KR102095263B1 - Polymerizable resin, active energy ray-curable composition, and article - Google Patents

Abstract

The present invention aims to provide a polymerizable resin containing a fluorine atom and a composition using the polymerizable unsaturated monomer capable of providing excellent scratch resistance even after saponification by adding it as an active energy ray-curable composition. It has a main chain formed by polymerization, and the main chain is a polymerizable resin having a fluorinated alkyl group (x) and a polymerizable unsaturated group (y) having 1 to 6 carbon atoms bonded to the fluorine atom as a side chain. Further, a polymerizable resin having a structure containing a silicone chain having a molecular weight of 2,000 or more at its one end, and an active energy ray-curable composition using the same are provided.

Description

Polymerizable resin, active energy ray-curable composition and article {POLYMERIZABLE RESIN, ACTIVE ENERGY RAY-CURABLE COMPOSITION, AND ARTICLE}

The present invention relates to a fluorine atom-containing polymerizable resin capable of imparting excellent scratch resistance to a cured coating film of the composition by adding it to the active energy ray-curable composition. Further, the present invention relates to an active energy ray-curable composition using the fluorine atom-containing polymerizable resin, and an article having a cured coating film of the composition.

On the surface layer of the polarizing plate serving as the outermost surface of the screen of the liquid crystal display, coatings having anti-glare properties and anti-reflection properties such as AG, AG / LR, and clear / LR are made, but scratch resistance is required because it is the outermost layer. As a method of improving the scratch resistance, a method (hard coating agent) of forming a crosslinked film obtained by using a multifunctional monomer such as a polyfunctional (meth) acrylate on the surface of a substrate is known, and a silicone-based coating material having good scratch resistance A method of adding a fluorine-based leveling agent, a method of adding inorganic compound particles such as silicon dioxide and aluminum oxide, and synthetic resin particles such as carbon or polyurethane resin, polystyrene resin, and acrylic resin have been proposed.

The polarizing plate is obtained by adding an optically transparent protective film having mechanical strength to both sides or one side of the polarizing film. As the protective film, a triacetyl cellulose (TAC) film is usually used.

To adhere the triacetylcellulose (TAC) film to the polarizing film, the surface of the TAC film needs to be saponified with caustic alkali or the like to hydrolyze some or most of the -OCOCH ₃ groups with a hydrophilic group -OH. have. To form a base layer and an outermost layer having anti-glare property or anti-reflection property on the TAC film and to perform saponification, 1. After saponifying the TAC film, a method of forming the above coating layer on one side of the film, 2. There are methods such as saponification after forming the above-mentioned coating layer on one side of the TAC film, but the method of 2. is usually performed from the viewpoint of production efficiency of the polarizing plate.

In the method of 2. above, in order to protect the coating layer from a saponifying agent such as caustic alkali when saponifying, a method of protecting the coating layer with a protective film is known. However, in recent years, in order to improve production efficiency or reduce cost, a coating layer that does not deteriorate the performance of the coating even if exposed to the saponifier is required even if the coating layer is not protected with a protective film. However, in general, since the surface of the cured coating film is significantly deteriorated by saponification treatment, there is a problem that sufficient scratch resistance is not obtained.

As a method for obtaining a protective layer having excellent scratch resistance, for example, a method using an active energy ray-curable composition containing a silicone compound having a radically polymerizable unsaturated group in a molecule is known (see Patent Document 1). However, the cured coating film of the active energy ray-curable composition to which this silicone compound is added is, for use in saponification (strong alkali treatment), such as a TAC film used for a polarizing plate of a liquid crystal display, the activity of the cured coating surface after saponification treatment There was a problem that it was significantly reduced and sufficient scratch resistance was not obtained.

Therefore, there has been a demand for a material capable of imparting excellent scratch resistance to the surface of the cured coating film, which can prevent scratches even after saponification treatment (strong alkali treatment).

Japanese Patent Publication No. 2004-182765

The problem to be solved by the present invention is to provide a polymerizable resin containing a fluorine atom that can provide excellent scratch resistance even after saponification by adding it to an active energy ray-curable composition. In addition, it is to provide an article having an active energy ray-curable composition using the polymerizable resin and a cured coating film of the composition.

As a result of repeated studies to solve the above problems, the present inventors are fluorinated polymerizable resins having a fluorinated alkyl group and a polymerizable unsaturated group, and those having a silicone chain at one end of the resin can be used as a surfactant. The active energy ray-curable composition containing this resin has been found to be capable of imparting excellent scratch resistance to the surface of the cured coating film even after saponification treatment, and the present invention has been completed.

That is, the present invention has a main chain formed by polymerization of a polymerizable unsaturated monomer, and the main chain includes a fluorinated alkyl group (x) and a polymerizable unsaturated group (y) having 1 to 6 carbon atoms bonded by fluorine atoms as side chains. It is a polymerizable resin to have, and the main chain further provides a polymerizable resin characterized by having a structure containing a silicone chain having a molecular weight of 2,000 or more at its one end.

In addition, the present invention provides an active energy ray-curable composition comprising the polymerizable resin and an active energy ray-curable resin (E) or an active energy ray-curable monomer (F) other than the polymerizable resin. will be.

In addition, the present invention provides an article characterized by having a cured coating film of the active energy ray-curable composition.

The polymerizable resin of the present invention is added to an active energy ray-curable composition to impart activity to the surface of the cured coating film, thereby obtaining excellent scratch resistance. In addition, since this scratch resistance can also be exhibited in a cured coating film subjected to saponification (strong alkali treatment), it is also useful as a material for a hard coating material of a TAC film used in a polarizing plate of a liquid crystal display.

1 is a chart of the IR spectrum of the polymerizable resin (1) obtained in Example 1. FIG.
Fig. 2 is a chart of the ¹³ C-NMR spectrum of the polymerizable resin (1) obtained in Example 1.
3 is a chart of GPC of the polymerizable resin (1) obtained in Example 1.
4 is a chart of the IR spectrum of the polymerizable resin (2) obtained in Example 2.
Fig. 5 is a chart of the ¹ H-NMR spectrum of the polymerizable resin (2) obtained in Example 2 (overall view).
Fig. 6 is a chart of the ¹ H-NMR spectrum of the polymerizable resin (2) obtained in Example 2 (25x magnification).
Fig. 7 is a chart of the ¹³ C-NMR spectrum of the polymerizable resin (2) obtained in Example 2 (overall view).
Fig. 8 is a chart of the ¹³ C-NMR spectrum of the polymerizable resin (2) obtained in Example 2 (25x magnification).
9 is a chart of the ¹⁹ F-NMR spectrum of the polymerizable resin (2) obtained in Example 2 (overall view).
10 is a chart of GPC of the polymerizable resin (2) obtained in Example 2.

The polymerizable resin of the present invention has a main chain formed by polymerization of a polymerizable unsaturated monomer, and the main chain is a fluorinated alkyl group (x) having 1 to 6 carbon atoms bonded to a fluorine atom as a side chain and a polymerizable unsaturated group (y ), And the main chain has a structure containing a silicone chain having a molecular weight of 2,000 or more at its one end. Although it is possible to have a single number of silicon chains or a plurality of silicon chains at this one end, in the present invention, having a single number (1) of silicon chains at one end is in terms of wear resistance and surface segregation of fluorine atoms. desirable.

As the fluorinated alkyl group (x), a carbon atom number of 4 to 6 is preferable because of a good balance of surface segregation property, water repellency, and environmental load reduction, and more preferably 6 carbon atoms.

Moreover, the equivalent of the polymerizable unsaturated group (y) in the polymerizable resin of the present invention is preferably in the range of 200 to 3,500 g / eq., And in the range of 250 to 2,000 g / eq. More preferably, the range of 300 to 1,500 g / eq. Is more preferable, and the range of 400 to 1,000 g / eq. Is particularly preferable.

The molecular weight of the silicone chain is 2,000 or more, and by having a silicone chain having such molecular weight, the activity of the silicone chain can be favorably expressed, and as a result, excellent friction resistance is provided by reducing friction on the surface of the coating film. can do. The molecular weight of the silicone chain is preferably 2,000 to 20,000 molecular weight, more preferably 5,000 to 10,000.

In the present invention, various types of polymerizable resins are obtained by changing the timing of polymerizing the raw materials. For example, a polymerizable unsaturated monomer (B) having a fluorinated alkyl group having 1 to 6 carbon atoms bonded to a fluorine atom described later and a polymerizable unsaturated monomer (C) having a reactive functional group (c1) are simultaneously added to the reaction system and reacted. In the case, it becomes a so-called random copolymer phase polymerizable resin. Moreover, when a polymerizable unsaturated monomer (B) and a polymerizable unsaturated monomer (C) are made to react separately, it becomes a polymerizable resin of a so-called block copolymer phase. Particularly, among the polymerizable resins of the present invention, a block copolymer is preferred because it is a polymerizable resin capable of imparting excellent scratch resistance even to a very thin film having a film thickness of about 0.1 µm by adding it to an active energy ray-curable composition.

Among the polymerizable resins of the present invention, the random polymer-like polymerizable resin has, for example, a number of carbon atoms in which a compound (A) having a functional group having a radical generating ability and a fluorine atom are bonded to one end of a silicone chain having a molecular weight of 2,000 or more. A polymerizable unsaturated monomer (B) having a 6-membered fluorinated alkyl group and a polymerizable unsaturated monomer (C) having a reactive functional group (c1) and a functional group (d1) and a polymerizable unsaturated group (d2) having reactivity with the functional group (c1) ). Specifically, the compound (D) is added to the copolymer (P) obtained by copolymerizing the polymerizable unsaturated monomer (B) and the polymerizable unsaturated monomer (C) by generating radicals from the compound (A). Obtained by reaction.

Moreover, among the polymerizable resins of the present invention, the block polymer-like polymerizable resin is, for example, fluorinated with 1 to 6 carbon atoms having a main chain formed by polymerization of a polymerizable unsaturated monomer and a fluorine atom as a side chain of the main chain. Has a first polymer segment (α) having an alkyl group (x), a main chain formed by polymerization of a polymerizable unsaturated monomer, and a second polymer segment (β) having a polymerizable unsaturated group (y) as a side chain of the main chain, Further, a polymerizable resin having a structure containing a silicone chain having a molecular weight of 2,000 or more at one end can be exemplified.

Such a block polymer phase polymerizable resin can be preferably obtained, for example, according to the following production method.

Method 1: Polymerizable unsaturated monomer having a compound (A) having a functional group having a radical generating ability and a fluorinated alkyl group (x) having 1 to 6 carbon atoms bonded to a fluorine atom at one end of a silicone chain having a molecular weight of 2,000 or more. Step (1) to obtain a polymer segment (p) containing a structure derived from the polymerizable unsaturated monomer (B) by introducing a) into the reaction system and generating radicals from the compound (A),

By introducing a polymerizable unsaturated monomer (C) having a reactive functional group (c1) into a reaction system containing the polymer segment (p) and generating radicals from the polymer segment (p), the polymer segment (p) and Step (2) of obtaining a polymer (Q1) comprising a polymer segment (q) containing a structure derived from a polymerizable unsaturated monomer (C),

In the reaction system containing the polymer (Q1), a compound (D) having a functional group (d1) and a polymerizable unsaturated group (d2) reactive with respect to the reactive functional group (c1) possessed by the polymer (Q1) are introduced, and the reactive functional group A manufacturing method comprising the step (3) of reacting a functional group (d1) having reactivity with (c1).

Method 2: A compound (A) having a functional group having a radical generating ability and a polymerizable unsaturated monomer (C1) having a reactive functional group (c1) are introduced into the reaction system at one end of a silicone chain having a molecular weight of 2,000 or more, and the compound (A Step (1-1) of obtaining a polymer segment (q) containing a structure derived from a polymerizable unsaturated monomer (C) by generating radicals from),

The polymer segment (q) and the polymerizable unsaturated monomer (B) are introduced into the reaction system containing the polymer segment (q) by introducing a polymerizable unsaturated monomer (B) and generating radicals from the polymer segment (q). Step (2-1) of obtaining a polymer (Q2) containing a polymer segment containing a derived structure,

In the reaction system containing the polymer (Q2), a compound (D) having a functional group (d1) and a polymerizable unsaturated group (d2) reactive with respect to the reactive functional group (c1) possessed by the polymer (Q2) are introduced, and the reactive functional group A manufacturing method comprising the step (3-1) of reacting a functional group (d1) having reactivity with (c1).

Examples of the functional group having a radical generating ability of the compound (A) include, for example, 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 The organic group etc. which have are mentioned. Here, in the case of copolymerizing the polymerizable unsaturated monomer (B) and the polymerizable unsaturated monomer (C) with the compound (A) by living radical polymerization, an organic group having a halogen atom as a functional group having the radical generating ability , An organic group having an alkyl tellurium group, an organic group having a dithioester group can be used, and in particular, the use of an organic group having a halogen atom from ease of synthesis, ease of polymerization control, and diversity of polymerizable unsaturated monomers applicable desirable.

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

In order to introduce the organic group having the halogen atom into one end of a compound containing a silicone chain having a molecular weight of 2,000 or more in the main chain, for example, a functional group capable of forming a bond by reaction to one end of a silicone chain having a molecular weight of 2,000 or more And a method of reacting a compound (a1) having a functional group capable of forming a bond by reacting with the functional group (a1) and a compound (a2) having an organic group having a halogen atom. Specifically, examples of the functional group at one end of the compound (a1) include a hydroxyl group, an isocyanate group, an epoxy group, a carboxy group, a carboxylic acid halide group, and a carboxylic acid anhydride group. As a specific example of the said compound (a1) which has these functional groups at one terminal, the compound represented by following formula (a1-1) can be illustrated preferably.

(In the formula, 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 a single bond. n is 20 to 200)

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

In addition, the following are mentioned as a functional group which the said compound (a2) has and the said compound (a1) can react and form a bond with the functional group which has at one end.

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

When the functional group of the compound (a1) is an isocyanate group, a functional group other than the organic group having a halogen atom of the compound (a2) is preferably a hydroxyl group. In addition, when the functional group of the compound (a1) is an epoxy group, the functional group other than the organic group having a halogen atom of the compound (a2) is preferably a carboxy group.

When the functional group of the compound (a1) is a carboxy group, an epoxy group is preferable as the functional group other than the organic group having a halogen atom of the compound (a2). Moreover, when the functional group which the said compound (a1) has is a carboxylic acid anhydride group, the functional group other than the organic group which has the halogen atom which the said compound (a2) has is a hydroxyl group.

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

As a specific method of introducing the organic group having the halogen atom to one end of the silicon chain, in the case where 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, dehydration esterification By reacting under conditions, a compound (A) 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 or more in the main chain 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 (a2) in a solvent such as toluene or tetrahydrofuran. Compound (A) having a functional group having the ability to initiate polymerization can be obtained by reacting the same. Moreover, in this reaction, a basic catalyst can be used as needed.

In addition, when the functional group at one end of the compound (a1) has 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, in the presence of a catalyst such as tin octylate, ( By reacting a1) and (a2), a compound having a functional group having a polymerization initiation ability can be obtained.

In addition, when the functional group at one end of the compound (a1) has 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, a basic catalyst such as triphenylphosphine or tertiary amine By reacting (a1) and (a2) in the presence of, a compound having a functional group having a polymerization initiation ability can be obtained.

As a specific example of the compound (A) containing a silicone chain having a molecular weight of 2,000 or more 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, for example, a compound represented by the following formula Can be lifted.

Next, the polymerizable unsaturated monomer (B) used in the present invention will be described. The polymerizable unsaturated monomer (B) has a fluorinated alkyl group having 1 to 6 carbon atoms directly bonded to the fluorine atom. In the present invention, the fluorinated alkyl group includes one having at least one carbon-carbon double bond in the skeleton of the fluorinated alkyl group. As a polymerizable unsaturated group which the said monomer (B) has, a carbon-carbon unsaturated double bond which has radical polymerization property is preferable, and a (meth) acryloyl group, vinyl group, maleimide group etc. are mentioned. Among these, the (meth) acryloyl group is preferable because it is easy to obtain raw materials, ease of controlling compatibility with each compounding component in the active energy ray-curable composition described later, or polymerization reactivity.

In addition, in this invention, "(meth) acrylate" means one or both of methacrylate and acrylate, and "(meth) acryloyl group" means one of a methacryloyl group and an acryloyl group, or Both sides, and "(meth) acrylic acid" means one or both of methacrylic acid and acrylic acid.

As a polymerizable unsaturated monomer (B) which has the said fluorinated alkyl group, what is represented by the following general formula (1) is mentioned, for example.

(In the formula (1), R represents a hydrogen atom or a methyl group, L represents any one of the following formulas (L-1) to (L-10), and Rf represents the following formula (Rf-1) -Represents any one group of (Rf-7))

N in said formula (L-1), (L-3), (L-4), (L-5), (L-6) and (L-7) represents the integer of 1-8. M in said formula (L-8), (L-9) and (L-10) represents the integer of 1-8, and n represents the integer of 0-8. Rf "in the formulas (L-6) and (L-7) represents any one of the following formulas (Rf-1) to (Rf-7).

In formulas (Rf-1) and (Rf-2), n is an integer from 1 to 6, n in (Rf-3) is an integer from 2 to 6, and n in (Rf-4) is from 4 to 6 It is an integer. M in said formula (Rf-5) is an integer of 1-5, n is an integer of 0-4, and the sum of m and n is 4-5. M in the formula (Rf-6) is an integer from 0 to 4, n is an integer from 1 to 4, p is an integer from 0 to 4, and the sum of m, n and p is 4 to 5.

Moreover, the following monomer (B-1)-(B-11) etc. are mentioned as a specific example of the said monomer (B). Moreover, these monomers (B) can be used only in one type or in combination of two or more types.

(N in formula is an integer of 0-5, Preferably it is an integer of 3-5)

Next, the polymerizable unsaturated monomer (C) having a reactive functional group (c1) will be described. Examples of the functional group (c1) of the monomer (C) include a hydroxyl group, an isocyanate group, an epoxy group, a carboxy group, a carboxylic acid halide group, and a carboxylic acid anhydride group. In addition, the polymerizable unsaturated group of the monomer (C) is preferably a carbon-carbon unsaturated double bond having radical polymerization property, and more specifically, includes a vinyl group, (meth) acryloyl group, maleimide group, and the like. (Meth) acryloyl group is more preferable from the viewpoint of easy polymerization.

As a specific example of the said monomer (C), 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) acrylic Rate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2- Unsaturated monomers having hydroxyl groups such as hydroxyethyl phthalate and lactone-modified (meth) acrylates having hydroxyl groups at the terminals; Isocyanates such as 2- (meth) acryloyloxyethyl isocyanate, 2- (2- (meth) acryloyloxyethoxy) ethyl isocyanate, and 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate Group-containing unsaturated monomers; Epoxy group-containing unsaturated monomers such as glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether; Carboxyl group-containing unsaturated monomers such as (meth) acrylic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylphthalic acid, maleic acid, and itaconic acid; And carboxylic acid anhydrides having unsaturated double bonds such as maleic anhydride and itaconic anhydride. These monomers (C) may be used alone or in combination of two or more.

In addition, when preparing the copolymer (P) or polymer (Q1) or polymer (Q2), which is an intermediate of the polymerizable resin of the present invention, in addition to the compound (A), monomer (B), monomer (C), these You may use other polymerizable unsaturated monomers which can be copolymerized with. Examples of such other polymerizable unsaturated monomers are methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and n -Pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylic (Meth) such as acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and (meth) acrylate with polyoxyalkylene chain Acrylic esters; Aromatic vinyls such as styrene, α-methylstyrene, p-methylstyrene, and p-methoxystyrene; Maleimides such as maleimide, methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, and cyclohexyl maleimide And the like.

Here, the mass ratio [(B) / (C)] of the compound (B) and the monomer (C) is preferably in the range of 10/90 to 90/10, because a cured product having high scratch resistance is obtained, The range of 20/80 to 80/20 is more preferable.

As a method for producing the copolymer (P) or the polymer (Q1) or the polymer (Q2) used in the present invention, the compound (A) is used as a radical polymerization initiator, and the monomer (B) or the monomer (C) is used. And a method for polymerizing living radicals. In general, in living radical polymerization, a polymer having a very narrow molecular weight distribution can be obtained by reacting a monomer with an active polymerization terminal protected by an atom or an atomic group reversibly generating a radical and reacting with a monomer. Examples of such living radical polymerization include atomic transfer radical polymerization (ATRP), reversible addition-cleaving radical polymerization (RAFT), radical polymerization via nitroxide (NMP), radical polymerization using organic tellurium (TERP), etc. Can be mentioned. When the copolymer (P) is produced by this living radical polymerization, a copolymer having a very narrow molecular weight distribution is obtained, which is preferable. There is no particular limitation as to which method to use, but the ATRP is preferred from the viewpoint of ease of control and the like. ATRP is polymerized using an organic halide or a sulfonyl halide compound or the like as an initiator, a transition metal compound, and a metal complex composed of a ligand.

The transition metal compound used in the ATRP is represented by M ^{n +} X ⁿ . The 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 +} . In addition, X is a halogen atom, an alkoxy group having 1 to 6 carbon atoms, (SO ₄ ) _1/2 , (PO ₄ ) _1/3 , (HPO ₄ ) _1/2 , (H ₂ PO ₄ ), tree Plate, hexafluorophosphate, methanesulfonate, arylsulfonate (preferably benzenesulfonate or toluenesulfonate), SeR ₁ , CN and R ₂ COO. Here, R ¹ represents an aryl, linear or branched alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), and R 2 is 1 to 5 times with hydrogen atom or halogen (property) It represents a linear or branched alkyl group having 1 to 6 carbon atoms (preferably a methyl group) which may be substituted with fluorine or chlorine 1 to 3 times. In addition, n represents the formal charge of a metal phase and is an integer of 0-7.

As the transition metal complex, transition metal complexes of groups 7, 8, 9, 10, and 11 are preferable, and complexes of 0-valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel are more preferable.

As the compound having a ligand capable of coordinating bonds with the transition metal, the compound having a ligand containing at least one nitrogen atom, oxygen atom, phosphorus atom, or sulfur atom capable of coordinating via a transition metal and a σ bond, transition metal And compounds having a ligand containing two or more carbon atoms capable of coordinating via and π bonds, and compounds having a ligand capable of coordinating with a transition metal through a μ bond or an η bond.

As specific examples of the compound having the above ligand, for example, when the central metal is copper, 2,2'-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyl And complexes with ligands such as polyamines such as diethylenetriamine and hexamethyltris (2-aminoethyl) amine. In addition, as the divalent ruthenium complex, dichlorotris (triphenylphosphine) ruthenium, dichlorotris (tributylphosphine) ruthenium, dichloro (cyclooctadiene) ruthenium, dichlorobenzene ruthenium, dichlorop-cementium ruthenium, dichloro (norbornadi N) ruthenium, cis-dichlorobis (2,2'-bipyridine) ruthenium, dichlorotris (1,10-phenanthroline) ruthenium, carbonylchlorohydridotris (triphenylphosphine) ruthenium, and the like. . Moreover, as a bivalent iron complex, a bistriphenylphosphine complex, a triazacyclononane complex, etc. are mentioned.

In addition, in the preparation of the copolymer (P), it is preferable to use a solvent. Examples of the solvent to be used include, for example, 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-based solvents such as dichloromethane and dichloroethane; Aromatic solvents such as toluene and xylene; Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Alcohol solvents such as methanol, ethanol, and isopropanol; And aprotic polar solvents such as dimethylformamide and dimethylsulfoxide. Moreover, the said solvent can be used individually or in combination of 2 or more types.

Moreover, the polymerization temperature at the time of manufacture of the said copolymer (P), a polymer (Q1), or a polymer (Q2) is preferable from room temperature to 100 degreeC.

When the copolymerization part consisting of the monomer (B) and the monomer (C) in the copolymer (P) is in the form of a block, the monomer (B) or the monomer (C) alone is the compound (A). ), After a living radical polymerization in the presence of a transition metal compound, a compound having a ligand capable of coordinating bonds with the transition metal, and a solvent, a monomer different from the living radical polymerized monomer is added, and further obtained by living radical polymerization. .

In order to obtain the polymerizable resin of the present invention, some or all of the reactive groups of the copolymer (P) or polymer (Q1) or polymer (Q2) prepared in the above method are reactive with the functional group (c1). A polymerizable unsaturated group (y) is introduced into the copolymer (P) using a compound (D) having a functional group (d1) and a polymerizable unsaturated group (d2). As a functional group (d1) which the said compound (D) has, a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group, a carboxylic acid anhydride group etc. are mentioned, for example. When the reactive functional group (c1) of the monomer (C) is a hydroxyl group, examples of the functional group (d1) include an isocyanate group, a carboxyl group, a carboxylic acid halide group, a carboxylic acid anhydride group, and an epoxy group, and the reactive functional group (c1) is an isocyanate group. In the case, a hydroxyl group is mentioned as a functional group (d1), and when the reactive functional group (c1) is an epoxy group, a carboxyl group or a hydroxyl group is mentioned as a functional group (d1), and when the reactive functional group (c1) is a carboxy group, a functional group An epoxy group and a hydroxyl group are mentioned as (d1). These may be used as a combination of a plurality of functional groups. Moreover, among these combinations, the combination of the reactive functional group (c1) is a hydroxyl group, the functional group (d1) is an isocyanate group, the reactive functional group (c1) is an epoxy group, and the functional group (d1) is preferably a combination of a carboxy group.

Moreover, the polymerizable unsaturated group (y) possessed by the monomer (D) is preferably a carbon-carbon unsaturated double bond having radical polymerization property, and more specifically, a vinyl group, (meth) acryloyl group, maleimide And the like. Among these, when the fluorinated polymerizable polymer of the present invention is added to the active energy ray-curable composition, the curability with the active energy ray-curable resin (E), the active energy ray-curable monomer (F), and the like described later is high, so (meta ) Acryloyl group is preferred, and acryloyl group is more preferred.

As specific examples of the compound (D), for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy Butyl (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) acryloyloxy Unsaturated monomers having hydroxyl groups such as ethyl-2-hydroxyethyl phthalate and lactone-modified (meth) acrylates having hydroxyl groups at the terminals; Isocyanates such as 2- (meth) acryloyloxyethyl isocyanate, 2- (2- (meth) acryloyloxyethoxy) ethyl isocyanate, and 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate Unsaturated monomer having a group; Unsaturated monomers having an epoxy group such as glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether; Carboxyl group-containing unsaturated monomers such as (meth) acrylic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylphthalic acid, maleic acid, and itaconic acid; And carboxylic acid anhydrides having unsaturated double bonds such as maleic anhydride and itaconic anhydride. Further, as having a plurality of polymerizable unsaturated groups, 2-hydroxy-3-acryloyloxypropyl methacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and the like can also be used. These compounds (D) can be used alone or in combination of two or more.

2-hydroxyethyl acrylate, 2-hydroxypropylacrylate, 3-hydroxypropylacrylate, 2-hydroxy Butyl acrylate, 4-hydroxybutyl acrylate, 1,4-cyclohexanedimethanol monoacrylate, N- (2-hydroxyethyl) acrylamide, 2-acryloyloxyethyl isocyanate, 1,1-bis (Acryloyloxymethyl) ethyl isocyanate 4-hydroxybutyl acrylate glycidyl ether and acrylic acid are preferred.

The method of reacting the compound (D) with the copolymer (P), the polymer (Q1), or the polymer (Q2) may be performed under the condition that the polymerizable unsaturated group of the compound (D) or the like does not polymerize, for example. For example, it is preferable to react by adjusting the temperature conditions in the range of 30 to 120 ° C. It is preferable to carry out this reaction 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 (c1) is a hydroxyl group and the functional group (d1) is an isocyanate group, p-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methyl as a polymerization inhibitor Phenol or the like is used, and dibutyltin dilaurate, dibutyltin diacetate, tin octylate, zinc octylate, etc. are used as the urethanization reaction catalyst, and reaction is carried out at a reaction temperature of 40 to 120 ° C, particularly 60 to 90 ° C. Preferred is the method. In addition, when the reactive functional group (c1) is an epoxy group, and the functional group (d1) is a carboxy group, or when the reactive functional group (c1) is a carboxy group, and the functional group (d1) is an epoxy group, p is a polymerization inhibitor. -Methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methylphenol, etc. are used, and tertiary amines such as triethylamine and quaternary tetramethylammonium chloride are used as catalysts for the esterification reaction. It is preferable to react at a reaction temperature of 80 to 130 ° C, particularly 100 to 120 ° C, using tertiary phosphines such as ammoniums and triphenylphosphine, quaternary phosphoniums such as tetrabutylphosphonium chloride, and the like. Do.

The organic solvent used in the reaction is preferably ketones, esters, amides, sulfoxides, ethers, hydrocarbons, and specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate , Butyl acetate, 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 boiling point and compatibility.

Among the polymerizable resins of the present invention obtained as described above, since the polymerizable resin in the form of a random copolymer can prevent gelation at the time of manufacture and has excellent antifouling properties, its number average molecular weight (Mn) is 3,000 to 100,000. It is preferable that it is a range, and it is more preferable that it is a range of 10,000-50,000. Moreover, it is preferable that weight average molecular weight (Mw) is the range of 3,000-150,000, and it is more preferable that it is the range of 10,000-75,000. Further, the dispersion degree (Mw / Mn) of the polymerizable resin of the present invention is preferably 1.0 to 1.5, more preferably 1.0 to 1.3, and most preferably 1.0 to 1.2.

Among the polymerizable resins of the present invention obtained as described above, the polymerizable resin in the form of a block copolymer can prevent gelation at the time of production and has excellent antifouling properties, so its number average molecular weight (Mn) ranges from 3,000 to 100,000. It is preferably, it is more preferably in the range of 6,000 to 50,000, and more preferably 8,000 to 25,000. Further, the weight average molecular weight (Mw) is preferably in the range of 3,000 to 150,000, more preferably in the range of 8,000 to 65,000, and more preferably 10,000 to 35,000. Further, the dispersion degree (Mw / Mn) of the polymerizable resin of the present invention is preferably 1.0 to 1.5, more preferably 1.0 to 1.4, and most preferably 1.0 to 1.3.

Here, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are the values converted into polystyrene based on gel permeation chromatography (hereinafter abbreviated as "GPC") measurement. In addition, the measurement conditions of GPC are as follows.

[GPC measurement conditions]

Measuring device: `` HLC-8220 GPC '' manufactured by Tosoh Corporation,

Column: Guard column made by Tosoh Corporation (HHR-H) (6.0 mmID × 4 cm) + Tosoh Corporation manufactured by “TSK-GEL GMHHR-N” (7.8 mm ID × 30 cm) + manufactured by Tosoh Corporation "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) + manufactured by Tosoh Corporation "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) + manufactured by Tosoh Corporation "TSK-GEL GMHHR- N '' (7.8 mm ID x 30 cm)

Detector: ELSD ("ELSD2000" manufactured by All Tech Japan Co., Ltd.)

Data processing: `` GPC-8020 Model II data analysis version 4.30 '' manufactured by Tosoh Corporation

Measurement conditions: column temperature 40 ° C

Development solvent tetrahydrofuran (THF)

Flow rate 1.0 ml / min

Sample: A 1.0% by mass tetrahydrofuran solution was filtered through a micro filter in terms of resin solid content (5 μl).

Standard sample: In accordance with the measurement manual of "GPC-8020 model II data analysis version 4.30", the following monodisperse polystyrene having a known molecular weight was used.

(Monodisperse 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

Further, the equivalent of the polymerizable unsaturated group in the polymerizable resin of the present invention is excellent in the scratch resistance of the cured coating film, so the range of 200 to 3,500 g / eq. Is preferable, and the range of 250 to 2,500 g / eq. Is more preferable. The range of 250 to 2,000 g / eq. Is more preferable, the range of 300 to 2,000 g / eq. Is more preferable, the range of 300 to 1,500 g / eq. Is more preferable, and 400 to 1,500 g / eq. The range of. Is more preferable, and the range of 400-1,000 g / eq. Is especially preferable.

In addition, when the polymerizable resin of the present invention is a block copolymer phase polymerizable resin, the ratio of the first polymer segment (α) and the second polymer segment (β) in the polymerizable resin is the mass ratio [(α) / (β )], Which is excellent in compatibility with other resins in the range of 10/90 to 90/10, and is also preferable because the silicone chain contributing to activity and scratch resistance can be favorably segregated on the surface of the coating film. The range which becomes -80/20 is more preferable, and the range which becomes 30 / 70-70 / 30 is more preferable.

The polymerizable resin of the present invention can be used as the subject of the active energy ray-curable composition itself, but because it has very excellent surface modification performance, by using it as a surface modifier (surfactant) added to the active energy ray-curable composition , It is possible to impart excellent scratch resistance 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, but as its main component, active energy ray-curable resins other than the polymerizable resin of the invention (E) or active energy ray-curable monomers (F) It contains. In addition, in the active energy ray-curable composition of the present invention, the active energy ray-curable resin (E) and the active energy ray-curable monomer (F) may be used alone, or may be used in combination. The polymerizable resin of the present invention is preferably used as a fluorine-based surfactant in the active energy ray-curable composition.

The active energy ray-curable resin (E) is urethane (meth) acrylate resin, unsaturated polyester resin, epoxy (meth) acrylate resin, polyester (meth) acrylate resin, acrylic (meth) acrylate resin, and Malay A resin having a mid group may be mentioned, but in the present invention, urethane (meth) acrylate resin is particularly preferred from the viewpoint of transparency and low shrinkage.

The urethane (meth) acrylate resin used herein includes resins having urethane bonds and (meth) acryloyl groups obtained by reacting an aliphatic polyisocyanate compound or an aromatic polyisocyanate compound with a (meth) acrylate compound having a hydroxyl group. You can.

Examples of the aliphatic polyisocyanate compound include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, and 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 xylylene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, cyclohexyl diisocyanate, etc. Can and again , There may be mentioned an aromatic polyester as the isocyanate compound, such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylyl diisocyanate, 1,5-naphthalene diisocyanate, Tolly dindi diisocyanate, 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, and 4-hydroxy Hydroxybutyl (meth) acrylate, 1,5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, hydroxypivalate neopentyl Mono (meth) acrylates of dihydric alcohols such as glycol mono (meth) acrylate; Trimethylolpropanedi (meth) acrylate, ethoxylated trimethylolpropane (meth) acrylate, propoxylated trimethylolpropanedi (meth) acrylate, glycerin di (meth) acrylate, bis (2- (meth) acrylic Mono or di (meth) acrylates of trivalent alcohols such as royloxyethyl) hydroxyethylisocyanurate, or mono and di () having hydroxyl groups modified by a part of their alcoholic hydroxyl groups with ε-caprolactone Meth) acrylate; Compounds having a monofunctional hydroxyl group and a trifunctional or higher (meth) acryloyl group such as pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate , Or, a polyfunctional (meth) acrylate having a hydroxyl group modified with the compound of ε-caprolactone; (Meth) acrylate having an oxyalkylene chain such as dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate compound; (Meth) acrylate compounds having a block structure of oxyalkylene chains such as polyethylene glycol-polypropylene glycol mono (meth) acrylate and polyoxybutylene-polyoxypropylene mono (meth) acrylate; And (meth) acrylate compounds having an oxyalkylene chain having a random structure such as poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate, poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate, and the like. You can.

The reaction of the above-described aliphatic polyisocyanate compound or aromatic polyisocyanate compound with an acrylate compound having a hydroxyl group can be carried out according to a conventional method in the presence of a urethanization catalyst. Examples of the urethanization catalyst that can be used herein include amines such as pyridine, pyrrole, triethylamine, diethylamine, and dibutylamine, phosphine such as triphenylphosphine and triethylphosphine, and dibutyltin. And organotin compounds such as dilaurate, octyltin trilaurate, octyltin 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 also have good sensitivity to active energy rays and excellent curability. desirable.

Next, the unsaturated polyester resin is a curable resin obtained by polycondensation of α, β-unsaturated dibasic acid or its acid anhydride, aromatic saturated dibasic acid or its acid anhydride, and glycols, and α, β-unsaturated dibasic salt Maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid, and esters thereof are mentioned as the base acid or its acid anhydride. Examples of the aromatic saturated dibasic acid or its acid anhydride include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, halogenated anhydride phthalic acid and esters thereof. Examples of the aliphatic or alicyclic saturated dibasic acid include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, hexahydro anhydride phthalic acid, 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, tetra And ethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, 2,2-di- (4-hydroxypropoxydiphenyl) propane, and the like. , Other oxides, such as ethylene oxide and propylene oxide, can also be used.

Next, as the epoxy (meth) acrylate resin, (meth) acrylic acid is reacted with epoxy groups of epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, and cresol novolak type epoxy resin. And those obtained by prescribing.

Further, as the resin having a maleimide group, a bifunctional maleimide urethane compound obtained by urethanizing N-hydroxyethyl maleimide and isophorone diisocyanate, a bifunctional maleimide obtained by esterifying maleimide acetic acid and polytetramethylene glycol Ester compounds, tetrafunctional maleimide ester compounds obtained by esterifying maleimidecaproic acid and tetraethylene oxide adducts of pentaerythritol, polyfunctional maleimide ester compounds obtained by esterifying maleimide acetic acid and polyhydric alcohol compounds, and the like. have. These active energy ray-curable resins (E) may be used alone or in combination of two or more.

Examples of the active energy ray-curable monomer (F) include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and a number average molecular weight of 150 to Polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate in the range of 1000, number average molecular weight 150 to 1000 Polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, hydroxypivalic acid ester neopentyl glycol di (meth) acrylate, bisphenol Adi (meth) acrylate, trimethylolpropane tri (meth) acrylate, pen Taerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropanedi (meth) acrylate, dipentaerythritolpenta (meth) acrylic Rate, dicyclopentenyl (meth) acrylate, methyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylic Late, octyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, etc. Aliphatic alkyl (meth) acrylate, glycerol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, Allyl (meta) Acrylate, 2-butoxyethyl (meth) acrylate, 2- (diethylamino) ethyl (meth) acrylate, 2- (dimethylamino) ethyl (meth) acrylate, γ- (meth) acryloxypropyl tree Methoxysilane, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypoly Propylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydipropylene glycol (meth) acrylate, phenoxypolypropylene glycol (meth) acrylate, polybutadiene (meth) acrylate, polyethylene glycol-poly Propylene glycol (meth) acrylate, polyethylene glycol-polybutylene glycol (meth) acrylate, polystyrylethyl (meth) acrylate, benzyl (meth) acrylate, cyclo Sil (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, methoxylated cyclodecatriene (meth) acrylate, phenyl (meth) ) Acrylate; Maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-stearyl Maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, 2-maleimideethyl-ethyl carbonate, 2-maleimideethyl-propyl carbonate, N-ethyl- (2-maleimideethyl) carbamate, N, And maleimides such as N-hexamethylene bismaleimide, polypropylene glycol-bis (3-maleimidepropyl) ether, bis (2-maleimideethyl) carbonate, and 1,4-dimaleimide cyclohexane. have.

Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and pentaerythritol tetra (meth) acrylic Trifunctional or higher polyfunctional (meth) acrylates such as rate are preferred. These active energy ray-curable monomers (E) may be used alone or in combination of two or more.

In the active energy ray-curable composition of the present invention, the amount of the polymerizable resin used in the present invention is 0.001 to 20 based on 100 parts by mass of the total amount of the active energy ray-curable resin (E) and the active energy ray-curable monomer (F). The range of parts by mass is preferable, the range of 0.01 to 15 parts by mass is more preferable, the range of 0.1 to 15 parts by mass is more preferable, the range of 0.1 to 10 parts by mass is more preferable, and the range of 0.5 to 15 parts by mass is particularly preferable. . When the use amount of the polymerizable resin of the present invention is within this range, leveling properties, water-repellent and oil-repellent properties and anti-fouling properties can be sufficient, and hardness and transparency after curing of the composition can also be sufficient. Moreover, since the ratio of the polymerizable resin of the present invention to 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, in the case of a thick film, the polymerizable resin of the present invention By setting the addition amount of low, and in the case of a thin film, by setting the addition amount of the polymerizable resin of the present invention high, the polymerizable resin of the present invention can be present on the surface of the coating film tightly, and high scratch resistance can be expected. desirable.

The polymerizable resin or active energy ray-curable composition of the present invention can be formed into a cured coating film by applying an active energy ray after being applied to a substrate. The active energy ray refers to ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When irradiating with ultraviolet rays as an active energy ray to form a cured coating film, it is preferable to add a photopolymerization initiator (G) to the polymerizable resin or an active energy ray-curable composition, and to improve the curability. In addition, if necessary, a photosensitizer may be further added to improve curability. On the other hand, in the case of using ionizing radiation such as electron beam, α-ray, β-ray, or γ-ray, it is cured promptly without using a photopolymerization initiator or photosensitizer, so it is particularly necessary to add a photopolymerization initiator (G) or photosensitizer none.

Examples of the photopolymerization initiator (G) include an intramolecular cleavage type photopolymerization initiator and a hydrogen drawing type photopolymerization initiator. As an intramolecular cleavage type photopolymerization initiator, for example, 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 Acetophenone compounds such as -2-morpholino (4-thiomethylphenyl) propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone; Benzoins such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; Acylphosphine oxide compounds such as 2,4,6-trimethylbenzoindiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; And benzyl, methylphenylglycoxyester, and the like.

On the other hand, as a hydrogen drawing type photopolymerization initiator, for example, benzophenone, o-benzoylbenzoate methyl-4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl -Benzophene such as diphenyl sulfide, acrylated benzophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3'-dimethyl-4-methoxybenzophenone Non-based compounds; Thioxanthone compounds such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and 2,4-dichlorothioxanthone; Aminobenzophenone-based compounds such as Mihiler-ketone and 4,4'-diethylaminobenzophenone; And 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, and camphorquinone.

Among the photopolymerization initiators (G), 1-hydroxycyclohexylphenyl ketone, from the viewpoint of excellent compatibility between the active energy ray-curable resin (E) and the active energy ray-curable monomer (F) in the active energy ray-curable composition, And benzophenone is preferred, particularly 1-hydroxycyclohexylphenylketone. These photoinitiators (G) can be used alone or in combination of two or more.

Further, examples of the photosensitizer include amines such as aliphatic amines and aromatic amines, ureas such as o-tolylthiourea, sodium diethyldithiophosphate, and s-benzylisothiuronium-p-toluenesulfo And sulfur compounds such as nate.

The amount of the photopolymerization initiator and photosensitizer used is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and more preferably 0.3 to 7 parts by mass, relative to 100 parts by mass of the nonvolatile component in the active energy ray-curable composition. Addition is more preferred.

In addition, the active energy ray-curable composition of the present invention may adjust the viscosity or refractive index, or adjust the color tone of the coating film or other coating properties, within a range not impairing the effect of the present invention depending on the purpose of use, properties, and the like. For the purpose of adjusting the properties of the coating or coating, various compounding materials, for example, various organic solvents, acrylic resins, phenol resins, polyester resins, polystyrene resins, urethane resins, urea resins, melamine resins, alkyd resins, epoxy resins, poly Various organic or inorganic particles such as amide resin, polycarbonate resin, petroleum resin, fluorine resin, various resins, PTFE (polytetrafluoroethylene), polyethylene, polypropylene, carbon, titanium oxide, alumina, copper, and silica particles , Polymerization initiator, polymerization inhibitor, antistatic agent, antifoaming agent, viscosity modifier, light stabilizer, weathering stabilizer, heat stabilizer, antioxidant, rust inhibitor, Slip agents, waxes, matt adjusters, release agents, compatibilizers, conductive adjusters, pigments, dyes, dispersants, dispersion stabilizers, silicone-based, hydrocarbon-based surfactants, and the like can be used in combination.

Of the above-mentioned respective blending components, the organic solvent is useful for appropriately adjusting the solution viscosity of the active energy ray-curable composition of the present invention, and in particular, it is easy to adjust the film thickness for thin film coating. As an organic solvent which can be used here, For example, 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; And ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. These solvents may be used alone or in combination of two or more.

The amount of the organic solvent used here varies depending on the application and the intended film thickness and viscosity, but is preferably in the range of 0.5 to 50 times the mass based on the total mass of the cured component.

As the active energy ray for curing the active energy ray-curable composition of the present invention, as described above, it is ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays, but as specific energy sources or curing devices, for example, Sterilization lamp, fluorescent lamp for ultraviolet light, carbon arc, xenon lamp, high pressure mercury lamp for radiation, medium or high pressure mercury lamp, ultra high pressure mercury lamp, electrodeless lamp, metal halide lamp, ultraviolet light using natural light, etc., or scanning type, curtain electron beam accelerator And electron beams.

Among these, ultraviolet rays are particularly preferable, and ultraviolet rays are preferably irradiated under an inert gas atmosphere such as nitrogen gas in order to avoid curing inhibition by oxygen or the like. Moreover, you may use heat as an energy source as needed, and after hardening with ultraviolet rays, you may heat-process.

The coating method of the active energy ray-curable composition of the present invention varies depending on the application, but, for example, gravure coater, roll coater, comma coater, knife coater, air knife coater, curtain coater, kiss coater, shower coater, foil coater, And a coating method using a spin coater, dipping, screen printing, spraying, applicator, bar coater, or the like, or a molding method using various molds.

Since the cured coating film of the polymerizable resin of the present invention has scratch resistance, it is possible to impart scratch resistance to the surface of the article by coating and curing the surface of the article. Moreover, since the leveling property can also be provided to the porcelain by adding the polymerizable resin of this invention to a porcelain, the active energy ray hardener composition of this invention has high leveling property. Moreover, since the cured coating film of the polymerizable resin of this invention is excellent in activity, it also has the effect of favorable touch operation, such as a touch panel. Moreover, the cured coating film of the polymerizable resin of this invention is also excellent in antifouling property.

The cured coating film of the polymerizable resin or the active energy ray-curable composition of the present invention has excellent scratch resistance and the like, so that it is possible to impart scratch resistance and the like to the surface of the article by applying and curing the surface of the article.

Examples of the article that can prevent scratches by using the polymerizable resin or the active energy ray-curable composition of the present invention include films for polarizing plates of liquid crystal displays (LCDs) such as TAC films; Various display screens such as plasma displays (PDPs) and organic EL displays; Touch panel; A casing or screen of an electronic terminal such as a mobile phone; A transparent protective film for a color filter for a liquid crystal display (hereinafter referred to as "CF"); Organic insulating film for liquid crystal TFT array; Inkjet ink for electronic circuit formation; Optical recording media such as CD, DVD, and Blu-ray Disc; Transfer film for insert mold (IMD, IMF); Rubber rollers for OA machines such as copy machines and printers; A glass surface of the reading portion of the OA device such as a copy machine or a scanner; Optical lenses such as cameras, video cameras, and glasses; Windshields of watches, such as wrist watches, glass surfaces; Windows of various vehicles such as automobiles and railway vehicles; Cover glass or film for solar cells; Various building materials such as decorative plates; Window glass in houses; And woodworking materials such as furniture, artificial / synthetic leather, various plastic molded products such as casings for home appliances, and FRP baths. 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, scratch resistance can be imparted to the article surface.

Further, examples of the porcelain that can impart abrasion resistance by adding the polymerizable resin of the present invention include a hard coating material of an LCD polarizing plate film such as a TAC film, an anti-glare (AG: anti-glare) coating material, or an anti-reflective (LR) coating material; Hard coating materials for various display screens such as plasma displays (PDPs) and organic EL displays; Hard coating material for touch panels; Color resist, printing ink, inkjet ink or paint for forming each pixel of RGB used in CF; CF black resist for black matrix, printing ink, inkjet ink or paint; Resin compositions for pixel partition walls such as plasma displays (PDPs) and organic EL displays; Paints or hard coating materials for electronic terminal casings such as mobile phones; A hard coating material for a screen of a mobile phone; Transparent protective coating for protecting the CF surface; Coatings for organic insulating films of liquid crystal TFT arrays; Inkjet ink for electronic circuit formation; Hard coating materials for optical recording media such as CD, DVD, and Blu-ray discs; Hard coating material for transfer films for insert molds (IMD, IMF); Coating materials for rubber rollers for OA devices such as copy machines and printers; A coating material for glass of the reading portion of an OA device such as a copy machine or a scanner; Coating materials for optical lenses such as cameras, video cameras, and glasses; Windshields of watches, such as wrist watches, coating materials for glass; Coating materials for windows of various vehicles such as automobiles and railway vehicles; Paint for an antireflection film of a solar cell cover glass or film; Printing ink or paints for various building materials such as decorative plates; Coatings for window glass in houses; Woodworking paints such as furniture; Artificial and synthetic leather coatings; Paints or coating materials for various plastic molded products such as casings for home appliances; And paints or coating materials for FRP baths.

Moreover, as an article which can provide abrasion resistance (scratch resistance) using the polymerizable resin of this invention or an active energy ray curable composition, the prism sheet or diffusion sheet etc. which are backlight members of LCD are mentioned. In addition, by adding the polymerizable resin of the present invention to a coating material for a prism sheet or a diffusion sheet, the leveling property of the coating material is improved, and scratch resistance (scratch resistance) and antifouling property can be imparted to the coating film of the coating material.

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

Moreover, as other uses which can use the polymerizable resin or active energy ray curable composition of this invention, the optical fiber cladding material, a waveguide, the sealing material of a liquid crystal panel, various optical sealing materials, optical adhesive etc. are mentioned.

Particularly, among the use of the coating material for a protective film of a polarizing plate for LCD, when the active energy ray-curable composition of the present invention is used as an anti-glare coating material, inorganic or organic fine particles such as silica fine particles, acrylic resin fine particles, and polystyrene resin fine particles can be used. It is preferable because it is excellent in anti-glare property by blending at a ratio of 0.1 to 0.5 times the total mass of the curing component in the active energy ray-curable composition.

In addition, when the polymerizable resin or active energy ray-curable composition of the present invention is used for an anti-glare coating material for a protective film of a polarizing plate for LCD, after contacting the mold having a surface shape of irregularities before curing the coating material, the opposite side to the mold It can also be applied to a transfer method that hardens by irradiating with an active energy ray from and embossing the surface of the coating layer to impart anti-glare properties.

[Example]

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. Moreover, the IR spectrum, ¹³ C-NMR spectrum, and GPC measurement conditions of the obtained polymerizable resin are as follows.

[IR spectrum measurement conditions]

Apparatus: `` NICOLET380 '' manufactured by Thermoelectron Corporation

Measurement method: KBr method

[ ¹³ C-NMR spectrum measurement conditions]

Apparatus: "JNM-ECA500" manufactured by Nippon Denshi Co., Ltd.

Solvent: DMSO-d ₆

[GPC measurement conditions]

Measuring device: `` HLC-8220 GPC '' manufactured by Tosoh Corporation,

Column: Guard column made by Tosoh Corporation (HHR-H) (6.0 mmID × 4 cm) + Tosoh Corporation manufactured by “TSK-GEL GMHHR-N” (7.8 mm ID × 30 cm) + manufactured by Tosoh Corporation "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) + manufactured by Tosoh Corporation "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) + manufactured by Tosoh Corporation "TSK-GEL GMHHR- N '' (7.8 mm ID x 30 cm)

Detector: ELSD ("ELSD2000" manufactured by All Tech Japan Co., Ltd.)

Data processing: `` GPC-8020 Model II data analysis version 4.30 '' manufactured by Tosoh Corporation

Measurement conditions: column temperature 40 ° C

Development solvent tetrahydrofuran (THF)

Flow rate 1.0 ml / min

Sample: A 1.0% by mass tetrahydrofuran solution was filtered through a micro filter in terms of resin solid content (5 μl).

Standard sample: In accordance with the measurement manual of "GPC-8020 model II data analysis version 4.30", the following monodisperse polystyrene having a known molecular weight was used.

(Monodisperse 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)

In a glass flask equipped with a stirring device, a thermometer, and a cooling tube, 26.4 g of isopropyl ether as a solvent, 25.2 g of a silicone compound having a hydroxyl group at one end represented by the following formula (a-1), and triethyl as a catalyst 0.66 g of amine was added and stirred for 30 minutes while maintaining the temperature in the flask at 5 ° C.

(In the formula, n is 65 on average)

Subsequently, 1.50 g of 2-bromoisobutyric acid bromide was added, stirred for 3 hours, heated to 40 ° C., and stirred for 8 hours. After the completion of the reaction, 80 g of ion-exchanged water was mixed and stirred, then left standing, and washing by a method of separating and removing the aqueous layer was repeated three times. Subsequently, 8 g of magnesium sulfate was added as a dehydrating agent and allowed to stand for 1 day to complete dehydration, followed by filtration of the dehydrating agent. Then, the solvent was distilled off under reduced pressure to obtain a compound containing one functional group having a radical generating ability and a silicone chain having a molecular weight of 2,000 or more, used in the present invention represented by the following formula (A-4).

(In the formula, n is 65 on average)

Subsequently, a nitrogen introduction tube, a stirring device, a thermometer, a cooling tube, and a dropping device were provided, and a nitrogen-substituted glass flask was added with 14.2 g of isopropyl alcohol, 14.2 g of methyl ethyl ketone, and 6.0 g of tridecafluorohexyl ethyl methacrylate. , 4.3 g of 2-hydroxyethyl methacrylate was added, and the mixture was heated to 35 ° C. while stirring under a stream of nitrogen and stirred for 2 hours. Subsequently, 0.335 g of cuprous chloride and 0.937 g of 2,2-bipyridyl were added, heated to 60 ° C., and stirred for 1 hour. Next, 15.04 g of the compound (A-4) was dissolved in 5.0 g of isopropyl alcohol and 5.0 g of methyl ethyl ketone, added, stirred for 4 hours while maintaining the temperature in the flask at 60 ° C., and then heated to 80 ° C. And stirred for 7 hours. The reaction mixture was dissolved in methanol and reprecipitated and purified with water / methanol to obtain a random copolymer (P-1).

Subsequently, 50.0 g of the obtained copolymer (P-1), 50.0 g of methyl ethyl ketone, and p-methoxyphenol as a polymerization inhibitor were placed in a glass flask equipped with a nitrogen introduction tube, a stirring device, a thermometer, a cooling tube, and a dropping device. 0.1 g, 0.03 g of octylic acid tin was added as a urethanization catalyst, stirring was started under an air stream, and 15.6 g of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour while maintaining at 60 ° C. After completion of the dropwise addition, the mixture was stirred at 60 ° C for 1 hour, then heated to 80 ° C and stirred for 10 hours to confirm the disappearance of the isocyanate group by IR spectrum measurement, and by adding 15.6 g of methyl ethyl ketone to have an active energy ray-curable group. The polymerizable resin (1) of the present invention 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 11,000, the weight average molecular weight 12,000, and the radically polymerizable unsaturated group equivalent were 904 g / eq. Moreover, the chart figure of the IR spectrum of the polymerizable resin (1) is shown in FIG. 1, the chart figure of the ¹³ C-NMR spectrum is shown in FIG. 2, and the chart figure of the GPC is shown in FIG.

Example 2 (status)

Equipped with a nitrogen introduction tube, a stirring device, a thermometer, and a cooling tube, in a nitrogen-substituted glass flask, isopropyl alcohol 30.70 g, methyl ethyl ketone 30.70 g, tridecafluorohexyl ethyl methacrylate 10.93 g, methoxybenzene 0.5470 It stirred at 25 degreeC for 1 hour, stirring g under nitrogen stream. Subsequently, 0.4510 g of cuprous chloride, 0.1130 g of copper bromide, and 1.581 g of 2,2-bipyridyl were added and stirred for 30 minutes. After raising the temperature to 60 ° C, 30 g of the compound (A-4) was added and stirred for 4 hours while maintaining the temperature in the flask at 60 ° C. Thereafter, 6.585 g of 2-hydroxyethyl methacrylate was added and stirred for 1 hour. Then, it heated up to 75 degreeC and stirred for 31 hours. 1.167 g of an aqueous 85% phosphoric acid solution was added under air, stirred for 2 hours, and the precipitated solid was separated. The catalyst was removed with an ion exchange resin, and the ion exchange resin was separated to obtain a block copolymer (Q1-1).

Subsequently, in a glass flask equipped with a nitrogen introduction tube, a stirring device, a thermometer, a cooling tube, and a dropping device, 32.54 g of the obtained copolymer (Q1-1), 36.70 g of methyl isobutyl ketone, p-methoxyphenol as a polymerization inhibitor 0.0149 parts by mass, 0.1116 g of dibutylhydroxytoluene, and 0.0111 g of tin octylate as a urethanization catalyst were added, stirring was started under an air stream, and 4.67 g of 2-acryloyloxyethyl isocyanate was maintained while maintaining 60 ° C. More. Thereafter, the mixture was stirred at 60 ° C for 1 hour, then heated to 80 ° C and stirred for 4 hours, confirming the disappearance of the isocyanate group by IR spectrum measurement, and adding 50.46 g of methyl isobutyl ketone to have an active energy ray-curable group. A methyl isobutyl ketone solution containing 30% by mass of the polymerizable resin (2) of the present invention was obtained. As a result of measuring the molecular weight of the obtained polymerizable resin (2) by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 10,500 and the weight average molecular weight was 12,000. In addition, a chart diagram of the IR spectrum of the polymerizable resin 2 is shown in Fig. 4, a chart diagram of the ¹ H-NMR spectrum (overall view), and a chart diagram of the ¹ H-NMR spectrum (magnification of 25 times) ) In Fig. 6, chart in ¹³ C-NMR spectrum (overall view), chart in ¹³ C-NMR spectrum (25x magnification) in Fig. 8, chart in ¹⁹ F-NMR spectrum Fig. 9 is a diagram (overall view) and a chart diagram of the GPC is shown in Fig. 10, respectively.

Example 3 (status)

Equipped with a nitrogen introduction tube, a stirring device, a thermometer, and a cooling tube, in a nitrogen-substituted glass flask, isopropyl alcohol 54.88 g, methyl ethyl ketone 54.88 g, 2-hydroxyethyl methacrylate 13.17 g, methoxybenzene 1.094 g The mixture was stirred at 25 ° C for 1 hour while stirring under a nitrogen stream. Subsequently, 0.9017 g of cuprous chloride, 0.2261 g of copper bromide, and 3.162 g of 2,2-bipyridyl were added and stirred for 30 minutes. After raising the temperature to 60 ° C, 60 g of the compound (A-4) was added and stirred for 3 hours while maintaining the temperature in the flask at 60 ° C. Thereafter, 21.87 g of tridecafluorohexyl ethyl methacrylate was added and stirred for 1 hour. Then, it heated up to 75 degreeC and stirred for 37.5 hours. 2.334 g of 85% aqueous phosphoric acid solution was added under air, stirred for 2 hours, and the precipitated solid was separated. The catalyst was removed with an ion exchange resin, and the ion exchange resin was separated to obtain a block copolymer (Q2-1).

Subsequently, 68.15 g of the obtained copolymer (Q2-1), 51.47 g of methyl isobutyl ketone, 51.47 g of methyl isobutyl ketone, and p-methoxyphenol as a polymerization inhibitor were provided in a glass flask equipped with a nitrogen introduction tube, a stirring device, a thermometer, a cooling tube, and a dropping device. 0.0311 parts by mass, 0.2335 g of dibutylhydroxytoluene, and 0.0234 g of tin octylate as a urethanization catalyst were added, stirring was started under air flow, and while maintaining 60 ° C., 9.69 g of 2-acryloyloxyethyl isocyanate was added. More. Thereafter, the mixture was stirred at 60 ° C for 1 hour, then heated to 80 ° C and stirred for 4 hours, confirming the disappearance of the isocyanate group by IR spectrum measurement, and adding 86.00 g of methyl isobutyl ketone to have an active energy ray-curable group. A methyl isobutyl ketone solution containing 30% by mass of the polymerizable resin (3) of the present invention was obtained. 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 10,100 and the weight average molecular weight was 14,000.

Example 4 (status)

Equipped with a nitrogen introduction tube, a stirring device, a thermometer, and a cooling tube, in a nitrogen-substituted glass flask, isopropyl alcohol 32.20 g, methyl ethyl ketone 32.20 g, tridecafluorohexyl ethyl methacrylate 12.97 g, methoxybenzene 0.6480 It stirred at 25 degreeC for 1 hour, stirring g under nitrogen stream. Subsequently, 0.5350 g of cuprous chloride, 0.1370 g of copper bromide, and 1.874 g of 2,2-bipyridyl were added and stirred for 30 minutes. After raising the temperature to 60 ° C, 30.06 g of the compound (A-4) was added and stirred for 4.5 hours while maintaining the temperature in the flask at 60 ° C. Then, 3.900 g of 2-hydroxyethyl methacrylate was added and stirred for 1 hour. Then, it heated up to 75 degreeC and stirred for 31 hours. 1.370 g of 36% hydrochloric acid was added under air, stirred for 2 hours, and the precipitated solid was separated. The catalyst was removed with an ion exchange resin, and the ion exchange resin was separated to obtain a block copolymer (Q1-2).

Subsequently, in a glass flask equipped with a nitrogen introduction tube, a stirring device, a thermometer, a cooling tube, and a dropping device, 31.61 g of the obtained copolymer (Q1-2), 19.16 g of methyl isobutyl ketone, p-methoxyphenol as a polymerization inhibitor 0.0137 parts by mass, 0.1025 g of dibutylhydroxytoluene and 0.0103 g of tin octylate as a urethanization catalyst were added, stirring was started under air flow, and while maintaining 60 ° C, 2.56 g of 2-acryloyloxyethyl isocyanate was added. More. Thereafter, the mixture was stirred at 60 ° C for 2 hours, then heated to 80 ° C and stirred for 3 hours, confirming the disappearance of the isocyanate group by IR spectrum measurement, and adding 56.44 g of methyl isobutyl ketone to have an active energy ray-curable group. A methyl isobutyl ketone solution containing 30% by mass of the polymerizable resin (4) of the present invention was obtained. As a result of measuring the molecular weight of the obtained polymerizable resin (4) by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 8,700 and the weight average molecular weight was 10,000.

Example 5 (status)

Equipped with a nitrogen introduction tube, a stirring device, a thermometer, and a cooling tube, in a nitrogen-substituted glass flask, isopropyl alcohol 30.28 g, methyl ethyl ketone 30.28 g, tridecafluorohexyl ethyl methacrylate 10.37 g, methoxybenzene 0.6480 It stirred at 25 degreeC for 1 hour, stirring g under nitrogen stream. Subsequently, 0.5350 g of cuprous chloride, 0.1370 g of copper bromide, and 1.874 g of 2,2-bipyridyl were added and stirred for 30 minutes. After raising the temperature to 60 ° C, 30.00 g of the compound (A-4) was added and stirred for 4 hours while maintaining the temperature in the flask at 60 ° C. Then, 9.37 g of 2-hydroxyethyl methacrylate was added and stirred for 1 hour. Then, it heated up to 75 degreeC and stirred for 30 hours. 1.383 g of 85% phosphoric acid was added under air, stirred for 2 hours, and the precipitated solid was separated. The catalyst was removed with an ion exchange resin, and the ion exchange resin was separated to obtain a block copolymer (Q1-3).

Subsequently, in a glass flask equipped with a nitrogen introduction tube, a stirring device, a thermometer, a cooling tube, and a dropping device, 33.93 g of the obtained copolymer (Q1-3), 22.64 g of methyl isobutyl ketone, p-methoxyphenol as a polymerization inhibitor 0.0162 parts by mass, 0.1215 g of dibutylhydroxytoluene, and 0.0122 g of tin octylate as a urethanization catalyst were added, stirring was started under air flow, and while maintaining 60 ° C, 6.576 g of 2-acryloyloxyethyl isocyanate was added. More. Thereafter, the mixture was stirred at 60 ° C for 2 hours, then heated to 80 ° C and stirred for 4 hours, confirming the disappearance of the isocyanate group by IR spectrum measurement, and adding 71.85 g of methyl isobutyl ketone to have an active energy ray-curable group. A methyl isobutyl ketone solution containing 30% by mass of the polymerizable resin (5) of the present invention was obtained. As a result of measuring the molecular weight of the obtained polymerizable resin (5) by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 10,500 and the weight average molecular weight was 13,400.

Example 6 (status)

In a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a dropping device, 134.05 g of n-heptane as a solvent and a silicone compound having a hydroxyl group at one end of the formula (a-1) (where n is The average of 130) was added to 300 g and 7.03 g of triethylamine as a catalyst, and the mixture was stirred for 30 minutes while maintaining the temperature in the flask at 40 ° C.

Subsequently, 12.79 g of 2-bromoisobutyric acid bromide was added and stirred at 40 ° C for 3 hours. Thereafter, 335.15 g of n-heptane and 600.00 g of 0.36% hydrochloric acid were mixed, stirred, and left standing, and the hydrochloric acid layer was separated and removed. Thereafter, 600 g of saturated aqueous sodium hydrogen carbonate solution was mixed, stirred, and then left standing. The saturated aqueous sodium hydrogen carbonate solution layer was separated and removed, and 600 g of ion-exchanged water was mixed and stirred to stand, and the ion exchange water layer was separated. Removed. Subsequently, 25 g of magnesium sulfate was added as a dehydrating agent, the mixture was shaken to dehydrate, and then the dehydrating agent was separated. Then, the solvent was distilled off under reduced pressure, and the obtained residue was dissolved in 303.25 g of isopropyl ether. 303.25 g of 0.36% hydrochloric acid was mixed, stirred and left standing, 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 left to stand, and the 1% sodium hydroxide aqueous solution layer was separated and removed, and 300 g of ion-exchanged water was mixed and stirred and left to stand, and the ion exchange water layer was separated. Order to remove it. Subsequently, 300 g of ion-exchanged water was mixed, stirred and left standing, and the ion-exchanged water layer was separated and removed. Then, 25 g of magnesium sulfate was added as a dehydrating agent, followed by shaking and dehydration, followed by filtration of the dehydrating agent. Thereafter, the solvent (A-4-1) used in the present invention represented by the following formula was obtained by distilling off the solvent under reduced pressure.

(In the formula, n is an average of 130)

Subsequently, a nitrogen-introducing tube, a stirring device, a thermometer, and a cooling tube were provided, and in a nitrogen-substituted glass flask, 56.08 g of isopropyl alcohol, 56.08 g of methyl ethyl ketone, 14.77 g of tridecafluorohexyl ethyl methacrylate, methoxy 0.7387 g of benzene was stirred at 25 ° C. for 1 hour while stirring under a stream of nitrogen. Subsequently, 0.6089 g of cuprous chloride, 0.1527 g of copper bromide, and 2.135 g of 2,2-bipyridyl were added and stirred for 30 minutes. After heating to 60 ° C, 60.00 g of the compound (A-4-1) was added, and the flask was stirred for 9 hours while maintaining the temperature at 60 ° C. Thereafter, 8.893 g of 2-hydroxyethyl methacrylate was added and stirred for 1 hour. Then, it heated up to 75 degreeC and stirred for 48 hours. 1.576 g of an aqueous 85% phosphoric acid solution was added under air, stirred for 2 hours, and the precipitated solid was separated. The catalyst was removed with an ion exchange resin, and the ion exchange resin was separated to obtain a block copolymer (Q1-4).

Subsequently, 58.56 g of the obtained copolymer (Q1-4), 39.04 g of methyl isobutyl ketone, and p-methoxyphenol as a polymerization inhibitor were placed in a glass flask equipped with a nitrogen introduction tube, a stirring device, a thermometer, a cooling tube, and a dropping device. 0.0260 parts by mass, 0.1949 g of dibutylhydroxytoluene and 0.0195 g of tin octylate as urethane catalyst were added, stirring was started under air flow, and while maintaining 60 ° C, 6.407 g of 2-acryloyloxyethyl isocyanate was added. More. Thereafter, the mixture was stirred at 60 ° C for 1 hour, then heated to 80 ° C and stirred for 5 hours, confirming the disappearance of the isocyanate group by IR spectrum measurement, and adding 112.54 g of methyl isobutyl ketone to have an active energy ray-curable group. A methyl isobutyl ketone solution containing 30% by mass of the polymerizable resin (6) of the present invention was obtained. As a result of measuring the molecular weight of the obtained polymerizable resin (6) by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 16,000 and the weight average molecular weight was 19,000.

Example 7 (status)

Equipped with a nitrogen introduction tube, a stirring device, a thermometer, and a cooling tube, into a nitrogen-substituted glass flask, isopropyl alcohol 69.37 g, methyl ethyl ketone 69.37 g, tridecafluorohexyl ethyl methacrylate 32.49 g, methoxybenzene 0.7387 It stirred at 25 degreeC for 1 hour, stirring g under nitrogen stream. Subsequently, 0.6089 g of cuprous chloride, 0.1527 g of copper bromide, and 2.135 g of 2,2-bipyridyl were added and stirred for 30 minutes. After the temperature was raised to 60 ° C, 60.00 g of the compound (A-4-1) was added, followed by stirring for 12 hours while maintaining the temperature in the flask at 60 ° C. Then, 31.27 g of 2-hydroxyethyl methacrylate was added and stirred for 1 hour. Then, it heated up to 75 degreeC and stirred for 81 hours. 1.576 g of an aqueous 85% phosphoric acid solution was added under air and stirred for 2 hours to separate the precipitated solids. The catalyst was removed with an ion exchange resin, and the ion exchange resin was separated to obtain a block copolymer (Q1-5).

Subsequently, in a glass flask equipped with a nitrogen introduction tube, a stirring device, a thermometer, a cooling tube, and a dropping device, 93.17 g of the obtained copolymer (Q1-5), 62.10 g of methyl isobutyl ketone, p-methoxyphenol as a polymerization inhibitor 0.0470 parts by mass, 0.3522 g of dibutylhydroxytoluene and 0.0352 g of tin octylate as a urethanization catalyst were added, stirring was started under air flow, and while maintaining 60 ° C, 24.23 g of 2-acryloyloxyethyl isocyanate was added. More. After that, the mixture was stirred at 60 ° C for 1 hour, then heated to 80 ° C and stirred for 5.5 hours, confirming the disappearance of the isocyanate group by IR spectrum measurement, and adding 211.8 g of methyl isobutyl ketone to have an active energy ray-curable group. A methyl isobutyl ketone solution containing 30% by mass of the polymerizable resin (7) of the present invention was obtained. As a result of measuring the molecular weight of the obtained polymerizable resin (7) by GPC (polystyrene equivalent molecular weight), it was number average molecular weight 24,400 and weight average molecular weight 31,300.

Comparative Example 1 (Preparation of surfactant for comparative control)

To a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a dropping device, 77.7 g of methyl isobutyl ketone was added as a solvent, and the temperature was raised to 105 ° C while stirring under a stream of nitrogen. Subsequently, 23 g of tridecafluorohexyl ethyl methacrylate, 10 g of a polymerizable unsaturated monomer having a silicone group represented by the following formula (hereinafter abbreviated as monomer (A'-1)), and glycidyl methacrylate 44.7 Two types of dropwise addition of a monomer solution in which g is dissolved in 53.4 g of methyl isobutyl ketone and a polymerization initiator solution in which 3.9 g of t-butylperoxy-2-ethylhexanoate is dissolved in 50.2 g of methyl isobutyl ketone as a radical polymerization initiator The liquids were each set in a separate dropping apparatus, and the flask was dripped over 3 hours while maintaining the inside at 105 ° C.

(In the formula, n is 65 on average)

After completion of the dropwise addition, after stirring at 105 ° C for 1.5 hours, a polymerization initiator solution in which 1.17 g of t-butylperoxy-2-ethylhexanoate was dissolved in 11.7 parts by mass of methyl isobutyl ketone was added dropwise over 45 minutes. , And stirred at 105 ° C for 8 hours. After completion of the reaction, 164 parts by mass of methyl isobutyl ketone was distilled off under reduced pressure to obtain a polymer (P-2) solution.

Subsequently, 0.1 g of p-methoxyphenol was added as a polymerization inhibitor, while maintaining the temperature in the flask at 80 ° C, 22.3 g of acrylic acid and 0.5 g of triphenylphosphine as a ring-opening reaction catalyst were added, and for 40 hours under air flow. It stirred and it confirmed that the acid value of solid content fell to 1 [mgKOH / g] or less by titration with 0.1 [mol / l] potassium hydroxide solution. Thereafter, 116.7 g of methyl isobutyl ketone was added to obtain a methyl isobutyl ketone solution containing 40% of a polymerizable resin (1 ') having an active energy ray-curable group. When the molecular weight of the obtained polymerizable resin (1 ') was measured by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 4,700 and the weight average molecular weight was 8,600, and the radical polymerizable unsaturated group equivalent was 323 g / eq.

Comparative Example 2 (statue)

A perfluoropolyether compound having a hydroxyl group at the sock end represented by the following formula (X-1) in a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a dropping device (hereinafter referred to as "Compound (X-1)") ), 20 g of diisopropyl ether as a solvent, 0.02 g of p-methoxyphenol as a polymerization inhibitor, and 3.1 g of triethylamine as a neutralizing agent, stirring was started under an air flow, and the flask was charged with 10 g. While maintaining at ° C, 2.7 g of acrylic acid chloride was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred for 1 hour at 10 ° C, heated, stirred for 1 hour at 30 ° C, heated to 50 ° C, and reacted by stirring for 10 hours, and disappearance of acrylic acid chloride was confirmed by gas chromatography measurement. Subsequently, after adding 40 g of diisopropyl ether as a solvent, washing with 80 g of ion-exchanged water was mixed, stirred, and then allowed to stand, followed by washing by separating and removing the aqueous layer. Subsequently, 0.02 parts by mass of p-methoxyphenol was added as a polymerization inhibitor, and 8 parts by mass of magnesium sulfate was added as a dehydrating agent to stand for 1 day, followed by complete dehydration, followed by filtration of the dehydrating agent.

(Wherein, X is a perfluoromethylene group and a perfluoroethylene group, per molecule, perfluoromethylene group on average 7, perfluoroethylene group on average 8 present, the number of fluorine atoms on average 46 In addition, the number average molecular weight by GPC is 1,500)

Next, the solvent represented by the following structural formula (B-1) was obtained by distilling off the solvent under reduced pressure.

(Wherein, X is a perfluoromethylene group and a perfluoroethylene group, per molecule, perfluoromethylene group on average 7, perfluoroethylene group on average 8 present, the number of fluorine atoms on average 46 to be)

Subsequently, 29.1 g of methyl isobutyl ketone was added as a solvent to a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a dropping device, and the temperature was raised to 105 ° C. while stirring under a stream of nitrogen. Subsequently, 38.5 g of monomer (B-1), 32.8 g of 2-hydroxyethyl methacrylate, 10.7 g of t-butyl peroxy-2-ethyl hexanoate as a radical polymerization initiator, and 58.1 g of methyl isobutyl ketone as a solvent were mixed. Three types of dropping solutions of one initiator solution were set in separate dropping devices, respectively, and the flask was kept dropping over 2 hours while maintaining the temperature at 105 ° C. After completion of the dropwise addition, the mixture was stirred at 105 ° C for 10 hours, and then the solvent was distilled off under reduced pressure to obtain a polymer (P-3).

Subsequently, 106.9 g of methyl ethyl ketone as a solvent, 0.1 g of p-methoxyphenol as a polymerization inhibitor, and 0.03 g of octylic acid tin as a urethanization catalyst were added to the polymer (P-3), and stirring was started under air flow. , 35.6 g of 2-acryloyloxyethyl isocyanate was added dropwise at 1 hour while maintaining at 60 ° C. After completion of the dropwise addition, the mixture was stirred at 60 ° C for 1 hour, heated to 80 ° C, and reacted by stirring for 10 hours. As a result, loss of the isocyanate group was confirmed by IR spectrum measurement. Subsequently, what was insoluble in the solution by filtration after dilution with methyl ethyl ketone as a solvent was separated, thereby obtaining a methyl ethyl ketone solution containing 20% by mass of a polymerizable resin (2 ') having an active energy ray-curable group. As a result of measuring the molecular weight of the polymerizable resin (2 ') by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 3,200, the weight average molecular weight was 87,000, and the radical polymerizable unsaturated group equivalent was 423 g / eq.

Comparative Example 3 (statue)

In a glass flask equipped with a stirring device, thermometer, cooling tube, and dropping device, 20 g of compound (X-1), 10 g of diisopropyl ether as a solvent, 0.006 g of p-methoxyphenol as a polymerization inhibitor, and triethylamine as a neutralizing agent 3.3 g was added, stirring was started under an air stream, and 3.1 g of methacrylic acid chloride was added dropwise over 2 hours while maintaining the inside of the flask at 10 ° C. After completion of the dropwise addition, the mixture was stirred for 1 hour at 10 ° C, heated up, stirred for 1 hour at 30 ° C, heated to 50 ° C and reacted by stirring for 10 hours, and disappearance of methacrylic acid chloride was confirmed by gas chromatography measurement. Became. Subsequently, after 70 g of diisopropyl ether was added as a solvent, 80 g of ion-exchanged water was mixed and stirred, and then washed and washed by a method of separating and removing the aqueous layer. Subsequently, 0.02 g of p-methoxyphenol was added as a polymerization inhibitor, and 8 g of magnesium sulfate was added as a dehydrating agent to stand for one day, followed by complete dehydration, followed by filtration of the dehydrating agent.

Subsequently, by distilling off the solvent under reduced pressure, a monomer represented by the following structural formula (B-2) was obtained.

(Wherein, X is a perfluoromethylene group and a perfluoroethylene group, per molecule, perfluoromethylene group on average 7, perfluoroethylene group on average 8 present, the number of fluorine atoms on average 46 to be)

To a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a dropping device, 96.7 g of methyl isobutyl ketone was added as a solvent, and the temperature was raised to 105 ° C while stirring under a stream of nitrogen. Subsequently, a monomer solution in which 74 g of monomer (B-2), 37 g of monomer (A'-1), and 45.4 g of 2-hydroxyethyl methacrylate were dissolved in 126 g of methyl isobutyl ketone, and t-butylper as a radical polymerization initiator Three types of dripping solution with a polymerization initiator solution in which 23.5 g of oxy-2-ethylhexanoate was dissolved in 67.8 g of methyl isobutyl ketone were set in separate dropping devices, and the flask was kept at 105 ° C for 2 hours at the same time. Dropped over. After completion of dropping, the mixture was stirred at 105 ° C for 10 hours to obtain a solution of polymer (P-4).

To the solution of the polymer (P-4), 0.2 g of p-methoxyphenol as a polymerization inhibitor and 0.06 g of tin octylate as a urethanization catalyst were added, stirring was started under air flow, and 60 ° C was maintained. , 49.1 g of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C for 1 hour, then heated to 80 ° C and stirred for 10 hours to confirm the disappearance of the isocyanate group by IR spectrum measurement. Subsequently, methyl isobutyl ketone was added to obtain a methyl isobutyl ketone solution containing 40% by mass of a polymerizable resin (3 ') having an active energy ray-curable group. When the molecular weight of the obtained polymerizable resin (3 ') was measured by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 2,700 and the weight average molecular weight was 8,000, and the radical polymerizable unsaturated group equivalent was 588 g / eq.

Comparative Example 4 (statue)

To a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a dropping device, 714 g of methyl isobutyl ketone was added as a solvent and heated to 105 ° C while stirring under a stream of nitrogen. Subsequently, a monomer solution in which 90 g of tridecafluorohexyl ethyl methacrylate, 360 g of the monomer (A'-1), and 264 g of 2-hydroxyethyl methacrylate were dissolved in 1106.4 g of methyl isobutyl ketone, and a radical polymerization initiator As a dropping agent, two kinds of dropping solutions with a polymerization initiator solution in which 107.2 g of t-butylperoxy-2-ethylhexanoate was dissolved in 321.6 g of methyl isobutyl ketone were set in separate dropping devices, and the flask was set to 105 ° C. While maintaining, the monomer solution was dripped over 2 hours, and the polymerization initiator solution over 2 hours and 20 minutes.

After completion of dropping, the mixture was stirred at 105 ° C for 1.5 hours. After completion of the reaction, 1660 g of methyl isobutyl ketone was distilled off under reduced pressure to obtain a polymer (p'-1) solution.

Subsequently, 0.399 g of p-methoxyphenol as a polymerization inhibitor, 2.993 g of dibutylhydroxytoluene, and 0.299 g of octylic acid tin as a urethanization catalyst were added, stirring was started under an air flow, and 60 ° C was maintained, 2 -282.25 g of acryloyloxyethyl isocyanate was added dropwise over 1 hour. Thereafter, the mixture was stirred at 60 ° C. for 2 hours, heated to 80 ° C., and stirred for 2 and a half hours. After confirming the disappearance of the isocyanate group by IR spectrum measurement, 1942.83 g of methyl isobutyl ketone was added, thereby adding an active energy ray-curable group. A methyl isobutyl ketone solution containing 30% by mass of the polymerizable resin for comparative control (4 ') was obtained. As a result of measuring the molecular weight of the obtained polymerizable resin (4 ') by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 2,335 and the weight average molecular weight was 6,115.

Example 8 (Preparation of active energy ray-curable composition)

As an example of the active energy ray-curable composition of the present invention, a composition for an antireflection film positioned on the outermost surface of a protective film of a polarizing plate was prepared. Specifically, 15 parts of a methyl isobutyl ketone dispersion containing 20% by mass of hollow silica fine particles (average particle diameter 50 nm), 1.6 parts of pentaerythritol triacrylate, 2-hydroxy-1- {4- [as photopolymerization initiator 0.1 parts of 4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one ("Irgacure 127" manufactured by Chiba Japan Co., Ltd.), solvent As a mixture, 81.8 parts by mass of methyl isobutyl ketone was mixed and dissolved to obtain a base composition for an antireflective coating composition.

To 99.2 parts of the base composition of the antireflective coating composition obtained above, a solution containing 50% of the polymerizable resin (1) is added so as to be 0.4 parts as a resin powder, and uniformly mixed to form an active energy ray-curable composition of the present invention (1 ) [Anti-reflective coating composition (1)] was prepared.

Using the obtained antireflection coating composition (1), an antireflection layer was prepared on the film having the antireflection layer and the hard coating layer in the following procedure.

<Preparation of coating composition for hard coating layer>

5-functional non-yellowing urethane acrylate 50 parts, dipentaerythritol hexaacrylate 50 parts, butyl acetate 25 parts, 1-hydroxycyclohexylphenyl ketone as a photopolymerization initiator ("Irgacure 184" manufactured by Chiba Specialty Chemicals) 5 parts, 54 parts of toluene, 28 parts of 2-propanol, 28 parts of ethyl acetate, and 28 parts of propylene glycol monomethyl ether were mixed and dissolved as a solvent to obtain a coating composition for a hard coating layer.

<Preparation of film having hard coating layer>

The obtained coating composition for hard coating layer was applied to a TAC film having a thickness of 80 µm using a bar coater No. 13, and then placed in a dryer at 60 ° C. for 5 minutes to volatilize the solvent, and a UV curing device (in a nitrogen atmosphere, high pressure mercury, etc.) Hardened by use and ultraviolet irradiation amount of 2 kJ / m 2), a hard coating film having a hard coating layer having a thickness of 10 μm on one side was produced.

<Preparation of film having anti-reflection layer and hard coating layer>

After coating the anti-reflective coating composition (1) with a bar coater No. 2 on the hard coating layer of the hard coating film obtained above, so as to have an application amount of 2 g / m 2, the solvent was volatilized by putting it in a dryer at 60 ° C. for 5 minutes, It was cured with an ultraviolet curing device (in a nitrogen atmosphere, using a high pressure mercury lamp, and an ultraviolet irradiation amount of 2 kJ / m 2) to produce a film having an antireflection layer and a hard coating layer with a thickness of 0.1 μm on a hard coating layer having a thickness of 10 μm. The following appearance, scratch resistance, and decontamination property were evaluated on the surface of the cured coating film of the antireflection coating composition of the obtained film. In addition, the reflectance of the antireflection film was measured. These evaluations were performed before and after performing the alkali treatment shown below. The evaluation results are shown in Table 1.

[Evaluation of appearance]

The antireflection film obtained above was placed on a black plate, and the presence or absence of whitening of the cured coating film of the antireflective coating composition was visually observed to evaluate the appearance according to the following criteria.

○: No white flowers were formed.

×: A white flower is formed.

[Evaluation of scratch resistance]

Torraiboa HEIDON reciprocating wear tester TYPE: Wear tester using 30S (manufactured by Shinto Chemical Co., Ltd.) and Bonstar No. 0000 (manufactured by Nihon Steel Wool Co., Ltd.) attached to a circular jig with a diameter of 27 mm The test was conducted with 30 reciprocating wears (500 g / cm 2 load). The number of scratches on the surface of the coating film after the test was counted, and the scratch resistance was evaluated according to the following criteria.

◎: Less than 5 scratches.

○: The number of scratches is less than 10.

△: The number of scratches is 10 or more and less than 50.

×: The number of scratches is 50 or more.

[Evaluation of fingerprint decontamination property]

Fingerprints are attached to the surface of the cured coating film of the antireflection coating composition of the antireflection film obtained above, and the degree of wiping when wiped 10 times with tissue paper is visually observed, thereby removing fingerprint contamination from the following criteria. Evaluated.

◎: The thing that can wipe the fingerprint completely.

(Circle): The traces of fingerprint attachment, or traces on the line along the wiped direction, are slightly left as compared to when attached.

X: The traces of adhesion of fingerprints, or traces on the line along the wiped direction, remained at a concentration of more than half when attached.

[Measurement of reflectance]

The reflectance was measured using a spectrophotometer ("UV-3100PC" manufactured by Shimadzu Corporation, Inc.) equipped with a 5 占 폚 specular reflection measuring device. Moreover, the reflectance was made into the value when it became the minimum value (lowest reflectance) in the vicinity of a wavelength of 550 nm.

<How to treat strong alkali (saponification) of hardened coating film>

The antireflection film obtained above was immersed in a 2.0 mol / L aqueous potassium hydroxide solution heated to 70 ° C for 1 minute, and then washed with water and dried at 100 ° C for 3 minutes to perform strong alkali treatment.

Comparative Example 5 (Preparation of active energy ray-curable composition for comparative control)

Example 8, except for the addition of 0.4 parts by mass of the methyl isobutyl ketone solution containing 40% of the polymerizable resin (1 ') as a resin powder, in place of the 50% solution of the polymerizable resin (1) used in Example 8 The operation was performed in the same manner to obtain an antireflective coating composition for comparison and control (1 '). This was used to perform evaluation in the same manner as in Example 8. The evaluation results are shown in Table 1.

Comparative Example 6 (statue)

In place of the solution containing 50% of the polymerizable resin (1) used in Example 8, the same operation as in Example 8 was carried out except that 0.4% by weight of the solution containing 20% of the polymerizable resin (2 ') as a resin powder was added. An antireflective coating composition (2 ') for comparative control was obtained. This was used to perform evaluation in the same manner as in Example 8. The evaluation results are shown in Table 1.

Comparative Example 7 (statue)

In place of the 50% -containing solution of the polymerizable resin (1) used in Example 8, except for adding 0.4 parts by weight of a 40% -containing solution of the polymerizable resin (3 ') as a resin powder, the same operation as in Example 8 was carried out. An antireflective coating composition (3 ') for comparative control was obtained. This was used to perform evaluation in the same manner as in Example 8. The evaluation results are shown in Table 1.

Comparative Example 8 (statue)

In place of the solution containing 50% of the polymerizable resin (1) used in Example 8, silicone oil ("Sirapurene FM-4421" manufactured by JNC Corporation), -C ₃ H ₆ was added to the sock end of the polydimethylsiloxane chain. The same operation as in Example 8 was performed except that 0.8 parts by mass (0.4 parts by mass of resin) of a methyl isobutyl ketone solution containing 50% by mass of OC ₂ H ₄ OH) was added, and the anti-reflective coating composition for comparative control was used. (4 '). This was used to perform evaluation in the same manner as in Example 8. The evaluation results are shown in Table 1.

Comparative Example 9 (statue)

Methyl containing 50% by mass of FM-0721K (silicone oil made by JNC, which has a polymerizable unsaturated group at one end) in place of the solution containing 50% of the polymerizable resin (1) used in Example 8. It was operated in the same manner as in Example 8, except that 0.8 parts by mass of the isobutyl ketone solution (0.4 parts by mass as the resin content) was obtained, thereby obtaining an antireflective coating composition for comparison (5 '). This was used to perform evaluation in the same manner as in Example 8. The evaluation results are shown in Table 2.

Comparative Example 10 (statue)

In place of the 50% -containing solution of the polymerizable resin (1) used in Example 8, a 50% by mass content of a tetrafunctional acrylate having a dimethylsiloxane chain ("BYK-UV3570" manufactured by BICCHEM Japan Co., Ltd.) The same operation as in Example 8 was performed except that 0.8 parts by mass of the methyl isobutyl ketone solution (0.4 parts by mass as the resin content) was added to obtain an antireflective coating composition for comparison (6 '). This was used to perform evaluation in the same manner as in Example 8. The evaluation results are shown in Table 2.

Comparative Example 11 (statue)

Nothing was added to the base resin composition of the active energy ray-curable composition prepared in Example 8, and the same operation as in Example 8 was performed to evaluate it. The evaluation results are shown in Table 2.

[Table 1]

[Table 2]

Example 9 (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 positioned 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, 2-hydroxy-1- {4- [as photopolymerization initiator 4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one ("Irgacure127" manufactured by Chiba Japan Co., Ltd.) 0.0092 parts, solvent As a mixture, 8.395 parts of methyl isobutyl ketone was mixed and dissolved to obtain a base composition of an antireflective coating composition.

With respect to 9.87 parts of the base composition of the antireflective coating composition obtained above, a solution containing 30% of the polymerizable resin (2) is added so as to be 0.04 parts as a resin powder, and uniformly mixed to form an active energy ray-curable composition of the present invention (2 ) [Anti-reflective coating composition (2)] was prepared.

Using the obtained antireflection coating composition (2), a film having an antireflection layer and a hard coating layer was prepared in the following procedure.

<Preparation of coating composition for hard coating layer>

30 parts of urethane acrylate ("UV1700B" manufactured by Nippon Kosei Chemical Co., Ltd.), 25 parts of butyl acetate, 1-hydroxycyclohexylphenyl ketone ("Irgacure 184" manufactured by Chiba Specialty Chemicals) as photopolymerization initiator 1.2 As a mass part and 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 coating layer.

<Preparation of film having hard coating layer>

The obtained coating composition for hard coating layer was applied to a PET film having a thickness of 188 μm using a bar coater No. 13, and then put in a dryer at 70 ° C. for 1 minute to volatilize the solvent, and a UV curing device (in a nitrogen atmosphere, high pressure mercury, etc Hardened by use and UV irradiation amount of 0.5 kJ / m 2), a hard coating film having a hard coating layer having a film thickness of 8 μm on one side was produced.

<Preparation of film having anti-reflection layer and hard coating layer>

After coating the anti-reflective coating composition (2) on the hard coating layer of the hard coating film obtained above with a bar coater No. 2, and putting it in a dryer at 50 ° C. for 1 minute and 30 seconds to volatilize the solvent, an ultraviolet curing device (nitrogen atmosphere Ha, using a high-pressure mercury lamp, and cured with an ultraviolet irradiation amount of 2 kJ / m 2) to produce a film (antireflection film) having an antireflection layer and a hard coating layer with a film thickness of 0.1 μm on a hard coating layer having a thickness of 8 μm. The surface of the cured coating film of the antireflection coating composition of the obtained film was evaluated for appearance, activity, and scratch resistance according to the following evaluation method. These measurements were performed before and after the alkali treatment. The evaluation results are shown in Table 3.

[Evaluation of appearance]

The film obtained above was visually observed for unevenness (crawling) of fine oil droplets formed on the cured coating film of the antireflective coating composition, and the appearance was evaluated based on the following criteria. The evaluation results are shown in Table 1.

○: No crawling was observed.

△: Partial crawling was observed.

X: The dot-like crawl is seen as a whole.

[Evaluation of activity]

Using a surface measuring instrument ("HEIDON-14D" manufactured by Shinto Chemical Co., Ltd.), fix the film obtained above on a sample stand to check the level, set a probe on the sample, and load tension with 100 g load. Measurement was performed under a condition of 0.3 m / min, and a dynamic friction coefficient was obtained. The smaller the coefficient of dynamic friction, the better the activity.

[Evaluation of scratch resistance]

Using # 0000 steel wool, the test was carried out with 500 loads of 10 repetitive wears. The number of scratches on the surface of the coating film after the test was counted, and the scratch resistance was evaluated according to the following criteria.

◎: Less than 5 scratches.

○: 5 or more and less than 10 scratches.

△: The number of scratches is 10 or more and less than 30.

×: The number of scratches is 30 or more.

Example 10 (status)

The procedure was evaluated in the same manner as in Example 9, except that 0.04 parts by mass of the solution containing 30% of the polymerizable resin (3) was added as a resin powder instead of the solution containing 30% of the polymerizable resin (2) used in Example 9. Was done. The evaluation results are shown in Table 3.

Example 11 (status)

The procedure was evaluated in the same manner as in Example 2, except that 0.04 parts by mass of the 30% solution of the polymerizable resin (4) was added as a resin powder instead of the 30% solution of the polymerizable resin (2) used in Example 9. Was done. The evaluation results are shown in Table 3.

Example 12 (status)

It was evaluated in the same manner as in Example 9, except that 0.04 parts by mass of the solution containing 30% of the polymerizable resin (5) was added as a resin powder instead of the solution containing 30% of the polymerizable resin (2) used in Example 9. Was done. The evaluation results are shown in Table 3.

Example 13 (status)

It was evaluated in the same manner as in Example 9, except that 0.04 parts by mass of the solution containing 30% of the polymerizable resin (6) was added as a resin powder instead of the solution containing 30% of the polymerizable resin (2) used in Example 9. Was done. The evaluation results are shown in Table 3.

Example 14 (status)

It was evaluated and operated in the same manner as in Example 9, except that 0.04 parts by mass of the solution containing 30% of the polymerizable resin (7) was added as a resin powder instead of the solution containing 30% of the polymerizable resin (2) used in Example 9. Was done. The evaluation results are shown in Table 3.

Comparative Example 12 (Preparation of active energy ray-curable composition for comparative control)

As in Example 9, instead of the solution containing 30% of the polymerizable resin (2) used in Example 9, 0.4 parts by mass of the solution containing 30% of the polymerizable resin for comparison (4 ') as a resin powder was added. It operated and evaluated. Table 4 shows the evaluation results.

Comparative Example 13 (statue)

To the base composition of the antireflective coating composition prepared in Example 9, nothing was added and operated in the same manner as in Example 9 to evaluate. The evaluation results are shown in Table 3.

[Table 3]

[Table 4]

Claims (16)

A polymerizable resin having a main chain formed by polymerization of a polymerizable unsaturated monomer, the main chain having a fluorinated alkyl group (x) and a polymerizable unsaturated group (y) having 1 to 6 carbon atoms bonded to the fluorine atom as a side chain, The main chain is a polymer resin having a structure containing a silicone chain having a molecular weight of 2,000 or more at one end thereof, and the polymerizable resin has a functional group having a functional group having a radical generating ability at one end of a silicone chain having a molecular weight of 2,000 or more (A) A polymerizable unsaturated monomer (B) having a fluorinated alkyl group having 1 to 6 carbon atoms bonded to a fluorine atom and a polymerizable unsaturated monomer (C) having a reactive functional group (c1) and a functional group having reactivity with the functional group (c1) (d1) and a polymerizable resin obtained using a compound (D) having a polymerizable unsaturated group (d2), as the polymerizable resin generates radicals from the compound (A). The copolymer (P) obtained by copolymerizing the polymerizable unsaturated monomer (B) and the polymerizable unsaturated monomer (C) is obtained by reacting the compound (D), and has a radical generating ability of the compound (A). The functional group is an organic group having a halogen atom, an organic group having an alkyltellurium group, or an organic group having a dithioester group, and the compound (A) is the polymerizable unsaturated monomer (B) and the polymerizable unsaturated monomer (C). The polymerizable resin characterized in that the polymerization method for copolymerizing is living radical polymerization. According to claim 1,
The polymerizable resin in which the silicone chain of the compound (A) is a silicone chain having a molecular weight of 2,000 to 20,000. According to claim 1,
A polymerizable resin in which the living radical polymerization is an atomic transfer radical polymerization performed in the presence of a polymerization initiator, a transition metal compound, and a compound having a ligand capable of coordinating bonds with the transition metal. According to claim 1,
The polymerizable resin wherein the reactive functional group (c1) is at least one functional group selected from the group consisting of a hydroxyl group, an isocyanate group, an epoxy group, a carboxy group, a carboxylic acid halide group and a carboxylic acid anhydride group. A polymerizable resin having a main chain formed by polymerization of a polymerizable unsaturated monomer, the main chain having a fluorinated alkyl group (x) and a polymerizable unsaturated group (y) having 1 to 6 carbon atoms bonded to the fluorine atom as a side chain, The main chain is a polymerizable resin characterized by having a structure comprising a silicone chain having a molecular weight of 2,000 or more at its one end, and the polymerizable resin is a main chain formed by polymerization of a polymerizable unsaturated monomer and a side chain of the main chain. As a first polymer segment (α) having a fluorinated alkyl group (x) having 1 to 6 carbon atoms bonded to a fluorine atom, and a main chain formed by polymerization of a polymerizable unsaturated monomer and a polymerizable unsaturated group (y) as a side chain of the main chain Polymeric resin, characterized in that it has a second polymer segment (β), and a structure comprising a silicone chain having a molecular weight of 2,000 or more at one end. The method of claim 5,
The reaction system is a compound (A) having a functional group having a radical generating ability and a polymerizable unsaturated monomer (B) having a fluorinated alkyl group (x) having 1 to 6 carbon atoms bonded to a fluorine atom at one end of a silicone chain having a molecular weight of 2,000 or more. A step (1) of introducing a polymer segment (p) containing a structure derived from the polymerizable unsaturated monomer (B) by introducing it into the compound and generating radicals from the compound (A);
By introducing a polymerizable unsaturated monomer (C) having a reactive functional group (c1) into the reaction system containing the polymer segment (p) and generating radicals from the polymer segment (p), the polymer segment (p) and Step (2) of obtaining a polymer (Q1) containing a polymer segment (q1) containing a structure derived from a polymerizable unsaturated monomer (C),
In the reaction system containing the polymer (Q1), a compound (D) having a functional group (d1) and a polymerizable unsaturated group (d2) reactive with respect to the reactive functional group (c1) possessed by the polymer (Q1) are introduced, and the reactive functional group A polymerizable resin obtained according to a production method comprising a step (3) of reacting a functional group (d1) having reactivity with (c1). The method of claim 5,
A compound (A) having a functional group having a radical generating ability and a polymerizable unsaturated monomer (C1) having a reactive functional group (c1) are added to one end of a silicone chain having a molecular weight of 2,000 or more into the reaction system, and radicals from the compound (A) Step (1-1) of obtaining a polymer segment (q) containing a structure derived from the polymerizable unsaturated monomer (C) by producing
The polymer segment (q) and the polymerizable unsaturated monomer (B) are introduced into the reaction system containing the polymer segment (q) by introducing a polymerizable unsaturated monomer (B) and generating radicals from the polymer segment (q). Step (2-1) of obtaining a polymer (Q2) containing a polymer segment containing a derived structure,
In the reaction system containing the polymer (Q2), a compound (D) having a functional group (d1) and a polymerizable unsaturated group (d2) reactive with respect to the reactive functional group (c1) possessed by the polymer (Q2) are introduced, and the reactive functional group A polymerizable resin obtained according to a production method comprising the step (3-1) of reacting a functional group (d1) having reactivity with (c1). The method according to any one of claims 5 to 7,
A polymerizable resin having the first polymer segment (α) and the second polymer segment (β) in a range of 20/80 to 80/20 in a mass ratio [(α) / (β)]. The method of claim 6 or 7,
The functional group having a radical generating ability of the compound (A) is composed of 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, or an organic group having an azo group Polymerizable resin which is one or more functional groups selected from the group. The method of claim 6 or 7,
The polymerizable resin in which the silicone chain of the compound (A) is a silicone chain having a molecular weight of 2,000 to 20,000. The method of claim 6 or 7,
The functional group having a radical generating ability of the compound (A) is an organic group having a halogen atom, an organic group having an alkyltellurium group, or an organic group having a dithioester group, and the polymerizable unsaturated monomer in the compound (A) The polymerizable resin in which the polymerization method for copolymerizing (B) and the polymerizable unsaturated monomer (C) is living radical polymerization. The method of claim 11,
A polymerizable resin in which the living radical polymerization is an atomic transfer radical polymerization performed in the presence of a polymerization initiator, a transition metal compound, and a compound having a ligand capable of coordinating bonds with the transition metal. The method of claim 6 or 7,
The polymerizable resin wherein the reactive functional group (c1) is at least one functional group selected from the group consisting of a hydroxyl group, an isocyanate group, an epoxy group, a carboxy group, a carboxylic acid halide group and a carboxylic acid anhydride group. The active energy comprising the polymerizable resin according to any one of claims 1 to 7, and an active energy ray-curable resin (E) or an active energy ray-curable monomer (F) other than the polymerizable resin. Sun-curable composition. An article comprising the cured coating film of the active energy ray-curable composition according to claim 14. Compound (A) having a functional group having a radical generating ability and a fluorinated alkyl group having 1 to 6 fluorinated alkyl groups having a fluorine atom bonded to one end of a silicone chain having a molecular weight of 2,000 or more, and a reactive functional group (c1) It is a method for producing a polymerizable resin using a polymerizable unsaturated monomer (C) having a functional group (d1) having a reactivity to the functional group (c1) and a compound (D) having a polymerizable unsaturated group (d2),
A production method in which the compound (D) is reacted with a copolymer (P) obtained by copolymerizing the polymerizable unsaturated monomer (B) and the polymerizable unsaturated monomer (C) by generating radicals from the compound (A). And
The functional group having a radical generating ability of the compound (A) is an organic group having a halogen atom, an organic group having an alkyltellurium group or an organic group having a dithioester group, and the polymerizable unsaturated monomer ( The polymerization method for copolymerizing B) and the polymerizable unsaturated monomer (C) is a living radical polymerization method.

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