphine oxide; benzyl, and methyl phenylglyoxylate ester.

  On the other hand, examples of the hydrogen abstraction type photopolymerization initiator include benzophenone, methyl 4-phenylbenzophenone, o-benzoylbenzoate, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide. Benzophenone compounds such as acrylated benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3′-dimethyl-4-methoxybenzophenone; 2-isopropylthioxanthone, 2,4 A thioxanthone compound such as dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone; an aminobenzophenone compound such as Michler's ketone and 4,4′-diethylaminobenzophenone; 2-chloro acridone, 2-ethyl anthraquinone, 9,10-phenanthrenequinone, camphorquinone, and the like.

  Among the photopolymerization initiators (F), the compatibility with the active energy ray curable resin (D) and the active energy ray curable monomer (E) in the active energy ray curable composition is excellent. Therefore, 1-hydroxycyclohexyl phenyl ketone and benzophenone are preferable, and 1-hydroxycyclohexyl phenyl ketone is particularly preferable. These photopolymerization initiators (F) can be used alone or in combination of two or more.

  Examples of the photosensitizer include amines such as aliphatic amines and aromatic amines, ureas such as o-tolylthiourea, sodium diethyldithiophosphate, s-benzylisothiuronium-p-toluenesulfonate, and the like. And sulfur compounds.

  These photopolymerization initiators and photosensitizers are preferably used in an amount of 0.01 to 20 parts by weight, preferably 0.1 to 15 parts by weight per 100 parts by weight of the non-volatile component in the active energy ray-curable composition. % Is more preferable, and 0.3 to 7 parts by mass is more preferable.

  Furthermore, the active energy ray-curable composition of the present invention is not limited to the effects of the present invention, depending on the purpose of use, characteristics, etc. Various compounding materials for the purpose of adjusting coating properties and coating film properties, such as various organic solvents, acrylic resins, phenol resins, polyester resins, polystyrene resins, urethane resins, urea resins, melamine resins, alkyd resins, epoxy resins, Various resins such as polyamide resin, polycarbonate resin, petroleum resin, fluororesin, various organic or inorganic particles such as PTFE (polytetrafluoroethylene), polyethylene, polypropylene, carbon, titanium oxide, alumina, copper, silica fine particles, polymerization start Agent, polymerization inhibitor, antistatic agent, antifoaming agent, viscosity modifier, light resistance stabilizer, weather resistance stabilizer, heat resistance Fixing agent, antioxidant, rust inhibitor, slip agent, wax, gloss adjuster, mold release agent, compatibilizer, conductivity modifier, pigment, dye, dispersant, dispersion stabilizer, silicone-based, hydrocarbon-based interface An activator or the like can be used in combination.

  Among the above components, the organic solvent is useful for appropriately adjusting the solution viscosity of the active energy ray-curable composition of the present invention. In particular, in order to perform thin film coating, the film thickness can be adjusted. It becomes easy. Examples of the organic solvent that can be used here include aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, isopropanol, and t-butanol; esters such as ethyl acetate and propylene glycol monomethyl ether acetate; Examples thereof include ketones such as methyl isobutyl ketone and cyclohexanone. These solvents can be used alone or in combination of two or more.

  Here, the amount of the organic solvent used varies depending on the intended use and the intended film thickness and viscosity, but is preferably in the range of 0.5 to 50 times the mass of the total mass of the curing component.

  As described above, the active energy ray for curing the active energy ray-curable composition of the present invention is an ionizing radiation such as an ultraviolet ray, an electron beam, an α ray, a β ray, and a γ ray. Or as a curing device, for example, a germicidal lamp, an ultraviolet fluorescent lamp, a carbon arc, a xenon lamp, a high-pressure mercury lamp for copying, a medium or high-pressure mercury lamp, an ultra-high pressure mercury lamp, an electrodeless lamp, a metal halide lamp, natural light, etc. Examples of the electron beam include ultraviolet rays, a scanning type, and a curtain type electron beam accelerator.

  Among these, ultraviolet rays are particularly preferable, and ultraviolet rays are preferably irradiated in an inert gas atmosphere such as nitrogen gas in order to avoid curing inhibition due to oxygen or the like. Further, if necessary, heat may be used as an energy source and heat treatment may be performed after curing with ultraviolet rays.

  The application method of the active energy ray-curable composition of the present invention varies depending on the application. For example, a gravure coater, roll coater, comma coater, knife coater, air knife coater, curtain coater, kiss coater, shower coater, wheeler coater, spin coater , Coating methods using dipping, screen printing, spraying, applicators, bar coaters, etc., or molding methods using various molds.

  Since the cured coating film of the polymerizable resin of the present invention has scratch resistance, it can be imparted to the surface of the article by applying and curing to the surface of the article. Moreover, since the polymerizable resin of the present invention can add leveling properties to the coating material by adding it to the coating material, the active energy ray curing agent composition of the present invention has high leveling properties. In addition, since the cured coating film of the polymerizable resin of the present invention is excellent in sliding property, it has an effect of improving the touch operation such as a touch panel. Furthermore, the cured coating film of the polymerizable resin of the present invention is also excellent in antifouling property. .

  Since the cured coating film of the polymerizable resin or active energy ray-curable composition of the present invention has excellent scratch resistance and the like, it can be applied to the surface of the article and cured to provide scratch resistance or the like on the surface of the article. Can be granted.

  Articles that can be prevented from being scratched using the polymerizable resin or active energy ray-curable composition of the present invention include a polarizing plate film for a liquid crystal display (LCD) such as a TAC film; a plasma display (PDP), an organic EL display Various display screens such as: Touch panel; Case or screen of electronic terminal such as mobile phone; Transparent protective film for color filter for liquid crystal display (hereinafter referred to as “CF”); Organic insulating film for liquid crystal TFT array; Electronic circuit formation Inkjet ink; optical recording media such as CD, DVD, Blu-ray disc; transfer film for insert mold (IMD, IMF); rubber roller for OA equipment such as copying machines and printers; reading unit of OA equipment such as copying machines and scanners Glass surface of the camera; optical camera, video camera, glasses, etc. Windshields of watches such as watches, glass surfaces; windows of various vehicles such as automobiles and railway vehicles; cover glasses or films for solar cells; various building materials such as decorative panels; window glass for houses; -Synthetic leather, various plastic molded products such as housings for home appliances, FRP bathtubs, etc. By applying the active energy ray-curable composition of the present invention to these article surfaces and irradiating active energy rays such as ultraviolet rays to form a cured coating film, it is possible to impart scratch resistance to the article surfaces. .

  Moreover, as a coating material that can impart the scratch resistance by adding the polymerizable resin of the present invention, a hard coating material for an LCD polarizing plate such as a TAC film, an anti-glare (AG: anti-glare) coating material or an anti-reflection ( LR) coating material; hard coating material for various display screens such as plasma display (PDP) and organic EL display; hard coating material for touch panel; color resist for forming each pixel of RGB used for CF, printing ink, Ink-jet ink or paint; Black resist for CF black matrix, printing ink, ink-jet ink or paint; Resin composition for pixel partition walls such as plasma display (PDP), organic EL display; For electronic terminal housing such as mobile phone Paint or hard coat material; hard coat for mobile phone screen Coating for transparent protective film protecting the CF surface; coating for organic insulating film of liquid crystal TFT array; inkjet ink for forming electronic circuit; hard coating material for optical recording media such as CD, DVD, Blu-ray disc; insert mold (IMD, IMF) hard coating material for transfer film; coating material for rubber rollers for OA equipment such as copiers and printers; glass coating material for reading parts of OA equipment such as copiers and scanners; cameras, video cameras, glasses, etc. Coating materials for optical lenses; windshields for watches such as watches; glass coating materials; coating materials for windows of various vehicles such as automobiles and railway vehicles; paints for antireflection films for solar cell cover glasses or films; Printing ink or paint for various building materials; coating material for window glass in houses; wood paint for furniture, etc .; artificial and synthetic leather Use coating material; consumer electronics enclosure such as various plastic article for paint or coating material; FRP tub paint or coating material, and the like.

  Furthermore, examples of articles that can impart scratch resistance (scratch resistance) using the polymerizable resin or active energy ray-curable composition of the present invention include prism sheets or diffusion sheets that are backlight members of LCDs. . In addition, by adding the polymerizable resin of the present invention to the prism sheet or diffusion sheet coating material, the leveling property of the coating material is improved and the coating film of the coating material is given scratch resistance (scratch resistance). can do.

  In addition, since the cured coating film of the polymerizable resin of the present invention has a low refractive index, as a coating material for a low refractive index layer in an antireflection layer for preventing reflection of fluorescent lamps on various display surfaces such as LCDs. Can also be used. Further, by adding the fluorine-containing curable resin of the present invention to the coating material for the antireflection layer, particularly the coating material for the low refractive index layer in the antireflection layer, the coating material can be applied while maintaining the low refractive index of the coating film. Abrasion resistance can also be imparted to the film surface.

  Further, other applications in which the polymerizable resin or the active energy ray-curable composition of the present invention can be used include optical fiber cladding materials, waveguides, liquid crystal panel sealing materials, various optical sealing materials, and optical adhesives. Agents and the like.

  In particular, among the coating materials for protective films for polarizing plates for LCDs, when the active energy ray-curable composition of the present invention is used as an antiglare coating material, inorganic or organic fine particles such as silica fine particles, acrylic resin fine particles, polystyrene resin fine particles, etc. Is blended at a ratio of 0.1 to 0.5 times the total mass of the curing component in the active energy ray-curable composition of the present invention, so that the antiglare property is excellent.

  In addition, when the polymerizable resin or active energy ray-curable composition of the present invention is used as an antiglare coating material for a protective film of a polarizing plate for LCD, it is in contact with a mold having an uneven surface shape before the coating material is cured. Then, it can be applied to a transfer method in which an active energy ray is irradiated from the side opposite to the mold and cured, and the surface of the coat layer is embossed to impart antiglare properties.

Hereinafter, the present invention will be described in more detail with reference to specific examples. In the examples, “parts” and “%” are based on mass unless otherwise specified. In addition, the measurement conditions of IR spectrum of the obtained polymeric resin, < ¹ > H-NMR spectrum, < ¹³ > C-NMR spectrum, < ¹⁹ > F-NMR spectrum, and GPC are as follows.

[IR spectrum measurement conditions]
Apparatus: “NICOLET380” manufactured by Thermo Electron Co., Ltd.
Measuring method: KBr method

^[1 H-NMR spectrum measurement conditions]
Apparatus: “JNM-ECA500” manufactured by JEOL Ltd.
Solvent: chloroform-d

[ ^13C -NMR spectrum measurement conditions]
Apparatus: “JNM-ECA500” manufactured by JEOL Ltd.
Solvent: chloroform-d

[ ¹⁹ F-NMR spectrum measurement conditions]
Apparatus: “JNM-ECA500” manufactured by JEOL Ltd.
Solvent: chloroform-d

[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HHR-H” (6.0 mm ID × 4 cm) manufactured by Tosoh Corporation + “TSK-GEL GMHHR-N” (7.8 mm ID × 30 cm) + Tosoh Corporation manufactured by Tosoh Corporation “TSK-GEL GMHHR-N” (7.8 mm ID × 30 cm) manufactured by Tosoh Corporation “TSK-GEL GMHHR-N” (7.8 mm ID × 30 cm) + “TSK− manufactured by Tosoh Corporation” GEL GMHHR-N "(7.8 mm ID x 30 cm)
Detector: ELSD ("ELSD2000" manufactured by Oltech Japan Co., Ltd.)
Data processing: “GPC-8020 Model II data analysis version 4.30” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min Sample: A 1.0% by mass tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (5 μl).
Standard sample: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II Data Analysis Version 4.30”.

(Monodispersed polystyrene)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
“F-288” manufactured by Tosoh Corporation
“F-550” manufactured by Tosoh Corporation

Example 1 (Preparation of polymerizable resin of the present invention)
In a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 136.76 g of n-heptane as a solvent, and 300. of a silicone compound having a hydroxyl group at one end represented by the following formula (a-1). 00 g and 10.48 g of triethylamine as a catalyst were charged, and the mixture was stirred for 30 minutes while maintaining the temperature in the flask at 5 ° C.

（式中、ｎは平均６５である。）

(Where n is an average of 65)

  Next, 19.10 g of 2-bromoisobutyric acid bromide was charged and stirred at room temperature for 3 hours. Thereafter, 341.89 g of n-heptane and 600 g of 0.36% hydrochloric acid were mixed and stirred and allowed to stand, and the hydrochloric acid layer was separated and removed. Thereafter, 600 g of a saturated aqueous sodium hydrogen carbonate solution is mixed and stirred, and then allowed to stand. The saturated aqueous sodium hydrogen carbonate solution layer is separated and removed, and further 600 g of ion-exchanged water is mixed and stirred, and then left to stand. The exchange water layer was separated and removed. Next, 8 g of magnesium sulfate was added as a dehydrating agent, shaken and dehydrated, and then the dehydrating agent was filtered off. Thereafter, the solvent was distilled off under reduced pressure, and the resulting residue was dissolved in 313.31 g of isopropyl ether. 300 g of 0.36% hydrochloric acid was mixed and stirred and allowed to stand, and the hydrochloric acid layer was separated and removed. Thereafter, 300 g of 1% aqueous sodium hydroxide solution was mixed and stirred, and then allowed to stand. The 1% aqueous sodium hydroxide solution layer was separated and removed, and further 300 g of ion-exchanged water was mixed and stirred, and then allowed to stand. The ion exchange water layer was separated and removed. Next, 8 g of magnesium sulfate was added as a dehydrating agent, shaken and dehydrated, and then the dehydrating agent was filtered off. Then, the compound (A-4) used by this invention represented by a following formula was obtained by distilling a solvent off under reduced pressure.

（式中、ｎは平均６５である。）

(Where n is an average of 65)

  Next, equipped with a nitrogen introduction tube, a stirrer, a thermometer, and a cooling tube, 31.39 g of isopropyl alcohol, 31.39 g of methyl ethyl ketone, 11.853 g of 2-hydroxyethyl methacrylate, and 0.547 g of methoxybenzene were added to a nitrogen-substituted glass flask. It stirred at 25 degreeC for 1 hour, stirring under nitrogen stream. Next, 0.451 g of cuprous chloride, 0.113 g of cupric bromide and 1.581 g of 2,2-bipyridyl were charged and stirred for 30 minutes. After the temperature was raised to 60 ° C., 30 g of a compound containing one silicone chain represented by the formula (A-4) was added, and the mixture was stirred for 4.5 hours while maintaining the temperature in the flask at 60 ° C. Thereafter, the temperature was raised to 75 ° C. and stirred for 21.5 hours. Under air, 1.167 g of 85% aqueous phosphoric acid solution was added and stirred for 2 hours, and the precipitated solid was separated by filtration. The catalyst was removed with an ion exchange resin, and the ion exchange resin was filtered off to obtain a polymer (p-1).

Next, 28.26 g of the obtained copolymer (p-1), 54.64 g of methyl isobutyl ketone, and a polymerization inhibitor were added to a glass flask equipped with a nitrogen introducing tube, a stirring device, a thermometer, a cooling tube, and a dropping device. P-methoxyphenol 0.0142g, dibutylhydroxytoluene 0.1070g, and urethanization catalyst 0.0107g tin octylate as a urethanization catalyst, stirring was started under an air stream, and 2-acryloyloxyethyl isocyanate was maintained at 60 ° C. 7.357 g was added. Then, after stirring at 60 ° C. for 2 hours, the temperature was raised to 80 ° C. and stirred for 5 hours, and disappearance of the isocyanate group was confirmed by IR spectrum measurement, and 33.97 g of methyl isobutyl ketone was added to obtain the following formula. A methyl isobutyl ketone solution containing 30% of the polymerizable resin (1) having a polymerizable unsaturated group was obtained. As a result of measuring the molecular weight of the obtained polymerizable resin (1) by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 8,400 and the weight average molecular weight was 11,000. The content of the silicone chain in the obtained polymerizable resin (1) was 50% based on the mass of the polymerizable resin (1). The IR spectrum chart of the polymerizable resin (1) is shown in FIG. 1, the ¹ H-NMR spectrum chart (overall view) is shown in FIG. 2, and the ¹ H-NMR spectrum chart (enlarged 25 times). ) in FIG. ^3, 13 C-NMR chart of spectrum (overall view) in FIG. ^4, 13 C-NMR chart of the spectrum (25 times enlarged view) in FIG. 5, FIG. 6 a chart of GPC Respectively.

式中ｎは平均で６５である。ｍは平均で１８である。Ｘは臭素原子または塩素原子である。

In the formula, n is 65 on average. m is 18 on average. X is a bromine atom or a chlorine atom.

Example 2 (same as above)
A nitrogen inlet tube, a stirrer, a thermometer, and a cooling tube are provided. A nitrogen-substituted glass flask is charged with 39.79 g of isopropyl alcohol, 39.79 g of methyl ethyl ketone, 23.05 g of 2-hydroxyethyl methacrylate, and 0.547 g of methoxybenzene in a nitrogen stream. The mixture was stirred at 25 ° C. for 1 hour with stirring at the bottom. Next, 0.451 g of cuprous chloride, 0.113 g of cupric bromide, and 1.581 g of 2,2-bipyridyl were charged and stirred for 30 minutes. After raising the temperature to 60 ° C., 30 g of a compound containing one silicone chain represented by the formula (A-4) was added, and the mixture was stirred for 4 hours while maintaining the temperature in the flask at 60 ° C. Thereafter, the temperature was raised to 75 ° C. and stirred for 24 hours. Under air, 1.167 g of 85% aqueous phosphoric acid solution was added and stirred for 2 hours, and the precipitated solid was separated by filtration. The catalyst was removed with an ion exchange resin, and the ion exchange resin was filtered off to obtain a polymer (p-2).

  Next, 38.73 g of the obtained copolymer (p-2), 31.69 g of methyl isobutyl ketone and a polymerization inhibitor were added to a glass flask equipped with a nitrogen introducing tube, a stirring device, a thermometer, a cooling tube, and a dropping device. P-methoxyphenol 0.0224 g, dibutylhydroxytoluene 0.1682 g as a urethanization catalyst, and 0.0168 g tin octylate as a urethanization catalyst. Stirring was started in an air stream, and 2-acryloyloxyethyl isocyanate was maintained at 60 ° C. 17.32 g was added. Then, after stirring at 60 ° C. for 2 hours, the temperature was raised to 80 ° C. and stirred for 5 hours, and disappearance of the isocyanate group was confirmed by IR spectrum measurement, and 99.00 g of methyl isobutyl ketone was added to add a polymerizable unsaturated group. A methyl isobutyl ketone solution containing 30% of polymerizable resin (2) having As a result of measuring the molecular weight of the obtained polymerizable resin (2) by GPC (polystyrene equivalent molecular weight), it was a number average molecular weight 15,500 and a weight average molecular weight 18,000. The content rate of the silicone chain in the obtained polymerizable resin (2) was 35% based on the mass of the polymerizable resin (2).

Example 3 (same as above)
A nitrogen inlet tube, a stirrer, a thermometer, and a cooling tube are provided. A nitrogen-substituted glass flask is charged with 27.44 g of isopropyl alcohol, 27.44 g of methyl ethyl ketone, 23.05 g of 2-hydroxyethyl methacrylate, and 0.547 g of methoxybenzene in a nitrogen stream. The mixture was stirred at 25 ° C. for 1 hour with stirring at the bottom. Next, 0.451 g of cuprous chloride, 0.113 g of cupric bromide, and 1.581 g of 2,2-bipyridyl were charged and stirred for 30 minutes. After raising the temperature to 60 ° C., 30 g of a compound containing one silicone chain represented by the formula (A-4) was added, and the mixture was stirred for 4 hours while maintaining the temperature in the flask at 60 ° C. Thereafter, the temperature was raised to 75 ° C. and stirred for 21 hours. Under air, 1.167 g of 85% aqueous phosphoric acid solution was added and stirred for 2 hours, and the precipitated solid was separated by filtration. The catalyst was removed with an ion exchange resin, and the ion exchange resin was filtered off to obtain a polymer (p-3).

  Next, 25.61 g of the obtained copolymer (p-3), 20.95 g of methyl isobutyl ketone, and a polymerization inhibitor were added to a glass flask equipped with a nitrogen introducing tube, a stirring device, a thermometer, a cooling tube, and a dropping device. P-methoxyphenol 0.0121 g, dibutylhydroxytoluene 0.0911 g, and urethanization catalyst 0.0091 g of tin octylate as a urethanization catalyst, stirring was started under an air stream, and 2-acryloyloxyethyl isocyanate was maintained at 60 ° C. 4.745 g was added. Then, after stirring at 60 ° C. for 2 hours, the temperature was raised to 80 ° C. and stirred for 5 hours, and then the disappearance of the isocyanate group was confirmed by IR spectrum measurement. A methyl isobutyl ketone solution containing 30% of a polymerizable resin (3) having As a result of measuring the molecular weight of the obtained polymerizable resin (3) by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 8,900 and the weight average molecular weight was 10,500. The content of the silicone chain in the obtained polymerizable resin (3) was 65% based on the mass of the polymerizable resin (3).

Example 4 (same as above)
In a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 134.05 g of n-heptane as a solvent and the above formula (a-1) (where n is 130 on average) are represented. 300 g of a silicone compound having a hydroxyl group at one end and 7.03 g of triethylamine as a catalyst were charged, and the mixture was stirred for 30 minutes while maintaining the temperature in the flask at 40 ° C.

  Next, 12.79 g of 2-bromoisobutyric acid bromide was charged and stirred at 40 ° C. for 3 hours. Thereafter, 335.15 g of n-heptane and 600 g of 0.36% hydrochloric acid were mixed, stirred and allowed to stand, and the hydrochloric acid layer was separated and removed. Thereafter, 600 g of a saturated aqueous sodium hydrogen carbonate solution is mixed and stirred, and then allowed to stand. The saturated aqueous sodium hydrogen carbonate solution layer is separated and removed, and further 600 g of ion-exchanged water is mixed and stirred, and then left to stand. The exchange water layer was separated and removed. Next, 25 g of magnesium sulfate was added as a dehydrating agent, shaken and dehydrated, and then the dehydrating agent was filtered off. Thereafter, the solvent was distilled off under reduced pressure, and the resulting residue was dissolved in 303.25 g of isopropyl ether. 303.25 g of 0.36% hydrochloric acid was mixed and stirred and allowed to stand, and the hydrochloric acid layer was separated and removed. Thereafter, 303.25 g of a 1% sodium hydroxide aqueous solution was mixed and stirred, and then allowed to stand. The 1% sodium hydroxide aqueous solution layer was separated and removed, and further 300.00 g of ion-exchanged water was mixed and stirred. It left still and the ion-exchange water layer was isolate | separated and removed. Thereafter, 300.00 g of ion-exchanged water was mixed again and stirred and allowed to stand, the ion-exchanged water layer was separated and removed, and then 25.00 g of magnesium sulfate was added as a dehydrating agent and shaken to dehydrate. Thereafter, the dehydrating agent was filtered off. Thereafter, by distilling off the solvent under reduced pressure, a compound containing one functional group having a radical generating ability and a silicone chain having a molecular weight of 10,000 used in the present invention represented by the following formula (A-4-1). Obtained.

（式中、ｎは平均１３０である。）

(Where n is an average of 130)

Example 4 (same as above)
A nitrogen-introduced tube, a stirrer, a thermometer, and a cooling tube are provided. A nitrogen-substituted glass flask is charged with 61.67 g of isopropyl alcohol, 61.67 g of methyl ethyl ketone, 22.23 g of 2-hydroxyethyl methacrylate, and 0.7387 g of methoxybenzene. The mixture was stirred at 25 ° C. for 1 hour with stirring at the bottom. Next, 0.6089 g of cuprous chloride, 0.1527 g of cupric bromide, and 2.135 g of 2,2-bipyridyl were charged and stirred for 30 minutes. After raising the temperature to 60 ° C., 60 g of a compound containing one silicone chain represented by the formula (A-4-1) was added, and the mixture was stirred for 4 hours while maintaining the temperature in the flask at 60 ° C. Thereafter, the temperature was raised to 75 ° C. and stirred for 30 hours. Under air, 1.575 g of 85% aqueous phosphoric acid solution was added and stirred for 2 hours, and the precipitated solid was separated by filtration. The catalyst was removed with an ion exchange resin, and the ion exchange resin was filtered off to obtain a polymer (p-4).

  Subsequently, 57.43 g of the obtained copolymer (p-4), 38.28 g of methyl isobutyl ketone, and a polymerization inhibitor were added to a glass flask equipped with a nitrogen introducing tube, a stirring device, a thermometer, a cooling tube, and a dropping device. P-methoxyphenol 0.0294 g, dibutylhydroxytoluene 0.2202 g, and urethanization catalyst 0.0220 g tin octylate as a urethanization catalyst, stirring was started under an air stream, and 2-acryloyloxyethyl isocyanate was maintained at 60 ° C. 15.98 g was added. Then, after stirring at 60 ° C. for 2 hours, the temperature was raised to 80 ° C. and stirred for 6 hours, and disappearance of the isocyanate group was confirmed by IR spectrum measurement, and 133 g of methyl isobutyl ketone was added to have a polymerizable unsaturated group. A methyl isobutyl ketone solution containing 30% of the polymerizable resin (4) was obtained. As a result of measuring the molecular weight of the obtained polymerizable resin (4) by GPC (polystyrene equivalent molecular weight), it was a number average molecular weight 17,500 and a weight average molecular weight 22,800. The content of the silicone chain in the obtained polymerizable resin (4) was 60% based on the mass of the polymerizable resin (4).

Example 5 (same as above)
A nitrogen-introduced glass flask equipped with a nitrogen inlet tube, a stirrer, a thermometer, and a condenser tube was charged with 85.02 g of isopropyl alcohol, 85.02 g of methyl ethyl ketone, 53.36 g of 2-hydroxyethyl methacrylate, and 0.7387 g of methoxybenzene in a nitrogen stream. The mixture was stirred at 25 ° C. for 1 hour with stirring at the bottom. Next, 0.6089 g of cuprous chloride, 0.1527 g of cupric bromide, and 2.135 g of 2,2-bipyridyl were charged and stirred for 30 minutes. After raising the temperature to 60 ° C., 60 g of a compound containing one silicone chain represented by the formula (A-4-1) was added, and the mixture was stirred for 4 hours while maintaining the temperature in the flask at 60 ° C. Thereafter, the temperature was raised to 75 ° C. and stirred for 48 hours. Under air, 1.575 g of 85% aqueous phosphoric acid solution was added and stirred for 2 hours, and the precipitated solid was separated by filtration. The catalyst was removed with an ion exchange resin, and the ion exchange resin was separated by filtration to obtain a polymer (p-5).

  Next, 78.71 g of the obtained copolymer (p-5), 52.45 g of methyl isobutyl ketone, and a polymerization inhibitor were added to a glass flask equipped with a nitrogen introducing tube, a stirring device, a thermometer, a cooling tube, and a dropping device. P-methoxyphenol 0.0467 g, dibutylhydroxytoluene 0.3505 g, and urethanization catalyst 0.0351 g tin octylate as a urethanization catalyst, stirring was started in an air stream, and 2-acryloyloxyethyl isocyanate was maintained at 60 ° C. 38.13 g was added. Then, after stirring at 60 ° C. for 2 hours, the temperature was raised to 80 ° C. and stirred for 8 hours, and then the disappearance of the isocyanate group was confirmed by IR spectrum measurement, and 220 g of methyl isobutyl ketone was added to have a polymerizable unsaturated group. A methyl isobutyl ketone solution containing 30% of the polymerizable resin (5) was obtained. As a result of measuring the molecular weight of the obtained polymerizable resin (5) by GPC (polystyrene equivalent molecular weight), it was a number average molecular weight 27,000 and a weight average molecular weight 35,000. The content of the silicone chain in the obtained polymerizable resin (5) was 37% based on the mass of the polymerizable resin (5).

Comparative Example 1 (Preparation of a polymerizable resin for comparison)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 976.5 g of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Next, 495 g of a polymerizable unsaturated monomer having a silicone group represented by the following formula (A′-1) (hereinafter abbreviated as “monomer (A′-1)”), 2- Polymerization in which 481.5 g of hydroxyethyl methacrylate was dissolved in 154.1 g of methyl isobutyl ketone and polymerization in which 65.4 g of t-butylperoxy-2-ethylhexanoate was dissolved in 247.9 g of methyl isobutyl ketone as a radical polymerization initiator. Two kinds of dropping solutions with the initiator solution are set in separate dropping devices, respectively, and dropping is started simultaneously while maintaining the inside of the flask at 105 ° C., and the monomer solution takes 2 hours and the polymerization initiator solution takes 2 hours and 40 minutes. It was dripped.

（式中、ｎは平均６５である。）

(Where n is an average of 65)

  After completion of dropping the monomer solution, the mixture was stirred at 105 ° C. for 2 hours, and then stirred at 115 ° C. for 2 hours. After completion of the reaction, 1860 parts by mass of methyl isobutyl ketone was distilled off under reduced pressure to obtain a polymer (p′-1) solution.

  Next, 0.600 g of p-methoxyphenol, 4.497 g of dibutylhydroxytoluene as a polymerization inhibitor, and 0.450 g of tin octylate as a urethanization catalyst were added, stirring was started in an air stream, and while maintaining 60 ° C., 2 -520.9g of acryloyloxyethyl isocyanate was dripped over 1 hour. Then, after stirring at 60 ° C. for 2 hours, by heating to 80 ° C. and stirring for 1 hour, after confirming disappearance of the isocyanate group by IR spectrum measurement, 3567 g of methyl ethyl ketone and 1886 of methyl isobutyl ketone were added. A methyl ethyl ketone / methyl isobutyl ketone solution containing 20% by mass of the comparative polymerizable resin (P′-1) having an active energy ray-curable group was obtained. As a result of measuring the molecular weight of the obtained polymerizable resin (P′-1) by GPC (polystyrene equivalent molecular weight), it was a number average molecular weight 3,500 and a weight average molecular weight 12,500. The content rate of the silicone chain in the obtained polymerizable resin (P′-1) was 33% based on the mass of the polymerizable resin (P′-1).

Comparative Example 2
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 1110 g of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Next, a monomer solution in which 750 g of monomer (A′-1) and 360 g of 2-hydroxyethyl methacrylate were dissolved in 118.1 g of methyl isobutyl ketone, and t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator were used. Two kinds of dripping liquids of 74.37 g of ate dissolved in 281.9 g of methyl isobutyl ketone and a polymerization initiator solution were set in separate dripping apparatuses, respectively, and dripping was started at the same time while keeping the inside of the flask at 105 ° C. The solution was added dropwise over 2 hours and the polymerization initiator solution was added over 2 hours and 40 minutes.

  After completion of dropping the monomer solution, the mixture was stirred at 105 ° C. for 2 hours, and then stirred at 115 ° C. for 2 hours. After completion of the reaction, 2005 g of methyl isobutyl ketone was distilled off under reduced pressure to obtain a polymer (p′-2) solution.

  Next, 0.5664 g of p-methoxyphenol, 4.248 g of dibutylhydroxytoluene as a polymerization inhibitor, and 0.4247 g of tin octylate as a urethanization catalyst were charged, and stirring was started under an air stream. -354.35 g of acryloyloxyethyl isocyanate was added dropwise over 1 hour. Then, after stirring at 60 ° C. for 2 hours, the temperature was raised to 80 ° C. and stirring was performed for 2 hours. After confirming disappearance of the isocyanate group by IR spectrum measurement, 3397.5 g of methyl ethyl ketone and 1557.3 g of methyl isobutyl ketone were added. Thus, a methyl ethyl ketone / methyl isobutyl ketone solution containing 20% by mass of a comparative polymerizable resin (P′-2) having an active energy ray-curable group was obtained. As a result of measuring the molecular weight of the obtained polymerizable resin (P′-2) by GPC (polystyrene conversion molecular weight), it was a number average molecular weight of 5,200 and a weight average molecular weight of 16,000. The content rate of the silicone chain in the obtained polymerizable resin (P′-2) was 50% based on the mass of the polymerizable resin (P′-2).

Example 6 (Preparation of active energy ray-curable composition of the present invention)
As an example of the active energy ray-curable composition of the present invention, a composition for an antireflection film located on the outermost surface of a protective film of a polarizing plate was prepared. Specifically, 1.265 parts of methyl isobutyl ketone dispersion containing 20% by mass of hollow silica fine particles (average particle diameter 60 nm), 0.207 parts of pentaerythritol triacrylate, and 2-hydroxy-1-as a photopolymerization initiator. 0.0092 part of {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one (“Irgacure 127” manufactured by Ciba Japan Co., Ltd.) As a solvent, 8.395 parts of methyl isobutyl ketone was mixed and dissolved to obtain a base composition of an antireflection coating composition.

  To 9.87 parts of the base composition of the antireflective coating composition obtained above, a 30% solution of the polymerizable resin (1) is added so that the resin content is 0.005 parts, and mixed uniformly. Then, the active energy ray-curable composition (1) of the present invention [antireflection coating composition (1)] was prepared.

  Using the obtained antireflection coating composition (1), a film having an antireflection layer and a hard coat layer was prepared according to the following procedure.

<Preparation of coating composition for hard coat layer>
30 parts of urethane acrylate (“UV1700B” of Nippon Synthetic Chemical Industry Co., Ltd.), 25 parts of butyl acetate, 1.2 parts by mass of 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator As a solvent, 11.78 parts of toluene, 5.892 parts of 2-propanol, 5.892 parts of ethyl acetate and 5.892 parts of propylene glycol monomethyl ether were mixed and dissolved to obtain a coating composition for a hard coat layer.

<Preparation of a film having a hard coat layer>
The obtained coating composition for a hard coat layer was applied to a bar coater no. 13 was applied to a PET film having a thickness of 188 μm, and then put into a dryer at 70 ° C. for 1 minute to volatilize the solvent, and an ultraviolet curing device (in a nitrogen atmosphere, using a high-pressure mercury lamp, an ultraviolet irradiation amount of 0.5 kJ) / M ² ) to prepare a hard coat film having a hard coat layer having a thickness of 8 μm on one side.

<Preparation of a film having an antireflection layer and a hard coat layer>
An antireflection coating composition (1) was applied to the bar coater No. 1 on the hard coat layer of the hard coat film obtained above. After coating at 2, the solvent is volatilized by putting in a dryer at 50 ° C. for 1 minute 30 seconds, and cured with an ultraviolet curing device (in a nitrogen atmosphere, using a high-pressure mercury lamp, an ultraviolet irradiation amount of ² kJ / m ² ). A film (antireflection film) having an antireflection layer having a thickness of 0.1 μm and a hardcoat layer on a 10 μm hardcoat layer was produced. The cured film surface of the antireflection coating composition of the obtained film was evaluated for the following appearance, slipperiness and scratch resistance. The evaluation results are shown in Table 1.

[Evaluation of appearance]
About the antireflection film obtained above, the unevenness of the cured coating film of the antireflection coating composition was visually observed, and the appearance was evaluated according to the following criteria. The evaluation results are shown in Table 1.
A: No unevenness.
○: Slightly uneven.
Δ: Some unevenness.
X: Overall unevenness.

[Evaluation of slipperiness]
Using a surface property measuring instrument (“HEIDON-14D” manufactured by Shinto Kagaku Co., Ltd.), fix the film obtained above on the sample stage and check the level, then set the probe on the sample and load at 100 g The measurement was performed under the condition of a pulling speed of 0.3 m / min, and the dynamic friction coefficient was obtained and evaluated according to the following criteria.
A: Dynamic friction coefficient is less than 0.15.
○: Dynamic friction coefficient is 0.15 or more and less than 0.20.
(Triangle | delta): A dynamic friction coefficient is 0.20 or more and less than 0.25.
X: Dynamic friction coefficient is 0.25 or more.

[Evaluation of scratch resistance]
The test was performed using # 0000 steel wool and subjected to 10 reciprocating wear at a load of 300 g. The number of scratches on the coating surface after the test was counted, and the scratch resistance was evaluated according to the following criteria. In addition, evaluation of evaluation of scratch resistance was performed before the alkali treatment shown below and after the alkali treatment, respectively.

A: The number of scratches is less than 10.
○: The number of scratches is 10 or more and less than 20.
Δ: The number of scratches is 20 or more and less than 30.
X: The number of scratches is 30 or more.

<Strong alkali (saponification) treatment method for cured coating film>
The antireflection film obtained above was immersed in a 2.0 mol / L potassium hydroxide aqueous solution heated to 70 ° C. for 1 minute, washed with water, dried at 100 ° C. for 3 minutes, and then subjected to a strong alkali treatment. .

Example 7 (same as above)
It replaces with the 30% containing solution of polymeric resin (1) used in Example 6, and is the same as Example 4 except having added 0.005 mass part as 30% containing solution of polymeric resin (2) as a resin part. Were evaluated. The evaluation results are shown in Table 1.

Example 8 (same as above)
It replaces with the 30% containing solution of polymeric resin (1) used in Example 6, and is the same as Example 4 except having added 0.005 mass part as 30% containing solution of polymeric resin (3) as a resin part. Were evaluated. The evaluation results are shown in Table 1.

Example 9 (same as above)
It replaces with the 30% containing solution of polymeric resin (1) used in Example 6, and is the same as Example 4 except having added 0.005 mass part as 30% containing solution of polymeric resin (4) as a resin part. Were evaluated. The evaluation results are shown in Table 1.

Example 10 (same as above)
It replaces with the 30% containing solution of polymeric resin (1) used in Example 6, and is the same as Example 4 except having added 0.005 mass part as 30% containing solution of polymeric resin (5) as a resin part. Were evaluated. The evaluation results are shown in Table 1.

Comparative Example 3 (Preparation of active energy ray curable composition for comparison)
Instead of the 30% containing solution of the polymerizable resin (1) used in Example 4, a 0.005 part by mass of a 20% containing solution of the comparative polymerizable resin (P′-1) was added as a resin component. Were evaluated in the same manner as in Example 2. The evaluation results are shown in Table 1.

Comparative Example 4 (same as above)
Instead of the 30% containing solution of the polymerizable resin (1) used in Example 4, a 0.005 part by mass of a 20% containing solution of the comparative polymerizable resin (P′-2) was added as a resin component. Were evaluated in the same manner as in Example 2. The evaluation results are shown in Table 1.

Claims (10)

At one end of the silicone chain of molecular weight 2,000 to 20,000, a halogen atom having radical generating ability, alkyl tellurium group, dithioester group, a compound having a functional group having a peroxide group or an azo group and (A),
A polymerizable unsaturated monomer (B) having a reactive functional group (b1) which is a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group or a carboxylic anhydride group ;
Into the reaction system,
(1) obtaining a polymer (P) containing a structure derived from the polymerizable unsaturated monomer (B) by generating a radical from the compound (A);
In the reaction system containing the polymer (P) , a reactive functional group (b1) which is a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group or a carboxylic acid anhydride group contained in the polymer (P). A compound (C) having a functional group (c1) and a polymerizable unsaturated group (c2) having reactivity with respect to
A step (2) of reacting a reactive functional group (b1) which is a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group or a carboxylic anhydride group with a reactive functional group (c1) ;
Hints, in resulting polymer resin, the content of the silicone chain, the production method of the polymerizable resin is 30 to 70 wt% based on the weight of the polymerizable resin as a reference.   The functional group having radical generating ability in the compound (A) is an organic group having a halogen atom, an alkyl tellurium group or a dithioester group, and the polymerizable unsaturated monomer (B) is added to the compound (A). 2. The method for producing a polymerizable resin according to claim 1, wherein the polymerization method for polymerizing is a living radical polymerization.   The method for producing a polymerizable resin according to claim 2, wherein the functional group having radical generating ability in the compound (A) is a halogen atom.   The polymerizable property according to claim 2 or 3, wherein the living radical polymerization is an atom transfer type radical polymerization performed in the presence of a polymerization initiator, a transition metal compound, and a compound having a ligand capable of coordinating with the transition metal. Manufacturing method of resin. Method for producing a polymerizable resin of any of claims 1-4 silicone chain is a silicone chain of molecular weight 4,000～12,000 said compound (A). A polymerizable resin having a structure obtained by polymerizing a polymerizable unsaturated monomer, the polymerizable resin having a structure in which one end of the structure contains a silicone chain ;
A polymerizable resin, wherein the molecular weight of the silicone chain is 2,000 to 20,000, and the content of the silicone chain is 30 to 70% by mass based on the mass of the polymerizable resin. The polymerizable resin according to claim 6 , wherein the silicone chain has a molecular weight of 4,000 to 12,000. The polymerizable resin according to claim 6 or 7, wherein the content of the silicone chain is 35 to 65% by mass based on the mass of the polymerizable resin. A polymerizable resin according to any one of claims 6 to 8 , and an active energy ray-curable resin (D) or an active energy ray-curable monomer (E) other than the polymerizable resin. An active energy ray-curable composition.   An article comprising a cured coating film of the active energy ray-curable composition according to claim 9.

Images