TWI609042B - Polymerizable resin, active energy ray-curable composition, article and method for manufacturing polymerizable resin - Google Patents

Description

Polymerizable resin, active energy ray-curable composition, article, and method for producing polymerizable resin

The present invention relates to a fluorine atom-containing polymerizable resin which is excellent in scratch resistance to a cured coating film of the composition by being added to an active energy ray-curable composition. Further, the present invention relates to an active energy ray-curable composition using a polymerizable resin containing a fluorine atom, and an article having a cured coating film having the composition.

For the surface layer of the polarizing plate which is the outermost surface of the screen of the liquid crystal display, it has been subjected to coating work such as AG, AG/LR, transparent/LR, etc., which has anti-glare or anti-reflection properties, and for the most surface layer, it is necessary to have resistance. Scratch. As a method of improving the scratch resistance, a method of forming a crosslinked film obtained by using a polyfunctional monomer such as a polyfunctional (meth)acrylate on a surface of a substrate (hard coating agent) as a scratch resistance is known. A good coating material, a method of adding a polyfluorene-based or fluorine-based leveling agent, adding inorganic compound particles such as cerium oxide or aluminum oxide, carbon, or a polyurethane resin, and a polystyrene resin. A method of synthesizing resin particles such as an acrylic resin.

The polarizing plate is obtained by bonding an optically transparent and mechanically strong protective film on both sides or a single side of the polarizing film; As the protective film, a triacetyl cellulose (TAC) film is generally used.

In order to adhere a triacetyl cellulose (TAC) film to a polarizing film, the surface of the TAC film is subjected to saponification treatment with caustic or the like to hydrolyze a part or a majority of the -OCOCH ₃ group into a hydrophilic group-OH. In order to form a base layer and a surface layer having anti-glare property or anti-reflection property in a TAC film, and performing saponification treatment, the following steps are performed: 1. After the saponification treatment is performed on the TAC film, the coating film layer is formed on one side of the film; The method of forming the coating layer on one side of the TAC film and then performing a saponification treatment or the like is generally carried out according to the production efficiency of the polarizing plate.

In the above method 2. In order to protect the coating layer from a saponification agent such as caustic alkali during the saponification treatment, a method of protecting the coating layer with a protective film is known. However, in recent years, in order to achieve an increase in production efficiency or cost reduction, a coating film layer which does not have a coating film layer protected by a protective film and which does not deteriorate under the above-described saponifier coating property is required. However, in general, since the surface of the cured coating film is largely deteriorated by the saponification treatment, there is a problem that sufficient scratch resistance cannot be obtained.

For example, a method of using an active energy ray-curable composition containing a polyfluorene oxide compound having a radical polymerizable unsaturated group in a molecule is known as a method of obtaining a protective layer having excellent scratch resistance (see Patent Document 1). However, the cured coating film of the active energy ray-curable composition to which the polyoxyxene compound is added, like the TAC film used for the polarizing plate of a liquid crystal display, is saponified in the application of the saponification treatment (strong alkali treatment). The smoothness of the surface of the cured coating film after the treatment is greatly lowered, and there is a problem that sufficient scratch resistance cannot be obtained.

Therefore, a saponification treatment (strong alkali treatment) is required. A material that can prevent scratches from imparting excellent scratch resistance to the surface of a hardened coating film.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-182765

An object of the present invention is to provide a fluorine atom-containing polymerizable resin which is excellent in scratch resistance on the surface of a coating film even after saponification treatment by adding an active energy ray-curable composition. Further, another object of the invention is to provide an active energy ray-curable composition using the polymerizable resin and an article having a cured coating film having the composition.

The inventors of the present invention have found that a fluorine-based polymerizable resin having a fluoroalkyl group and a polymerizable unsaturated group, and having a polyoxygen chain at one end of the resin, can be used as an interface. The active energy ray-curable composition containing the resin can impart 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 provides a polymerizable resin having a main chain formed by polymerization of a polymerizable unsaturated monomer, and the main chain has fluorine having 1 to 6 carbon atoms bonded to a fluorine atom. a polymerizable resin having an alkyl group (x) and a polymerizable unsaturated group (y) as a side chain, characterized in that the main chain system further has a molecular weight of 2,000 or more at one end thereof. The structure of the polyoxygen chain.

Furthermore, 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 other than the polymerizable resin (F) ).

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

The polymerizable resin of the present invention can impart smoothness to the surface of the cured coating film and obtain excellent scratch resistance by being added to the active energy ray-curable composition. Further, this scratch resistance can also be exhibited in a cured coating film which has been subjected to a saponification treatment (strong alkali treatment), and a material for a hard coat material of a TAC film used as a polarizing plate for a liquid crystal display.

Fig. 1 is a chart showing the IR spectrum of the polymerizable resin (1) obtained in Example 1.

Fig. 2 is a chart showing the ¹³ C-NMR spectrum of the polymerizable resin (1) obtained in Example 1.

Fig. 3 is a chart of GPC of the polymerizable resin (1) obtained in Example 1.

Fig. 4 is a chart showing the IR spectrum of the polymerizable resin (2) obtained in Example 2.

Fig. 5 is a chart (total figure) of the ¹ H-NMR spectrum of the polymerizable resin (2) obtained in Example 2.

Fig. 6 is a chart (25-fold enlarged view) of the ¹ H-NMR spectrum of the polymerizable resin (2) obtained in Example 2.

Fig. 7 is a chart (total figure) of ¹³ C-NMR spectrum of the polymerizable resin (2) obtained in Example 2.

Fig. 8 is a chart (25-fold enlarged view) of the ¹³ C-NMR spectrum of the polymerizable resin (2) obtained in Example 2.

Fig. 9 is a chart (total figure) of the ¹⁹ F-NMR spectrum of the polymerizable resin (2) obtained in Example 2.

Fig. 10 is a chart showing the GPC of the polymerizable resin (2) obtained in Example 2.

[Formation of the Invention]

The polymerizable resin of the present invention has a main chain formed by polymerization of a polymerizable unsaturated monomer, and the main chain has a fluoroalkyl group (x) having a fluorine atom bonded to a fluorine atom of 1 to 6 and The polymerizable unsaturated group (y) is a side chain polymerizable resin, and the main chain system further has a structure in which a polyfluorene chain having a molecular weight of 2,000 or more is contained at one end thereof. At the one-side end, there may be a single polyoxygen chain, or a plurality of strips. In the present invention, a single strip (one strip) is aggregated at one end of the viewpoint based on the surface segregation resistance of the fluorine atom. The oxygen chain is preferred.

The fluoroalkyl group (x) is preferably a balance of surface segregation property, water and oil repellency, and environmental burden reduction, and is preferably a carbon number of 4 to 6, more preferably 6 carbon atoms.

Moreover, the hardening coating film which is excellent in abrasion resistance is said to have the equivalent of the polymerizable unsaturated group (y) in the polymerizable resin of the present invention. Preferably, the range is from 200 to 3,500 g/eq., more preferably from 250 to 2,000 g/eq., and preferably from 300 to 1,500 g/eq., particularly preferably from 400 to 1,000 g/eq. .

The molecular weight of the aforementioned polyoxygen chain needs to be 2,000 or more. By passing through the polyoxygen chain having such a molecular weight, the smoothness of the polyoxygen chain can be appropriately exhibited, and as a result, excellent friction resistance can be imparted by lowering the friction of the surface of the coating film. The molecular weight of the polyoxygen chain is preferably from 2,000 to 20,000, more preferably from 5,000 to 10,000.

In the present invention, various types of polymerizable resins can be obtained by changing the time point at which the raw materials are polymerized. For example, a polymerizable unsaturated monomer (B) having a fluoroalkyl group having 1 to 6 carbon atoms bonded to a fluorine atom described later and a polymerizable unsaturated monomer having a reactive functional group (c1) will be described later. When (C) is simultaneously added to the reaction system to cause a reaction, a so-called random copolymer-like polymerizable resin is formed. Moreover, when the polymerizable unsaturated monomer (B) and the polymerizable unsaturated monomer (C) are individually reacted, a so-called block copolymer-like polymerizable resin is formed. In particular, in the polymerizable resin of the present invention, a polymerizable resin which imparts excellent scratch resistance to a coating film having a film thickness of about 0.1 μm and which is extremely thin can be added to the active energy ray-curable composition. In other words, a block copolymer is preferred.

In the polymerizable resin of the present invention, for example, a compound (A) having a functional group having a radical generating ability at one end of a polyfluorene chain having a molecular weight of 2,000 or more can be used. a polymerizable unsaturated monomer (B) having a fluorine atom having 1 to 6 carbon atoms bonded to a fluorine atom, a polymerizable unsaturated monomer (C) having a reactive functional group (c1), and having a pair Reactive member of the aforementioned functional group (c1) It is obtained by the compound (D) of the energy group (d1) and the polymerizable unsaturated group (d2). Specifically, the copolymer (P) is obtained by reacting the compound (P) with the compound (D); the copolymer (P) is a polymerizable unsaturated monomer (B) by generating a radical from the compound (A). It is obtained by copolymerization with the aforementioned polymerizable unsaturated monomer (C).

Further, among the polymerizable resins of the present invention, the block polymer-like polymerizable resin may be exemplified by having a main chain formed by polymerization of a polymerizable unsaturated monomer and a carbon atom having a fluorine atom bonded thereto. a fluoroalkyl group (x) of 1 to 6 as a first polymer segment (α) of a side chain of the main chain; and a main chain formed by polymerization of a polymerizable unsaturated monomer and a polymerizable unsaturated group (y) a second polymer segment (β) which is a side chain of the main chain, and further has a polymerizable resin having a structure in which a polyfluorene chain having a molecular weight of 2,000 or more is contained at one end.

The polymerizable resin in the form of such a block polymer can be suitably obtained by, for example, the following production method: Method 1: A production method comprising the following steps: Step (1), which is a polysiloxane having a molecular weight of 2,000 or more. a unilateral end of the chain, a compound (A) having a functional group having a radical generating ability, and a polymerizable unsaturated monomer having a fluoroalkyl group (x) having 1 to 6 carbon atoms bonded to a fluorine atom. (B) charged into the reaction system to obtain a polymer segment (p) comprising a structure derived from the aforementioned polymerizable unsaturated monomer (B) by generating a radical from the above compound (A); Step (2) ), in a reaction system containing the polymer segment (p), charged with a polymerizable unsaturated monomer (C) having a reactive functional group (c1), from which the polymer segment (p) Producing free radicals, resulting in the inclusion of polymers a segment (p) and a polymer (Q1) comprising a polymer segment (q) derived from the structure of the polymerizable unsaturated monomer (C); and a step (3) in which the polymer (Q1) is contained In the reaction system, a compound (D) having a functional group (d1) reactive with a reactive functional group (c1) of the polymer (Q1) and a polymerizable unsaturated group (d2) is charged, and The reactive functional group (c1) is reacted with a reactive functional group (d1).

Method 2: a production method comprising the following steps: Step (1-1), which is a compound (A) having a functional group having a radical generating ability at a one-side end of a polyfluorene chain having a molecular weight of 2,000 or more, and The polymerizable unsaturated monomer (C) having a reactive functional group (c1) is charged into a reaction system, and a radical derived from the polymerizable unsaturated monomer (C) is obtained by generating a radical from the above compound (A). a polymer segment (q) of the structure; a step (2-1) in which a polymerizable unsaturated monomer (B) is charged in a reaction system containing the polymer segment (q), The polymer segment (q) generates a radical to obtain a polymer (Q2) comprising a polymer segment (q) and a polymer segment comprising a structure derived from the polymerizable unsaturated monomer (B); Step (3-1), which is contained in a reaction system containing a polymer (Q2), having a functional group (d1) having reactivity with a reactive functional group (c1) possessed by the polymer (Q2) And the compound (D) of the polymerizable unsaturated group (d2), and reacting the reactive functional group (c1) with the reactive functional group (d1).

Examples of the functional group having a radical generating ability of the compound (A) include an organic group having a halogen atom, an organic group having an alkylidene group, an organic group having a dithioester group, and a peroxide group. An organic group, an organic group having an azo group, or the like. Active free radical When the compound (A) is copolymerized with the polymerizable unsaturated monomer (B) and the polymerizable unsaturated monomer (C), the functional group having a radical generating ability can be used as an organic group of a halogen atom. An organic group having an alkylidene group or an organic group having a dithioester group, particularly based on ease of synthesis, ease of polymerization control, and diversity of applicable polymerizable unsaturated monomers, preferably using a halogen atom Organic base.

The organic group having a halogen atom may, for example, be 2-bromo-2-methylpropenyloxy, 2-bromo-propenyloxy or p-chlorosulfonyl benzhydryloxy.

In order to introduce the organic group having a halogen atom into the one-side terminal of the compound having a polyfluorene oxide chain having a molecular weight of 2,000 or more in the main chain, for example, a method of reacting the compound (a1) with the compound (a2) may be mentioned, wherein The compound (a1) has a functional group capable of forming a bond by a reaction at a single-sided end of a polyfluorene chain having a molecular weight of 2,000 or more; the compound (a2) has a function capable of reacting with the functional group to form a bond An organic group having a halogen atom. Specifically, examples of the functional group of the one-side terminal of the compound (a1) include a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group, and a carboxylic anhydride group. As a specific example of the above-mentioned compound (a1) having a functional group at one terminal end, a compound represented by the following formula (a1-1) can be appropriately listed: (wherein X is a functional group capable of forming a bond by a 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 ~200).

Thereto, as the R _6, examples thereof include methyl stretch, stretching propyl, isopropyl and the like extending above alkylene of 1 carbon atom, two or more alkylene ether group, alkylene group linked to an ether bond .

In addition, as the functional group which the compound (a2) has, and can bond with the functional group which the said compound (a1) has the one side terminal, and the bond formation, the following are mentioned.

For example, when the functional group of the compound (a1) is a hydroxyl group, the functional group other than the organic group having a halogen atom of the compound (a2) is preferably an isocyanate group, a carboxylic acid halide group or a carboxyl group. Anhydride group. Further, as another method, a carboxyl group may be first formed by reacting a hydroxyl group of the compound (a1) with an acid anhydride, and a compound having an epoxy group and an organic group having a halogen atom may be the above compound (a2). Further, the reaction is carried out to introduce an organic group having a halogen atom at one end of the above compound (a1).

When the functional group of the compound (a1) is an isocyanate group, the functional group other than the organic group having a halogen atom which the compound (a2) has 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 which the compound (a2) has is preferably a carboxyl group.

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

In the combination of the functional group of the compound (a1) and the 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 The functional group other than the organic group having a halogen atom which the compound (a2) has is a combination of a carboxylic acid halide group, and is preferred from the viewpoint of easy reaction. The following conditions can be mentioned as reaction conditions at the time of this combination.

As a specific method of introducing the above-mentioned organic group having a halogen atom to the one-side terminal of the polyoxynoxy chain, when the functional group at the one-terminal end of the above compound (a1) is a hydroxyl group, the aforementioned compound (a2) is a carboxyl group having a halogen group. In the case of an acid, a compound having a functional group having a polymerization initiation ability at one side of a compound having a polyfluorene oxide chain having a molecular weight of 2,000 or more in a main chain can be obtained by carrying out a reaction under deesterification conditions. . Further, when the functional group at the one terminal 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 (a) are used in a solvent such as toluene or tetrahydrofuran. A2) The reaction, the compound (A) having a functional group having a polymerization initiation ability can be obtained in the same manner. In addition, an alkaline catalyst can be used as needed in the reaction.

Further, when the functional group at the one terminal end of the compound (a1) is an isocyanate group, and the compound (a2) has a halogen group and a hydroxyl group which is a functional group reactive with the isocyanate group, The reaction of (a1) with (a2) in the presence of a catalyst of the type can give a compound having a functional group having a polymerization initiation ability.

Furthermore, when the unilateral terminal of the aforementioned compound (a1) is functional The base is an epoxy group, and the compound (a2) has a halogen group and a carboxyl group which is a functional group reactive with the epoxy group, in the presence of a basic catalyst such as triphenylphosphine or a tertiary amine. By reacting (a1) with (a2), a compound having a functional group having a polymerization initiation ability can be obtained.

Specific examples of the compound (A) having a polyfluorene oxide chain having a molecular weight of 2,000 or more and having a functional group having a radical generating ability at one end of the main chain, which is used in the present invention, may be mentioned. For example, the compound represented by the following formula:

Next, the polymerizable unsaturated monomer (B) used in the present invention will be described. The polymerizable unsaturated monomer (B) has a fluoroalkyl group having 1 to 6 carbon atoms directly bonded to a fluorine atom. In the present invention, the fluoroalkyl group also contains one or more carbon-carbon double bonds in the skeleton of the fluoroalkyl group. By. The polymerizable unsaturated group which the monomer (B) has is preferably a radically polymerizable carbon-carbon unsaturated double bond, and examples thereof include a (meth)acryl fluorenyl group, a vinyl group, and a butylene group.醯imino group and the like. Among these, it is preferable that the ease of handling of the raw materials, the ease of compatibility with each of the blending components in the active energy ray-curable composition described later, or the polymerization reactivity are good, and (meth) is preferable. Acryl sulfhydryl.

Further, in the present invention, "(meth) acrylate" means one or both of methacrylate and acrylate; "(meth) propylene fluorenyl" means methacryl fluorenyl and acryl fluorenyl One or both; "(meth)acrylic" means one or both of methacrylic acid and acrylic acid.

The polymerizable unsaturated monomer (B) having a fluoroalkyl group may, for example, be represented by the following formula (1): (In the above 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)~( Any of Rf-7).

-OC _n H _2n - (L-1)

-OCH ₂ CH ₂ OCH ₂ - (L-2)

n in the above formulae (L-1), (L-3), (L-4), (L-5), (L-6), and (L-7) represents an integer of 1-8. m in the above formulae (L-8), (L-9), and (L-10) represents an integer of 1 to 8, and n represents an integer of 0 to 8. Rf" in the above formulae (L-6) and (L-7) represents any one of the following formulae (Rf-1) to (Rf-7).

-C _n F _2n+1 (Rf-1)

-C _n F _2n H (Rf-2)

-C _n F _2n-1 (Rf-3)

_{-C n F 2n-3 (Rf} -4)

-C _m F _2m OC _n F _2n CF ₃ (Rf-5)

-C _m F _2m OC _n F _2n OC _p F _2p CF ₃ (Rf-6)

-CF ₂ OC ₂ F ₄ OC ₂ F ₄ OCF ₃ (Rf-7)

n in the above formulae (Rf-1) and (Rf-2) is an integer of 1 to 6, and n in (Rf-3) is an integer of 2 to 6, and n in (Rf-4) is 4 to 6 The integer. m in the above formula (Rf-5) is an integer of 1 to 5, n is an integer of 0 to 4, and the total of m and n is 4 to 5. m in the above formula (Rf-6) is an integer of 0 to 4, n is an integer of 1 to 4, p is an integer of 0 to 4, and the total of m, n, and p is 4 to 5.

Further, specific examples of the monomer (B) include the following monomers (B-1) to (B-11). Further, these monomers (B) may be used alone or in combination of two or more.

(where n is an integer from 0 to 5, preferably an integer from 3 to 5).

Next, the polymerizable unsaturated monomer (C) having a reactive functional group (c1) will be described. As the function of the aforementioned monomer (C) The group (c1) may, for example, be a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group or a carboxylic anhydride group. Further, the polymerizable unsaturated group of the monomer (C) is preferably a radically polymerizable carbon-carbon unsaturated double bond, and more specifically, a vinyl group or a (meth) acrylonitrile group. The maleic acid imide group or the like is more preferably a (meth) acrylonitrile group based on the viewpoint of easy polymerization.

Specific examples of the monomer (C) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate. 2-hydroxybutyl methacrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono(meth) acrylate, N-(2-hydroxyethyl) (A) Acrylamide, glycerol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl ( a methyl group acrylate, 2-(meth) propylene oxirane ethyl 2-hydroxyethyl phthalate, and a hydroxyl group-containing unsaturated monomer such as a lactone modified (meth) acrylate at the terminal; 2-(methyl)propene oxime ethyl isocyanate, 2-(2-(methyl) propylene oxyethoxy) ethyl isocyanate, isocyanate-1, 1- bis (( An isocyanate group-containing unsaturated monomer such as methyl propylene oxide methyl ethyl acrylate; an epoxy group-containing unsaturated monomer such as glycidyl methacrylate or 4-hydroxybutyl acrylate propyl propyl ether (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(methyl) propylene oxiranium decanoic acid, maleic acid An unsaturated monomer having a carboxyl group such as an acid or methylene succinic acid; an acid anhydride having an unsaturated double bond such as maleic anhydride or methylene succinic anhydride; and the like. These monomers (C) may be used alone or in combination of two or more.

Also, when manufacturing an intermediate of the polymerizable resin of the present invention In addition to the aforementioned compound (A), monomer (B), and monomer (C), the copolymer (P), the polymer (Q1) or the polymer (Q2) may be used in combination with Polymerized other polymerizable unsaturated monomers. Examples of such other polymerizable unsaturated monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, and (methyl). ) isobutyl acrylate, n-amyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethyl (meth) acrylate Hexyl hexyl ester, decyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, isodecyl (meth) acrylate, with poly (Meth) acrylates such as (meth) acrylates of alkylene oxide chains; aromatic vinyls such as styrene, α-methylstyrene, p-methylstyrene, and p-methoxystyrene; ; maleimide, methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexyl cis Equinone imine, octyl maleimide, dodecyl maleimide, octadecyl maleimide, phenyl maleimide, cyclohexyl Maleimide And other maleimide and the like.

Here, the mass ratio [(B)/(C)] of the compound (B) to the monomer (C) is preferably 10/90 to 90/10, which is obtained by a hardened material having high scratch resistance. The range is preferably in the range of 20/80 to 80/20.

The method for producing the copolymer (P), the polymer (Q1) or the polymer (Q2) used in the present invention includes the above-mentioned compound (A) as a radical polymerization initiator, and the monomer (B) Or a method in which the aforementioned monomer (C) is subjected to living radical polymerization. In general, in living radical polymerization, dormant seeds whose living polymerization ends are protected by atoms or radicals are reversibly A radical is generated and reacted with a monomer, whereby a polymer having a very small molecular weight distribution can be obtained. Examples of such living radical polymerization include atom transfer radical polymerization (ATRP), reversible addition-cleavage type radical polymerization (RAFT), radical polymerization (NMP) via a nitrogen-oxygen medium, and use of organic hydrazine. Free radical polymerization (TERP) and the like. When the copolymer (P) is produced by living radical polymerization, a copolymer having a very small molecular weight distribution can be obtained, and it is preferred. Which of these methods is to be used is not particularly limited, and is preferably the aforementioned ATRP based on the ease of control or the like. The ATRP is polymerized by using an organic halide or a sulfonium halide compound as a starting agent and a metal complex containing a transition metal compound and a ligand as a catalyst.

ATRP transition metal compound is used in the M ^{n +} X ⁿ represents. The Mn ⁺ as the transition metal may include 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 Selected from the group of ⁺ , V ³⁺ , Zn ⁺ , Zn ²⁺ , Au ⁺ , Au ²⁺ , Ag ⁺ and Ag ²⁺ . Further, X may be 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 ), a triflate, a hexafluorophosphate, a methanesulfonate, an arylsulfonate (preferably a besylate or tosylate), a group of SeR ₁ , CN and R ₂ COO Selected from the group. Here, R ¹ represents an aryl group, a linear or branched alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), and R 2 represents a hydrogen atom, which may be substituted 1 to 5 times by halogen. A linear or branched alkyl group having 1 to 6 carbon atoms (preferably a methyl group) is preferably used (1 to 3 times by fluorine or chlorine substitution). Furthermore, n represents a formal charge on a metal and is an integer from 0 to 7.

As the transition metal complex, a transition metal complex of Groups 7, 8, 9, 10, 11 is preferred, and more preferably a zero-valent copper, a monovalent copper, a divalent ruthenium, a divalent iron or a divalent nickel. Complex compound.

Examples of the compound having a ligand capable of coordinating bonding with the above transition metal include a ligand containing one or more nitrogen atoms, oxygen atoms, phosphorus atoms or sulfur atoms which can coordinate with a transition metal via a sigma bond. a compound having a ligand comprising a ligand of two or more carbon atoms which can be coordinated to a transition metal via a π bond, and a compound having a ligand capable of coordinating with a transition metal via a μ bond or an η bond.

Specific examples of the compound having the aforementioned ligand, for example, when the central metal is copper, may be exemplified with 2,2'-bipyridine and derivatives thereof, 1,10-morpholine and derivatives thereof, tetramethyl B. A complex formed by a ligand such as a polyamine such as diamine, pentamethyldiethylenetriamine or hexamethylgin(2-aminoethyl)amine. Further, as the divalent ruthenium complex, dichlorostilbene (triphenylphosphine) ruthenium, dichlorostilbene (tributylphosphine) ruthenium, dichloro(cyclooctadiene) ruthenium, dichlorophenylhydrazine, and dichloro-p-iso are mentioned. Propyl toluene, dichloro (nordecadiene) ruthenium, cis-dichlorobis(2,2'-bipyridyl) ruthenium, dichlorostilbene (1,10-morpholine) ruthenium, carbonyl chlorohydrin Triphenylphosphine), etc. Further, examples of the divalent iron complex compound include a bistriphenylphosphine complex and a triazacyclononane complex.

Further, in the production of the aforementioned copolymer (P), a solvent is preferably used. The solvent to be used may, for example, be an ester solvent such as ethyl acetate, butyl acetate or propylene glycol monomethyl ether acetate; or diisopropyl ether, dimethoxyethane or diethylene glycol dimethyl ether. Ether solvent; halogen solvent such as dichloromethane or dichloroethane; aromatic solvent such as toluene or xylene; ketone solution such as methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone An alcohol solvent such as methanol, ethanol or isopropanol; an aprotic polar solvent such as dimethylformamide or dimethylhydrazine; and the like. Further, the above solvents may be used alone or in combination of two or more.

Further, the polymerization temperature at the time of production of the copolymer (P), the polymer (Q1) or the polymer (Q2) is preferably in the range of room temperature to 100 °C.

When the copolymerized portion composed of the monomer (B) and the monomer (C) in the copolymer (P) is formed into a block shape, the monomer (B) or the monomer (C) may be used. The living radical polymerization is carried out separately in the presence of the above compound (A), a transition metal compound, a compound having a ligand capable of coordinating bonding with the transition metal, and a solvent, and is added after being subjected to living radical polymerization. The monomer monomer is further obtained by living radical polymerization.

In order to obtain the polymerizable resin of the present invention, a part or all of the aforementioned reactive groups of the copolymer (P), the polymer (Q1) or the polymer (Q2) produced by the above method are used. The functional group (d1) having a functional group (c1) and the compound (D) having a polymerizable unsaturated group (d2) are introduced into the polymerizable unsaturated group (y) in the copolymer (P). The functional group (d1) which the compound (D) has may, for example, be a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group or a carboxylic anhydride group. 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 anhydride group, and an epoxy group; When the functional group (c1) is an isocyanate group, the functional group (d1) may be a hydroxyl group; and when the reactive functional group (c1) is an epoxy group, the functional group (d1) may, for example, be a carboxyl group or a hydroxyl group; When the reactive functional group (c1) is a carboxyl group, the functional group (d1) may be a ring. Oxyl, hydroxyl. These may also employ a combination of a plurality of functional groups. Further, among these combinations, it is preferred that the reactive functional group (c1) is a hydroxyl group and the functional group (d1) is a combination of isocyanate groups, and the reactive functional group (c1) is an epoxy group and the aforementioned functional group ( D1) is a combination of carboxyl groups.

Further, the polymerizable unsaturated group (y) of the monomer (D) is preferably a carbon-carbon unsaturated double bond having a radical polymerizable property, and more specifically, a vinyl group or a (meth) group Acryl fluorenyl group, maleimide group, and the like. In the above, when the fluorine-containing polymerizable polymer of the present invention is added to the active energy ray-curable composition, the active energy ray-curable resin (E) and the active energy ray-curable monomer (F) to be described later are used. The hardenability is higher, preferably (meth) acrylonitrile, more preferably propylene sulfhydryl.

Specific examples of the compound (D) include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate. 2-hydroxybutyl methacrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono(meth) acrylate, N-(2-hydroxyethyl) (A) Acrylamide, glycerol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl ( a methyl group acrylate, 2-(meth) propylene oxirane ethyl 2-hydroxyethyl phthalate, and a hydroxyl group-containing unsaturated monomer such as a lactone modified (meth) acrylate at the terminal; 2-(methyl)propene oxime ethyl isocyanate, 2-(2-(methyl) propylene oxyethoxy) ethyl isocyanate, isocyanate-1, 1- bis (( An isocyanate group-containing unsaturated monomer such as methyl propylene oxide methyl ethyl acrylate; an epoxy group-containing unsaturated monomer such as glycidyl methacrylate or 4-hydroxybutyl acrylate propyl propyl ether (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(methyl) propylene hydride An unsaturated monomer having a carboxyl group such as oxyethyl decanoic acid, maleic acid or methylene succinic acid; an acid anhydride having an unsaturated double bond such as maleic anhydride or methylene succinic anhydride; and the like. Further, as a plurality of polymerizable unsaturated groups, 2-hydroxy-3-propenyl propyl methacrylate, neopentyl tetraacrylate, and dipentaerythritol pentaacrylate may be used. These compounds (D) may be used alone or in combination of two or more.

Among the specific examples of the above compound (D), particularly preferred from the viewpoint of polymerization hardenability under ultraviolet irradiation, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and 3-hydroxypropyl acrylate are preferred. Ester, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 1,4-cyclohexanedimethanol monoacrylate, N-(2-hydroxyethyl) acrylamide, isocyanate-2-propene Ethyloxyethyl ester, isocyanate-1,1-bis(acryloxymethyl)ethyl ester, 4-hydroxybutyl acrylate epoxypropyl ether, acrylic acid.

The method of reacting the above-mentioned copolymer (P), polymer (Q1) or polymer (Q2) with the above-mentioned compound (D) is carried out under the condition that the polymerizable unsaturated group possessed by the compound (D) or the like does not undergo polymerization. It is sufficient to carry out, for example, it is preferred to adjust the temperature conditions to a range of from 30 to 120 ° C for the reaction. The reaction is preferably carried out in the presence of a catalyst or a polymerization inhibitor, if necessary in the presence of an organic solvent.

For example, when the aforementioned reactive functional group (c1) is a hydroxyl group and the aforementioned functional group (d1) is an isocyanate group, it is preferred to use p-methoxyphenol, hydroquinone, 2,6-di-tertiary Base-4-methylphenol or the like as a polymerization inhibitor, and uses dibutyltin dilaurate, dibutyltin diacetate, tin octylate, zinc octoate or the like as a urethanization catalyst, at a reaction temperature of 40 to 120 ° C Especially, the method of reacting at 60~90 °C. also, When the reactive functional group (c1) is an epoxy group, the functional group (d1) is a carboxyl group, or the reactive functional group (c1) is a carboxyl group, and the functional group (d1) is an epoxy group, it is preferably In order to use p-methoxyphenol, hydroquinone, 2,6-di-tertiary butyl-4-methylphenol or the like as a polymerization inhibitor, a tertiary amine such as triethylamine or a tetramethyl chloride is used. A quaternary ammonium such as ammonium or a tertiary phosphine such as triphenylphosphine or a quaternary hydrazine such as tetrabutylphosphonium chloride is used as an esterification reaction catalyst at a reaction temperature of 80 to 130 ° C, particularly 100 to 120 ° C. Let it react.

The organic solvent used in the above reaction is preferably a ketone, an ester, a guanamine, an anthracene, an ether or a hydrocarbon, and specific examples thereof include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl azine, diethyl ether Diisopropyl ether, tetrahydrofuran, two Alkane, toluene, xylene, and the like. These can be appropriately selected by considering the boiling point and compatibility.

In the polymerizable resin of the present invention obtained as described above, the polymerizable resin in the form of a random copolymer is excellent in the number average molecular weight (Mn) because it can prevent gelation during production and has excellent antifouling properties. It is in the range of 3,000 to 100,000, more preferably in the range of 10,000 to 50,000. Further, the weight average molecular weight (Mw) is preferably in the range of 3,000 to 150,000, more preferably in the range of 10,000 to 75,000. Further, the degree of dispersion (Mw/Mn) of the polymerizable resin of the present invention is preferably from 1.0 to 1.5. More preferably 1.0 to 1.3, and most preferably 1.0 to 1.2.

In the polymerizable resin of the present invention obtained as described above, the polymerizable resin in the form of a block copolymer prevents coagulation during production. The gelation and antifouling property are excellent, and the number average molecular weight (Mn) thereof is preferably in the range of 3,000 to 100,000, more preferably in the range of 6,000 to 50,000, and still 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 still more preferably in the range of 10,000 to 35,000. Further, the degree of dispersion (Mw/Mn) of the polymerizable resin of the present invention is preferably from 1.0 to 1.5, more preferably from 1.0 to 1.4, most preferably from 1.0 to 1.3.

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

[GPC measurement conditions]

Measuring device: "HLC-8220 GPC" manufactured by TOSOH Co., Ltd.; pipe column: protective column "HHR-H" manufactured by TOSOH Co., Ltd. (6.0 mm I.D. × 4 cm)

+TSK-GEL GMHHR-N manufactured by TOSOH Co., Ltd. (7.8mmI.D.×30cm)

+TSK-GEL GMHHR-N manufactured by TOSOH Co., Ltd. (7.8mmI.D.×30cm)

+TSK-GEL GMHHR-N manufactured by TOSOH Co., Ltd. (7.8mmI.D.×30cm)

+TSK-GEL GMHHR-N manufactured by TOSOH Co., Ltd. (7.8mmI.D.×30cm)

Detector: ELSD ("Alltech Japan Co., Ltd." ELSD2000")

Data Processing: "GPC-8020 Type II Data Analysis Version 4.30" by TOSOH Co., Ltd.

Measurement conditions: column temperature 40 ° C

Developing solvent Tetrahydrofuran (THF)

Flow rate 1.0ml/min

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

Standard sample: The following monodisperse polystyrene having a known molecular weight was used in accordance with the above-mentioned "GPC-8020 Type II Data Analysis Version 4.30" measurement manual.

(monodisperse polystyrene)

"A-500" made by TOSOH Co., Ltd.

"A-1000" made by TOSOH Co., Ltd.

"A-2500" made by TOSOH Co., Ltd.

"A-5000" made by TOSOH Co., Ltd.

"F-1" made by TOSOH Co., Ltd.

"F-2" made by TOSOH Co., Ltd.

"F-4" made by TOSOH Co., Ltd.

"F-10" made by TOSOH Co., Ltd.

"F-20" made by TOSOH Co., Ltd.

"F-40" made by TOSOH Co., Ltd.

"F-80" made by TOSOH Co., Ltd.

"F-128" made by TOSOH Co., Ltd.

"F-288" made by TOSOH Co., Ltd.

"F-550" made by TOSOH Co., Ltd.

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

In addition, when the polymerizable resin of the present invention is a block copolymer-like polymerizable resin, it is excellent in compatibility with other resins, and can contribute to the smoothness and scratch resistance of the surface of the coating film. In terms of good segregation, the ratio of the first polymer segment (α) to the second polymer segment (β) in the polymerizable resin is preferably 10 in terms of mass ratio [(α) / (β)] The range of /90~90/10 is better in the range of 20/80~80/20, and better in the range of 30/70~70/30.

The polymerizable resin of the present invention can be used as a main component of an active energy ray-curable composition, but has excellent surface modification properties and is used as an active energy ray-curable composition. The surface modifier (surfactant) imparts excellent scratch resistance to the cured film.

In the active energy ray-curable composition of the present invention, the polymerizable resin of the present invention is added, and the main component contains the active energy ray-curable resin (E) or active other than the polymerizable resin of the present invention. Energy ray hardening monomer (F). Further, 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 singly or in combination. Further, the polymerizable resin of the present invention is preferably used as a fluorine-based surfactant in the active energy ray-curable composition.

Examples of the active energy ray-curable resin (E) include a urethane (meth) acrylate resin, an unsaturated polyester resin, an epoxy (meth) acrylate resin, and a polyester (meth) acrylate resin. In the present invention, in particular, from the viewpoint of transparency or low shrinkage, an acryl oxime (meth) acrylate resin, a resin having a maleimide group, and the like are preferable. Formate (meth) acrylate resin.

The urethane (meth) acrylate resin used herein may be an amine group obtained by reacting an aliphatic polyisocyanate compound or an aromatic polyisocyanate compound with a hydroxyl group-containing (meth) acrylate compound. A resin having an acid ester bond and a (meth) acrylonitrile group.

Examples of the aliphatic polyisocyanate compound include butyl butyl diisocyanate, amyl diisocyanate, hexyl diisocyanate, heptyl diisocyanate, and octyl diisocyanate. , diisocyanate diacetate, 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, diisocyanate didecyl ester, diiso 2-methylammonium cyanate, 2,2,4-trimethylhexyl diisocyanate, 2,4,4-trimethylhexyl hexanoate, isophorone Diisocyanate, norbornane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated diisocyanate, xylyl hydrogen diisocyanate, tetramethyl dimethyl benzene diisocyanate, diisocyanate ring Further, examples of the aromatic polyisocyanate compound include toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, dylyl diisocyanate, and diisocyanate-1,5. - naphthyl ester, tolidine diisocyanate, diphenyl isocyanate and the like.

Further, examples of the acrylate compound having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate. 4-hydroxybutyl methacrylate, 1,5-pentanediol mono(meth) acrylate, 1,6-hexanediol mono(meth) acrylate, neopentyl glycol mono(methyl) Mono(meth)acrylate of diol such as acrylate, hydroxytrimethylacetic acid neopentyl glycol mono(meth)acrylate; trimethylolpropane di(meth)acrylate, ethoxylated trishydroxyl Propane (meth) acrylate, trimethylolpropane di(meth) acrylate, glycerol di(meth) acrylate, bis(2-(methyl) propylene phthalate One or two (meth) acrylate of a trihydric alcohol such as oxyethyl)hydroxyethyl ester, or mono- and di(meth)acrylic acid having a hydroxyl group which is a part of the alcoholic hydroxyl group modified by ε-caprolactone An ester; a monofunctional hydroxyl group and a trifunctional or the like having neopentyl tetra(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate ( a methyl methacrylate compound, a polyfunctional (meth) acrylate which further modifies the hydroxyl group of the compound with ε-caprolactone; dipropylene glycol mono(meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene glycol (Meth) acrylate compound having an oxyalkylene chain such as (meth) acrylate or polyethylene glycol mono(meth) acrylate; polyethylene glycol-polypropylene glycol mono(meth) acrylate, polyoxygen a (meth) acrylate compound having a block structure of an oxyalkylene chain such as butyl-polyoxypropyl-propyl (meth) acrylate; poly(ethylene glycol-butane diol)-(methyl) (meth) acrylate compound having a random structure of an alkylene oxide chain such as acrylate, poly(propylene glycol-butanediol) mono(meth)acrylate or the like.

The above aliphatic polyisocyanate compound or aromatic poly The reaction of the isocyanate compound with the hydroxy group-containing acrylate compound can be carried out in the usual manner in the presence of a urethane catalyst. Specific examples of the urethane-based catalyst which can be used herein include amines such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine; and phosphines such as triphenylphosphine and triethylphosphine; An organic tin compound such as dibutyltin dilaurate, octyl trilaurate, octyl diacetate, dibutyltin diacetate or tin octylate; or an organometallic compound such as zinc octylate.

Among these urethane acrylate resins, in particular, those obtained by reacting an aliphatic polyisocyanate compound with a hydroxyl group-containing (meth) acrylate compound are excellent in transparency from a cured coating film and active energy rays. The viewpoint of good sensitivity and excellent hardenability is preferred.

Next, the unsaturated polyester resin is a curable resin obtained by condensation polymerization of an α,β-unsaturated dibasic acid or an anhydride thereof, an aromatic saturated dibasic acid or an anhydride thereof, and a diol, and is α. The β-unsaturated dibasic acid or an anhydride thereof may, for example, be maleic acid, maleic anhydride, fumaric acid, methylene succinic acid or methyl succinic acid. Chlorine maleic acid, and the like. Examples of the aromatic saturated dibasic acid or an acid anhydride thereof include decanoic acid, phthalic anhydride, isophthalic acid, p-citric acid, nitric acid, tetrahydrophthalic anhydride, and endomethylene tetrahydrophthalic anhydride. Halogenated phthalic anhydride and such esters. Examples of the aliphatic or alicyclic saturated dibasic acid include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, sebacic acid, glutaric acid, hexahydrophthalic anhydride, and the like. Ester and the like. Examples of the diols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,4-butanediol, and 2-methylpropane-1,3-diol. , neopentyl glycol, triethylene glycol, tetraethylene glycol, 1,5- Pentylene glycol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene carbonate, 2,2-bis(4-hydroxypropoxydiphenyl)propane, etc. An oxide such as ethylene oxide or propylene oxide is used.

Next, examples of the epoxy (meth) acrylate resin include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, and a cresol novolac type epoxy resin. The epoxy group of an epoxy resin, such as a resin, is reacted with (meth)acrylic acid.

Further, examples of the resin having a maleimide group include a bifunctional group obtained by subjecting N-hydroxyethyl maleimide and isophorone diisocyanate to ureidolation. a butylene diimine urethane compound, a bifunctional maleimide ester compound obtained by esterifying maleimide and acetic acid with polybutanediol, and a maleic acid a 4-functional maleimide ester compound obtained by esterifying a diterpene hexanoic acid with a tetraethylene oxide adduct of neopentyl alcohol, and a maleimide acetic acid and a polyol A polyfunctional maleimide ester compound obtained by esterification of a compound. 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, and triethylene glycol di(meth)acrylic acid. Polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(methyl) ester having an ester and a number average molecular weight in the range of 150 to 1000 An acrylate, a polypropylene glycol di(meth)acrylate, a neopentyl glycol di(meth)acrylate, a 1,3-butanediol di(meth)acrylate having a number average molecular weight of 150 to 1000, 1,4-butanediol II Methyl) acrylate, 1,6-hexanediol di(meth)acrylate, hydroxytrimethyl acetate neopentyl glycol di(meth)acrylate, bisphenol A di(meth)acrylate , trimethylolpropane tri(meth)acrylate, neopentyl tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, neopentyl tetra(meth)acrylate, trishydroxyl Methyl propane di(meth)acrylate, dipentaerythritol penta(meth)acrylate, dicyclopentenyl (meth)acrylate, methyl (meth)acrylate, propyl (meth)acrylate, Butyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, (methyl) An aliphatic (meth)acrylic acid alkyl ester such as isodecyl acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate or isostearyl (meth)acrylate; Triol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, (methyl) ) allyl acrylate, 2-butoxyethyl (meth)acrylate, (meth) propylene Acid-2-(diethylamino)ethyl ester, 2-(dimethylamino)ethyl (meth)acrylate, γ-(meth)acryloxypropyltrimethoxydecane, (methyl) 2-methoxyethyl acrylate, methoxydiethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, nonyl phenoxy polyethylene glycol (meth) acrylate, Nonylphenoxy polypropylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy dipropylene glycol (meth) acrylate, phenoxy polypropylene glycol (meth) acrylate, polybutylene Alkene (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polyethylene glycol-polybutylene glycol (meth) acrylate, polystyrene ethyl (meth) acrylate, ( Methyl methacrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isodecyl (meth)acrylate, methoxy Cyclonetriene (meth) acrylate, phenyl (meth) acrylate; maleimide, N-methyl maleimide, N-ethylbutylene Amine, N-propyl maleimide, N-butyl maleimide, N-hexyl maleimide, N-octyl maleimide, N-dodecane Isobutylene diimide, N-octadecyl maleimide, N-phenyl maleimide, N-cyclohexyl maleimide, 2-cis Butylene diamine imine ethyl-ethyl carbonate, 2-m-butylenediamine ethyl propyl carbonate, uric acid-N-ethyl-(2-m-butylene iminoacetate) , N,N-extended bis-bis-butenylene diimide, polypropylene glycol-bis(3-maleoximeimidopropyl) ether, bis(2-maleimide) And a maleimide such as 1,4-dimethyleneimine cyclohexane or the like.

Among these, in particular, from the viewpoint of excellent hardness of the cured coating film, trimethylolpropane tri(meth)acrylate, neopentyl tris(meth)acrylate, and hexa(meth)acrylic acid are preferred. A trifunctional or higher polyfunctional (meth) acrylate such as neopentyl ester or neopentyl tetra(meth)acrylate. 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 of the present invention is 100 parts by mass based on the total of the active energy ray-curable resin (E) and the active energy ray-curable monomer (F). It is preferably in the range of 0.001 to 20 parts by mass, more preferably in the range of 0.01 to 15 parts by mass, more preferably in the range of 0.1 to 15 parts by mass, even more preferably in the range of 0.1 to 10 parts by mass, particularly preferably 0.5 to 15 parts by mass. The range of parts by mass. When the amount of the polymerizable resin of the present invention is in this range, the leveling property, water and oil repellency, and antifouling property can be made more sufficient, and the composition can be hardened after hardening. Degree or transparency is more sufficient. In addition, since the ratio of the polymerizable resin of the present invention to the surface layer portion of the coating film is changed according to the film thickness when the active energy ray-curable composition of the present invention is formed into a coating film, when a thick film is used, The addition amount of the polymerizable resin of the present invention is set to be low, and when it is a film, the addition amount of the polymerizable resin of the present invention is set to be high, whereby the polymerizable resin of the present invention can be uniformly obtained. It is present on the surface of the coating film and is expected to have high scratch resistance.

The polymerizable resin or active energy ray-curable composition of the present invention can form a cured coating film by applying an active energy ray after being applied to a substrate. The active energy ray means free radiation such as ultraviolet rays, electron beams, alpha rays, beta rays, and gamma rays. When the coating film is cured by irradiation of ultraviolet rays as an active energy ray, it is preferred to add a photopolymerization initiator (G) to the polymerizable resin or the active energy ray-curable composition to improve the hardenability. Further, a photosensitizer may be further added as necessary to enhance the hardenability. Further, when free radiation such as an electron beam, an α line, a β line, or a γ line is used, even if a photopolymerization initiator or a photosensitizer is not used, it can be hardened rapidly, so that it is not particularly necessary to add a photopolymerization initiator ( G) or a photosensitizer.

Examples of the photopolymerization initiator (G) include an intramolecular cleavage type photopolymerization initiator and a hydrogen absorbing photopolymerization initiator. Examples of the intramolecular splitting type photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and benzyldimethylketal. 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- Phytyl (4-methylthiophenyl) propan-1-one, 2-benzyl-2-dimethylamino-1-(4- An acetophenone compound such as phenyl phenyl) butanone; benzoin such as benzoin, benzoin methyl ether, benzoin isopropyl ether; 2,4,6-trimethylbenzoin diphenylphosphine oxide, double (2 a fluorenyl phosphine oxide compound such as 4,6-trimethylbenzylidene phenylphosphine oxide; benzamidine or methyl phenyl glyoxylate.

Further, examples of the hydrogen capture type photopolymerization initiator include diphenyl ketone, phthalic acid benzoic acid methyl-4-phenyl diphenyl ketone, and 4,4'-dichlorodiphenyl ketone. Hydroxydiphenyl ketone, 4-benzylidene-4'-methyl-diphenyl sulfide, propylene diphenyl ketone, 3,3',4,4'-tetra (tributyl peroxide) a diphenyl ketone compound such as carbonyl)diphenyl ketone or 3,3'-dimethyl-4-methoxydiphenyl ketone; 2-isopropylthioxanthone or 2,4-dimethyl a thioxanthone compound such as thioxanthone, 2,4-diethylthiaxanone or 2,4-dichlorothiazinone; Michler's ketone, 4,4'-di An aminodiphenyl ketone compound such as ethylaminodiphenyl ketone; 10-butyl-2-chloroacridone, 2-ethyl hydrazine, 9,10-phenanthrenequinone, camphorquinone, etc. .

In the photopolymerization initiator (F), the compatibility of the active energy ray-curable resin (E) and the active energy ray-curable monomer (F) in the active energy ray-curable composition is excellent. Preferred is 1-hydroxycyclohexyl phenyl ketone and diphenyl ketone, particularly preferably 1-hydroxycyclohexyl phenyl ketone. These photopolymerization initiators (G) may be used alone or in combination of two or more.

In addition, examples of the photosensitizer include amines such as aliphatic amines and aromatic amines; ureas such as o-tolylthiourea; sodium diethyldithiophosphate and s-benzoic acid; A sulfur compound such as s-benzyl thiouronium-p-toluene sulfonate or the like.

Non-volatile in the hardenable composition relative to the active energy ray The amount of the photopolymerization initiator and the photosensitizer is preferably from 0.01 to 20 parts by mass, more preferably from 0.1 to 15% by mass, even more preferably from 0.3 to 7 parts by mass, per 100 parts by mass of the component.

Further, 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 adjust other coating properties or coating film, within the range not impairing the effects of the present invention, depending on the purpose of use, characteristics, and the like. For the purpose of physical properties, various blending materials such as various organic solvents, acrylic resins, phenol resins, polyester resins, polystyrene resins, urethane resins, urea resins, melamine resins, alkyd resins can be used in combination. Various resins such as epoxy resin, polyamide resin, polycarbonate resin, petroleum resin, fluororesin, etc.; PTFE (polytetrafluoroethylene), polyethylene, polypropylene, carbon, titanium oxide, aluminum oxide, copper, ruthenium Various organic or inorganic particles such as stone particles; polymerization initiators, polymerization inhibitors, antistatic agents, defoamers, viscosity modifiers, light stabilizers, weather stabilizers, heat stabilizers, antioxidants, rust inhibitors, A lubricant, a wax, a gloss modifier, a mold release agent, a phase solvent, a conductivity adjuster, a pigment, a dye, a dispersant, a dispersion stabilizer, a polysiloxane, a hydrocarbon surfactant, etc. .

Among 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, for film coating, it is easier to adjust the film thickness. Examples of the organic solvent that can be used herein include aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, isopropanol, and tertiary butanol; and esters such as ethyl acetate and propylene glycol monomethyl ether acetate. Classes; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. These solvents can be used alone Or use two or more types together.

Here, the amount of the organic solvent varies depending on the application and the target film thickness or viscosity, but is preferably in the range of 0.5 to 50 times by mass based on the total mass of the hardened component.

As the active energy ray which hardens the active energy ray-curable composition of the present invention, such as the above, there are free radiation of ultraviolet rays, electron beams, α rays, β rays, and γ wires, but as a specific energy source or curing device, For example, ultraviolet light using a germicidal lamp, a fluorescent lamp for ultraviolet light, a carbon arc, a xenon lamp, a high pressure mercury lamp for photocopying, a medium pressure or high pressure mercury lamp, an ultrahigh pressure mercury lamp, an electrodeless lamp, a metal halide lamp, natural light, or the like, Or use a scanning type, an electron beam of a curtain type electron beam accelerator, or the like.

Among these, ultraviolet rays are particularly preferred, and in order to avoid hardening inhibition by oxygen or the like, it is preferred to irradiate ultraviolet rays in an inert gas atmosphere such as nitrogen. Further, heat may be used as an energy source in combination with heat, and then heat-treated by ultraviolet rays.

The application method of the active energy ray-curable composition of the present invention varies depending on the application, and examples thereof include a gravure coater, a roll coater, a comma coater, a knife coater, and an air knife. Coating machine, curtain coater, kiss coater, shower coater, Wheeler coater, spin coater, dip coater, screen printing, A coating method such as a spray, an applicator, a bar coater, or the like, or a molding method using various molds.

The cured coating film of the polymerizable resin of the present invention is resistant to The scratch resistance can be imparted to the surface of the article by scratch resistance by being applied to the surface of the article and hardened. Further, the polymerizable resin of the present invention can impart a leveling property to the coating material by being added to the coating material, whereby the active energy ray-hardening composition of the present invention has high leveling property. Further, the cured coating film of the polymerizable resin of the present invention is excellent in smoothness, and has an effect of good touch operation such as a touch panel. Further, the cured coating film of the polymerizable resin of the present invention is 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, and is applied to the surface of the article and cured to impart scratch resistance to the surface of the article.

Examples of the article which can prevent scratches by using the polymerizable resin or the active energy ray-curable composition of the present invention include a film for a polarizing plate of a liquid crystal display (LCD) such as a TAC film; a plasma display (PDP) and an organic EL. Various display screens such as displays; touch panels; outer casings or screens of electronic terminals such as mobile phones; transparent protective films for color filters for liquid crystal displays (hereinafter referred to as "CF"); organic insulating films for liquid crystal TFT arrays; electronic circuits Forming ink for jetting; optical recording medium such as CD, DVD, Blu-ray disc; transfer film for insert molding (IMD, IMF); OA machine rubber roller for copying machine, printer, etc.; copier, scanning Glass surface of reading part of OA machine such as machine; optical lens of camera, camera, glasses, etc.; windproof and glass surface of watch such as watch; window of various vehicles such as automobile and railway vehicle; coated glass or film for solar cell ; various building materials such as veneer panels; window glass for residential buildings; woodworking materials for furniture, artificial and synthetic leather, and exterior molding of home appliances, etc. Products, FRP bathtubs, etc. By applying the active energy ray-curable composition of the present invention to the surface of such articles and irradiating an active energy ray such as ultraviolet rays to form a cured coating film, the surface of the article can be imparted with scratch resistance.

In addition, as a coating material which can provide the abrasion resistance of the polymerizable resin of the present invention, a hard coat material for a film for a polarizing plate of an LCD such as a TAC film, and an anti-glare (AG: anti-glare) coating layer can be given. Material or anti-reflective (LR) coating material; hard coating material for various display screens such as plasma display (PDP), organic EL display; hard coating material for touch panel; for forming RGB paintings used in CF Color resists, printing inks, jet inks or coatings; black photoresists for black matrix of CF, printing inks, jet inks or coatings; pixels for plasma display (PDP), organic EL displays, etc. a resin composition for a bulkhead; a coating or hard-coating material for an electronic terminal housing such as a mobile phone; a hard-coating material for a screen of a mobile phone; a coating for a transparent protective film for protecting a CF surface; Coating for organic insulating film; jet printing ink for electronic circuit formation; hard coating material for optical recording medium such as CD, DVD, Blu-ray disc, etc.; hard coating material for transfer film for embedded forming (IMD, IMF); For OA machines such as copiers and printers Coating materials for rolls; coating materials for glass for reading parts of OA machines such as copiers and scanners; coating materials for optical lenses for cameras, cameras, glasses, etc.; windproof and glass coating materials for watches and the like Coating materials for windows of various vehicles such as automobiles and railway vehicles; coatings for anti-reflective coatings for coated glass or film for solar cells; printing inks or coatings for various building materials such as veneer panels; Layer materials; woodworking coatings for furniture; coating materials for artificial and synthetic leather; various plastics such as home exterior frames Coatings or coating materials for shaped products; coatings or coating materials for FRP bathtubs.

Further, examples of the article which can impart scratch resistance (scratch resistance) by using the polymerizable resin or the active energy ray-curable composition of the present invention include a ruthenium sheet or a diffusion sheet which is a backlight element of an LCD. Further, by adding the polymerizable resin of the present invention to a coating material for a sheet or a diffusion sheet, the coating film can be imparted with scratch resistance (scratch resistance) while improving the leveling property of the coating material. ) and antifouling properties.

In addition, the cured coating film of the polymerizable resin of the present invention has a low refractive index, and a coating material for a low refractive index layer in an antireflection layer for preventing glare of various display surfaces such as an LCD such as a fluorescent lamp can be used. Further, by adding the fluorinated curable resin of the present invention to the coating material for the reflective layer, particularly the coating material for the low refractive index layer in the antireflection layer, the low refractive index of the coating film can be maintained, and it is also possible to impart The surface of the coating film is scratch resistant.

Further, as other applications in which the polymerizable resin or the active energy ray-curable composition of the present invention can be used, an optical fiber clad material, a waveguide, a sealing material for a liquid crystal panel, and various optical seals are exemplified. Materials, optical adhesives, etc.

In particular, in the use of a coating material for a protective film for a polarizing plate for LCD, when the active energy ray-curable composition of the present invention is used as an anti-blind coating material, in each of the above compositions, In the active energy ray-curable composition, the ratio of 0.1 to 0.5 times the total mass of the hardened component is mixed with inorganic or organic fine particles such as vermiculite fine particles, acrylic resin fine particles, and polystyrene resin fine particles. Excellent in glare and better.

Further, when the polymerizable resin or the active energy ray-curable composition of the present invention is used as an anti-blind coating material for a protective film for a polarizing plate for LCD, it can also be applied to a surface which contacts the uneven surface before hardening the coating material. After the shape of the mold, the active energy ray is irradiated from the opposite side of the mold to be hardened, and the surface of the coating layer is embossed to impart an anti-glare transfer method.

[Examples]

Hereinafter, specific embodiments of the present invention will be described in more detail. In the example, "parts" and "%" are quality benchmarks if not stated in advance. Further, the IR spectrum, ¹³ C-NMR spectrum and GPC measurement conditions of the obtained polymerizable resin were as follows.

[IR Spectrometric Conditions]

Device: "NICOLET380" manufactured by Thermo Electron Co., Ltd.

Measuring method: KBr method

[ ¹³ C-NMR Spectrometric Conditions]

Device: "JNM-ECA500" manufactured by Nippon Electronics Co., Ltd.

Solvent: DMSO-d ₆

[GPC measurement conditions]

Measuring device: "HLC-8220 GPC" manufactured by TOSOH Co., Ltd.; pipe column: "HHR-H" (6.0mmI.D. × 4cm) manufactured by TOSOH Co., Ltd. + "TSK-GEL" manufactured by TOSOH Co., Ltd. GMHHR-N" (7.8mmI.D.×30cm) + made by TOSOH Co., Ltd. "TSK-GEL GMHHR-N" (7.8mmI.D.×30cm) + "TSK-GEL GMHHR-N" (7.8mmI.D.×30cm) manufactured by TOSOH Co., Ltd. + "TSK-GEL" manufactured by TOSOH Co., Ltd. GMHHR-N" (7.8mmI.D.×30cm)

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

Data Processing: "GPC-8020 Type II Data Analysis Version 4.30" by TOSOH Co., Ltd.

Measurement conditions: column temperature 40 ° C

Developing solvent Tetrahydrofuran (THF)

Flow rate 1.0ml/min

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

Standard sample: The following monodisperse polystyrene having a known molecular weight was used in accordance with the above-mentioned "GPC-8020 Type II Data Analysis Version 4.30" measurement manual.

(monodisperse polystyrene)

"A-500" made by TOSOH Co., Ltd.

"A-1000" made by TOSOH Co., Ltd.

"A-2500" made by TOSOH Co., Ltd.

"A-5000" made by TOSOH Co., Ltd.

"F-1" made by TOSOH Co., Ltd.

"F-2" made by TOSOH Co., Ltd.

"F-4" made by TOSOH Co., Ltd.

"F-10" made by TOSOH Co., Ltd.

"F-20" made by TOSOH Co., Ltd.

"F-40" made by TOSOH Co., Ltd.

"F-80" made by TOSOH Co., Ltd.

"F-128" made by TOSOH Co., Ltd.

"F-288" made by TOSOH Co., Ltd.

"F-550" made by TOSOH Co., Ltd.

Example 1 (modulation of a 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 and 25.2 g of a polyxanthene compound having a hydroxyl group at one terminal end represented by the following formula (a-1) and 0.66 were charged. g Triethylamine as a catalyst was stirred for 30 minutes while maintaining the temperature inside the flask at 5 °C.

(where n is an average of 65).

Next, 1.50 g of 2-bromoisobutylphosphonium bromide was charged and stirred for 3 hours, and the temperature was raised to 40 ° C and stirred for 8 hours. After the completion of the reaction, the mixture was stirred and washed by mixing and stirring 80 g of ion-exchanged water, and the aqueous layer was separated and removed. Next, the dehydrating agent was filtered off by adding 8 g of magnesium sulfate as a dehydrating agent and allowing to stand for one day to completely dehydrate. Then, by distilling off the solvent under reduced pressure, a functional group having a radical generating ability and a polyoxyl group having a molecular weight of 2,000 or more, which are used in the present invention represented by the following formula (A-4), are obtained. Chain of compounds.

(where n is an average of 65).

Next, 14.2 g of isopropyl alcohol, 14.2 g of methyl ethyl ketone, and 6.0 g of methacrylic acid were placed in a nitrogen-substituted glass flask equipped with a nitrogen gas introduction tube, a stirring device, a thermometer, a cooling tube, and a dropping device. Fluorohexylethyl ester and 4.3 g of 2-hydroxyethyl methacrylate were heated to 35 ° C while stirring under a nitrogen gas stream, and stirred for 2 hours. Next, 0.335 g of cuprous chloride and 0.937 g of 2,2-bipyridine were charged, and the mixture was heated to 60 ° C and stirred for 1 hour. Next, 15.04 g of the above compound (A-4) was added and dissolved in 5.0 g of isopropyl alcohol and 5.0 g of methyl ethyl ketone, and the mixture was stirred at a temperature of 60 ° C for 4 hours, and then heated to 80 ° C. Stir for 7 hours. The reaction mixture was dissolved in methanol, and reprecipitated by water/methanol to give a random copolymer (P-1).

Next, 50.0 g of the obtained copolymer (P-1), 50.0 g of methyl ethyl ketone, and 0.1 g of a polymerization inhibitor were placed in a glass flask equipped with a nitrogen gas introduction tube, a stirring device, a thermometer, a cooling tube, and a dropping device. P-methoxyphenol, 0.03 g of tin octylate as a urethane catalyst, was stirred under air flow, and while maintaining 60 ° C, 15.6 g of isocyanate-2-propene oxide was dropped over 1 hour. ester. After the completion of the dropwise addition, the mixture was stirred at 60 ° C for 1 hour, and then heated to 80 ° C and stirred for 10 hours. Thus, the disappearance of the isocyanate group was confirmed by IR spectrum measurement, and the active energy was obtained by adding 15.6 g of methyl ethyl ketone. A linear curable group of the polymerizable resin (1) of the present invention.

The molecular weight of the obtained polymerizable resin (1) was measured by GPC (molecular weight converted to polystyrene), and the number average molecular weight was 11,000, the weight average molecular weight was 12,000, and the radical polymerizable unsaturated group equivalent was 904 g/eq. Further, the spectrum of the IR spectrum of the polymerizable resin (1) is shown in Fig. 1, the spectrum of the ¹³ C-NMR spectrum is shown in Fig. 2, and the map of GPC is shown in Fig. 3.

Example 2 (ibid.)

30.70 g of isopropyl alcohol, 30.70 g of methyl ethyl ketone, and 10.93 g of decafluorohexyl methacrylate, in a glass flask equipped with a nitrogen gas introduction tube, a stirring device, a thermometer, a cooling tube and a nitrogen atmosphere, 0.5470 g of methoxybenzene was stirred at 25 ° C for 1 hour while stirring under a nitrogen stream. Next, 0.4510 g of cuprous chloride, 0.1130 g of copper bromide, and 1.581 g of 2,2-bipyridine were charged and stirred for 30 minutes. After the temperature was raised to 60 ° C, 30 g of the above compound (A-4) was added, and the mixture was stirred at a temperature of 60 ° C for 4 hours. Thereafter, 6.585 g of 2-hydroxyethyl methacrylate was charged and stirred for 1 hour. Thereafter, the temperature was raised to 75 ° C and stirred for 31 hours. 1.167 g of an 85% aqueous phosphoric acid solution was added under air and stirred for 2 hours, and the precipitated solid component was filtered off. The catalyst was removed using an ion exchange resin, and the ion exchange resin was filtered off to obtain a block copolymer (Q1-1).

Next, 32.54 g of the obtained copolymer (Q1-1), 36.70 g of methyl isobutyl ketone, and 0.0149 parts by mass were placed in a glass flask equipped with a nitrogen gas introduction tube, a stirring device, a thermometer, a cooling tube, and a dropping device as polymerization inhibition. The mixture of p-methoxyphenol, 0.1116g of dibutylhydroxytoluene and 0.0111g of tin octylate as the urethane catalyst, was stirred under air flow, while maintaining 60 ° C, adding 4.67 g of isocyanic acid. 2-propenyloxyethyl ester. Thereafter, the mixture was stirred at 60 ° C for 1 hour, and then heated to 80 ° C and stirred for 4 hours. Thus, it was confirmed by IR spectrum measurement that the isocyanate group disappeared, and by adding 50.46 g of methyl isobutyl ketone, 30 mass was obtained. % of a methyl isobutyl ketone solution of the polymerizable resin (2) of the present invention having an active energy ray-curable group. The molecular weight of the obtained polymerizable resin (2) was measured by GPC (molecular weight converted to polystyrene), and the number average molecular weight was 10,500, and the weight average molecular weight was 12,000. In addition, the spectrum of the IR spectrum of the polymerizable resin (2) is shown in Fig. 4, the spectrum of the ¹ H-NMR spectrum (the whole figure) is shown in Fig. 5, and the spectrum of the ¹ H-NMR spectrum (25 times). The enlarged view is shown in Fig. 6 , the map of ¹³ C-NMR spectrum (the whole figure) is shown in Fig. 7, and the map of ¹³ C-NMR spectrum (25-fold enlarged view) is shown in Fig. 8, and ¹⁹ F is shown. The map of the -NMR spectrum (whole graph) is shown in Fig. 9, and the map of GPC is shown in Fig. 10.

Example 3 (ibid.)

In a glass flask equipped with a nitrogen gas introduction tube, a stirring device, a thermometer, a cooling tube and replaced with nitrogen, 54.88 g of isopropyl alcohol, 54.88 g of methyl ethyl ketone, and 13.17 g of 2-hydroxyethyl methacrylate were used. 1.094 g of methoxybenzene was stirred at 25 ° C for 1 hour while stirring under a nitrogen stream. Next, 0.9017 g of cuprous chloride, 0.2261 g of copper bromide, and 3.162 g of 2,2-bipyridine were charged and stirred for 30 minutes. After the temperature was raised to 60 ° C, 60 g of the above compound (A-4) was added, and the mixture was stirred at a temperature of 60 ° C for 3 hours. Thereafter, 21.87 g of tridecafluorohexyl methacrylate was charged and stirred for 1 hour. Thereafter, the temperature was raised to 75 ° C and stirred for 37.5 hours. 2.34 g of an 85% aqueous phosphoric acid solution was added under air and stirred for 2 hours, and the precipitated solid component was filtered off. The catalyst was removed using an ion exchange resin, and the ion exchange resin was filtered off to obtain a block copolymer (Q2-1).

Next, 68.15 g of the obtained copolymer (Q2-1), 51.47 g of methyl isobutyl ketone, and 0.0311 parts by mass were placed in a glass flask equipped with a nitrogen gas introduction tube, a stirring device, a thermometer, a cooling tube, and a dropping device as polymerization inhibition. The mixture of p-methoxyphenol, 0.2335 g of dibutylhydroxytoluene and 0.0234 g of tin octylate as the urethane catalyst, was stirred under air flow, while maintaining 60 ° C, adding 9.69 g of isocyanic acid. 2-propenyloxyethyl ester. Thereafter, the mixture was stirred at 60 ° C for 1 hour, and then heated to 80 ° C and stirred for 4 hours. Thus, it was confirmed by IR spectrum measurement that the isocyanate group disappeared, and by adding 86.00 g of methyl isobutyl ketone, 30 mass was obtained. % of a methyl isobutyl ketone solution of the polymerizable resin (3) of the present invention having an active energy ray-curable group. The molecular weight of the obtained polymerizable resin (3) was measured by GPC (molecular weight converted to polystyrene), and the number average molecular weight was 10,100, and the weight average molecular weight was 14,000.

Example 4 (ibid.)

In a glass flask equipped with a nitrogen gas introduction tube, a stirring device, a thermometer, a cooling tube and replaced with nitrogen, 32.20 g of isopropyl alcohol, 32.20 g of methyl ethyl ketone, and 12.97 g of tridecafluorohexyl methacrylate were used. 0.6480 g of methoxybenzene was stirred at 25 ° C for 1 hour while stirring under a nitrogen stream. Next, 0.5350 g of cuprous chloride, 0.1370 g of copper bromide, and 1.874 g of 2,2-bipyridine were charged and stirred for 30 minutes. After the temperature was raised to 60 ° C, 30.06 g of the above compound (A-4) was added, and the mixture was stirred at a temperature of 60 ° C for 4.5 hours. Thereafter, 3.900 g of 2-hydroxyethyl methacrylate was charged and stirred for 1 hour. Thereafter, the temperature was raised to 75 ° C and stirred for 31 hours. 1.370 g of 36% hydrochloric acid was added under air and stirred for 2 hours, and the precipitated solid component was filtered off. Use ion exchange resin to remove the catalyst and filter out the ion exchange tree The block copolymer (Q1-2) was obtained by fat.

Next, 31.61 g of the obtained copolymer (Q1-2), 19.16 g of methyl isobutyl ketone, and 0.0137 parts by mass were placed in a glass flask equipped with a nitrogen gas introduction tube, a stirring device, a thermometer, a cooling tube, and a dropping device as polymerization inhibition. The mixture of p-methoxyphenol, 0.1025 g of dibutylhydroxytoluene and 0.0103 g of tin octoate as the urethane catalyst, was stirred under air flow, while maintaining 60 ° C, adding 2.56 g of isocyanic acid. 2-propenyloxyethyl ester. Thereafter, the mixture was stirred at 60 ° C for 2 hours, and then heated to 80 ° C and stirred for 3 hours. Thus, it was confirmed by IR spectrum measurement that the isocyanate group disappeared, and by adding 56.44 g of methyl isobutyl ketone, 30 mass was obtained. A methyl isobutyl ketone solution of the polymerizable resin (4) of the present invention having an active energy ray-curable group. The molecular weight of the obtained polymerizable resin (4) was measured by GPC (molecular weight converted to polystyrene), and the number average molecular weight was 8,700, and the weight average molecular weight was 10,000.

Example 5 (ibid.)

In a glass flask equipped with a nitrogen gas introduction tube, a stirring device, a thermometer, a cooling tube and replaced with nitrogen, 30.28 g of isopropyl alcohol, 30.28 g of methyl ethyl ketone, and 10.37 g of tridecafluorohexyl methacrylate were used. 0.6480 g of methoxybenzene was stirred at 25 ° C for 1 hour while stirring under a nitrogen stream. Next, 0.5350 g of cuprous chloride, 0.1370 g of copper bromide, and 1.874 g of 2,2-bipyridine were charged and stirred for 30 minutes. After the temperature was raised to 60 ° C, 30.00 g of the above compound (A-1) was added, and the mixture was stirred at a temperature of 60 ° C for 4 hours. Thereafter, 9.37 g of 2-hydroxyethyl methacrylate was charged and stirred for 1 hour. Thereafter, the temperature was raised to 75 ° C and stirred for 30 hours. 1.383 g of 85% phosphoric acid was added under air and stirred for 2 hours, and the precipitated solid component was filtered off. Use away The sub-exchange resin removes the catalyst, and the ion exchange resin is filtered off to obtain a block copolymer (Q1-3).

Next, 33.93 g of the obtained copolymer (Q1-3), 22.64 g of methyl isobutyl ketone, and 0.0162 parts by mass were placed in a glass flask equipped with a nitrogen gas introduction tube, a stirring device, a thermometer, a cooling tube, and a dropping device as polymerization inhibition. The mixture of p-methoxyphenol, 0.1215 g of dibutylhydroxytoluene and 0.0122 g of tin octylate as the urethane catalyst, was stirred under air flow, while maintaining 60 ° C, adding 6.576 g of isocyanic acid. 2-propenyloxyethyl ester. Thereafter, the mixture was stirred at 60 ° C for 2 hours, and then heated to 80 ° C and stirred for 4 hours. Thus, it was confirmed by IR spectrum measurement that the isocyanate group disappeared, and by adding 71.85 g of methyl isobutyl ketone, 30 mass was obtained. % of a methyl isobutyl ketone solution of the polymerizable resin (5) of the present invention having an active energy ray-curable group. The molecular weight of the obtained polymerizable resin (5) was measured by GPC (molecular weight converted to polystyrene), and the number average molecular weight was 10,500, and the weight average molecular weight was 13,400.

Example 6 (ibid.)

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 300 g of a polyxanthene compound having a hydroxyl group at one terminal end represented by the above formula (a-1) were charged. In the middle, n was 130) on average, and 7.03 g of triethylamine as a catalyst was stirred for 30 minutes while maintaining the temperature inside the flask at 40 °C.

Next, 12.79 g of 2-bromoisobutylphosphonium bromide was charged 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 stirred and stirred, and the hydrochloric acid layer was separated and removed. Thereafter, 600 g of a saturated aqueous solution of sodium hydrogencarbonate was stirred and stirred, and then allowed to stand to make saturated hydrogencarbonate. The sodium aqueous layer was separated and removed, and then 600 g of ion-exchanged water was mixed and stirred, and the ion-exchanged water layer was separated and removed. Next, 25 g of magnesium sulfate as a dehydrating agent was added and mixed by shaking to dehydrate, and then the dehydrating agent was filtered off. Thereafter, the solvent was distilled off under reduced pressure, and the obtained residue was dissolved in 303.25 g of isopropyl ether. After stirring 303.25 g of 0.36% hydrochloric acid, the mixture was allowed to stand, and the hydrochloric acid layer was separated and removed. Thereafter, 303.25 g of a 1% aqueous sodium hydroxide solution was stirred and stirred, and the mixture was allowed to stand, and the 1% aqueous sodium hydroxide layer was separated and removed. Further, 300 g of ion-exchanged water was further stirred and stirred, and then allowed to stand to separate the ion-exchanged water layer. And removed. Thereafter, 300 g of ion-exchanged water was further stirred and stirred, and the ion-exchanged aqueous layer was separated and removed. Then, 25 g of magnesium sulfate as a dehydrating agent was added, and the mixture was shaken and dehydrated, and then the dehydrating agent was filtered off. Then, the solvent was distilled off under reduced pressure to obtain the compound (A-4-2) used in the present invention represented by the above formula.

(where n is an average of 130).

56.08 g of isopropanol, 56.08 g of methyl ethyl ketone, and 14.77 g of tridecafluorohexyl methacrylate were placed in a nitrogen-substituted glass flask equipped with a nitrogen gas introduction tube, a stirring device, a thermometer, and a cooling tube. 0.7387 g of methoxybenzene was stirred at 25 ° C for 1 hour while stirring under a nitrogen stream. Next, 0.6089 g of cuprous chloride, 0.1527 g of copper bromide, and 2.135 g of 2,2-bipyridine were charged and stirred for 30 minutes. After heating to 60 ° C, 60.00 g of the above compound (A-4-1) was added to maintain the temperature inside the flask. Stir at 60 ° C for 9 hours. Thereafter, 8.893 g of 2-hydroxyethyl methacrylate was charged and stirred for 1 hour. Thereafter, the temperature was raised to 75 ° C and stirred for 48 hours. 1.576 g of an 85% aqueous phosphoric acid solution was added under air and stirred for 2 hours, and the precipitated solid component was filtered off. The catalyst was removed using an ion exchange resin, and the ion exchange resin was filtered off to obtain a block copolymer (Q1-4).

Next, 58.56 g of the obtained copolymer (Q1-4), 39.04 g of methyl isobutyl ketone, and 0.0260 parts by mass were placed in a glass flask equipped with a nitrogen gas introduction tube, a stirring device, a thermometer, a cooling tube, and a dropping device as polymerization inhibition. The mixture of p-methoxyphenol, 0.1949 g of dibutylhydroxytoluene and 0.0195 g of tin octylate as the urethane catalyst, was stirred under air flow, while maintaining 60 ° C, adding 6.407 g of isocyanic acid. 2-propenyloxyethyl ester. Thereafter, the mixture was stirred at 60 ° C for 2 hours, and then heated to 80 ° C and stirred for 5 hours. Thus, it was confirmed by IR spectrum measurement that the isocyanate group disappeared, and further, by adding 112.54 g of methyl isobutyl ketone, 30 mass was obtained. % of a methyl isobutyl ketone solution of the polymerizable resin (6) of the present invention having an active energy ray-curable group. The molecular weight of the obtained polymerizable resin (6) was measured by GPC (molecular weight converted to polystyrene), and the number average molecular weight was 16,000, and the weight average molecular weight was 19,000.

Example 7 (ibid.)

In a glass flask equipped with a nitrogen gas introduction tube, a stirring device, a thermometer, a cooling tube and replaced with nitrogen, 69.37 g of isopropyl alcohol, 69.37 g of methyl ethyl ketone, and 32.49 g of tridecafluorohexyl methacrylate were used. 0.7387 g of methoxybenzene was stirred at 25 ° C for 1 hour while stirring under a nitrogen stream. Next, 0.6089 g of cuprous chloride, 0.1527 g of copper bromide, and 2.135 g of 2,2-bipyridine were charged and stirred for 30 minutes. After heating to 60 ° C, add 60.00g The above compound (A-4-1) was stirred for 12 hours while maintaining the temperature inside the flask at 60 °C. Thereafter, 31.27 g of 2-hydroxyethyl methacrylate was charged and stirred for 1 hour. Thereafter, the temperature was raised to 75 ° C and stirred for 81 hours. 1.576 g of an 85% aqueous phosphoric acid solution was added under air and stirred for 2 hours, and the precipitated solid component was filtered off. The catalyst was removed using an ion exchange resin, and the ion exchange resin was filtered off to obtain a block copolymer (Q1-5).

Next, 93.17 g of the obtained copolymer (Q1-5), 62.10 g of methyl isobutyl ketone, and 0.0470 parts by mass were placed in a glass flask equipped with a nitrogen gas introduction tube, a stirring device, a thermometer, a cooling tube, and a dropping device as polymerization inhibition. The mixture of p-methoxyphenol, 0.3522g of dibutylhydroxytoluene and 0.0352g of tin octylate as the urethane catalyst, was stirred under air flow, while maintaining 60 ° C, adding 24.23 g of isocyanic acid. 2-propenyloxyethyl ester. Thereafter, the mixture was stirred at 60 ° C for 1 hour, and then heated to 80 ° C and stirred for 5.5 hours. Thus, it was confirmed by IR spectrum measurement that the isocyanate group disappeared, and by adding 211.8 g of methyl isobutyl ketone, 30 mass was obtained. A methyl isobutyl ketone solution of the polymerizable resin (7) of the present invention having an active energy ray-curable group. The molecular weight of the obtained polymerizable resin (7) was measured by GPC (molecular weight converted to polystyrene), and the number average molecular weight was 24,400, and the weight average molecular weight was 31,300.

Comparative Example 1 (Comparison of comparative surfactants)

77.7 g of methyl isobutyl ketone as a solvent was placed in 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 nitrogen gas stream. Next, 23 g of tetrafluorohexyl methacrylate and 5 g of a polymerizable unsaturated monomer having a polydecyloxy group represented by the following formula were dissolved in 53.4 g of methyl isobutyl ketone [hereinafter abbreviated as a monomer solution of monomer (A'-1)] and 44.7 g of glycidyl methacrylate; and 50.2 g of methyl isobutyl ketone containing 3.9 g of a tertiary butyl group as a radical polymerization initiator Polymerization initiator solution of peroxy-2-ethylhexanoate The two dropping solutions were placed in each dropping device, and the inside of the flask was kept at 105 ° C while being dropped for 3 hours.

(where n is an average of 65).

After the completion of the dropwise addition, after stirring at 105 ° C for 1.5 hours, 11.7 parts by mass of a polymerization initiator dissolved in 1.17 g of tertiary butyl peroxy-2-ethylhexanoate dissolved in methyl isobutyl ketone was added dropwise over 45 minutes. After the dropwise addition was completed, the mixture was 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.

Next, 0.1 g of p-methoxyphenol as a polymerization inhibitor was charged, and 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 charged under air flow. After stirring for 40 hours, titration was carried out using a 0.1 [mol/l] potassium hydroxide solution, and it was confirmed that the acid value of the solid component was lowered to 1 [mgKOH/g] or less. Thereafter, by adding 116.7 g of methyl isobutyl ketone, a methyl isobutyl ketone solution containing 40% of the polymerizable resin (1') having an active energy ray-curable group was obtained. The molecular weight of the obtained polymerizable resin (1') was measured by GPC (molecular weight converted to polystyrene), and the number average molecular weight was 4,700, the weight average molecular weight was 8,600, and the radical polymerizable unsaturated group equivalent was 323 g/eq. .

Comparative Example 2 (ibid.)

20 g of a perfluoropolyether compound having a hydroxyl group at both terminals represented by the following formula (X-1) was placed in a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a dropping device (hereinafter abbreviated 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, while stirring in an air stream, while maintaining the inside of the flask 2.7 g of acrylonitrile chloride was dropped on one side at 10 ° C for 1 hour. After completion of the dropwise addition, the mixture was stirred at 10 ° C for 1 hour, and the mixture was heated at 30 ° C for 1 hour. Then, the mixture was heated to 50 ° C and stirred for 10 hours to carry out a reaction, and it was confirmed by gas chromatography that the propylene chloride disappeared. Next, 40 g of diisopropyl ether as a solvent was added, and the mixture was stirred and washed three times by mixing and stirring 80 g of ion-exchanged water, and then allowing the aqueous layer to be separated and removed. Then, 0.02 parts by mass of p-methoxyphenol as a polymerization inhibitor was added, and 8 parts by mass of magnesium sulfate as a dehydrating agent was added thereto, and the mixture was allowed to stand for one day to be completely dehydrated, and then the dehydrating agent was filtered off.

(wherein, X is a perfluoromethyl group and a perfluoroethyl group, and in each molecule, there are 7 perfluoromethyl groups, 8 perfluoroethyl groups, and an average of 46 atoms; Further, the number average molecular weight obtained by using GPC was 1,500).

Next, the solvent was distilled off under reduced pressure to obtain a monomer represented by the following formula (B-1): (wherein, X is a perfluoromethyl group and a perfluoroethyl group. In each molecule, there are 7 perfluoromethyl groups, 8 perfluoroethyl groups, and an average of 46 fluorine atoms.) .

Next, 29.1 g of methyl isobutyl ketone as a solvent was placed in 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 nitrogen gas stream. Next, 38.5 g of the monomer (B-1), 32.8 g of 2-hydroxyethyl methacrylate, and 10.7 g of a tertiary butylperoxy-2-ethylhexanoic acid as a radical polymerization initiator were mixed. The ester and 58.1 g of a starting solution of methyl isobutyl ketone as a solvent were placed in each dropping device, and the inside of the flask was kept at 105 ° C while being dropped over 2 hours. After completion of the dropwise addition, the mixture was stirred at 105 ° C for 10 hours, and then the solvent was evaporated under reduced pressure to give polymer (P-3).

Next, the polymer (P-3) was charged with 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 tin octylate as a urethane catalyst. The stirring was started under an air flow, and while maintaining 60 ° C, 35.6 g of isocyanate-2-propenyloxyethyl ester was dropped over 1 hour. After the completion of the dropwise addition, the mixture was stirred at 60 ° C for 1 hour, and then heated to 80 ° C and stirred for 10 hours to carry out a reaction. As a result, it was confirmed by IR spectrum measurement that the isocyanate group disappeared. Then, after diluting with methyl ethyl ketone as a solvent, the insoluble matter in the solution is filtered off by filtration to obtain a methyl group containing 20% by mass of the polymerizable resin (2') having an active energy ray-curable group. Ethyl ketone solution. The molecular weight of the polymerizable resin (2') was measured by GPC (molecular weight converted to polystyrene), and the number average molecular weight was 3,200, a weight average molecular weight of 87,000, and a radical polymerizable unsaturated group equivalent of 423 g/eq.

Comparative Example 3 (ibid.)

20 g of the compound (X-1), 10 g of diisopropyl ether as a solvent, 0.006 g of p-methoxyphenol as a polymerization inhibitor, and 3.3 g were placed in a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a dropping device. The triethylamine of the neutralizer was stirred under a stream of air, and 3.1 g of methacrylic acid chloride was dropped over 2 hours while maintaining the inside of the flask at 10 °C. After completion of the dropwise addition, the mixture was stirred at 10 ° C for 1 hour, and the mixture was heated at 30 ° C for 1 hour. Then, the mixture was heated to 50 ° C and stirred for 10 hours to carry out a reaction, and it was confirmed by gas chromatography that the methyl propylene chloride disappeared. Next, after dissolving 70 g of diisopropyl ether as a solvent, it was washed by mixing and stirring 80 g of ion-exchanged water, and then allowing the aqueous layer to be separated and removed, and repeated three times. Next, 0.02 g of p-methoxyphenol as a polymerization inhibitor was added, and 8 g of magnesium sulfate as a dehydrating agent was added and allowed to stand for one day to completely dehydrate the mixture, and then the dehydrating agent was filtered off.

Next, the solvent was distilled off under reduced pressure to obtain a monomer represented by the following structural formula (B-2): (wherein, X is a perfluoromethyl group and a perfluoroethyl group. In each molecule, there are 7 perfluoromethyl groups, 8 perfluoroethyl groups, and an average of 46 fluorine atoms.) .

96.7 g of methyl isobutyl ketone as a solvent was placed in 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 nitrogen gas stream. Next, 126 g of methyl isobutyl ketone was dissolved in a monomer solution of 74 g of monomer (B-2), 37 g of monomer (A'-1) and 45.4 g of 2-hydroxyethyl methacrylate; and 67.8 a polymerization initiator solution in which 33.5 g of a tertiary butylperoxy-2-ethylhexanoate as a radical polymerization initiator is dissolved in g methyl isobutyl ketone, and the three drip liquids are respectively loaded under each drop. In the apparatus, the inside of the flask was kept at 105 ° C while being dropped over 2 hours. After the completion of the dropwise addition, the mixture was stirred at 105 ° C for 10 hours to obtain a solution of the polymer (P-4).

To the solution of the above polymer (P-4), 0.2 g of p-methoxyphenol as a polymerization inhibitor and 0.06 g of tin octylate as a urethane catalyst were charged, and stirring was started while maintaining a stream of air. 49.1 g of isocyanate-2-propenyloxyethyl ester was added dropwise at 60 ° C for 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C for 1 hour, and then heated to 80 ° C and stirred for 10 hours to carry out a reaction. Thus, it was confirmed by IR spectrum measurement that the isocyanate group disappeared. Then, methyl ethyl ketone was added to obtain a methyl ethyl ketone solution containing 40% by mass of the polymerizable resin (3') having an active energy ray-curable group. The molecular weight of the obtained polymerizable resin (3') was measured by GPC (molecular weight converted to polystyrene), and the number average molecular weight was 2,700, the weight average molecular weight was 8,000, and the radical polymerizable unsaturated group equivalent was 588 g/eq. .

Comparative Example 4 (ibid.)

In a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a dropping device, 714 g of methyl isobutyl ketone as a solvent was placed, and the temperature was raised to 105 ° C while stirring under a nitrogen gas stream. Next, 1106.4 g of methyl a monomer solution of 90 g of decafluorohexyl methacrylate, 360 g of the above monomer (A'-1) and 264 g of 2-hydroxyethyl methacrylate dissolved in isobutyl ketone; and 321.6 g of methyl a polymerization initiator solution containing 107.2 g of a tertiary butyl peroxy-2-ethylhexanoate as a radical polymerization initiator in the butyl ketone. The two dropping solutions are respectively placed in each dropping device, and The inside of the flask was kept at 105 ° C while the monomer solution was dropped for 2 hours, and the polymerization initiator solution was dropped over 2 hours and 20 minutes.

After the completion of the dropwise addition, 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.

Next, 0.399 g of p-methoxyphenol as a polymerization inhibitor, 2.993 g of dibutylhydroxytoluene, and 0.299 g of tin octylate as a urethane catalyst were charged, and stirring was started while maintaining a gas flow rate of 60. At ° C, 282.25 g of isocyanate-2-propenyloxyethyl ester was added dropwise over 1 hour. Thereafter, the mixture was stirred at 60 ° C for 2 hours, and then heated to 80 ° C and stirred for 2 and a half hours. Thus, after the disappearance of the isocyanate group by IR spectrum measurement, the addition of 1942.83 g of methyl isobutyl ketone was obtained. A solution of a methyl isobutyl ketone of a comparative comparative polymerizable resin (4') containing 30% by mass of an active energy ray-curable group. The molecular weight of the obtained polymerizable resin (4') was measured by GPC (molecular weight converted to polystyrene), and the number average molecular weight was 2,335 and the weight average molecular weight was 6,115.

Example 8 (modulation 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 which is located on the outermost surface of the protective film of the polarizing plate is prepared. Specifically, 15 parts of hollow vermiculite particles containing 20% by mass are mixed Methyl isobutyl ketone dispersion (average particle diameter: 50 nm), 1.6 parts of neopentyl tetraacrylate, 0.1 part of 2-hydroxy-1-{4-[4-(2- as a photopolymerization initiator) Hydroxy-2-methyl-propenyl)-benzyl]-phenyl}-2-methyl-propan-1-one ("IRGACURE 127" manufactured by Ciba Japan Co., Ltd.), and 81.8 parts by mass as a solvent The methyl isobutyl ketone is allowed to dissolve to obtain a base composition of the antireflective coating composition.

With respect to the base composition of the obtained antireflective coating composition of 99.2 parts, 0.4 part of a solution containing 50% of the polymerizable resin (1) is added as a resin component, and uniformly mixed to prepare an active energy ray of the invention. Curable composition (1) [antireflective coating composition (1)].

Using the obtained antireflective coating composition (1), an antireflection layer was prepared for a film having an antireflection layer and a hard coat layer in accordance with the following procedure.

<Preparation of Coating Composition for Hard Coating>

Mix 50 parts of 5-functional non-yellowing urethane acrylate, 50 parts of dipentaerythritol hexaacrylate, 25 parts of butyl acetate, and 5 parts of 1-hydroxycyclohexyl phenyl ketone as photopolymerization initiator ("IRGACURE 184" manufactured by Ciba Speciality Chemicals Co., Ltd.), 54 parts of toluene as a solvent, 28 parts of 2-propanol, 28 parts of ethyl acetate, and 28 parts of propylene glycol monomethyl ether were dissolved to obtain a coating composition for a hard coat layer. .

<Modulation of film with hard coat layer>

The obtained coating composition for a hard coat 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 then an ultraviolet curing device (under a nitrogen atmosphere; using a high pressure) A mercury lamp; an ultraviolet irradiation amount of ² kJ/m ² ) was hardened to form a hard coat film having a hard coat layer having a film thickness of 10 μm on one side.

<Modulation of film having antireflection layer and hard coat layer>

The antireflective coating composition (1) was applied onto the hard coat layer of the obtained hard coat film by using a bar coater No. 2, and the coating amount was changed to 2 g/m ² , and then placed in a dryer at 60 ° C for 5 minutes to prepare a solvent. Volatile, and then hardened by an ultraviolet curing device (under a nitrogen atmosphere; using a high-pressure mercury lamp; ultraviolet irradiation amount of ² kJ/m ² ) to form an anti-reflective layer and a hard coat having a film thickness of 0.1 μm on a hard coat layer having a thickness of 10 μm. Film of the layer. The surface of the cured coating film of the antireflective coating composition of the obtained film was evaluated for the following appearance, scratch resistance, and soiling property. Further, the reflectance of the antireflection film was measured. These evaluations were carried out separately before and after the alkali treatment shown below. The evaluation results are shown in Table 1.

[Evaluation of appearance]

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

○: No whitening occurred.

×: Whitening occurred.

[Evaluation of scratch resistance]

A TriboGear HEIDON reciprocating wear tester TYPE: 30S (manufactured by Shinto Scientific Co., Ltd.) was used to mount a Bonstar No. 0000 (made by Japan SteelWool Co., Ltd.) abrasion tester (500 g) on a round jig having a diameter of 27 mm. /cm ² load), 30 times back and forth for testing. The number of scratches generated on the surface of the coating film after the test was counted, and the scratch resistance was evaluated according to the following criteria.

◎: The number of scratches is less than 5.

○: 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 dirty eraser]

The surface of the hardened coating film of the antireflection coating composition of the antireflection film obtained above was adhered with a finger to visually observe the erasing condition when the facial tissue was wiped back and forth 10 times, and the fingerprint was evaluated according to the following criteria. Erasing.

◎: The fingerprint is completely erased.

○: The trace of the fingerprint or the linear mark along the erasing direction is slightly residual when it is attached.

×: The adhesion mark of the fingerprint or the linear mark in the erasing direction remains at a concentration of one-half or more of the adhesion.

[Measurement of reflectance]

The reflectance was measured by a spectrophotometer ("UV-3100PC" manufactured by Shimadzu Corporation) equipped with a specular reflectance measuring device of 5 °C. Further, the reflectance is a value obtained by reaching a minimum value (lowest reflectance) near a wavelength of 550 nm.

<Method for treating strong alkali (saponification) of hardened coating film>

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

Comparative Example 5 (Comparison of the active energy ray-curable composition for comparison)

In addition to 0.4 parts by mass of a methyl isobutyl ketone solution containing 40% of the polymerizable resin (1') as a resin component, instead of the solution containing 50% of the polymerizable resin (1) used in Example 8, In the same manner as in Example 8, a comparative antireflective coating composition (1') was obtained. The evaluation was carried out in the same manner as in Example 8. The evaluation results are shown in Table 1.

Comparative Example 6 (ibid.)

The same procedure as in Example 8 was carried out except that 0.4 parts by mass of a solution containing 20% of the polymerizable resin (2') was added as a resin component instead of the solution containing 50% of the polymerizable resin (1) used in Example 8. Operation, a comparative control antireflective coating composition (2') was obtained. The evaluation was carried out in the same manner as in Example 8. The evaluation results are shown in Table 1.

Comparative Example 7 (ibid.)

The same procedure as in Example 8 was carried out except that a solution containing 40% by mass of the polymerizable resin (3') was added as a resin component, instead of the solution containing 50% of the polymerizable resin (1) used in Example 8. Operation, a comparative control antireflective coating composition (3') was obtained. The evaluation was carried out in the same manner as in Example 8. The evaluation results are shown in Table 1.

Comparative Example 8 (ibid.)

In addition to 0.8 parts by mass (0.4 parts by mass based on the resin component), 50% by mass of eucalyptus oil ("Silaplane FM-4421" manufactured by JNC Co., Ltd.; -C ₃ at both ends of the polydimethyl siloxane chain) was contained. H ₆ OC ₂ H ₄ OH's) in methyl isobutyl ketone solution, instead of outside the system and the embodiment solution containing 50% of the polymerizable resin (1) used in Example 8 in the same manner as the eighth embodiment, to obtain a comparative The antireflective coating composition (4') was used for comparison. The evaluation was carried out in the same manner as in Example 8. The evaluation results are shown in Table 1.

Comparative Example 9 (ibid.)

In addition to 0.8 parts by mass (0.4 parts by mass based on the resin component), a methyl isobutyl ketone solution containing 50% by mass of FM-0721K (an oil of JNC Co., Ltd.; a polymerizable unsaturated group at one end) was added. The anti-reflective coating composition (5') for comparison was obtained in the same manner as in Example 8 except that the solution containing 50% of the polymerizable resin (1) used in Example 8 was used. The evaluation was carried out in the same manner as in Example 8. The evaluation results are shown in Table 2.

Comparative Example 10 (ibid.)

In addition to 0.8 parts by mass (0.4 parts by mass based on the resin component), a methyl ester having a 50% by mass of a tetrafunctional acrylate having a dimethyl siloxane chain ("BYK-UV3570" manufactured by BYK Japan Co., Ltd.) was added. The butyl ketone solution was treated in the same manner as in Example 8 except that the solution containing 50% of the polymerizable resin (1) used in Example 8 was used to obtain a comparative antireflective coating composition (6'). The evaluation was carried out in the same manner as in Example 8. The evaluation results are shown in Table 2.

Comparative Example 11 (ibid.)

The component was added and evaluated in the same manner as in Example 8 except that no component was added to the base resin composition of the active energy ray-curable composition prepared in Example 8. The evaluation results are shown in Table 2.

Example 9 (Modulation 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 which is located on the outermost surface of the protective film of the polarizing plate is prepared. Specifically, 1.265 parts of a methyl isobutyl ketone dispersion containing 20% by mass of hollow vermiculite fine particles (average particle diameter of 60 nm), 0.207 parts of neopentyl triacrylate, and 0.0092 parts were mixed as a photopolymerization initiator. 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl]-phenyl}-2-methyl-propan-1-one (Ciba Japan) "IRGACURE 127" manufactured by Co., Ltd.) and 8.395 parts of methyl isobutyl ketone as a solvent were 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, 0.04 part of a solution containing 30% of the polymerizable resin (2) was added as a resin component, and uniformly mixed to prepare an active energy ray of the invention. Hardenable composition (2) [antireflective coating composition (2)].

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

<Preparation of Coating Composition for Hard Coating>

30 parts of urethane acrylate ("UV1700B" of Nippon Synthetic Chemical Co., Ltd.), 25 parts of butyl acetate, and 1.2 parts of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator (Ciba Speciality) "IRGACURE 184" manufactured by Chemicals Co., Ltd., 11.78 parts of toluene as a solvent, 5.892 parts of 2-propanol, 5.892 parts of ethyl acetate, and 5.892 parts of propylene glycol monomethyl ether were dissolved to obtain a coating composition for a hard coat layer.

<Modulation of film with hard coat layer>

The obtained coating composition for a hard coat layer was applied to a PET film having a thickness of 188 μm using a bar coater No. 13, and then placed in a dryer at 70 ° C for 1 minute to volatilize the solvent, followed by an ultraviolet curing device (under a nitrogen atmosphere; using a high pressure) A mercury lamp; an ultraviolet irradiation amount of 0.5 kJ/m ² ) was hardened to form a hard coat film having a hard coat layer having a film thickness of 8 μm on one side.

<Modulation of film having antireflection layer and hard coat layer>

The antireflective coating composition (2) was applied onto the hard coat layer of the obtained hard coat film by using a bar coater No. 2, and then placed in a dryer at 50 ° C for 1 minute and 30 seconds to evaporate the solvent, and then an ultraviolet curing device was used. (In a nitrogen atmosphere; using a high-pressure mercury lamp; ultraviolet irradiation amount of ² kJ/m ² ), it is hardened to form a film having an antireflection layer and a hard coat layer having a film thickness of 0.1 μm on a hard coat layer having a film thickness of 8 μm (antireflection film) ). The surface of the cured coating film of the obtained antireflective coating composition was evaluated for appearance, smoothness, and scratch resistance in accordance with the following evaluation methods. These measurements were carried out separately before and after the above-mentioned alkali treatment. The results of the assessment are shown in Table 3.

[Evaluation of appearance]

Observing the antireflective coating composition visually on the film obtained above The unevenness of the fine oil droplets formed on the hardened coating film (cissing) was evaluated according to the following criteria. The evaluation results are shown in Table 1.

○: No shrinkage holes were observed at all.

△: A part of the point-like shrinkage hole was visible.

×: A dot-like shrinkage hole is visible as a whole.

[Assessment of smoothness]

Using the surface measuring machine ("HEIDON-14D" manufactured by Shinto Scientific Co., Ltd.), the film obtained above was fixed on a sample stage, and it was confirmed that the film was placed on the sample, and the probe was placed on the sample to carry a load of 100 g. The measurement was carried out under the conditions of a stretching speed of 0.3 m/min, and the dynamic friction coefficient was obtained. The smaller the dynamic friction coefficient, the better the smoothness.

[Evaluation of scratch resistance]

The test was carried out by using #0000 steel wool and rubbing 10 times back and forth with a load of 500 g. The number of scratches generated on the surface of the coating film after the test was counted, and the scratch resistance was evaluated according to the following criteria.

◎: The number of scratches is less than 5.

○: The number of scratches is 5 or more and less than 10.

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

×: The number of scratches is 30 or more

Example 10 (ibid.)

The same operation as in Example 9 was carried out except that 0.04 parts by mass of a solution containing 30% of the polymerizable resin (3) was added as a resin component instead of the solution containing 30% of the polymerizable resin (2) used in Example 9. And to assess. The results of the assessment are shown in Table 3.

Example 11 (ibid.)

The same operation as in Example 2 was carried out except that 0.04 parts by mass of a solution containing 30% of the polymerizable resin (4) was added as a resin component instead of the solution containing 30% of the polymerizable resin (2) used in Example 9. And to assess. The results of the assessment are shown in Table 3.

Example 12 (ibid.)

The same operation as in Example 9 was carried out except that 0.04 parts by mass of a solution containing 30% of the polymerizable resin (5) was added as a resin component instead of the solution containing 30% of the polymerizable resin (2) used in Example 9. And to assess. The results of the assessment are shown in Table 3.

Example 13 (ibid.)

The same operation as in Example 9 was carried out except that 0.04 parts by mass of a solution containing 30% of the polymerizable resin (6) was added as a resin component instead of the solution containing 30% of the polymerizable resin (2) used in Example 9. And to assess. The results of the assessment are shown in Table 3.

Example 14 (ibid.)

The same operation as in Example 9 was carried out except that 0.04 parts by mass of a solution containing 30% of the polymerizable resin (7) was added as a resin component instead of the solution containing 30% of the polymerizable resin (2) used in Example 9. And to assess. The results of the assessment are shown in Table 3.

Comparative Example 12 (Comparison of active energy ray-curable composition for comparison)

The same procedure as in Example 9 was carried out except that 0.04 parts by mass of a solution containing 30% of the polymerizable resin (4') was added as a resin component instead of the solution containing 30% of the polymerizable resin (2) used in Example 9. Operate and evaluate. The results of the assessment are shown in Table 4.

Comparative Example 13 (ibid.)

The evaluation was carried out in the same manner as in Example 9 except that any of the components of the base resin composition of the antireflective coating composition prepared in Example 9 was not added. The results of the assessment are shown in Table 3.

Claims (16)

A polymerizable resin characterized by having a main chain formed by polymerization of a polymerizable unsaturated monomer, and the main chain has a fluoroalkyl group having 1 to 6 carbon atoms bonded to a fluorine atom (x) a polymerizable resin having a polymerizable unsaturated group (y) as a side chain, the main chain further having a structure comprising a polyfluorene chain having a molecular weight of 2,000 or more at one end thereof; the polymerizable resin is used at a molecular weight of 2,000 The compound (A) having a functional group having a radical generating ability at one end of the above polyoxygen chain, and a polymerizable unsaturated monomer having a fluoroalkyl group having 1 to 6 carbon atoms bonded to a fluorine atom (B) a polymerizable unsaturated monomer (C) having a reactive functional group (c1) and a functional group (d1) having a reactivity with the functional group (c1) and a polymerizable unsaturated group (d2) a polymerizable resin obtained by reacting a compound (D) with a compound (P) obtained by reacting a compound (P) with a compound (D), which generates a radical from the compound (A) And obtaining the polymerizable unsaturated monomer (B) by copolymerizing the polymerizable unsaturated monomer (C); and having the compound (A) The functional group derived from the group generating ability is an organic group having a halogen atom, an organic group having an alkylidene group or an organic group having a dithioester group, and the compound (A) and the polymerizable unsaturated monomer (B) The polymerization method in which the polymerizable unsaturated monomer (C) is copolymerized is living radical polymerization. The polymerizable resin according to claim 1, wherein the polyoxonium chain possessed by the compound (A) is a polyfluorene chain having a molecular weight of 2,000 to 20,000. The polymerizable resin according to claim 1, wherein the living radical polymerization is atomic transfer in the presence of a polymerization initiator, a transition metal compound, and a compound having a ligand coordinately bonded to the transition metal. Type free radical polymerization. The polymerizable resin according to claim 1, wherein the reactive functional group (c1) is one or more selected from the group consisting of a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group, and a carboxylic acid anhydride group. Functional group. A polymerizable resin characterized by having a main chain formed by polymerization of a polymerizable unsaturated monomer, and the main chain has a fluoroalkyl group having 1 to 6 carbon atoms bonded to a fluorine atom (x) a polymerizable resin having a polymerizable unsaturated group (y) as a side chain, the main chain further having a structure comprising a polyfluorene chain having a molecular weight of 2,000 or more at one end thereof; the polymerizable resin having: polymerized A main chain formed by polymerization of an unsaturated monomer and a fluoroalkyl group (x) having 1 to 6 carbon atoms bonded to a fluorine atom as a first polymer segment of the side chain of the main chain (α) And 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, and further having a single The side end contains a structure of a polyfluorene chain having a molecular weight of 2,000 or more. The polymerizable resin according to claim 5, which is obtained by the production method comprising the following steps: Step (1), which has a radical generating ability at one end of a polyfluorene chain having a molecular weight of 2,000 or more. The functional group-containing compound (A) and the polymerizable unsaturated monomer (B) having a fluoroalkyl group (x) having 1 to 6 carbon atoms bonded to a fluorine atom are charged into the reaction system, Compound (A) generates a radical to obtain a polymer segment (p) comprising a structure derived from the polymerizable unsaturated monomer (B); and step (2), which comprises the polymer segment (p) Reaction system The polymerizable unsaturated monomer (C) having a reactive functional group (c1) is charged therein to obtain a polymer segment (p) and inclusion by generating a radical from the polymer segment (p). a polymer (Q1) derived from the polymer segment (q) of the structure of the polymerizable unsaturated monomer (C); and a step (3), which is contained in a reaction system containing the polymer (Q1) Having a functional group (d1) reactive with a reactive functional group (c1) of the polymer (Q1) and a compound (D) having a polymerizable unsaturated group (d2), and a reactive functional group (c1) ) reacts with a reactive functional group (d1). The polymerizable resin of claim 5, which is obtained by a production method comprising the following steps: step (1-1), which has a radical formation at one end of a polyfluorene chain having a molecular weight of 2,000 or more. The functional group-functional compound (A) and the reactive functional group (c1)-containing polymerizable unsaturated monomer (C) are charged into a reaction system, and a radical is generated from the compound (A) to obtain a content. a polymer segment (q) derived from the structure of the polymerizable unsaturated monomer (C); and a step (2-1) in which a polymerization property is charged in a reaction system containing the polymer segment (q) The unsaturated monomer (B), by generating a radical from the polymer segment (q), obtains a polymerization comprising the polymer segment (q) and a structure derived from the polymerizable unsaturated monomer (B) a polymer (Q2) of the segment; and a step (3-1) in a reaction system containing the polymer (Q2), having a reactive functional group possessed by the polymer (Q2) ( C1) Combination of reactive functional group (d1) and polymerizable unsaturated group (d2) (D), and reacting the reactive functional group (c1) with a reactive functional group (d1). The polymerizable resin according to any one of claims 5 to 7, which has the first polymer segment (α) in a range of 20/80 to 80/20 by mass ratio [(α)/(β)] ) with a second polymer segment (β). The polymerizable resin according to claim 6 or 7, wherein the functional group having a radical generating ability of the compound (A) is selected from the group consisting of an organic group having a halogen atom, an organic group having an alkylhydrazine group, and a disulfide group. One or more functional groups in the group of the organic group of the ester group, the organic group having a peroxide group, or the organic group having an azo group. The polymerizable resin according to claim 6 or 7, wherein the polyfluorene chain of the compound (A) is a polyfluorene chain having a molecular weight of 2,000 to 20,000. The polymerizable resin according to claim 6 or 7, wherein the compound having a radical generating ability of the compound (A) is an organic group having a halogen atom, an organic group having an alkyl group or a dithioester group. The polymerization method in which the compound (A) is copolymerized with the polymerizable unsaturated monomer (B) and the polymerizable unsaturated monomer (C) is a living radical polymerization. The polymerizable resin according to claim 11, wherein the living radical polymerization is an atom transfer type in the presence of a polymerization initiator, a transition metal compound, and a compound having a ligand coordinately bonded to the transition metal. Radical Polymerization. The polymerizable resin according to claim 6 or 7, wherein the reactive functional group (c1) is one selected from the group consisting of a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group, and a carboxylic acid anhydride group. The above functional groups. An active energy ray hardening composition characterized by containing as requested The polymerizable resin according to any one of items 1 to 13, and the active energy ray-curable resin (E) or the active energy ray-curable monomer (F) other than the polymerizable resin. An article characterized by having a cured coating film of the active energy ray-curable composition of claim 14. A method for producing a polymerizable resin, which is characterized by using a compound (A) having a functional group having a radical generating ability at one end of a polyfluorene chain having a molecular weight of 2,000 or more, and a carbon having a fluorine atom bonded thereto a polymerizable unsaturated monomer (B) having a fluoroalkyl group having 1 to 6 atoms, a polymerizable unsaturated monomer having a reactive functional group (c1) (C), and having a reaction with the functional group (c1) A method for producing a polymerizable resin of a compound (D1) having a functional group (d1) and a polymerizable unsaturated group (d2); and a method for producing a copolymer (P) and reacting the compound (D), the copolymerization The substance (P) is obtained by copolymerizing the polymerizable unsaturated monomer (B) with the polymerizable unsaturated monomer (C) by generating a radical from the compound (A); the compound (A) has The functional group having a radical generating ability is an organic group having a halogen atom, an organic group having an alkylhydrazine group or an organic group having a dithioester group, and the compound (A) and the polymerizable unsaturated monomer are B) The polymerization method in which the polymerizable unsaturated monomer (C) is copolymerized is living radical polymerization.