JP2013155236A - Fluorine atom-containing silicone-based polymerizable resin, active energy ray-curable composition using the same, and cured material and article thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluorine atom-containing silicone-based polymerizable resin, which can provide excellent scratch resistance to a cured coating surface of an active energy ray-curable composition by adding it to the composition, the scratch resistance being never deteriorated even when the cured coating surface is treated with a chemical agent such as strong alkali, an active energy ray-curable composition using the same, a cured material of the composition, and an article having a cured coating of the composition.SOLUTION: The fluorine atom-containing polymerizable resin is a polymer having a 4-6C fluorinated alkyl, a silicone chain, an adamantyl group and a polymerizable unsaturated group. The active energy ray-curable composition includes the resin. The cured material of the composition and the article having the cured coating of the composition are also provided.

Description

  The present invention relates to a fluorine atom-containing silicone-based polymerizable resin that can be added to an active energy ray-curable composition to impart excellent scratch resistance to a cured coating film of the composition. The present invention also relates to an active energy ray-curable composition using the fluorine atom-containing silicone-based polymerizable resin, a cured product thereof, and an article having a cured coating film of the composition.

  Conventionally, a hard coat made of an active energy ray-curable composition for preventing scratches on the outermost surface of a flat panel display screen such as a liquid crystal display (LCD), a plasma display (PDP), and an organic EL display (OELD). A hard coat layer is provided by applying and curing the material.

  As a method of improving the scratch resistance by providing the hard coat layer, a hard coat material containing a polyfunctional monomer such as polyfunctional (meth) acrylate was applied to the surface layer of the polarizing plate and cured. A method of providing a cured coating film is known. However, although this cured coating film can be increased in hardness to some extent, the scratch resistance is insufficient.

  Therefore, by adding a silicone additive to the active energy ray curable composition or by adding a silicone compound having a radically polymerizable unsaturated group in the molecule, the cured coating film is provided with slipperiness, It has been proposed to improve the scratch resistance (see, for example, Patent Document 1). However, the cured coating film of the active energy ray-curable composition to which the silicone compound is added is saponified like a triacetyl cellulose (hereinafter abbreviated as “TAC”) film used for a polarizing plate of a liquid crystal display. In applications where the treatment (strong alkali treatment) is carried out, there has been a problem that the slipperiness of the surface of the cured coating film is greatly lowered after the saponification treatment, and sufficient scratch resistance cannot be obtained.

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

JP 2004-182765 A

  The problem to be solved by the present invention is that by adding to the active energy ray curable composition, it is possible to impart excellent scratch resistance to the cured coating film surface of the composition, It is to provide a fluorine atom-containing silicone-based polymerizable resin that can exhibit excellent scratch resistance even when treated with a chemical such as a strong alkali. Moreover, it is providing the article | item which has an active energy ray curable composition using this silicone type polymeric resin, its hardened | cured material, and the cured coating film of this composition.

  As a result of intensive studies to solve the above problems, the present inventors have found that a resin having a fluorine alkyl group, a silicone chain, an adamantyl group and a polymerizable unsaturated group in the polymer structure (fluorine-containing polymerizable resin). The active energy ray-curable composition containing) has been found to be capable of imparting excellent scratch resistance to the surface of the cured coating film, no deterioration in scratch resistance after the saponification treatment, etc. Was completed.

  That is, the present invention provides a fluorine atom-containing silicone-based polymerizable resin, which is a polymer having a fluorinated alkyl group, a silicone chain, an adamantyl group, and a polymerizable unsaturated group.

  In addition, the present invention includes an active energy ray comprising the fluorine atom-containing silicone-based polymerizable resin and an active energy ray-curable resin (E) or an active energy ray-curable monomer (F). A curable composition is provided.

  Furthermore, the present invention provides a cured product obtained by applying the fluorine atom-containing silicone-based polymerizable resin or the active energy ray-curable composition to a substrate and irradiating and curing the active energy ray. It is to provide.

  Furthermore, the present invention provides an article characterized by having a cured coating film of the fluorine atom-containing silicone-based polymerizable resin or active energy ray-curable composition.

  The adamantane skeleton of the fluorine atom-containing silicone-based polymerizable resin of the present invention imparts very hard properties to the resulting cured product. Further, the fluorinated alkyl group has high surface segregation and water / oil repellency, and the silicone chain has surface segregation, water repellency and high slip. By combining these group and chain properties, the cured coating film is provided with slipperiness and excellent scratch resistance. And this abrasion resistance can be exhibited also in the cured coating film by which the saponification process (strong alkali process) was carried out. Moreover, the said cured coating film is excellent also in antifouling property. In addition, the active energy ray-curable composition containing a fluorine atom-containing silicone-based polymerizable resin is excellent in leveling properties. Therefore, it is also useful as a material for a hard coat material of a TAC film used for a polarizing plate of a liquid crystal display.

FIG. 1 is an IR spectrum chart of the fluorine atom-containing silicone-based polymerizable resin (1) obtained in Example 1. 2 is a chart of the ¹³ C-NMR spectrum of the fluorine atom-containing silicone polymerizable resin (1) obtained in Example 1. FIG. FIG. 3 is a GPC chart of the fluorine atom-containing silicone-based polymerizable resin (1) obtained in Example 1.

  The fluorine atom-containing silicone-based polymerizable resin of the present invention has a fluorinated alkyl group, a silicone chain, an adamantyl group, and a polymerizable unsaturated group in the structure of the polymer. As the fluorinated alkyl group in the fluorine-containing silicone-based polymerizable resin of the present invention, those having 4 to 6 carbon atoms are preferable because of a good balance of surface segregation, water and oil repellency, and reduction of environmental load. More preferred are those having 6 carbon atoms. As the silicone chain, those having a molecular weight of 400 to 20,000 are preferable from the viewpoint of good compatibility with other resins and slipperiness to the cured product surface, and more preferably 420 to 10,000.

  As content of the fluorinated alkyl group in the fluorine atom-containing silicone-based polymerizable resin in the present invention, 3 to 30% by mass is compatible with other resins, surface segregation, and water repellency to the cured product surface. It is preferable because oil repellency is improved, and 5 to 25% by mass is more preferable. As a content rate of a silicone chain, 5-50 mass% is preferable from the compatibility with other resin and the smoothness provision of hardened | cured material surface becoming favorable, and 15-30 mass% is more preferable. As content rate of an adamantyl group, 5-50 mass% is preferable from the hardness of hardened | cured material becoming favorable, and 15-30 mass% is more preferable.

  Moreover, since the equivalent of the polymerizable unsaturated group in the fluorine atom-containing silicone-based polymerizable resin in the present invention is 200 to 3,500 g / eq. The range of 250 to 2,000 g / eq. The range of 300-1500 g / eq. Is more preferable, 400-1,000 g / eq. The range of is particularly preferable.

  Although there is no restriction | limiting in particular in manufacturing the fluorine atom containing silicone type polymeric resin of this invention, For example, the following two methods can be illustrated preferably.

(Manufacturing method 1)
A polymerizable unsaturated monomer (A) having a fluorinated alkyl group, a polymerizable unsaturated monomer (B) having a silicone group, and a polymerizable unsaturated monomer having an adamantyl group having a reactive functional group (c1) The polymer (P1) obtained by copolymerizing the saturated monomer (C1) as an essential monomer component, the functional group (d) having reactivity with the functional group (c1) and the polymerizability A method of reacting the compound (D) having an unsaturated group.

(Manufacturing method 2)
A polymerizable unsaturated monomer (A) having a fluorinated alkyl group, a polymerizable unsaturated monomer (B) having a silicone group, and a polymerizable unsaturated monomer having an adamantyl group having a reactive functional group (c1) A polymerizable unsaturated monomer (C2) having an adamantyl group not having a saturated monomer (C1) or a reactive functional group (c1), and a polymerizable unsaturated monomer having a reactive functional group (c3) A functional group (d) having reactivity to the functional group (c1) or the functional group (c3) to the polymer (P2) obtained by copolymerizing (C3) as an essential monomer component And one or more compounds (D) having a polymerizable unsaturated group.

  Among the above production methods, production method 1 is more preferable because a fluorine atom-containing silicone-based polymerizable resin having a high adamantyl group content can be easily obtained.

  The polymerizable unsaturated monomer (A) used in the production method is a monomer having a fluorinated alkyl group. In the present invention, the fluorinated alkyl group includes those having an ether bond by an oxygen atom and those having one or more carbon-carbon double bonds in the skeleton of the fluorinated alkyl group. The polymerizable unsaturated group possessed by the monomer (A) is preferably a carbon-carbon unsaturated double bond having radical polymerizability, and examples thereof include a (meth) acryloyl group, a vinyl group, and a maleimide group. Among these, (meth) acryloyl is easy because of the availability of raw materials, the ease of controlling the compatibility with each compounding component in the active energy ray-curable composition described later, or the good polymerization reactivity. Groups are preferred.

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

  As a polymerizable unsaturated monomer (A) used with the said manufacturing method, what is represented by following General formula (1) is mentioned, for example.

（上記一般式（１）中、Ｒは水素原子又はメチル基を表し、Ｌは、下記式（Ｌ−１）〜（Ｌ−１０）のいずれか１つの基を表し、Ｒｆは下記式（Ｒｆ−１）〜（Ｒｆ−７）のいずれか１つの基を表す。）

(In the general 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) to any one of (Rf-7).

  N in the above formulas (L-1), (L-3), (L-5), (L-6) and (L-7) represents an integer of 1 to 8. M in the above formulas (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 formulas (L-6) and (L-7) represents any one of the following formulas (Rf-1) to (Rf-7).

  N in the above formulas (Rf-1) to (Rf-4) represents an integer of 4 to 6. M in the said formula (Rf-5) is an integer of 1-5, n is an integer of 0-4, and the sum total of m and n is 4-5. 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 4 5.

  Moreover, the following monomers (A-1)-(A-11) etc. are mentioned as a specific example of the said monomer (A). These monomers (A) can be used alone or in combination of two or more.

（式中のｎは３〜５の整数を表す。）

(In the formula, n represents an integer of 3 to 5.)

  Examples of the polymerizable unsaturated monomer (B) having a silicone group used in the present invention include those represented by the following general formula (1) or (2).

  (In the formula, R, R ′, R ″ and R ′ ″ each independently represents an alkyl group having 1 to 18 carbon atoms or a phenyl group, and n is the number of repeating units. Represents an integer.)

  Moreover, as a polymerizable unsaturated group which the said monomer (B) has, the carbon-carbon unsaturated double bond which has radical polymerizability is preferable, and a (meth) acryloyl group, a vinyl group, a maleimide group, etc. are mentioned. . Among these, (meth) acryloyl is easy because of the availability of raw materials, the ease of controlling the compatibility with each compounding component in the active energy ray-curable composition described later, or the good polymerization reactivity. Groups are preferred.

  Specific examples of the monomer (B) include monomers represented by the following general formulas (B1) to (B8). Moreover, these monomers (A) can be used alone or in combination of two or more.

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ^{3 to} R ⁶ and R ^{10 to} R ¹⁷ each independently represents an alkyl group having 1 to 18 carbon atoms or a phenyl group, and R ^{2 and} R ^7. to R ⁹ and R ¹⁸ to R ²⁰ each independently represent an alkyl group or a phenyl group having 1 to 8 carbon atoms. Further, m and l each independently represents an integer of 1 to 6, n is 0 to 250 R, s, t, v, w, x, y, z each independently represents an integer of 1 to 250.

  The mass ratio [(A) / (B)] between the compound (A) and the monomer (B) is 10/90 to 90/10 because a cured product having high scratch resistance is obtained. The range is preferable, the range of 20/80 to 80/20 is more preferable, the range of 25/75 to 75/25 is still more preferable, and the range of 40/60 to 60/40 is most preferable.

  (C1) used in the present invention has an adamantyl group having a reactive functional group (c1). The adamantyl group is an organic group having the following adamantane structure.

  Examples of the reactive functional group (c1) possessed by the adamantyl group of the monomer (C1) include a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group, and an acid anhydride group. The polymerizable unsaturated group possessed by the monomer (C1) is preferably a carbon-carbon unsaturated double bond having radical polymerizability, and more specifically, a vinyl group, a (meth) acryloyl group, a maleimide group, or the like. (Meth) acryloyl group is more preferable from the viewpoint of easy polymerization. These monomers (C1) can be used alone or in combination of two or more different reactive functional groups (c1) and polymerizable unsaturated groups.

  As said monomer (C1) which has a (meth) acryloyl group as a polymerizable unsaturated group, the compound represented by the following general formula (C1-1) is mentioned, for example.

（式中、Ｌは前記反応性官能基（ｃ１）を表し、Ｘ及びＹは２価の有機基又は単結合を表し、Ｒは水素原子、メチル基又はＣＦ_３を表す。）

(In the formula, L represents the reactive functional group (c1), X and Y represent a divalent organic group or a single bond, and R represents a hydrogen atom, a methyl group, or CF ₃ ).

  In the general formula (C1-1), the organic group having the reactive functional group (c1) represented by -XL and the bonding position of Y may be bonded to any carbon atom in the adamantane structure. Moreover, you may have 2 or more about -XL. Furthermore, part or all of the hydrogen atoms bonded to the carbon atoms constituting the adamantane structure may be substituted with fluorine atoms, alkyl groups, or the like. Further, X and Y in the general formula (C1-1) are a divalent organic group or a single bond. Examples of the divalent organic group include carbon atoms such as a methylene group, a propyl group, and an isopropylidene group. The alkylene group of number 1-8 is mentioned.

  More specific examples of the monomer (C1) include compounds represented by the following formulas (C1-1-1) to (C1-1-5).

  The monomer (C2) used in the production method 2 is a polymerizable unsaturated monomer having an adamantyl group, and the adamantyl group is the same as the monomer (C1). The polymerizable unsaturated group of the monomer (C2) is preferably a carbon-carbon unsaturated double bond having radical polymerizability, and more specifically, a vinyl group, a (meth) acryloyl group, a maleimide. A (meth) acryloyl group is more preferable from the viewpoint of easy polymerization. These monomers (C2) can be used alone or in combination of two or more.

  As said monomer (C2) which has a (meth) acryloyl group as a polymerizable unsaturated group, the compound represented by the following general formula (C2-1) is mentioned, for example.

（式中、Ｒは水素原子、メチル基又はＣＦ_３を表す。）

(In the formula, R represents a hydrogen atom, a methyl group or CF _3. )

  The (meth) acryloyl group may be bonded to any carbon atom in the adamantane structure. Moreover, the hydrogen atom couple | bonded with the carbon atom which comprises the adamantane structure in the said general formula (C2-1) may substitute the one part or all part by the fluorine atom, the alkyl group, etc.

  More specific examples of the monomer (C2) include compounds represented by the following formulas (C2-1-1) to (C2-1-3).

  Mass ratio of compound (A) to monomer (C1) [(A) / (C1)] or Mass ratio of compound (A) to monomer (C2) [(A) / (C2)] Is preferably in the range of 8/92 to 70/30, more preferably in the range of 15/85 to 60/40, and in the range of 20/80 to 50/50 since a cured product having high scratch resistance can be obtained. Is more preferable, and the range of 25/75 to 35/65 is most preferable.

Further, the mass ratio [[(A) + (B)] / (C1)] of the sum of the compound (A) and the monomer (B) and the monomer (C1) or the compound (A) and the monomer (C1) The mass ratio [[(A) + (B)] / (C2)] of the sum of the monomer (B) and the monomer (C2) is preferably in the range of 15/85 to 70/30. The range of 30-60 / 40 is more preferable.

  The said monomer (C3) used as the raw material of the fluorine atom containing silicone type polymeric resin of this invention in the said manufacturing method 2 is demonstrated. Examples of the reactive functional group (c3) possessed by the monomer (C3) include a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group, and an acid anhydride group. Further, the polymerizable unsaturated group possessed by the monomer (C3) is preferably a carbon-carbon unsaturated double bond having radical polymerizability, and more specifically, a vinyl group, (meth) acryloyl group, maleimide. A (meth) acryloyl group is more preferable from the viewpoint of easy polymerization.

  Specific examples of the monomer (C3) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4 -Hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, N- (2-hydroxyethyl) (meth) acrylamide, glycerin mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene Glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, lactone modified with a hydroxyl group at the terminal (meth) Unsaturated monomer having hydroxyl group such as acrylate; 2- (meth) acryloyloxyethyl isocyanate, 2- (2- (meth) acryloyloxyethoxy) ethyl isocyanate, 1,1-bis ((meth) acryloyloxymethyl) Unsaturated monomers having an isocyanate group such as ethyl isocyanate; unsaturated monomers having an epoxy group such as glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether; (meth) acrylic acid, 2- (meth) acryloyloxyethyl Unsaturated monomers having a carboxyl group such as succinic acid, 2- (meth) acryloyloxyethylphthalic acid, maleic acid and itaconic acid; acid anhydrides having an unsaturated double bond such as maleic anhydride and itaconic anhydride Etc. These monomers (C3) can be used alone or in combination of two or more.

  Moreover, in the said manufacturing method 1 or 2, when manufacturing the said polymer (P1) or (P2) which is an intermediate body of the fluorine atom containing silicone type polymeric resin of this invention, the said compound (A), single quantity In addition to the body (B), the monomer (C1), the monomer (C2), and the monomer (C3), other polymerizable unsaturated monomers (C4) that can be copolymerized with these are used. It doesn't matter. Such other polymerizable unsaturated monomers (C4) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth). Acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl ( (Meth) acrylates such as (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylate having a polyoxyalkylene chain; styrene, α-methylstyrene, p -Methyls Aromatic vinyls such as len and p-methoxystyrene; maleimides such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide, etc. Can be mentioned.

  In the said manufacturing method 1 or 2, the said compound (D) used as the raw material of the fluorine atom containing silicone type polymeric resin of this invention is demonstrated. Examples of the functional group (d) possessed by the compound (D) include a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group, and an acid anhydride. When the reactive functional group (c1) or (c3) of the monomer (C1) or (C3) is a hydroxyl group, an isocyanate group, a carboxyl group, a carboxylic acid halide group, an epoxy as the functional group (d) When the reactive functional group (c1) or (c3) is an isocyanate group, the functional group (d) includes a hydroxyl group, and the reactive functional group (c1) or (c3) is an epoxy group. When the functional group (d) is a carboxyl group or a hydroxyl group, and the reactive functional group (c1) or (c3) is a carboxyl group, the functional group (d) is an epoxy group or a hydroxyl group. Is mentioned.

  Here, in the production method 2, when the monomer (C1) and the monomer (C3) are used in combination, the reactive functional group (c1) and the reactive functional group (c3) included in these monomers are In the case of different functional groups, and when the reactive functional groups (c1) and (c3) react with a common functional group, they are reactive with the reactive functional groups (c1) and (c3). One type of compound (D) having a functional group (d) can be used. In addition, when the reactive functional group (c1) and the reactive functional group (c3) do not react with a common functional group, a compound having a functional group (d) having reactivity with the reactive functional group (c1) ( It is preferable to use two or more compounds (D) such as D) and a compound (D) having a functional group (d) having reactivity with the reactive functional group (c3).

  The polymerizable unsaturated group possessed by the compound (D) is preferably a carbon-carbon unsaturated double bond having radical polymerizability, more specifically, a vinyl group, a (meth) acryloyl group, a maleimide group, and the like. (Meth) acryloyl groups are more preferred from the viewpoint of good curability in the active energy ray-curable resin composition described below.

  Specific examples of the compound (D) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxy Butyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, N- (2-hydroxyethyl) (meth) acrylamide, glycerin mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (Meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, lactone-modified (meth) acrylate having a hydroxyl group at the terminal Unsaturated monomer having a hydroxyl group such as relate; 2- (meth) acryloyloxyethyl isocyanate, 2- (2- (meth) acryloyloxyethoxy) ethyl isocyanate, 1,1-bis ((meth) acryloyloxymethyl) Unsaturated monomers having an isocyanate group such as ethyl isocyanate; unsaturated monomers having an epoxy group such as glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether; (meth) acrylic acid, 2- (meth) acryloyloxyethyl Unsaturated monomers having a carboxyl group such as succinic acid, 2- (meth) acryloyloxyethylphthalic acid, maleic acid and itaconic acid; acid anhydrides having an unsaturated double bond such as maleic anhydride and itaconic anhydride Etc. Moreover, 2-hydroxy-3-acryloyloxypropyl methacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate etc. can also be used as what has a several polymerizable unsaturated group. These compounds (D) can be used alone or in combination of two or more.

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

  Next, a more specific method for producing the fluorine atom-containing silicone-based polymerizable resin of the present invention will be described using the raw materials listed above.

  In the above production method 1 or 2, the production method of the polymer (P1) or (P2), which is an intermediate of the fluorine atom-containing silicone-based polymerizable resin of the present invention, is the compound ( A), the monomer (B), the monomer (C1), and, if necessary, another polymerizable unsaturated monomer (C4), in the case of production method 2, the compound (A ), The monomer (B), the monomer (C1), the monomer (C2), the monomer (C3), and other polymerizable unsaturated monomers (if necessary) A method of polymerizing C4) in an organic solvent using a polymerization initiator can be mentioned. As the organic solvent used here, ketones, esters, amides, sulfoxides, ethers, hydrocarbons are preferable. Specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, Examples include propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene and the like. These are appropriately selected in consideration of boiling point, compatibility, and polymerizability. Examples of the polymerization initiator include peroxides such as benzoyl peroxide and azo compounds such as azobisisobutyronitrile. Furthermore, chain transfer agents such as lauryl mercaptan, 2-mercaptoethanol, thioglycerol, ethylthioglycolic acid, octylthioglycolic acid and the like can be used as necessary.

  In production method 1 or 2, the polymer (P1) or (P2) obtained as described above is reacted with the functional group (d) having a reactivity with the functional group (c1) or (c3) and polymerization. The fluorine atom-containing silicone-based polymerizable resin of the present invention can be obtained by reacting the compound (D) having a polymerizable unsaturated group.

  The method of reacting the compound (D) with the polymer (P1) or (P2) may be performed under the condition that the polymerizable unsaturated group contained in the compound (D) or the like is not polymerized. It is preferable to adjust the reaction within a range of ˜120 ° C. This reaction is preferably carried out in the presence of a catalyst or a polymerization inhibitor, and if necessary in the presence of an organic solvent.

  For example, when the functional group (c1) or (c3) is a hydroxyl group and the functional group (d) is an isocyanate group, p-methoxyphenol, hydroquinone, 2,6-di-t is used as a polymerization inhibitor. -Butyl-4-methylphenol or the like is used, and dibutyltin dilaurate, dibutyltin diacetate, tin octylate, zinc octylate or the like is used as the urethanization reaction catalyst, and the reaction temperature is 40 to 120 ° C, particularly 60 to 90 ° C. The method of making it react with is preferable. When the functional group (c1) or (c3) is an epoxy group and the functional group (d) is a carboxyl group, or the functional group (c1) or (c3) is a carboxyl group When the functional group (d) is an epoxy group, p-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methylphenol or the like is used as a polymerization inhibitor, and the esterification reaction catalyst is used. Reaction temperature using tertiary amines such as triethylamine, quaternary ammoniums such as tetramethylammonium chloride, tertiary phosphines such as triphenylphosphine, quaternary phosphoniums such as tetrabutylphosphonium chloride, etc. It is preferable to make it react at 80-130 degreeC, especially 100-120 degreeC.

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

  Since the fluorine atom-containing silicone-based polymerizable resin of the present invention obtained as described above has excellent antifouling properties, its number average molecular weight (Mn) is preferably in the range of 1,000 to 10,000. The range of 1,500 to 8,000 is more preferable. Moreover, it is preferable that a weight average molecular weight (Mw) is the range of 2,000-50,000, and it is more preferable that it is the range of 3,000-35,000. These number average molecular weight (Mn) and weight average molecular weight (Mw) can be determined by the above GPC measurement.

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

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

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

  Although the fluorine atom-containing silicone-based polymerizable resin of the present invention can be used as a main component of the active energy ray-curable composition itself, it has an extremely excellent surface modification performance, so that it is active energy ray-curable. By using as a surface modifier to be added to the composition, excellent scratch resistance can be imparted to the cured coating film.

  The active energy ray-curable composition of the present invention is obtained by adding the fluorine atom-containing silicone-based polymerizable resin of the present invention. The main component thereof is an active energy ray-curable resin (E) or active energy. Contains a linear curable monomer (F). In the active energy ray-curable composition of the present invention, the active energy ray-curable resin (E) and the active energy ray-curable monomer (F) may be used alone or in combination. It doesn't matter. The fluorine atom-containing silicone-based polymerizable resin of the present invention is preferably used as a fluorine-based surfactant in the active energy ray-curable composition.

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

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

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

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

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

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

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

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

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

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

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

  In the active energy ray-curable composition of the present invention, when the fluorine atom-containing silicone-based polymerizable resin of the present invention is used as a fluorosurfactant, the amount used thereof is the active energy ray-curable resin (E) and The range of 0.01-20 mass parts is preferable with respect to a total of 100 mass parts of the active energy ray-curable monomer (F), more preferably 0.1-15 mass parts, and 0.5-10. The range of parts by mass is more preferable. If the amount of the fluorine atom-containing silicone-based polymerizable resin of the present invention is within this range, the leveling property, water / oil repellency and antifouling property can be made sufficient, and the hardness after curing of the composition And transparency can be sufficient. Moreover, the ratio of the fluorine atom-containing silicone-based polymerizable resin of the present invention in the surface layer portion of the coating film changes depending on the film thickness when the active energy ray-curable composition of the present invention is formed into a coating film. In this case, the addition amount of the fluorine atom-containing silicone polymerizable resin of the present invention is set low, and in the case of a thin film, the addition amount of the fluorine atom-containing silicone polymerizable resin of the present invention is set high. The fluorine atom-containing silicone-based polymerizable resin of the present invention can be uniformly present on the surface of the coating film, which is preferable because high scratch resistance can be expected.

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

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

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

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

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

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

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

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

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

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

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

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

  Since the cured coating film of the fluorine atom-containing silicone-based polymerizable resin of the present invention has scratch resistance, it can impart scratch resistance to the surface of the article by coating and curing on the surface of the article. Moreover, since the silicone-based polymerizable resin of the present invention can add leveling properties to the coating material by adding it to the coating material, the active energy ray curing agent composition of the present invention has high leveling properties. Have.

  As an article that can prevent scratching by imparting scratch resistance to the surface using the fluorine atom-containing silicone-based polymerizable resin or active energy ray-curable composition of the present invention, a liquid crystal display (LCD) such as a TAC film (LCD) ) Polarizing plate film; prism sheet or diffusion sheet as LCD backlight member; various display screens such as plasma display (PDP), organic EL display (hard coat layer, antireflection layer, etc. located on the outermost surface); Touch panel; mobile phone casing or mobile phone screen; optical recording medium such as CD, DVD, Blu-ray disc; transfer film for insert mold (IMD, IMF); rubber roller for OA equipment such as copier, printer; Glass surface of the reading part of OA equipment such as a scanner; camera, video camera Optical lenses such as glasses, windshields for watches such as watches, glass surfaces; windows for various vehicles such as automobiles and railway vehicles; various building materials such as decorative panels; window glass for houses; woodwork materials for furniture, artificial and synthetic leather And various plastic molded articles such as housings for home appliances, FRP bathtubs, and the like. By applying the fluorine atom-containing silicone-based polymerizable resin or active energy ray-curable composition of the present invention to the surface of these articles and irradiating active energy rays such as ultraviolet rays to form a cured coating film, Abrasion resistance can be imparted. Further, the fluorine atom-containing silicone-based polymerizable resin of the present invention can be added to various paints suitable for each article, applied and dried, thereby imparting scratch resistance to the article surface.

Hereinafter, the present invention will be described in more detail with reference to specific examples. In the examples, “parts” and “%” are based on mass unless otherwise specified. The measurement conditions of IR spectrum, ¹³ C-NMR spectrum and GPC of the obtained fluorine atom-containing silicone-based polymerizable resin are as follows.

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

[ ^13C -NMR spectrum measurement conditions]
Apparatus: “JNM-ECA500” manufactured by JEOL Ltd.
Solvent: DMSO-d ₆

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

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

Example 1 (Preparation of fluorine-containing polymerizable resin)
A glass flask equipped with a stirrer, thermometer, condenser, and dropping device was charged with 80.2 g of methyl isobutyl ketone as a solvent and heated to 90 ° C. while stirring under a nitrogen stream. Next, 12.1 g of tridecafluorohexylethyl methacrylate and a polymerizable unsaturated monomer having a silicone group represented by the following formula (B1-1) (hereinafter abbreviated as “monomer (B1-1)”) A monomer solution prepared by dissolving 35 g and 33.1 g of 3-hydroxy-1-adamantyl methacrylate in 148.8 g of methyl isobutyl ketone, and t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator A polymerization initiator solution in which 4.8 g was dissolved in 11.7 g of methyl isobutyl ketone was set in separate dropping devices, and dropped simultaneously over 2 hours while maintaining the inside of the flask at 90 ° C. After completion of dropping, the mixture was stirred at 90 ° C. for 9 hours to obtain a polymer (P-1) solution.

（式中、ｎは平均６５である。）

(Where n is an average of 65)

Next, 0.1 g of p-methoxyphenol as a polymerization inhibitor and 0.03 g of tin octylate as a urethanization catalyst were charged into the polymer (P-1) solution, and stirring was started under an air stream. While maintaining the above, 19.8 g of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at 60 ° C. for 2 hours, then heated to 80 ° C. and stirred for 8 hours. The disappearance of the isocyanate group was confirmed by IR spectrum measurement, methyl isobutyl ketone was added, and a methyl isobutyl ketone solution containing 20% of the fluorine atom-containing silicone polymerizable resin (1) of the present invention was obtained. As a result of measuring the molecular weight of the obtained fluorine atom-containing silicone-based polymerizable resin (1) by GPC, the number average molecular weight was 4,800, the weight average molecular weight was 13,000, and the radical polymerizable unsaturated group equivalent was 710 g / eq. . Met. An IR spectrum chart of the fluorine atom-containing silicone-based polymerizable resin (1) is shown in FIG. 1, a ¹³ C-NMR spectrum chart is shown in FIG. 2, and a GPC chart is shown in FIG.

Example 2 (same as above)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 38.8 g of methyl isobutyl ketone as a solvent and heated to 87 ° C. while stirring under a nitrogen stream. Next, 12 g of tridecafluorohexylethyl methacrylate, 18 g of the monomer (B1-1), 43.8 g of 3-hydroxy-1-adamantyl methacrylate, a monomer solution in 122 g of methyl isobutyl ketone, and radical polymerization A polymerization initiator solution in which 4.8 g of t-butylperoxy-2-ethylhexanoate as an initiator was dissolved in 11.5 g of methyl isobutyl ketone was set in separate dropping devices, and the flask was kept at 87 ° C. It was dripped simultaneously over 2 hours. After completion of dropping, the mixture was stirred at 87 ° C. for 13 hours, and then 122.8 parts of the solvent was distilled off under reduced pressure to obtain a polymer (P-2) solution.

  Next, 0.1 g of p-methoxyphenol as a polymerization inhibitor and 0.03 g of tin octylate as a urethanization catalyst were charged into the polymer (P-2) solution, and stirring was started under an air stream. While maintaining, 26.2 g of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at 60 ° C. for 2 hours, then heated to 80 ° C. and stirred for 9 hours. The disappearance of the isocyanate group was confirmed by IR spectrum measurement, methyl isobutyl ketone and methyl ethyl ketone were added, and a methyl isobutyl ketone / methyl ethyl ketone solution containing 20% of the fluorine atom-containing silicone polymerizable resin (2) of the present invention was obtained. As a result of measuring the molecular weight of the obtained fluorine atom-containing silicone-based polymerizable resin (2) by GPC, the number average molecular weight was 5,500, the weight average molecular weight was 28,000, and the radical polymerizable unsaturated group equivalent was 540 g / eq. Met.

Example 3 (same as above)
A glass flask equipped with a stirrer, thermometer, condenser, and dropping device was charged with 80.2 g of methyl isobutyl ketone as a solvent and heated to 90 ° C. while stirring under a nitrogen stream. 2- [Bis- (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyloxymethyl) -methoxycarbonylamino] -ethyl methacrylate 12 0.1 g, monomer (B1-1) 35 g, 3-hydroxy-1-adamantyl methacrylate 33.1 g dissolved in methyl isobutyl ketone 148.8 g, and a radical polymerization initiator t- A polymerization initiator solution prepared by dissolving 4.8 g of butylperoxy-2-ethylhexanoate in 11.7 g of methyl isobutyl ketone was set in separate dropping devices, and dropped simultaneously over 2 hours while maintaining the inside of the flask at 90 ° C. did. After completion of dropping, the mixture was stirred at 90 ° C. for 9 hours to obtain a polymer (P-3) solution.

  Next, 0.1 g of p-methoxyphenol as a polymerization inhibitor and 0.03 g of tin octylate as a urethanization catalyst were charged into the polymer (P-3) solution, and stirring was started in an air stream at 60 ° C. While maintaining the above, 19.8 g of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at 60 ° C. for 2 hours, then heated to 80 ° C. and stirred for 8 hours. The disappearance of the isocyanate group was confirmed by IR spectrum measurement, methyl isobutyl ketone was added, and a methyl isobutyl ketone solution containing 20% of the fluorine atom-containing silicone-based polymerizable resin (3) of the present invention was obtained. As a result of measuring the molecular weight of the obtained fluorine atom-containing silicone-based polymerizable resin (3) by GPC, the number average molecular weight was 4,800, the weight average molecular weight was 13,000, and the radical polymerizable unsaturated group equivalent was 710 g / eq. . Met.

Example 4 (same as above)
A glass flask equipped with a stirrer, thermometer, condenser, and dropping device was charged with 80.2 g of methyl isobutyl ketone as a solvent and heated to 90 ° C. while stirring under a nitrogen stream. Next, 12.1 g of tridecafluorohexylethyl methacrylate, 29 g of the monomer (B1-1), and a polymerizable unsaturated monomer having a silicone group represented by the following formula (B1-2) (hereinafter, “ Abbreviated as “monomer (B1-2)”), a monomer solution obtained by dissolving 63.1 g of 3-hydroxy-1-adamantyl methacrylate in 148.8 g of methyl isobutyl ketone, and a radical polymerization initiator. A polymerization initiator solution in which 4.8 g of t-butylperoxy-2-ethylhexanoate was dissolved in 11.7 g of methyl isobutyl ketone was set in a separate dropping device, and the flask was kept at 90 ° C. for 2 hours at the same time. And dripped. After completion of dropping, the mixture was stirred at 90 ° C. for 9 hours to obtain a polymer (P-4) solution.

  Subsequently, 0.1 g of p-methoxyphenol as a polymerization inhibitor and 0.03 g of tin octylate as a urethanization catalyst were charged into the polymer (P-4) solution, and stirring was started in an air stream at 60 ° C. While maintaining the above, 19.8 g of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at 60 ° C. for 2 hours, then heated to 80 ° C. and stirred for 8 hours. The disappearance of the isocyanate group was confirmed by IR spectrum measurement, methyl isobutyl ketone was added, and a methyl isobutyl ketone solution containing 20% of the fluorine atom-containing silicone polymerizable resin (4) of the present invention was obtained. As a result of measuring the molecular weight of the obtained fluorine atom-containing silicone-based polymerizable resin (4) by GPC, the number average molecular weight was 4,200, the weight average molecular weight was 11,000, and the radical polymerizable unsaturated group equivalent was 710 g / eq. . Met.

Example 5 (Preparation of active energy ray-curable composition)
As a UV curable coating composition, Unidic 17-806 (Butyl acetate solution containing 80% UV curable urethane acrylate resin manufactured by DIC Corporation) 125 parts, Irgacure 184 (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator 5 parts, 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 mixed and dissolved to obtain 268 parts of an ultraviolet curable coating composition.

  An active energy ray-curable composition is obtained by adding 2.5 parts of a fluorine atom-containing silicone-based polymerizable resin (1) as a surfactant to 268 parts by mass of the resin composition obtained above, and mixing the mixture uniformly. (5) was obtained.

This active energy ray-curable composition (5) was applied to bar coater No. 13 was applied to an acrylonitrile-butadiene-styrene copolymer synthetic resin (ABS) plate having a thickness of 2 mm and then placed in a dryer at 60 ° C. for 5 minutes to volatilize the solvent. Next, the dried coating film was cured by irradiating with ultraviolet rays (UV) using an ultraviolet curing device (under a nitrogen atmosphere, a high-pressure mercury lamp, an ultraviolet irradiation amount of ² kJ / m ² ). Next, the cured coating film was immersed in a 2.0 mol / L potassium hydroxide aqueous solution heated to 70 ° C. for 1 minute, washed with water, dried at 100 ° C. for 3 minutes, and coated film for evaluation (5 ) Using the obtained coating film for evaluation (5), the scratch resistance test was evaluated according to the following method. The evaluation results are shown in Table 1.

<Scratch resistance evaluation method>
Abrasion test with Tribogear HEIDON reciprocating wear tester TYPE: 30S (manufactured by Shinto Kagaku Co., Ltd.) and Bonstar No0000 (ultrafine steel wool produced by Nippon Steel Wool Co., Ltd.) attached to a circular jig with a diameter of 27 mm at machine (500 g / cm ² load), after by 30 reciprocating wear, count the number of possible wound, was evaluated according to the following criteria.

A: The number of scratches is less than 10.
○: The number of scratches is 10 or more and less than 20.
Δ: The number of scratches is 20 or more and less than 50.
X: The number of scratches is 50 or more.

Example 6 (same as above)
An evaluation coating film (6) was prepared in the same manner as in Example 5 except that the fluorine atom-containing silicone polymerizable resin (2) was used in place of the fluorine atom-containing silicone polymerizable resin (1). Using the obtained coating film for evaluation (6), the scratch resistance test and the antifouling property after the friction treatment were evaluated in the same manner as in Example 5. The evaluation results are shown in Table 1.

Example 7 (same as above)
An evaluation coating film (7) was prepared in the same manner as in Example 5 except that the fluorine atom-containing silicone polymerizable resin (3) was used in place of the fluorine atom-containing silicone polymerizable resin (1). Using the obtained coating film for evaluation (7), the scratch resistance test and the antifouling property after the friction treatment were conducted in the same manner as in Example 3. The evaluation results are shown in Table 1.

Example 8 (same as above)
An evaluation coating film (8) was prepared in the same manner as in Example 5 except that the fluorine atom-containing silicone polymerizable resin (4) was used instead of the fluorine atom-containing silicone polymerizable resin (1). Using the obtained coating film for evaluation (8), the scratch resistance test and the antifouling property after the friction treatment were evaluated in the same manner as in Example 5. The evaluation results are shown in Table 1.

Comparative Example 1 (Preparation of active energy ray-curable composition for comparison)
Silaplane FM-4421 (silicone oil manufactured by Chisso Corporation) in place of the fluorine atom-containing silicone-based polymerizable resin (1), having —C ₃ H ₆ OC ₂ H ₄ OH at both ends of the polydimethylsiloxane chain The coating film for evaluation for comparison (1) was used in the same manner as in Example 5 except that 2.5 parts by mass of perfluoroalkyl group, adamantyl group and polymerizable unsaturated group were not used. created. A scratch resistance test was carried out in the same manner as in Example 5 using the obtained comparative coating film for evaluation (1 ′). The evaluation results are shown in Table 1.

Comparative Example 2 (same as above)
Silaplane FM-0721K (silicone oil manufactured by Chisso Corporation, which does not have a perfluoroalkyl group or an adamantyl group, but has a polymerizable unsaturated group at one end instead of the fluorine atom-containing silicone-based polymerizable resin (1) The coating film for evaluation for comparison (2 ′) was prepared in the same manner as in Example 5 except that 2.5 parts by mass was used. A scratch resistance test was conducted in the same manner as in Example 5 using the obtained comparative coating film for evaluation (2 ′). The evaluation results are shown in Table 1.

Comparative Example 3 (same as above)
Silaplane FM-0741K (silicone oil manufactured by Chisso Corp. instead of fluorosurfactant (1). It does not have a perfluoroalkyl group or adamantyl group, but has a polymerizable unsaturated group at one end. The coating film for evaluation for comparison (2 ′) was prepared in the same manner as in Example 5 except that 2.5 parts by mass of the component was used. A scratch resistance test was conducted in the same manner as in Example 5 using the obtained comparative coating film for evaluation (2 ′). The evaluation results are shown in Table 1.

Comparative Example 4 (same as above)
In Example 3, a comparative evaluation coating film (4 ′) was prepared in the same manner as in Example 3 except that the fluorosurfactant (1) was not added. A scratch resistance test was conducted in the same manner as in Example 3 by using the obtained comparative coating film for evaluation (4 ′). The evaluation results are shown in Table 1.

Claims (9)

  A fluorine atom-containing silicone-based polymerizable resin, which is a polymer having a fluorinated alkyl group, a silicone chain, an adamantyl group, and a polymerizable unsaturated group.   2. The fluorine atom-containing silicone-based polymerizable resin according to claim 1, wherein the fluorinated alkyl group has 4 to 6 carbon atoms and the silicone chain has a molecular weight of 2,000 to 20,000.   A polymerizable unsaturated monomer (A) having a fluorinated alkyl group having 4 to 6 carbon atoms, a polymerizable unsaturated monomer (B) having a silicone group, and a reactive functional group (c1) The polymer (P1) obtained by copolymerizing a polymerizable unsaturated monomer (C1) having an adamantyl chain as an essential monomer component has a functionality reactive to the functional group (c1). 2. The fluorine atom-containing silicone-based polymerizable resin according to claim 1, obtained by reacting a group (d) and a compound (D) having a polymerizable unsaturated group.   A polymerizable unsaturated monomer (A) having a fluorinated alkyl group having 4 to 6 carbon atoms, a polymerizable unsaturated monomer (B) having a silicone chain, and a reactive functional group (c1) A polymerizable unsaturated monomer (C1) having an adamantyl group or a polymerizable unsaturated monomer (C2) having an adamantyl group not having a reactive functional group (c1) and a reactive functional group (c3) The polymer (P2) obtained by copolymerizing a polymerizable unsaturated monomer (C3) as an essential monomer component is reactive to the functional group (c1) or the functional group (c3). The fluorine atom-containing silicone-based polymerizable resin according to claim 1, which is obtained by reacting a functional group (d) having at least one compound and at least one compound (D) having a polymerizable unsaturated group.   The reactive functional group (c1) or the reactive functional group (c3) is at least one functional group selected from the group consisting of a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group, and an acid anhydride group. The functional group (d) of the compound (D) is reactive with the reactive functional group (c1), and is a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group, and an acid anhydride. The fluorine atom-containing silicone-based polymerizable resin according to claim 2 or 3, which is at least one functional group selected from the group consisting of physical groups.   When the mass ratio [(A) / (B)] of the compound (A) and the monomer (B) is in the range of 10/90 to 90/10, the compound (A) and the monomer (B) And the mass ratio of the sum to the monomer (C1) [[(A) + (B)] / (C1)] or the sum of the compound (A) and the monomer (B) and the monomer (C2 The mass ratio [[(A) + (B)] / (C2)] to the range of 15/85 to 70/30 is a fluorine atom-containing silicone-based polymerizable resin according to claim 3.   A fluorine atom-containing silicone-based polymerizable resin according to any one of claims 1 to 6, and an active energy ray-curable resin (E) or an active energy ray-curable monomer (F). An active energy ray-curable composition.   The fluorine atom-containing silicone-based polymerizable resin according to any one of claims 1 to 6 or the active energy ray-curable composition according to claim 5 is applied to a substrate and cured by irradiation with active energy rays. A cured product characterized by comprising   An article having a cured coating film of the fluorine atom-containing silicone-based polymerizable resin according to any one of claims 1 to 6 or the active energy ray-curable composition according to claim 5.

Images