JPH10182558A - Fluorine-containing polyfunctional (meth)acrylic ester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound that is excellent in low refractive index, surface hardness and adhesiveness and is useful as a component of the raw materials for anti-reflection coating or clad in optical fiber. SOLUTION: This compound is represented by formula I (X is a 1-14C fluoroalkyl bearing 3 or more F atoms or a 3-14C fluorocycloalkyl bearing 4 or more F atoms; Y<1> -Y<3> are H, acryloyl, methacryloyl; Z is H, a 1-3C alkyl; (n) and (m) are each 0 or 1 where n+m=1). The compound of formula I is prepared by subjecting a carboxylic acid of formula II and a fluorine-containing diepoxide to ring-opening reaction, esterifying the product with (meth)acryloyl chloride and purifying the reaction mixture. Since the compound of formula I has plural (meth)acryloyl groups, a three-dimensional network structure is formed by curing through crosslinking polymerization to give hardened coating layer with high surface hardness having excellent scuffing resistance, wearing resistance, heat resistance and weather resistance. In addition, the compound bearing hydroxyl groups increases the adhesion of the cured coating layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a fluorine-containing polyfunctional (meta-functional) material which exhibits high surface hardness, good adhesion and low refractive index after cross-linking polymerization and can be used as a raw material component such as an antireflection film or a cladding material of an optical fiber. ) Acrylic esters.

[0002]

2. Description of the Related Art Since a compound having a fluorine atom has a low refractive index, it can be used as an antireflection film or a cladding material for an optical fiber. In any case, the performance improves as the refractive index decreases. For example, a polymer of a fluorine-containing (meth) acrylate, a copolymer with another monomer, a tetrafluoroethylene polymer, a copolymer of vinylidene fluoride and tetrafluoroethylene, or a copolymer of vinylidene fluoride and hexafluoropropylene Applications of polymers and the like to optical fibers have been proposed (JP-A-59-84203, JP-A-59-84204, JP-A-59-98116, JP-A-59-147001, JP-A-59-
No. 204002).

Recently, a fluorine-containing alkyl ester polymer of acrylic acid, a fluorine-containing alkyl ester polymer of methacrylic acid, or a product name "CYTOP" (manufactured by Asahi Glass Co., Ltd.)
Attempts have been made to apply a solvent-soluble low refractive index fluoropolymer such as a non-crystalline perfluoro resin such as trade name "Teflon AF" (manufactured by DuPont, USA) to an anti-reflection film (Japanese Patent Laid-Open No. 64-64). No. 16873, JP-A-1-149
808, JP-A-6-115023). However, these fluorine-containing resins are all non-crosslinkable resins, and have the drawback that the surface hardness after curing is low, the abrasion resistance is poor, and the adhesion is insufficient.

In order to improve the surface hardness, fluorine-containing monofunctional (meth) acrylate or fluorine-containing bifunctional (meth)
A crosslinked polymer obtained by appropriately mixing an acrylate and a non-fluorine-containing polyfunctional (meth) acrylate has been proposed (JP-A-58-105943, JP-A-62-199643). JP-A-62-2500
No. 47). These crosslinked polymers are fluorinated (meth)
Fluorine content and non-fluorine-containing polyfunctionality in acrylic ester
By adjusting the mixing ratio with the (meth) acrylate, the low refractive index and the surface hardness can be adjusted within a certain range. However, the fluorinated monofunctional (meth) acrylate and the polyfunctional (meth) acrylate are incompatible with each other at an arbitrary ratio. Therefore, a sufficiently low refractive index cannot be achieved. On the other hand, the fluorinated bifunctional (meth) acrylate and the polyfunctional (meth) acrylate are compatible at an arbitrary ratio. However, if the content of fluorine atoms in the crosslinked polymer is increased to lower the refractive index, the crosslink density decreases. Therefore, low refractive index and surface hardness cannot be satisfactorily compatible, and it is difficult to impart surface hardness to the optical fiber and the antireflection film. In addition, there is a problem in adhesion.

[0005] Improvement of adhesion, and other fluorine-containing (meth)
For the purpose of using acrylic acid esters as raw materials, fluorine-containing hydroxy (meth) acrylic acid esters have been proposed (JP-A-4-321660, JP-A-4-356443, JP-A-4-356444). ). However, since these are monofunctional (meth) acrylates, they have the disadvantage that the surface hardness after curing is low and the abrasion resistance is poor.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a fluorine-containing polyfunctional (meth) acrylate ester which provides a fluorine-containing compound which can satisfy a low refractive index, surface hardness and adhesion.

[0007]

According to the present invention, the following formula is provided.
There is provided a fluorine-containing polyfunctional (meth) acrylate represented by (1).

[0008]

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(Wherein X represents a C1-14 fluoroalkyl group having 3 or more fluorine atoms or a C3-14 fluorocycloalkyl group having 4 or more fluorine atoms; Y ¹ and Y ^{1 2} and Y ³ represent a hydrogen atom, an acryloyl group or a methacryloyl group, and at least two of Y ¹ , Y ² and Y ³ are the same or different groups and represent an acryloyl group or a methacryloyl group; Z represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. N and m each represent 0 or 1, and n + m = 1.)

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The fluorine-containing polyfunctional (meth) of the present invention
The acrylate can be represented by the above formula (1). In the formula (1), when n = 1 and m = 0, the following formula is used.
(1a), and when n = 0 and m = 1, it can be expressed by the following equation (1b).

[0011]

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Specifically, in the above formula (1a), Y ¹ ,
^Two of Y ² and Y ^{3 represent} an acryloyl group or a methacryloyl group, and the other one represents a hydrogen atom, and has a (meth) acryloyl group and a hydroxyl group. The formula (1b)
Wherein ^{two of} Y ¹ , Y ² and Y ^{3 represent} an acryloyl group or a methacryloyl group, and the other one represents a hydrogen atom, wherein the fluorine-containing difunctional (meth) acrylic acid having a (meth) acryloyl group and a hydroxyl group Ester (hereinafter referred to as diester B); in the above formula (1a), Y ¹ , Y ² and Y ³ are the same or different groups, and represent an acryloyl group or a methacryloyl group, and a fluorine-containing trifunctional (meth) acrylate ester
(Hereinafter referred to as triester A); in the above formula (1b),
Y ¹ , Y ² and Y ³ are the same or different groups and represent an acryloyl group or a methacryloyl group, a fluorine-containing trifunctional
(Meth) acrylic acid ester (hereinafter referred to as triester B). In the formula (1), when X has more than 12 carbon atoms, production is difficult.

Examples of the diester A include 3-perfluorohexyl-2-hydroxypropyl = 2,2-bis ((meth) acryloyloxymethyl) propionate and 3-perfluorohexyl-2-((meth) acryloyloxy)
Propyl = 2-((meth) acryloyloxymethyl) -2
-(Hydroxymethyl) propionate, 3-perfluorooctyl-2-hydroxypropyl = 2,2-bis
((Meth) acryloyloxymethyl) propionate, or 3-perfluorooctyl-2-((meth) acryloyloxy) propyl = 2-((meth) acryloyloxymethyl) -2- (hydroxymethyl) propionate .

As the diester B, 2-perfluorohexyl- (1-hydroxymethyl) ethyl = 2,2-bis ((meth) acryloyloxymethyl) propionate;
2-perfluorohexyl-1-((meth) acryloyloxymethyl) ethyl = 2-((meth) acryloyloxymethyl) -2- (hydroxymethyl) propionate, 2
-Perfluorooctyl- (1-hydroxymethyl) ethyl = 2,2-bis ((meth) acryloyloxymethyl) propionate or 2-perfluorooctyl-1-
((Meth) acryloyloxymethyl) ethyl = 2-((meth) acryloyloxymethyl) -2- (hydroxymethyl) propionate and the like are preferred.

As the triester A, 3-perfluorobutyl-2- (meth) acryloyloxypropyl =
2,2-bis ((meth) acryloyloxymethyl) propionate, 3-perfluorohexyl-2- (meth) acryloyloxypropyl = 2,2-bis ((meth) acryloyloxymethyl) propionate, 3-perfluorooctyl-2 -(Meth) acryloyloxypropyl =
2,2-bis ((meth) acryloyloxymethyl) propionate, 3-perfluorocyclopentylmethyl-2
-(Meth) acryloyloxypropyl = 2,2-bis
((Meth) acryloyloxymethyl) propionate, 3
-Perfluorocyclohexylmethyl-2- (meth) acryloyloxypropyl = 2,2-bis ((meth) acryloyloxymethyl) propionate or 3-perfluorocycloheptylmethyl-2- (meth) acryloyloxypropyl = 2,2- Bis ((meth) acryloyloxymethyl) propionate and the like are preferred.

As the triester B, 2-perfluorobutyl- (1- (meth) acryloyloxymethyl) ethyl = 2,2-bis ((meth) acryloyloxymethyl) propionate, 2-perfluorohexyl- (1- ( (Meth) acryloyloxymethyl) ethyl = 2,2-bis
((Meth) acryloyloxymethyl) propionate, 2
-Perfluorooctyl- (1- (meth) acryloyloxymethyl) ethyl = 2,2-bis ((meth) acryloyloxymethyl) propionate, 2-perfluorocyclopentylmethyl- (1- (meth) acryloyloxymethyl) ethyl = 2 , 2-Bis ((meth) acryloyloxymethyl) propionate, 2-perfluorocyclohexylmethyl- (1- (meth) acryloyloxymethyl) ethyl = 2,2-bis ((meth) acryloyloxymethyl)
Propionate or 2-perfluorocycloheptylmethyl- (1- (meth) acryloyloxymethyl) ethyl = 2,2-bis ((meth) acryloyloxymethyl) propionate is preferably exemplified.

These diester A, diester B, triester A and triester B can be used alone or as a mixture when used as a raw material such as a low refractive index resin (hereinafter, a mixture of diester A and diester B). Is referred to as a "diester mixture", a mixture of triester A and triester B is referred to as a "triester mixture", and a mixture of a diester and a triester, a diester mixture or a triester mixture is collectively referred to as an "ester mixture". In some cases).

Preferred examples of the method for producing the fluorine-containing polyfunctional (meth) acrylate of the present invention include the following two kinds of production methods. The first manufacturing method is
(a) a carboxylic acid having two hydroxymethyl groups represented by the following formula (2) (hereinafter referred to as carboxylic acid C):
By reacting with a fluorine-containing diepoxide represented by the following formula (3) (hereinafter referred to as epoxide D) by a usual ring-opening reaction in the presence of a catalyst, represented by the following formulas (4) and (5) A mixture of hydroxyfluoroalkyl 2,2-bis (hydroxymethyl) carboxylate (hereinafter referred to as ester E), and (b) an esterification reaction between the ester E and (meth) acrylic acid chloride. Can produce an ester mixture.

[0019]

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(X and Z in the formula are the same as X and Y in the formula (1)).

The carboxylic acid C used in the reaction (a) is, for example, 2,2-bis (hydroxymethyl)
Acetic acid, 2,2-bis (hydroxymethyl) propionic acid,
2,2-bis (hydroxymethyl) butyric acid, 2,2-bis
(Hydroxymethyl) valeric acid is preferred. Examples of the epoxide D include 3-trifluoromethyl-1,2-epoxypropane, 3-perfluoroethyl-1,2-epoxypropane, 3-perfluoropropyl-1,2-epoxypropane, and 3-perfluorobutyl-1 , 2-epoxypropane, 3-perfluoropentyl-1,2-epoxypropane, 3-perfluorohexyl-1,2-epoxypropane, 3-perfluoroheptyl-1,2-epoxypropane, 3-perfluorooctyl-1,2 -Epoxypropane, 3-perfluorononyl-1,2-epoxypropane, 3-perfluorodecyl-1,2-epoxypropane, 3-perfluoroundecyl-1,2-epoxypropane, 3-perfluorododecyl-1,2- Epoxy propane, 3-perfluorotri Sill 1,2-epoxypropane, 3
-(Perfluoro-1-methylethyl) -1,2-epoxypropane, 3- (perfluoro-2-methylpropyl)
-1,2-epoxypropane, 3- (perfluoro-3
-Methylbutyl) -1,2-epoxypropane, 3- (perfluoro-4-methylpentyl) -1,2-epoxypropane, 3- (perfluoro-5-methylhexyl)-
1,2-epoxypropane, 3- (perfluoro-6-
Methylheptyl) -1,2-epoxypropane, 3- (perfluoro-7-methyloctyl) -1,2-epoxypropane, 3- (perfluoro-8-methylnonyl)-
1,2-epoxypropane, 3- (perfluoro-9-
Methyldecyl) -1,2-epoxypropane, 3- (perfluoro-10-methylundecyl) -1,2-epoxypropane, 3- (perfluoro-11-methyldodecyl) -1,2-epoxypropane, 3- ( Perfluoro-
Preferred is 12-methyltridecyl) -1,2-epoxypropane.

The reaction ratio of the carboxylic acid C and the epoxide D in the reaction (a) is as follows:
Carboxylic acid C is preferably 0.8 to 5 mol, particularly 1.0 to 1.8 mol per 1 mol. Examples of the catalyst used in the reaction (a) include tertiary amines such as triethylamine and benzyldimethylamine; and quaternary ammonium salts such as tetraethylammonium bromide and tetramethylammonium bromide. The addition amount of the catalyst is desirably 0.001 to 5% by weight, particularly 0.01 to 2.5% by weight based on the total amount of the reaction mixture. The reaction temperature of the reaction (a) is preferably from 40 to 200 ° C, particularly preferably from 80 to 120 ° C, and the reaction time is preferably from 1 to 48 hours, particularly preferably from 2 to 12 hours. The mixture of the ester E produced by the reaction (a) is subjected to chloroform, methylene chloride, trifluoromethylbenzene, ethyl acetate or ethyl acetate to remove a catalyst or the like, if necessary, before being subjected to the next reaction (b). And then washed with an aqueous alkali solution such as sodium hydroxide or sodium carbonate, or water. If necessary, vacuum distillation, recrystallization,
It can also be purified by column chromatography or the like.

In the reaction (b), the ester E and (meth)
The charge ratio when reacting with acrylic acid chloride is 1 mol of ester E when a diester mixture is produced.
1.6 to 10 mol of (meth) acrylic acid chloride
1, particularly preferably 2.0 to 4.0 mol. On the other hand, when producing a triester mixture, ester E 1 mol
(Meth) acrylic chloride 2.4 to 15mo
1, particularly preferably 3.0 to 6.0 mol. The reaction
In order to capture the hydrochloric acid generated in (b), a tertiary alkylamine such as triethylamine and benzyldimethylamine, or a base such as pyridine can be added to the reaction system. When the diester mixture is produced, the amount of the base added is 1.6 to 10.0 m per 1 mol of the ester E.
ol, particularly preferably 2.0 to 4.5 mol. On the other hand, when producing a triester mixture, the ester E 1mo
2.4-15.0 mol, especially 3.0-7.
0 mol is preferred. The reaction (b) is preferably performed in a suitable solvent. Suitable solvents include, for example, chloroform, methylene chloride, trifluoromethylbenzene or mixtures thereof. The solvent is used in an amount of 20 to 2,000 parts by weight, especially 100 to 50 parts by weight, based on 100 parts by weight of the total of ester E, (meth) acrylic acid chloride and base.
It is preferable to use 0 parts by weight. The reaction temperature of the reaction (b) is preferably from -60 to 20C, particularly preferably from -40 to 0C, and the reaction time is preferably from 0.1 to 12 hours, particularly preferably from 0.5 to 2 hours. After the completion of the reaction (b), the system containing the produced ester mixture can be subjected to various treatments as necessary.
For example, a small amount of alcohols such as methanol and ethanol, water, or the like can be added to the reaction system in order to decompose excess (meth) acrylic acid chloride in the reaction system. It can also be washed with an acidic aqueous solution such as dilute hydrochloric acid. If necessary, purification can be performed by distillation under reduced pressure, recrystallization, column chromatography, or the like. When performing vacuum distillation, a polymerization inhibitor such as, for example, hydroquinone, hydroquinone monoethyl ether, and tert-butylcatechol can be added to prevent polymerization. The addition amount of the polymerization inhibitor is preferably 0.001 to 2% by weight, particularly preferably 0.005 to 0.2% by weight, based on the total amount of the mixture after the reaction (c).

The diester mixture produced by the above reaction (b) is usually a mixture of four types of structural isomers, two types each of diester A and diester B. Specifically, diester A ¹ represented by the following formulas (6) to (9) (formula
(6)), diester A ² (formula (7)), diester B ¹ (formula
(8)) and diester B ² (formula (9)).

[0025]

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(Where X, Y ¹ , Y ² , Y ³ and Z are
The same as X, Y ¹ , Y ² , Y ³ and Z in (1). ).

From these mixtures, diester A ¹ , diester A ² , diester B ¹ or diester B ² , or diester A consisting of diester A ¹ and diester A ² , or diester B consisting of diester B ¹ and diester B ² The desired product can be obtained by separation and isolation. On the other hand, the triester mixture is a mixture of structural isomers of triester A and triester B. Therefore, the target product can be obtained by separating and isolating triester A and triester B from the triester mixture in the same manner as diester A and diester B. In any case, examples of the separation and isolation methods include methods such as preparative liquid chromatography.

In the second production method, (c) the carboxylic acid C is first prepared by the method described in JP-A-63-99038, that is, the carboxylic acid C is converted to (meth) acrylic acid,
Acrylic acid chloride or (meth) acrylic acid ester may be reacted in the presence of an appropriate catalyst as required, for example, by a method of reacting 2,2-bis represented by the following general formula (10).
((Meth) acryloyloxymethyl) carboxylic acid (hereinafter referred to as carboxylic acid F) to produce

[0029]

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[0030] (wherein Y ^1, Y ² and Z are the same as Y ^1, Y ² and Z in the formula (1)). (d) Next, an ester mixture is obtained by reacting the carboxylic acid F with the epoxide D by a usual ring opening reaction in the presence of a catalyst. The ester mixture obtained by this reaction has the formula
A mixture of the diester A ¹ represented by (6) and the diester B ¹ represented by the formula (8) is obtained.

The charging ratio of the carboxylic acid C to the (meth) acrylic acid chloride in the reaction (c) is
1.6 to 1 (meth) acrylic acid chloride per 1 mol
0 mol, especially 2.0 to 4.0 mol is desirable. In the above reaction (c), in order to capture hydrochloric acid generated in the reaction, triethylamine, benzyldimethylamine or the like is used.
Bases such as tertiary alkylamines or pyridine can be added.
The amount of the base added was 1.6 per mol of carboxylic acid C.
10 to 10 mol, particularly 2.0 to 4.5 mol is desirable.
The reaction (c) is preferably performed in a suitable solvent. Suitable solvents include, for example, chloroform, methylene chloride, trifluoromethylbenzene, and the like. The solvent is preferably used in an amount of 20 to 2000 parts by weight, more preferably 100 to 500 parts by weight, based on 100 parts by weight of the total amount of carboxylic acid C, (meth) acrylic acid chloride and base. The reaction (c) is preferably carried out at a reaction temperature of -60 to 20C, preferably -40 to 0C. The reaction time is preferably 0.1 to 12 hours, particularly preferably 0.5 to 2 hours.

The carboxylic acid F produced by the reaction (c) can be subjected to various treatments as required before being subjected to the next reaction (d). For example, a small amount of alcohols such as methanol and ethanol, water or the like can be added to decompose excess (meth) acrylic acid chloride in the reaction system. It can also be washed with an acidic aqueous solution such as dilute hydrochloric acid. If necessary, it can be purified by distillation under reduced pressure, recrystallization, column chromatography or the like. When performing distillation under reduced pressure, a polymerization inhibitor such as hydroquinone, hydroquinone monoethyl ether, tert-butyl catechol and the like can be added to prevent polymerization. The amount added is 0.00% of the total amount of the mixture after the reaction.
1 to 2% by weight, particularly 0.005 to 0.2% by weight is desirable.

In the reaction (d), the reaction mixture ratio of reacting the epoxide D with the carboxylic acid F is 0.8 to 5 mol of the carboxylic acid F to 1 mol of the epoxide D,
In particular, 1.0 to 1.8 mol is desirable. Examples of the catalyst used in the reaction (d) include known catalysts such as tertiary amines such as triethylamine and benzyldimethylamine; and quaternary ammonium salts such as tetraethylammonium bromide and tetramethylammonium bromide. The catalyst was added in an amount of 0.001 to 0.001 in the total amount of the reaction mixture.
5.0 wt%, especially 0.01 to 2.5 wt% is desirable. In the reaction (d), it is preferable to add a polymerization inhibitor to prevent polymerization. Preferred examples of the polymerization inhibitor include hydroquinone, hydroquinone monoethyl ether, tert-butylcatechol and the like. The addition amount of the polymerization inhibitor is 0.001 to 2% by weight, particularly 0.005 to 0.2% by weight in the total amount of the reaction mixture.
Is desirable. The reaction (d) is performed at a reaction temperature of 40 to 200.
C., preferably 80 to 120.degree. Reaction time is 1-4
8 hours, especially 2 to 12 hours is desirable.

After the completion of the reaction (d), the resulting mixture containing the diester mixture can be subjected to various treatments as necessary, and then used. For example, to dissolve in an organic solvent such as chloroform, methylene chloride, and trifluoromethylbenzene to remove a catalyst and the like, sodium hydroxide,
It can be washed with an alkaline aqueous solution such as sodium carbonate. If necessary, it can be purified by distillation under reduced pressure, recrystallization, column chromatography or the like. When performing vacuum distillation, a polymerization inhibitor such as hydroquinone, hydroquinone monoethyl ether, tert.
-It is desirable to add butyl catechol and the like. The addition amount is preferably 0.001 to 2% by weight, particularly preferably 0.005 to 0.2% by weight based on the total amount of the mixture after the reaction. On the other hand, when producing a triester mixture, (e) the reaction (c) and
1 equivalent of the diester mixture obtained via (d)
It is obtained by subjecting (meth) acrylic acid chloride to an esterification reaction.

The diester mixture in the reaction (e)
The charging ratio with (meth) acrylic acid chloride is preferably 0.8 to 5 mol, particularly 1.0 to 2.0 mol of (meth) acrylic acid chloride per 1 mol of the diester mixture.

A tertiary alkylamine such as triethylamine and benzyldimethylamine or a base such as pyridine can be added to capture the hydrochloric acid generated in the reaction (e). The amount of the base added is 0.8 to 5.0 mol, particularly 1.0 to 2.5 mol, per 1 mol of the diester mixture.
l is preferred. The reaction (e) is preferably performed in a suitable solvent. Suitable solvents include, for example, chloroform, methylene chloride, trifluoromethylbenzene, and the like. The solvent is 20 to 100 parts by weight of the total amount of the diester mixture, (meth) acrylic acid chloride and the base.
It is preferable to use 2,000 parts by weight, particularly 100 to 500 parts by weight. The reaction temperature of the reaction (e) is -60 to 20.
° C, especially -40 to 0 ° C, and the reaction time is 0.1 to
12 hours, especially 0.5 to 2 hours is desirable.

After the completion of the reaction (e), the system containing the produced ester mixture can be subjected to various treatments as required. For example, in order to decompose excess (meth) acrylic acid chloride in the reaction system, a small amount of alcohols such as methanol and ethanol, water and the like can be added to the reaction system. It can also be washed with an acidic aqueous solution such as dilute hydrochloric acid. If necessary, vacuum distillation,
It can also be purified by recrystallization, column chromatography or the like. When performing vacuum distillation, to prevent polymerization,
For example, a polymerization inhibitor such as hydroquinone, hydroquinone monoethyl ether, and tert-butyl catechol can be added. The polymerization inhibitor is added in an amount of 0.001 to 2% by weight, preferably
5 to 0.2% by weight is preferred. The triester mixture formed in the reaction (e) is a mixture of structural isomers of triester A and triester B. The desired product can be obtained by separating and isolating triester A and triester B from this mixture. Separation and isolation can be performed, for example, by a method such as preparative liquid chromatography.

The fluorinated polyfunctional (meth) acrylate of the present invention can be cured as it is by crosslinking polymerization to form a cured film having excellent abrasion resistance, adhesion and the like. Used as a mixture. Diester A or diester B may be further subjected to a reaction step to obtain another fluorine-containing polyfunctional acrylate, followed by crosslinking polymerization. For example, a urethane (meth) acrylate or the like is synthesized by reacting the diester A or the diester B of the present invention with an isocyanate compound and the like, and these are cured by cross-linking polymerization to obtain a cured film.

[0039]

Since the fluorine-containing polyfunctional (meth) acrylate of the present invention has a plurality of (meth) acryloyl groups, it exhibits a three-dimensional network structure when cured by cross-linking polymerization and has a high surface hardness. A cured film having excellent scratch resistance, abrasion resistance, heat resistance, weather resistance and the like can be obtained. Further, diester A and diester B having a hydroxyl group can improve the adhesion of the cured film. The resulting cured product has high light transmittance and low refractive index, and also has excellent adhesion, and a low refractive index that requires abrasion resistance, adhesion, etc. of antireflection coatings, cladding materials for optical fibers, etc. Useful as a resin material.

[0040]

The present invention will be described below in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Example 1-1 In a reactor equipped with a stirrer, a cooling pipe, and a gas introduction pipe, 3-perfluorooctyl-1,2-epoxypropane 476 was added.
g (1.0 mol), 161 g (1.5 mol) of 2-bis (hydroxymethyl) propionic acid, 6.4 g of tetraethylammonium bromide, 600 ml of isopropyl alcohol
Was gradually heated in an oil bath to 95 to 100 ° C., stirred at the same temperature for 4 hours, and then cooled to room temperature. 5 L of water was added to the obtained reaction solution to precipitate a paste-like substance. The precipitate was filtered, dissolved in 1000 ml of ethyl acetate, washed three times with 1000 ml of water, and the solvent was distilled off under reduced pressure to obtain white crystals. This is represented by the following chemical formulas (11) and (1)
It is considered to be a mixture of compounds having the structure shown in 2).

[0041]

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In a reactor equipped with a stirrer, a thermometer, a gas inlet tube and a dropping funnel, 303.6 g of the white crystals obtained in the above reaction, 303.6 g of triethylamine, and 1000 ml of chloroform.
And under ice cooling 271.5 g of acrylic acid chloride
(3.0 mol) was dissolved in 300 ml of chloroform and added dropwise from a dropping funnel so that the temperature of the reaction solution did not exceed 5 ° C. After the completion of the dropwise addition, the mixture was stirred for 2 hours while cooling with ice. Chloroform was distilled off under reduced pressure, and the resulting yellow crystals were further purified with ethyl acetate /
Purification by column chromatography using a mixed solvent of n-hexane (volume ratio 1: 4) as a developing solvent, and 215 g of a white crystalline product G (30% yield) by distilling off the solvent under reduced pressure.
I got

A part of the obtained product G was further separated by using high performance liquid chromatography. Column is TSK gel
Using Silica-60 (inner diameter 21.5 mm: length 300 mm: manufactured by Tosoh Corporation), a mixed solvent of ethyl acetate / n-hexane (volume ratio 1: 5) was fractionated at a flow rate of 5 ml / min. The detection was performed using an ultraviolet detector at a wavelength of 230 nm. Compounds G-1, G-2, G-3 and G-4 obtained as a result of the separation are compounds having the structures represented by the following chemical formulas (13), (14), (15) and (16), respectively. Was. Hereinafter, ¹ H-NMR of these compounds,
The results of ¹⁹ F-NMR and Exact MS are shown together with the structural formula.

[0044]

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(G-1 analysis result) ¹ H-NMR (δ (ppm) CDCl _{3 /} TMS): 6.43 (dd, 2H); 6.11 (d
d, 1H); 6.11 (dd, 1H); 5.88 (dd, 2H); 4.53-4.31 (m, 1H); 4.4
3,4.36 (ABq, 2H); 4.41,4.39 (ABq, 2H); 4.28,4.12 (dABq, 2
H); 2.49 to 2.20 (m, 2H); 1.33 (s, 3H) ¹⁹ F-NMR (δ (ppm) CDCl ₃ / CFCl ₃ ): −123.10; −120.4
7; -119.72; -118.91; -118.60; -109.76; -77.79 Exact MS: measured value; 718.0865, theoretical; C ₂₂ H ₁₉ F
₁₇ O ₇ : 718.0859

[0046]

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(G-2 analysis result) ¹ H-NMR (δ (ppm) CDCl _{3 /} TMS): 6.44 (dd, ¹ H); 6.42 (d
d, 1H); 6.12 (dd, 1H); 6.11 (dd, 1H); 5.89 (dd, 1H); 5.88 (dd,
1H); 5.38-5.35 (m, 1H); 4.43,4.34 (ABq, 2H); 4.28,4.12 (d
ABq, 2H); 3.90,3.74 (ABq, 2H); 2.49 ~ 2.21 (m, 2H); 1.33 (s,
3H) ¹⁹ F-NMR (δ (ppm) CDCl ₃ / CFCl ₃ ): −123.11; −120.4
7; -119.72; -118.92; -118.60; -109.76; -77.79 Exact MS: measured value; 718.0862, theoretical; C ₂₂ H ₁₉ F
₁₇ O _7: 718.0859

[0048]

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(G-3 analysis result) ¹ H-NMR (δ (ppm) CDCl _{3 /} TMS): 6.42 (dd, 2H); 6.11 (d
d, 1H); 6.11 (dd, 1H); 5.88 (dd, 2H); 5.38-5.34 (m, 1H); 4.4
3,4.36 (ABq, 2H); 4.41,4.39 (ABq, 2H); 3.89,3.75 (dABq, 2
H); 2.49 to 2.20 (m, 2H); 1.32 (s, 3H) ¹⁹ F-NMR (δ (ppm) CDCl ₃ / CFCl ₃ ): −123.10; −120.4
7; -119.71; -118.91; -118.60; -109.76; -77.78 Exact MS: measured value; 718.0862, theoretical; C ₂₂ H ₁₉ F
₁₇ O ₇ : 718.0859

[0050]

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(G-4 analysis result) ¹ H-NMR (δ (ppm) CDCl _{3 /} TMS): 6.44 (dd, ¹ H); 6.42 (d
d, 1H); 6.12 (dd, 1H); 6.11 (dd, 1H); 5.89 (dd, 1H); 5.88 (dd,
1H); 5.39-5.34 (m, 1H); 4.43,4.36 (ABq, 2H); 4.29,4.13 (d
ABq, 2H); 3.90,3.75 (ABq, 2H); 2.49 ~ 2.20 (m, 2H); 1.33 (s,
3H) ¹⁹ F-NMR (δ (ppm) CDCl ₃ / CFCl ₃ ): −123.10; −120.4
6; -119.72; -118.91; -118.61; -109.76; -77.79 Exact MS: measured value; 718.0856, theoretical; C ₂₂ H ₁₉ F
₁₇ O _7: 718.0859 replacing Example 1-2 3-perfluorooctyl-1,2-epoxypropane, except for using 3-perfluorohexyl-1,2-epoxypropane 376.1g (1.0mol) is performed In the same manner as in Example 1-1, 198 g of a white crystalline product H was obtained through a compound having a structure represented by the following chemical formulas (17) and (18).
(32% yield).

[0052]

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A part of the obtained product H was prepared in Example 1-1.
Separation was performed using high performance liquid chromatography in the same manner as described above. Compounds H-1, H-2, H-3 and H-4 obtained
Was a compound having a structure represented by the following chemical formulas (19), (20), (21) and (22), respectively. The results of ¹ H-NMR, ¹⁹ F-NMR and Exact MS of these compounds are shown below together with the structural formulas.

[0054]

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(H-1 analysis result) ¹ H-NMR (δ (ppm) CDCl _{3 /} TMS): 6.43 (dd, 2H); 6.12 (d
d, 1H); 6.11 (dd, 1H); 5.88 (dd, 2H); 4.53-4.31 (m, 1H); 4.4
3,4.37 (ABq, 2H); 4.41,4.39 (ABq, 2H); 4.28,4.12 (dABq, 2
H); 2.49 to 2.21 (m, 2H); 1.34 (s, 3H) ¹⁹ F-NMR (δ (ppm) CDCl ₃ / CFCl ₃ ): −123.09; −120.3
9; -119.89; -118.89; -109.39; -77.90 Exact MS: measured value; 618.0931, theoretical; C ₂₀ H ₁₉ F
₁₃ O ₇ : 618.0923

[0056]

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(H-2 analysis result) ¹ H-NMR (δ (ppm) CDCl _{3 /} TMS): 6.44 (dd, ¹ H); 6.42 (d
d, 1H); 6.11 (dd, 1H); 6.10 (dd, 1H); 5.88 (dd, 1H); 5.88 (dd,
1H); 5.38-5.35 (m, 1H); 4.43,4.34 (ABq, 2H); 4.28,4.12 (d
ABq, 2H); 3.90,3.75 (ABq, 2H); 2.49 ~ 2.21 (m, 2H); 1.32 (s,
3H) ¹⁹ F-NMR (δ (ppm) CDCl ₃ / CFCl ₃ ): −123.09; −120.3
9; -119.88; -118.89; -109.38; -77.90 Exact MS: measured value; 618.0921, theoretical; C ₂₀ H ₁₉ F
₁₃ O ₇ : 618.0923

[0058]

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(H-3 analysis result) ¹ H-NMR (δ (ppm) CDCl _{3 /} TMS): 6.42 (dd, 2H); 6.11 (d
d, 1H); 6.11 (dd, 1H); 5.87 (dd, 2H); 5.37-5.34 (m, 1H); 4.4
3,4.36 (ABq, 2H); 4.41,4.40 (ABq, 2H); 3.89,3.75 (dABq, 2
H); 2.49 to 2.20 (m, 2H); 1.33 (s, 3H) ¹⁹ F-NMR (δ (ppm) CDCl ₃ / CFCl ₃ ): −123.08; −120.3
9; -119.88; -118.89; -109.39; -77.90 Exact MS: measured value; 618.0919, theoretical; C ₂₀ H ₁₉ F
₁₃ O ₇ : 618.0923

[0060]

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(H-4 analysis result) ¹ H-NMR (δ (ppm) CDCl _{3 /} TMS): 6.44 (dd, ¹ H); 6.42 (d
d, 1H); 6.12 (dd, 1H); 6.11 (dd, 1H); 5.89 (dd, 1H); 5.87 (dd,
1H); 5.38-5.33 (m, 1H); 4.43,4.36 (ABq, 2H); 4.30,4.14 (d
ABq, 2H); 3.90,3.75 (ABq, 2H); 2.49 ~ 2.21 (m, 2H); 1.33 (s,
3H) ¹⁹ F-NMR (δ (ppm) CDCl ₃ / CFCl ₃ ): −123.09; −120.3
9; -119.88; -118.88; -109.39; -77.89 Exact MS: measured value; 618.0929, theoretical; C ₂₀ H ₁₉ F
₁₃ O ₇ : 618.0923 Example 1-3 In a reactor equipped with a stirrer, thermometer, gas inlet tube and dropping funnel, 2,2-bis (hydroxymethyl) propionic acid 2 was added.
01g (1.5mol), trimethylamine 304g (3.0
mol) and 600 ml of chloroform, and 406 g (4.5 mol) of acrylic acid chloride was added to chloroform 40 under ice cooling.
The reaction solution was dissolved in 0 ml and added dropwise from a dropping funnel so that the temperature of the reaction solution did not exceed 5 ° C. After the completion of the dropwise addition, the mixture was stirred for 2 hours while cooling with ice. Chloroform was distilled off under reduced pressure, and the obtained yellow crystals were further subjected to a mixed solvent of ethyl acetate / n-hexane (volume ratio 1: 1:
Purification was performed by column chromatography using 4) as a developing solvent, and the solvent was distilled off under reduced pressure to obtain 2,2-bis (acryloyloxymethyl) propionic acid represented by the following chemical formula (23) as white crystals.

[0062]

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In a reactor equipped with a stirrer, a cooling pipe and a gas introduction pipe, 290 g (1.2 mol) of 2,2-bis (acryloyloxymethyl) propionic acid obtained in the above reaction,
Perfluorooctyl-1,2-epoxypropane 47
6 g (1.0 mol), 2-bis (hydroxymethyl) propionic acid 161 g (1.2 mol), tetraethylammonium bromide 6.4 g, isopropyl alcohol 600
Then, the mixture was gradually heated in an oil bath to 95 to 100 ° C., stirred at the same temperature for 4 hours, and then cooled to room temperature. 5 L of water was added to the obtained reaction solution to precipitate a paste-like substance. The precipitate was filtered, dissolved in 1000 ml of ethyl acetate, washed three times with 1000 ml of water, and the solvent was distilled off under reduced pressure to obtain a product I as white crystals. A part of this was separated using high performance liquid chromatography in the same manner as in Example 1-1. The obtained compounds I-1 and I-2 were compounds having the structures represented by the chemical formulas (13) and (15), respectively. ¹ H-NMR, ¹⁹ F-NM of the compound obtained below
R shows the result of Exact MS.

(I-1 analysis result) ¹ H-NMR (δ (ppm) CDCl _{3 /} TMS): 6.44 (dd, 2H); 6.11 (d
d, 1H); 6.11 (dd, 1H); 5.88 (dd, 2H); 4.54-4.31 (m, 1H); 4.4
3,4.36 (ABq, 2H); 4.41,4.39 (ABq, 2H); 4.28,4.12 (dABq, 2
H); 2.49 to 2.20 (m, 2H); 1.34 (s, 3H) ¹⁹ F-NMR (δ (ppm) CDCl ₃ / CFCl ₃ ): −123.10; −120.4
6; -119.72; -118.91; -118.60; -109.76; -77.78 Exact MS: measured value; 718.0856, theoretical; C ₂₂ H ₁₉ F
₁₇ O ₇ : 718.0859 (I-2 analysis result) ¹ H-NMR (δ (ppm) CDCl _{3 /} TMS): 6.42 (dd, 2H); 6.11 (d
d, 1H); 6.11 (dd, 1H); 5.88 (dd, 2H); 5.37-5.34 (m, 1H); 4.4
3,4.36 (ABq, 2H); 4.41,4.38 (ABq, 2H); 3.89,3.75 (dABq, 2
H); 2.48 to 2.20 (m, 2H); 1.32 (s, 3H) ¹⁹ F-NMR (δ (ppm) CDCl ₃ / CFCl ₃ ): −123.10; −120.4
7; -119.72; -118.91; -118.60; -109.76; -77.79 Exact MS: measured value; 718.0852, theoretical; C ₂₂ H ₁₉ F
₁₇ O ₇ : 718.059 Example 2-1 A 3-perfluorooctyl-1,2-epoxypropane 476 was placed in a reactor equipped with a stirrer, a cooling pipe, and a gas introduction pipe.
g (1.0 mol), 161 g (1.2 mol) of 2,2-bis (hydroxymethyl) propionic acid, 6.4 g of tetraethylammonium bromide, isopropyl alcohol 60
0 ml and gradually heated in an oil bath to 95-100 ° C.
After stirring at the same temperature for 4 hours, the mixture was cooled to room temperature.
5 L of water was added to the obtained reaction solution to precipitate a paste-like substance. The precipitate was filtered, dissolved in 1000 ml of ethyl acetate, washed three times with 1000 ml of water, and the solvent was distilled off under reduced pressure to obtain white crystals. This white crystal is considered to be a mixture of the compounds having the structures represented by the chemical formulas (11) and (12).

In a reactor equipped with a stirrer, thermometer, gas inlet tube and dropping funnel, the white crystals 5
35 g, 455.4 g of triethylamine and 1000 ml of chloroform were charged. Then, under ice-cooling, 479.6 g (4.5 mol) of acrylic acid chloride was added to chloroform 45.
The reaction solution was dissolved in 0 ml and added dropwise from a dropping funnel so that the temperature of the reaction solution did not exceed 5 ° C. After the completion of the dropwise addition, the mixture was stirred for 2 hours while cooling with ice. Chloroform was distilled off under reduced pressure, and the obtained yellow crystals were further subjected to a mixed solvent of ethyl acetate / n-hexane (volume ratio 1: 1:
Purification was performed by column chromatography using 4) as a developing solvent, and the solvent was distilled off under reduced pressure to obtain 232 g (yield 30%) of the target product J as white crystals.

A part of the obtained product J was prepared in Example 1-1.
Separation was performed using high performance liquid chromatography in the same manner as described above.
The desired products J-1 and J-2 obtained as a result of the separation are:
The structures were represented by the following chemical formulas (24) and (25), respectively.
¹ H-NMR, ¹⁹ F-NMR,
9 shows the results of Exact MS.

[0067]

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(J-1 analysis result) ¹ H-NMR (δ (ppm) CDCl _{3 /} TMS): 6.43 (dd, ¹ H); 6.42 (d
d, 2H); 6.12 (dd, 1H); 6.11 (dd, 1H); 6.10 (dd, 1H); 5.89 (dd,
2H); 5.88 (dd, 1H); 5.57 ~ 5.64 (m, 1H); 4.46,4.41 (ABq, 2
H); 4.41,4.39 (ABq, 2H); 4.27,4.23 (dABq, 2H); 2.68 ~ 2.31
(m, 2H); 1.30 (s, 3H) ¹⁹ F-NMR (δ (ppm) CDCl ₃ / CFCl ₃ ): −123.10; −120.4
7; -119.72; -118.91; -118.60; -109.76; -77.79 Exact MS: Measured: 772.0969, theory: C ₂₅ H ₂₁ F
₁₇ O ₈ : 772.0965

[0069]

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(J-2 analysis result) ¹ H-NMR (δ (ppm) CDCl _{3 /} TMS): 6.44 (dd, ¹ H); 6.42 (d
d, 2H); 6.12 (dd, 1H); 6.11 (dd, 1H); 6.11 (dd, 1H); 5.89 (dd,
1H); 5.88 (dd, 2H); 5.38-5.34 (m, 1H); 4.43,4.36 (ABq, 2
H); 4.41,4.39 (ABq, 2H); 4.29,4.13 (dABq, 2H); 2.68 ~ 2.31
(m, 2H); 1.30 (s, 3H) ¹⁹ F-NMR (δ (ppm) CDCl ₃ / CFCl ₃ ): −123.10; −120.4
7; -119.71; -118.91; -118.60; -109.76; -77.78 Exact MS: Measured: 772.0962, theory: C ₂₅ H ₂₁ F
₁₇ O _8: 772.0965 replacing Example 2-2 3-perfluorooctyl-1,2-epoxypropane, except for using 3-perfluorohexyl-1,2-epoxypropane 376.1g (1.0mol) is performed In the same manner as in Example 2-1, 215 g of the target product K as white crystals via the compound having the structure represented by the chemical formulas (17) and (18).
(32% yield). A part of the obtained product K was separated using high performance liquid chromatography in the same manner as in Example 1-1. The obtained target products K-1 and K-2 were compounds having the structures represented by the following chemical formulas (26) and (28), respectively. ¹ H-NMR, ¹⁹ F-N of the compound obtained below
The results of MR and Exact MS are shown.

[0071]

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(K-1 analysis result) ¹ H-NMR (δ (ppm) CDCl _{3 /} TMS): 6.44 (dd, ¹ H); 6.43 (d
d, 1H); 6.42 (dd, 1H); 6.12 (dd, 1H); 6.11 (dd, 1H); 6.10 (dd,
1H); 5.89 (dd, 2H); 5.88 (dd, 1H); 5.57 ~ 5.64 (m, 1H); 4.47,
4.41 (ABq, 2H); 4.41,4.39 (ABq, 2H); 4.28,4.23 (dABq, 2H);
2.68 to 2.31 (m, 2H); 1.30 (s, 3H) ¹⁹ F-NMR (δ (ppm) CDCl ₃ / CFCl ₃ ): −123.09; −120.3
9; -119.89; -118.89; -109.39; -77.90 Exact MS: Measured: 672.1023, theory: C ₂₃ H ₂₁ F
₁₃ O ₈ : 672.1029

[0073]

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(K-2 analysis result) ¹ H-NMR (δ (ppm) CDCl _{3 /} TMS): 6.43 (dd, ¹ H); 6.42 (d
d, 2H); 6.12 (dd, 1H); 6.11 (dd, 1H); 6.11 (dd, 1H); 5.88 (dd,
1H); 5.87 (dd, 2H); 5.37-5.34 (m, 1H); 4.43,4.36 (ABq, 2
H); 4.41,4.39 (ABq, 2H); 3.88,4.75 (dABq, 2H); 2.48-2.21
(m, 2H); 1.33 (s, 3H) ¹⁹ F-NMR (δ (ppm) CDCl ₃ / CFCl ₃ ): −123.08; −120.3
9; -119.88; -118.89; -109.39; -77.90 Exact MS: Measured: 672.1018, theory: C ₂₃ H ₂₁ F
₁₃ O ₈ : 672.1029 Example 2-3 A product I was obtained in the same manner as in Example 1-3. A reactor equipped with a stirrer, thermometer, gas inlet tube and dropping funnel was charged with 574 g of product I, 151.8 g of triethylamine and 1000 ml of chloroform. Next, 159.8 g (1.5 mol) of acrylic acid chloride was dissolved in 150 ml of chloroform under ice-cooling, and added dropwise from a dropping funnel so that the temperature of the reaction solution did not exceed 5 ° C. After the completion of the dropwise addition, the mixture was stirred for 2 hours while cooling with ice. Chloroform was distilled off under reduced pressure, and the obtained yellow crystals were further mixed with an ethyl acetate / n-hexane mixed solvent.
Purification was performed by column chromatography using (volume ratio of 1: 4) as a developing solvent, and the solvent was distilled off under reduced pressure to obtain 208 g (yield 27%) of the target product L as white crystals.

A part of the obtained product L was prepared in Example 1-1.
Separation was performed using high performance liquid chromatography in the same manner as described above.
The obtained target products L-1 and L-2 are represented by the chemical formula (2)
The structures were as shown in 4) and (25). ¹ H-NMR, ¹⁹ F-NMR and Exact MS of the compound obtained below
The result is shown.

(L-1 analysis result) ¹ H-NMR (δ (ppm) CDCl _{3 /} TMS): 6.43 (dd, ¹ H); 6.42 (d
d, 2H); 6.12 (dd, 1H); 6.11 (dd, 1H); 6.10 (dd, 1H); 5.89 (dd,
2H); 5.88 (dd, 1H); 5.57 ~ 5.64 (m, 1H); 4.46,4.41 (ABq, 2
H); 4.41,4.39 (ABq, 2H); 4.27,4.23 (dABq, 2H); 2.68 ~ 2.31
(m, 2H); 1.30 (s, 3H) ¹⁹ F-NMR (δ (ppm) CDCl ₃ / CFCl ₃ ): −123.10; −120.4
7; -119.72; -118.91; -118.60; -109.76; -77.79 Exact MS: Measured: 772.0969, theory: C ₂₅ H ₂₁ F
₁₇ O ₈ : 772.0965 (result of L-2 analysis) ¹ H-NMR (δ (ppm) CDCl _{3 /} TMS): 6.44 (dd, ¹ H); 6.42 (d
d, 2H); 6.12 (dd, 1H); 6.11 (dd, 1H); 6.11 (dd, 1H); 5.89 (dd,
1H); 5.88 (dd, 2H); 5.38-5.34 (m, 1H); 4.43,4.36 (ABq, 2
H); 4.41,4.39 (ABq, 2H); 4.29,4.13 (dABq, 2H); 2.68 ~ 2.31
(m, 2H); 1.30 (s, 3H) ¹⁹ F-NMR (δ (ppm) CDCl ₃ / CFCl ₃ ): −123.10; −120.4
7; -119.71; -118.91; -118.60; -109.76; -77.78 Exact MS: Measured: 772.0962, theory: C ₂₅ H ₂₁ F
₁₇ O ₈ : 772.0965

Claims (1)

[Claims] 1. A fluorine-containing polyfunctional compound represented by the following formula (1):
(Meth) acrylic acid esters. Embedded image (Wherein X is a carbon number of 1 to 1 having 3 or more fluorine atoms)
4 represents a fluoroalkyl group or a fluorocycloalkyl group having 3 to 14 carbon atoms having 4 or more fluorine atoms,
Y ¹ , Y ² and Y ³ represent a hydrogen atom, an acryloyl group or a methacryloyl group, and at least two of Y ¹ , Y ² and Y ³ are the same or different groups and are an acryloyl group or a methacryloyl Z represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. n and m are 0
Or 1 and n + m = 1. )