JP2011012023A - Fluorine-containing adamantane derivative having polyfunctional group and resin composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition giving a cured product having an excellent low refractive index, high heat resistance and scratch resistance and especially improved surface hardness compared with conventional products, a fluorine-containing adamantane derivative included in the composition, a method for producing the derivative, and a reaction intermediate useful for production of the fluorine-containing adamantane derivative.SOLUTION: There are provided the fluorine-containing adamantane derivative expressed by general formula (I) [wherein Gis for example a single bond; Rand Rare each for example a specific organic group; Xis a specific functional group; a is an integer of 1-4; b is an integer of 10-15; a+b=16; c is an integer of 1-10; and d is an integer of 1-10], a method for producing the derivative, a resin composition containing the derivative, and a reaction intermediate useful for the production of the fluorine-containing adamantane derivative.

Description

  The present invention relates to a fluorine-containing adamantane derivative having a polyfunctional group and a resin composition containing the same. Specifically, a fluorine-containing adamantane derivative having three or more functional groups that are a (meth) acryloyloxy group or a cyclic ether group, excellent in low refractive index, heat resistance and scratch resistance, particularly improved in surface hardness, antireflection film Fluorine-containing materials that provide useful cured products for optical fibers, optical waveguides, volume holograms, hologram memory materials, coating materials, nanoimprint monomers, surface modifiers, industrial tube materials, sealing materials, and polymer electrolyte membranes The present invention relates to a resin composition containing an adamantane derivative, a reaction intermediate useful for the production of the fluorinated adamantane derivative, and a method for efficiently producing the fluorinated adamantane derivative.

Adamantane has a structure in which four cyclohexane rings are condensed into a cage shape, is a highly symmetric and stable compound, and its derivative exhibits a unique function. It is known that it is useful as a raw material for these. Since adamantane has, for example, optical characteristics, heat resistance, and the like, attempts have been made to use it for an optical disk substrate, an optical fiber, a lens, or the like (for example, see Patent Documents 1 and 2). In addition, an attempt has been made to use adamantane esters as a resin material for a photoresist by utilizing its acid sensitivity, dry etching resistance, ultraviolet transmittance, and the like (see, for example, Patent Document 3).
In recent years, flat panel displays using liquid crystals, organic electroluminescence (EL) elements, etc. have higher definition, higher viewing angle, higher image quality, higher frequency of electronic circuits, circuits and communications using light, etc. Considerations are being made to improve and improve the performance of electronic components.

Among them, fluorine-based organic materials are used for the low refractive index layer of antireflection films for displays, optical fibers for communication, optical waveguides, and the like, and improvements in these fluorine-based materials have been made. In general, a compound having a fluorine atom exhibits a low refractive index, and a low-refractive-index fluorine-containing resin material is used as an antireflection film for liquid crystal or organic EL displays, full-lens lenses, lenticular lenses, lenses such as microlens arrays, optical fibers, etc. And application to optical waveguides are being studied. For example, in an antireflection film, a low refractive index layer and a high refractive index layer are alternately laminated to prevent reflection. As a resin for the low refractive index layer, a linear fluorine-containing acrylate polymer is used. Is used (see, for example, Patent Documents 4 and 5). However, since these are linear, sufficient surface hardness cannot be obtained, and there is a problem in scratch resistance and the like. In addition, an antireflection film having improved adhesion to the antireflection layer by using a resin composition containing a (meth) acrylate-based polymer having an epoxy group for a hard coat layer has been disclosed (for example, Patent Documents). 6), the applicant discloses that a fluorine-containing adamantane derivative having a polymerizable group is used as a resin composition that provides a cured product having a good heat resistance and surface hardness and a low refractive index, which is useful for an antireflection film and the like. (For example, refer to Patent Document 7). However, the surface hardness of the cured product using these resin compositions is not fully satisfactory, and there is room for improvement.
In addition, in optical fibers and optical waveguides, it is well known that C—H bonds of organic compounds cause light loss. However, as a countermeasure, a material in which C—H bonds are replaced with C—F bonds is used. ing. One of them is a linear fluorine-containing acrylate resin (see, for example, Patent Document 8), but the heat resistance that can withstand heat generation during communication and solder reflow is not sufficient.

JP-A-6-305044 Japanese Patent Laid-Open No. 9-302077 Japanese Patent Laid-Open No. 4-39665 Japanese Patent Laid-Open No. 11-2702 JP 2001-48943 A JP 2004-212619 A WO2007 / 020901 pamphlet JP 2002-182046 A

  In view of the above circumstances, the present invention is a fluorine-containing adamantane derivative used for a resin composition that is excellent in low refractive index, heat resistance and scratch resistance, and particularly provides a cured product having improved surface hardness than before, and its production. It is an object of the present invention to provide a method, a resin composition containing the method, and a reaction intermediate useful for the production of the fluorine-containing adamantane derivative.

As a result of diligent investigations, the present inventors have found that the above object can be achieved by using a fluorine-containing adamantane derivative having three or more functional groups which are a (meth) acryloyloxy group or a cyclic ether group. Completed the invention.
That is, the present invention is a fluorine-containing adamantane derivative having a polyfunctional group and a method for producing the same, a resin composition containing the same, and a reaction intermediate useful for producing the fluorine-containing adamantane derivative as described below.

1. A fluorine-containing adamantane derivative represented by the following general formula (I).

[In formula (I), G ¹ represents a single bond, a hetero atom or a divalent group containing a hetero atom, and R ¹ and R ² are each independently a hydrogen atom; substituted with a halogen atom or a hydroxyl group. An aliphatic hydrocarbon group that may contain an oxygen atom; and an organic group represented by the following formula (I-1), wherein X ¹ represents a hydroxyl group and 1 type chosen from groups represented by following formula (I-2)-(I-4) is shown. a is an integer of 1 to 4, b is an integer of 10 to 15, and a + b = 16. c is an integer of 1 to 10, and d is an integer of 1 to 10. A plurality of G ¹ , R ¹ , R ² and X ¹ may be the same or different from each other, and a plurality of c and d may be the same or different from each other.

[In formula (I-1), G ² represents a single bond, a hetero atom or a divalent group containing a hetero atom, and R ³ and R ⁴ are each independently a hydrogen atom; substituted with a halogen atom or a hydroxyl group. An aliphatic hydrocarbon group that may be present; and an aliphatic hydrocarbon group that may contain an oxygen atom. X ¹ is the same as defined above. e is 0 or an integer of 1 to 10, and f is 0 or an integer of 1 to 10. A plurality of G ² , R ³ , R ⁴ and X ¹ may be the same or different, and a plurality of e and f may be the same or different. ]

[In the formula (I-2), R ⁵ represents one selected from a hydrogen atom, a methyl group and a trifluoromethyl group. In formula (I-4), R ⁶ represents a hydrocarbon group having 1 to 5 carbon atoms. ]
However, the general formula (I) satisfies any of the following (1) to (3).
(1) When a = 1, at least ^two of R ¹ and R ² are organic groups represented by the formula (I-1), and three or more of X ¹ are represented by the formula (I-2) ) To (I-4).
(2) When a = 2, at least one of the plurality of R ¹ and R ² is an organic group represented by the formula (I-1), and three or more of X ¹ are represented by the formula (I -2) to (I-4) are selected from the groups represented by (I-4).
(3) When a = 3 or 4, three or more of X ¹ are one selected from the groups represented by the formulas (I-2) to (I-4). ]
2. 2. The fluorine-containing adamantane derivative according to 1, wherein a = 2 in the general formula (I).
3. 3. The fluorine-containing adamantane derivative according to 1 or 2 above, wherein d = 1 and G ¹ is a single bond in the general formula (I).
4). 4. The fluorine-containing adamantane derivative as described in any one of 1 to 3 above, wherein in the general formula (I), at least one of X ¹ is the formula (I-2).
5. The fluorine-containing adamantane derivative according to any one of 1 to 4, wherein c = 3 in the general formula (I).
6). A fluorine-containing adamantane derivative represented by the following general formula (II).

[In formula (II), G ¹ represents any of a single bond, an ether bond, an ester bond and an amide bond, and R ⁷ and R ⁸ are each independently a hydrogen atom; substituted with a halogen atom or a hydroxyl group. An aliphatic hydrocarbon group which may contain an oxygen atom; and an organic group represented by the following formula (II-1). a is an integer of 1 to 4, b is an integer of 10 to 15, and a + b = 16. c is an integer of 1 to 10, and d is an integer of 1 to 10. A plurality of G ¹ , R ⁷ and R ⁸ may be the same or different from each other, and a plurality of c and d may be the same or different from each other.

[In formula (II-1), G ² represents a single bond, a hetero atom or a divalent group containing a hetero atom, and R ³ and R ⁴ are each independently a hydrogen atom; substituted with a halogen atom or a hydroxyl group. 1 type chosen from the aliphatic hydrocarbon group which may contain; and the aliphatic hydrocarbon group which may contain an oxygen atom. e is 0 or an integer of 1 to 10, and f is 0 or an integer of 1 to 10. A plurality of G ² , R ⁵ and R ⁶ may be the same or different, and a plurality of e and f may be the same or different. ]
However, the general formula (II) satisfies any of the following (4) to (6).
(4) When a = 1, at least two of R ⁷ and R ⁸ are organic groups represented by the formula (II-1).
(5) When a = 2, at least one of the plurality of R ⁷ and R ⁸ is an organic group represented by the formula (II-1).
(6) When a = 3 or 4, R ⁷ and R ⁸ may not be an organic group represented by the formula (II-1). ]
7). 7. The fluorine-containing adamantane derivative according to 6 above, wherein a = 2 in the general formula (II).
8). 8. The fluorine-containing adamantane derivative according to 6 or 7, wherein d = 1 and G ¹ is a single bond in the general formula (II).
9. The fluorine-containing adamantane derivative according to any one of 6 to 8, wherein c = 3 in the general formula (II).
10. 10. Said 1 which makes the fluorine-containing adamantane derivative (II) in any one of said 6-9 react with the hydroxyl-reactive compound which has group represented by following formula (II-2)-(II-4). Of producing a fluorine-containing adamantane derivative (I).

[In formula (II-2), R ⁵ represents one selected from a hydrogen atom, a methyl group and a trifluoromethyl group. In formula (II-4), R ⁶ represents a hydrocarbon group having 1 to 5 carbon atoms. ]
11. After reacting at least one hydroxyl group in the fluorine-containing adamantane derivative (II) according to any one of 6 to 9 with a glycidyl group-containing hydroxyl group-reactive compound, (meth) acrylic anhydride is reacted, 2. The method for producing a fluorinated adamantane derivative (I) according to 1 above, wherein a group represented by the formula (I-2) is introduced.
12 10. The fluorinated adamantane derivative having a hydroxyl group selected from perfluoroadamantane monool, perfluoroadamantane diol, perfluoroadamantane triol, and perfluoroadamantane tetraol and the halogen-containing alcohol compound are reacted. A method for producing a fluorinated adamantane derivative (II).
13. 2. A resin composition comprising the fluorine-containing adamantane derivative (I) described in 1 above.
14 14. The resin composition as described in 13 above, which contains a thermal polymerization initiator and / or a photopolymerization initiator.
15. Hardened | cured material formed by hardening | curing the resin composition of said 13 or 14.
16. 16. An antireflection film comprising the fluorine-containing adamantane derivative (I) described in 1 or the cured product described in 15.

  Some resin compositions containing a fluorinated adamantane derivative give a cured product having a low refractive index, heat resistance and surface hardness. The fluorinated adamantane derivative of the present invention has three functional groups. Since the present invention is characterized by the above, the present invention is excellent in low refractive index, heat resistance and scratch resistance by curing the resin composition containing the fluorine-containing adamantane derivative, and particularly the surface hardness is remarkably improved. Cured product can be provided.

[Fluorine-containing adamantane derivative (I) having a polyfunctional group]
The fluorine-containing adamantane derivative having a polyfunctional group of the present invention is a compound represented by the following general formula (I) [hereinafter, sometimes referred to as a fluorine-containing adamantane derivative (I). ].

In the above formula (I), G ¹ represents a single bond, a hetero atom or a divalent group containing a hetero atom, preferably a single bond. In the present invention, the hetero atom is an oxygen atom, a sulfur atom, a nitrogen atom or the like, and examples of the divalent group containing the hetero atom include a carbonyl group, —NH—, —CONH— and the like.
R ¹ and R ² are each independently a hydrogen atom; an aliphatic hydrocarbon group that may be substituted with a halogen atom or a hydroxyl group; an aliphatic hydrocarbon group that may contain an oxygen atom; and the following formula (I-1) 1 type chosen from the organic group represented by these is shown. In the present invention, the aliphatic hydrocarbon group includes not only a chain type but also a cyclic type.
X ¹ represents one type selected from a hydroxyl group and groups represented by the following formulas (I-2) to (I-4).
a is an integer of 1 to 4 (preferably an integer of 2 to 4 and more preferably 2), b is an integer of 10 to 15 and a + b = 16. c is an integer of 1 to 10 (preferably 3), and d is an integer of 1 to 10 (preferably 1). A plurality of G ¹ , R ¹ , R ² and X ¹ may be the same or different from each other, and a plurality of c and d may be the same or different from each other.

In the above formula (I-1), G ² represents a single bond, a hetero atom or a divalent group containing a hetero atom, preferably a single bond.
R ³ and R ⁴ each independently represents a hydrogen atom; an aliphatic hydrocarbon group that may be substituted with a halogen atom or a hydroxyl group; and an aliphatic hydrocarbon group that may contain an oxygen atom. Show.
Examples of the aliphatic hydrocarbon group in the present invention include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, and a cyclopentyl group. Hexyl group, methylcyclopentyl group, hexyl group, cyclohexyl group, methylcyclohexyl group, and ethylcyclohexyl group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

X ¹ represents one kind selected from a hydroxyl group and groups represented by the following formulas (I-2) to (I-4) as described above.
In the general formula (I), at least one of X ¹ is preferably a group represented by the following formula (I-2).
e is 0 or an integer of 1 to 10, and f is 0 or an integer of 1 to 10. A plurality of G ² , R ³ , R ⁴ and X ¹ may be the same or different from each other, and a plurality of e and f may be the same or different from each other.

In said formula (I-2), R < ⁵ > shows 1 type chosen from a hydrogen atom, a methyl group, and a trifluoromethyl group. In said formula (I-4), R < ⁶ > shows a C1-C5 hydrocarbon group.
Specific groups represented by the above formulas (I-2) to (I-4) include acryloyloxy group, methacryloyloxy group, α-trifluoromethylacryloyloxy group, α-fluoroacryloyloxy group, glycidyloxy. Group, (3-methyloxetane-3-yl) methyloxy group, (3-ethyloxetane-3-yl) methyloxy group, (3-propyloxetane-3-yl) methyloxy group and (3-butyloxetane- 3-yl) methyloxy group and the like. Among these, an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, and a (3-methyloxetane-3-yl) methyloxy group are preferable. Particularly preferred are acryloyloxy group, methacryloyloxy group and glycidyloxy group.

However, since the fluorine-containing adamantane derivative (I) of the present invention is a compound having three or more functional groups which are a (meth) acryloyloxy group or a cyclic ether group, the general formula (I) is represented by the following (1) It is important to satisfy any one of (3).
(1) When a = 1, at least ^two of R ¹ and R ² are organic groups represented by the formula (I-1), and three or more of X ¹ are represented by the formula (I-2) ) To (I-4).
(2) When a = 2, at least one of the plurality of R ¹ and R ² is an organic group represented by the formula (I-1), and three or more of X ¹ are represented by the formula (I -2) to (I-4) are selected from the groups represented by (I-4).
(3) When a = 3 or 4, three or more of X ¹ are one selected from the groups represented by the formulas (I-2) to (I-4).

[Method for producing fluorine-containing adamantane derivative (I) having a polyfunctional group]
The fluorine-containing adamantane derivative having a polyfunctional group represented by the general formula (I) of the present invention is a reaction intermediate [hereinafter referred to as reaction intermediate] which is a fluorine-containing adamantane derivative represented by the following general formula (II). Sometimes called. And a hydroxyl group-reactive compound having a group represented by the following formulas (II-2) to (II-4).

(Reaction intermediate)
The reaction intermediate is a fluorine-containing adamantane derivative having a hydroxyl group represented by the following general formula (II).

In the above formula (II), G ¹ , a, b, c and d are the same as described above.
R ⁷ and R ⁸ are each independently a hydrogen atom; an aliphatic hydrocarbon group that may be substituted with a halogen atom or a hydroxyl group; an aliphatic hydrocarbon group that may contain an oxygen atom; and the following formula (II-1) 1 type chosen from the organic group represented by these is shown.

In the above formula (II), G ² , R ³ , R ⁴ , e and f are the same as described above.
However, since the fluorine-containing adamantane derivative represented by the above general formula (I) has three or more functional groups which are a (meth) acryloyloxy group or a cyclic ether group, the above general formula (II) which is a reaction intermediate It is important to satisfy any of the following (4) to (6).
(4) When a = 1, at least two of R ⁷ and R ⁸ are organic groups represented by the formula (II-1).
(5) When a = 2, at least one of the plurality of R ⁷ and R ⁸ is an organic group represented by the formula (II-1).
(6) When a = 3 or 4, R ⁷ and R ⁸ may not be an organic group represented by the formula (II-1).

(Hydroxyl-reactive compound)
A hydroxyl-reactive compound is a compound having groups represented by the following formulas (II-2) to (II-4).

In the above formula (II-2), R ⁵ is the same as described above. In the above formula (II-4), R ⁶ is the same as described above.
Examples of the hydroxyl group-reactive compound having a (meth) acryloyl group represented by the above formula (II-2) include acrylic acid, methacrylic acid, α-trifluoromethylacrylic acid, α-fluoroacrylic acid, and acrylic acid chloride. Methacrylic acid chloride, α-trifluoromethylacrylic acid chloride, α-fluoroacrylic acid chloride, acrylic acid anhydride, methacrylic acid anhydride and α-trifluoromethylacrylic acid anhydride.
Examples of the hydroxyl-reactive compound having a glycidyl group represented by the above formula (II-3) or the hydroxyl-reactive compound having an oxetane group represented by the above formula (II-4) include epichlorohydrin, Epibromohydrin, 3-chloromethyl-3-methyloxetane and 3-chloromethyl-3-ethyloxetane, 3-bromomethyl-3-methyloxetane and 3-bromomethyl-3-ethyloxetane.

(Production method)
In the method for producing the fluorine-containing adamantane derivative (I) of the present invention, the reaction between the reaction intermediate and the hydroxyl-reactive compound having a (meth) acryloyl group represented by the formula (II-2) is generally known. Examples of the azeotropic dehydration method, the acid chloride method, the acid anhydride method, and the like.

As the azeotropic dehydration method, a reaction intermediate and acrylic acid, methacrylic acid, α-trifluoromethylacrylic acid, α-fluoroacrylic acid, or the like can be used.
The reaction temperature is about 50 to 200 ° C, preferably 100 to 180 ° C. When temperature is less than 50 degreeC, reaction rate falls and reaction time becomes long. When the temperature exceeds 200 ° C., side reactions occur or coloring becomes intense.
The reaction pressure is about 0.01 to 10 MPa in absolute pressure, desirably normal pressure to 1 MPa. When the pressure exceeds 10 MPa, there is a problem in terms of safety, and a special device is required, which is not industrially useful. When the pressure is less than 0.01 MPa, the reaction time becomes longer.
The catalyst used for this reaction is an acid catalyst usually used in this method, and examples thereof include acids such as sulfuric acid and p-toluenesulfonic acid, and the addition concentration of the acid depends on the type. , About 0.01 to 20 mol%, preferably 0.05 to 10 mol% with respect to the reaction intermediate.

As the solvent, a solvent having a solubility of the reaction intermediate of 0.5% by mass or more, desirably 5% by mass or more is used. Specific examples thereof include nonane, decane, undecane, cyclohexane, methylcyclohexane, ethylcyclohexane, toluene, xylene, and mixed solvents thereof. The amount of the solvent is such that the concentration of the reaction intermediate is about 0.5% by mass or more, desirably 5% by mass or more. At this time, the reaction intermediate may be in a suspended state, but is preferably dissolved.
If necessary, hydroquinone, methoquinone, phenothiazine, methoxyphenothiazine or the like may be added as a polymerization inhibitor. The addition concentration in the case of adding is about 10 to 10000 mass ppm, preferably 50 to 5000 mass ppm with respect to the raw material alcohol.
The reaction time is about 1 minute to 24 hours, preferably 1 hour to 10 hours.
The obtained reaction product can be purified by distillation, crystallization, column separation or the like, if necessary, and the purification method can be selected depending on the properties of the reaction product and the type of impurities.

As the acid chloride method, the above reaction intermediate and acrylic acid chloride, methacrylic acid chloride, α-trifluoromethylacrylic acid chloride, α-fluoroacrylic acid chloride and the like can be used.
The reaction temperature is about −50 to 100 ° C., preferably 0 to 50 ° C. When the temperature is lower than −50 ° C., special equipment is required, which is not industrially useful. When the temperature exceeds 100 ° C., side reactions occur or coloring becomes intense.
The reaction pressure is about 0.01 to 10 MPa in absolute pressure, desirably normal pressure to 1 MPa. If this pressure exceeds 10 MPa, there is a problem in safety and a special device is required, which is not useful industrially. When the pressure is less than 0.01 MPa, the reaction time becomes longer.
In the case of the acid chloride method, a base is added as a scavenger for the acid generated by the reaction. As such a base, organic amines such as triethylamine, tributylamine, pyridine, dimethylaminopyridine, and inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, and potassium phosphate are used. be able to. The use ratio of the base to the reaction intermediate is an amount such that the base / reaction intermediate (molar ratio) is about 0.5 to 20, preferably 1 to 10.

As the solvent, a solvent having a solubility of the reaction intermediate of about 0.5% by mass or more, desirably 5% by mass or more is used. Specifically, hexane, heptane, cyclohexane, toluene, dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), diethyl ether, tetrahydrofuran (THF), ethyl acetate, Examples include dichloromethane and chloroform.
If necessary, hydroquinone, methoquinone, phenothiazine, methoxyphenothiazine or the like may be added as a polymerization inhibitor. In this case, the addition amount of the polymerization inhibitor is about 10 to 10000 mass ppm, preferably 50 to 5000 mass ppm, based on the acid chloride used.
The reaction time is about 1 minute to 24 hours, preferably 1 hour to 10 hours.
The obtained reaction product can be purified by distillation, crystallization, column separation or the like, if necessary, and the purification method can be selected depending on the properties of the reaction product and the type of impurities.

As the acid anhydride method, the above reaction intermediate, acrylic acid anhydride, methacrylic acid anhydride, α-trifluoromethyl acrylic acid anhydride, and the like can be used.
The reaction temperature is about −50 to 100 ° C., preferably 0 to 50 ° C. When the temperature is lower than −50 ° C., special equipment is required, which is not industrially useful. When the temperature exceeds 100 ° C., side reactions occur or coloring becomes intense.
The reaction pressure is about 0.01 to 10 MPa in absolute pressure, desirably normal pressure to 1 MPa. If this pressure exceeds 10 MPa, there is a problem in safety and a special device is required, which is not useful industrially. When the pressure is less than 0.01 MPa, the reaction time becomes longer.
In the case of the acid anhydride method, a base is added as a scavenger for the acid generated by the reaction. As such a base, organic amines such as triethylamine, tributylamine, pyridine, dimethylaminopyridine, and inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, and potassium phosphate should be used. Can do.
The use ratio of the base to the reaction intermediate pair is an amount such that the base / reaction intermediate (molar ratio) is about 0.5 to 5, preferably 1 to 3.

As the solvent, a solvent having a solubility of the reaction intermediate of about 0.5% by mass or more, desirably 5% by mass or more is used. Specifically, hexane, heptane, cyclohexane, toluene, dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), diethyl ether, tetrahydrofuran (THF), ethyl acetate, Examples include dichloromethane and chloroform. At this time, the reaction intermediate may be in a suspended state, but is preferably dissolved.
If necessary, hydroquinone, methoquinone, phenothiazine, methoxyphenothiazine or the like may be added as a polymerization inhibitor. In this case, the addition amount of the polymerization inhibitor is about 10 to 10000 mass ppm, preferably 50 to 5000 mass ppm, with respect to the acid anhydride to be used.
The reaction time is about 1 minute to 24 hours, preferably 1 hour to 10 hours.
The obtained reaction product can be purified by distillation, crystallization, column separation or the like, if necessary, and the purification method can be selected depending on the properties of the reaction product and the type of impurities.

Further, in the method for producing a fluorine-containing adamantane derivative (I) of the present invention, the reaction intermediate and a hydroxyl-reactive compound having a cyclic ether group represented by the formula (II-3) and the formula (II-4) This reaction can be carried out in the presence of a basic catalyst.
The reaction temperature is about 0 to 200 ° C, preferably 50 to 150 ° C. When temperature is less than 0 degreeC, reaction rate falls and reaction time becomes long. When the temperature exceeds 200 ° C., side reactions occur or coloring becomes intense.
The reaction pressure is about 0.01 to 10 MPa in absolute pressure, desirably normal pressure to 1 MPa. When the pressure exceeds 10 MPa, there is a problem in terms of safety, and a special device is required, which is not industrially useful. Conversely, when the pressure is less than 0.01 MPa, the reaction time becomes longer.
The basic catalyst used in this reaction includes sodium amide, triethylamine, tributylamine, trioctylamine, pyridine, N, N-dimethylaniline, 1,5-diazabicyclo [4,3,0] nonene-5 (DBN). 1,8-diazabicyclo [5,4,0] undecene-7 (DBU), tetramethylammonium chloride, tetraethylammonium chloride, sodium hydroxide, potassium hydroxide, sodium hydride, sodium phosphate, potassium phosphate, carbonic acid Sodium, potassium carbonate, silver oxide, sodium methoxide, potassium t-butoxide and the like can be mentioned. The basic catalyst is used in an amount of about 0.01 to 20 mol%, preferably 0.05 to 10 mol%, based on the reaction intermediate, although it depends on the type.

As the solvent, a solvent having a solubility of the reaction intermediate of 0.5% by mass or more, desirably 5% by mass or more is used. Specific examples include hexane, heptane, toluene, dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), ethyl acetate, diethyl ether, tetrahydrofuran (THF), and mixed solvents thereof. A compound having a cyclic ether group may also be used as a solvent. The amount of the solvent is such that the concentration of the reaction intermediate is about 0.5% by mass or more, desirably 5% by mass or more. At this time, the reaction intermediate may be in a suspended state, but is preferably dissolved.
The reaction time is about 1 minute to 24 hours, preferably 1 hour to 10 hours.
The obtained reaction product can be purified by distillation, crystallization, column separation or the like, if necessary, and the purification method can be selected depending on the properties of the reaction product and the type of impurities.

Furthermore, as a method for producing the fluorinated adamantane derivative (I) of the present invention, after reacting a glycidyl group-containing hydroxyl group-reactive compound with at least one of the hydroxyl groups in the reaction intermediate represented by the general formula (II) By reacting (meth) acrylic anhydride, two (meth) acryloyloxy groups represented by the above formula (I-2) can be simultaneously introduced into one hydroxyl group of the reaction intermediate.
The production method in this case performs a ring-opening reaction with a generally known acid anhydride of an epoxy group according to the following reaction conditions.

The reaction temperature is about 50 to 200 ° C, preferably 70 to 150 ° C. When temperature is less than 50 degreeC, reaction rate falls and reaction time becomes long. When the temperature exceeds 200 ° C., side reactions occur or coloring becomes intense.
The reaction pressure is about 0.01 to 10 MPa in absolute pressure, desirably normal pressure to 1 MPa. When the pressure exceeds 10 MPa, there is a problem in terms of safety, and a special device is required, which is not industrially useful. Conversely, when the pressure is less than 0.01 MPa, the reaction time becomes longer.
The catalyst used in this reaction is preferably a basic catalyst, organic amines such as triethylamine, tributylamine, dimethylaminopyridine, quaternary ammonium such as tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide Salt, triphenylphosphine and the like. The basic catalyst is used in an amount of about 0.01 to 20 mol%, preferably 0.05 to 10 mol%, based on the fluorine-containing adamantane derivative (I), although it depends on the type.

Although no solvent may be used, it is preferable to use a solvent. As the solvent, a solvent having a solubility of the fluorine-containing adamantane derivative (I) of 0.5% by mass or more, desirably 5% by mass or more is used. Specifically, cyclohexane, methylcyclohexane, ethylcyclohexane, toluene, xylene, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethylacetamide (DMAc), dimethyl Examples thereof include sulfoxide (DMSO), propylene glycol monomethyl ether acetate, and mixed solvents thereof. The amount of the solvent is such that the concentration of the fluorinated adamantane derivative (I) is about 0.5% by mass or more, preferably 5% by mass or more. At this time, the fluorinated adamantane derivative (I) may be in a suspended state, but is preferably dissolved.
The reaction time is about 1 minute to 24 hours, preferably 1 hour to 10 hours.
The obtained reaction product can be purified by distillation, crystallization, column separation or the like, if necessary, and the purification method can be selected depending on the properties of the reaction product and the type of impurities.

(Method for producing reaction intermediate)
The reaction intermediate represented by the general formula (II) may be produced by any method as long as a reaction intermediate having a hydroxyl group can be produced. For example, perfluoroadamantane monool, perfluoroadamantanediol, perfluoroadamantane triol and perfluoroadamantane. It can be produced by reacting a hydroxyl group of a fluorine-containing adamantane derivative having a hydroxyl group selected from tetraol with a halogen-containing alcohol compound.
The reaction temperature is about 0 to 200 ° C, preferably 50 to 150 ° C. When temperature is less than 50 degreeC, reaction rate falls and reaction time becomes long. When the temperature exceeds 200 ° C., side reactions occur or coloring becomes intense.
The reaction pressure is about 0.01 to 10 MPa in absolute pressure, desirably normal pressure to 1 MPa. When the pressure exceeds 10 MPa, there is a problem in terms of safety, and a special device is required, which is not industrially useful. Conversely, when the pressure is less than 0.01 MPa, the reaction time becomes longer.
As the catalyst used in this reaction, potassium iodide is particularly preferable for the purpose of increasing the reaction rate, and the amount used is about 0.01 mol% to 20 mol%, preferably about 0.1 mol% with respect to the fluorine-containing adamantane derivative having a hydroxyl group. 05 to 10 mol%.

As the solvent, a solvent having a solubility of the fluorine-containing adamantane derivative having a hydroxyl group of 0.5% by mass or more, desirably 5% by mass or more is used. Specifically, hexane, heptane, toluene, xylene, dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), ethyl acetate, diethyl ether, Examples thereof include dioxane and a mixed solvent thereof, and a halide may be used as a solvent. The amount of the solvent is such that the concentration of the fluorine-containing adamantane derivative having a hydroxyl group is about 0.5% by mass or more, desirably 5% by mass or more. At this time, the fluorine-containing adamantane derivative having a hydroxyl group may be in a suspended state, but is preferably dissolved.
The reaction time is about 1 minute to 24 hours, preferably 1 hour to 10 hours.
The obtained reaction product can be purified by distillation, crystallization, column separation or the like, if necessary, and the purification method can be selected depending on the properties of the reaction product and the type of impurities.

  Examples of the reaction intermediate which is a fluorine-containing adamantane derivative represented by the general formula (II) include perfluoro-1,3,5-tri (2-hydroxyethoxy) adamantane, perfluoro-1,3,5. , 7-tetra (2-hydroxyethoxy) adamantane, perfluoro-1- (2,2′-hydroxymethyl-3-hydroxypropoxy) adamantane, perfluoro-1- (2,2′-hydroxymethyl-3-hydroxy Propoxy) adamantane, perfluoro-1,3-bis (2,2′-hydroxymethyl-3-hydroxypropoxy) adamantane, perfluoro-1,3,5-tri (2-hydroxypropoxy) adamantane, perfluoro-1 , 3,5,7-tetra (2-hydroxypropoxy) adamantane, perfluoro 1,3-bis (2-hydroxymethyl-3-hydroxypropoxy) adamantane, perfluoro-2,4-bis (2-hydroxymethyl-3-hydroxypropoxy) adamantane, perfluoro-1,3,5-tris ( 2-hydroxymethyl-3-hydroxypropoxy) adamantane, perfluoro-2- (2,2′-hydroxymethyl-3-hydroxypropoxy) adamantane, perfluoro-4-oxo-1- (2,2′-dihydroxymethyl) -3-hydroxypropoxy) adamantane, perfluoro-4-oxo-1- (2,2′-dihydroxymethyl-3-hydroxypropoxy) adamantane, perfluoro-2,4-bis [(2,3-dihydroxypropoxy) Ethoxy] adamantane, perfluoro-1,3-bis [(2 , 3-Dihydroxypropoxy) ethoxy] adamantane, perfluoro-1,3,5-tris [(2,3-dihydroxypropoxy) ethoxy] adamantane, perfluoro-1,3,5-tri (2-hydroxybutoxy) adamantane Perfluoro-1,3,5,7-tetra (2-hydroxybutoxy) adamantane, perfluoro-1,3,5-tri (2-hydroxypentyloxy) adamantane, perfluoro-1,3,5,7 Tetra (2-hydroxypentyloxy) adamantane, perfluoro-1,3,5-tris [(2-hydroxyethoxy) ethoxy] adamantane, perfluoro-1,3,5,7-tetra [(2-hydroxyethoxy ) Ethoxy] adamantane, perfluoro-1,3-bis (2,3-dihydroxy) (Ropoxy) adamantane, perfluoro-2,4-bis (2,3-dihydroxypropoxy) adamantane, perfluoro-1,3,5-tri (2,3-dihydroxypropoxy) adamantane, perfluoro-1,3,5 , 7-tetra (2,3-dihydroxypropoxy) adamantane and the like.

[Resin composition]
The resin composition of the present invention contains the fluorine-containing adamantane derivative (I). In the resin composition of the present invention, a mixed resin of the fluorine-containing adamantane derivative (I) and other polymerizable monomers and / or epoxy resins can also be used.
Other polymerizable monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, ethylene glycol di (meth) acrylate, 1,3-propanediol di ( (Meth) acrylate, 1,4-butanediol di (meth) acrylate, 1H, 1H-perfluoropropyl (meth) acrylate, 1H, 1H-perfluorobutyl (meth) acrylate, 1H, 1H-perfluorohexyl (meth) Acrylate, 1H, 1H-perfluorooctyl (meth) acrylate, 1H, 1H-perfluorodecyl (meth) acrylate, perfluoro-1-adamantyl (meth) acrylate, perfluoro-2-adamantyl (meth) acrylate, 1H, 1 , 6H, 6H-perfluoro-1,6-hexanediol di (meth) acrylate, 1H, 1H, 8H, 8H-perfluoro-1,8-octanediol di (meth) acrylate, 1H, 1H, 10H, 10H -Perfluoro-1,10-decanediol di (meth) acrylate and perfluoro-1,3-adamantanediol di (meth) acrylate and the like. Among these, those containing fluorine are preferable. These can be used alone or in combination of two or more.

  Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin (bisphenol A diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol F diester). Glycidyl ether, bisphenol Z diglycidyl ether, tetramethylbisphenol A diglycidyl ether, bisphenol AF diglycidyl ether, bisphenol C diglycidyl ether, etc.), novolac epoxy resins such as phenol novolac epoxy resin and cresol novolac epoxy resin, fat Nitrogen-containing ring epoxy resins such as cyclic epoxy resins, triglycidyl isocyanurate, and hydantoin epoxy resins Hydrogenated bisphenol A type epoxy resin, aliphatic epoxy resin, glycidyl ester type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin and dicyclo ring type epoxy resin, naphthalene type epoxy which are the mainstream of low water absorption rate cured type Examples thereof include resins, polyfunctional epoxy resins such as trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, and pentaerythritol polyglycidyl ether, fluorine-containing epoxy resins such as bisphenol AF type epoxy resin, and (meth) acrylic acid glycidyl ester. Among these, an epoxy resin containing fluorine or having no aromatic ring is preferable. These can be used alone or in combination of two or more.

The epoxy resin may be solid or liquid at normal temperature, but generally, the epoxy resin used preferably has an average epoxy equivalent of 200 to 2000. When the epoxy equivalent is 200 or more, the cured product of the epoxy resin composition does not become brittle and an appropriate strength can be obtained. On the other hand, if the epoxy equivalent is 2000 or less, the glass transition temperature (Tg) of the cured product is not lowered and becomes appropriate.
In the mixed resin of the fluorinated adamantane derivative (I) and the other polymerizable monomer and / or epoxy resin, the content of the fluorinated adamantane derivative (I) is preferably 5% by mass or more, more preferably 10% by mass. % Or more. When the content of the fluorinated adamantane derivative (I) is 5% by mass or more, the optical properties, long-term heat resistance and electrical properties of the resin composition of the present invention are sufficient.

The resin composition of the present invention can be cured by polymerization using a thermal polymerization initiator and / or a photopolymerization initiator.
Any thermal polymerization initiator may be used as long as it reacts with a group having an unsaturated bond, an epoxy group, or an oxetanyl group by heat. For example, benzoyl peroxide, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cumene hydrol Examples thereof include organic peroxides such as peroxide and t-butyl hydroperoxide, and azo initiators such as azobisisobutyronitrile. These can be used alone or in combination of two or more.
Any photopolymerization initiator may be used as long as it reacts with a group having an unsaturated bond, an epoxy group or an oxetanyl group by light. For example, acetophenones, benzophenones, benzyls, benzoin ethers, benzyl diketals Thioxanthones, acylphosphine oxides, acylphosphinic acid esters, aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, aromatic iodosyl salts, aromatic sulfoxonium salts and metallocene compounds. These can be used alone or in combination of two or more.
The amount of the thermal polymerization initiator and / or photopolymerization initiator used is 0 with respect to 100 parts by mass of the fluorine-containing adamantane derivative (I) or the mixed resin (hereinafter sometimes referred to as “resin component”). It is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass. By setting the content of the polymerization initiator within the above range, good physical properties such as polymerization and optical properties are exhibited.

For the resin composition of the present invention, conventionally used, for example, a curing accelerator, a deterioration preventing agent, a modifier, a silane coupling agent, a defoaming agent, an inorganic powder, a solvent, and a leveling agent are used as necessary. Various known additives such as mold release agents, dyes, and pigments may be appropriately blended.
The curing accelerator is not particularly limited, and examples thereof include 1,8-diazabicyclo [5.4.0] undecene-7, triethylenediamine, tris (2,4,6-dimethylaminomethyl) phenol, and the like. Tertiary amines, imidazoles such as 2-ethyl-4-methylimidazole, 2-methylimidazole, triphenylphosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, tetra-n-butylphosphonium O, O- Examples thereof include phosphorus compounds such as diethyl phosphorodithioate, quaternary ammonium salts, organometallic salts, and derivatives thereof. These may be used alone or in combination. Among these curing accelerators, it is preferable to use tertiary amines, imidazoles, and phosphorus compounds.
It is preferable that the content rate of a hardening accelerator is 0.01-8.0 mass parts with respect to 100 mass parts of said resin components, More preferably, it is 0.1-3.0 mass parts. By making the content rate of a hardening accelerator into the said range, sufficient hardening acceleration effect is acquired and discoloration is not seen by the hardened | cured material obtained.

Examples of the degradation inhibitor include conventionally known degradation inhibitors such as phenol compounds, amine compounds, organic sulfur compounds, and phosphorus compounds.
Examples of phenolic compounds include Irganox 1010 (Irganox 1010, trade name, manufactured by Ciba Specialty Chemicals), Irganox 1076 (Irganox 1076, trade name, manufactured by Ciba Specialty Chemicals), Irganox 1330 (Irganox 1330, manufactured by Ciba Specialty Chemicals) , Irganox 3114 (Irganox 3114, Ciba Specialty Chemicals, trademark), Irganox 3125 (Irganox 3125, Ciba Specialty Chemicals, trademark), Irganox 3790 (Irganox 3790, Ciba Specialty Chemicals, trademark) ) BHT, Cyanox 1790 (Cyanox 1790, trade name, manufactured by Cyanamid Co., Ltd.), Smither A-80 (SumilizerGA-80, manufactured by Sumitomo Chemical Co., Ltd., trademark) can be exemplified commercially available products such as.

Examples of amine compounds include Irgas Tab FS042 (trade name, manufactured by Ciba Specialty Chemicals), GENOX EP (trade name, compound name; dialkyl-N-methylamine oxide) manufactured by Ciba Specialty Chemicals, and ADEKA, which is a hindered amine system. ADK STAB LA-52, LA-57, LA-62, LA-63, LA-67, LA-68, LA-77, LA-82, LA-87, LA-94 manufactured by CSC, Tinuvin 123 manufactured by CSC, 144, 440, 662, Chimassorb 2020, 119, 944, Hoechst Hostavin N30, Cytec Cyasorb UV-3346, UV-3526, GLC Uval 299, Clariant SanduvorPR-31, etc. Can do.
Examples of the organic sulfur compounds include DSTP (Yoshitomi, trademark), DLTP (Yoshitomi, trademark), DLTOIB (Yoshitomi, trademark), and DMTP (Yoshitomi, trademark). ), Seenox 412S (trade name, manufactured by Sipro Kasei Co., Ltd.), Cyanox 1212 (trade name, manufactured by Cyanamid Co., Ltd.), and the like.

  Examples of the modifying agent include conventionally known modifying agents such as glycols, silicones, and alcohols. As a silane coupling agent, conventionally well-known silane coupling agents, such as a silane type and a titanate type, are mentioned, for example. Examples of the defoaming agent include conventionally known defoaming agents such as silicone. As the inorganic powder, those having a particle size of several nanometers to 10 μm can be used depending on applications, and examples thereof include known inorganic powders such as glass powder, silica powder, titania, zinc oxide, and alumina. As the solvent, when the epoxy resin is a powder, or as a coating dilution solvent, an aromatic solvent such as toluene or xylene, or a ketone solvent such as methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone can be used.

The resin composition of the present invention is obtained by mixing the above resin component, thermal polymerization initiator and / or photopolymerization initiator and various additives, and injecting into a mold (resin mold) to be molded, or by coating. After forming into a shape, it is photocured by heat curing or irradiation with ultraviolet rays or the like. In the case of thermosetting, the curing temperature is usually about 30 to 200 ° C, preferably 50 to 150 ° C. Setting it to 30 ° C. or higher does not cause poor curing, and setting it to 200 ° C. or lower prevents coloring and the like from occurring. The curing time varies depending on the resin component and the polymerization initiator used, but 0.5 to 6 hours are preferable.
If photocuring by irradiation of ultraviolet irradiation intensity of ultraviolet rays, kind of the resin component and polymerization initiator is optional because it is determined from the film thickness and the like of the cured product, usually 100~5000mJ / cm ² or so, preferably 500 to 4000 mJ / cm ² . Post-heating may be performed after the ultraviolet irradiation, and it is preferably performed at 70 to 200 ° C. for 0.5 to 12 hours.
The molding method is not particularly limited, such as injection molding, blow molding, press molding, and the like, but it is preferably manufactured by injection molding using a pellet-shaped resin composition in an injection molding machine.

  A cured product obtained by curing the resin composition of the present invention has a low refractive index, is excellent in heat resistance and scratch resistance, and has a particularly greatly improved surface hardness. As described above, since the cured product of the present invention has excellent characteristics, an antireflection film, an optical fiber, an optical waveguide, a volume hologram, a hologram memory material, a coating material, a nanoimprint monomer, a surface modifier, an industrial tube material, and a seal. It is useful for materials and solid polymer fuel cell electrolyte membranes.

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, the obtained cured products were evaluated as follows.
(Pencil hardness)
In accordance with JIS K5600-5-4, the pencils that could be scratched were evaluated based on 14 levels from 6B (soft) to 6H (hard).

[Production Example 1] Production of perfluoroadamantane-1,3-diol 5 L of 1,1,2-trichlorotrifluoroethane was added to a 10 L reactor equipped with a power stirrer, a nitrogen gas introduction tube, and a fluorine gas introduction tube. I put it in. The reactor was maintained at 0-10 ° C., the nitrogen flow rate was set to 2 L / min, and the fluorine flow rate was set to 500 mL / min. Two minutes later, 600 mL of a 1,1,2-trichlorotrifluoroethane solution of 252 g [FW: 252.31, 1.0 mol] of adamantanedi-1,3-ol diacetate prepared in advance was added at a rate of 30 mL / hour. Added in.
After the addition was completed (20 hours), the nitrogen flow rate was reduced to 1.2 L / min and the fluorine flow rate was reduced to 300 mL / min. After purging with nitrogen, water was added for hydrolysis. The reaction mixture was treated by a conventional method, and perfluoroadamantane-1,3-diol represented by the following formula was obtained by crystallization [FW: 420.10, 315 g, 0.75 mol, isolated yield 75.0%. ].

Nuclear magnetic resonance spectroscopy (NMR): (solvent: chloroform-d) JNM-ECA500 manufactured by JEOL Ltd.
[ ¹ H-NMR]: 2.24 (s, 1H, OH)
[ ¹⁹ F-NMR]: −221.02 (s, 2F), −120.83 (s, 12F)
-Gas chromatograph-mass spectrometry (GC-MS): EI (Shimadzu Corporation GCMS-QP2010)
420 (M ⁺ , 10.0%), 401 (5.6%), 381 (5.0%), 333 (13.2%), 305 (9.3%), 131 (100%), 69 (26.0%)

[Example 1] Synthesis of perfluoro-1,3-bis (2,3-dihydroxy-1-propoxy) adamantane (synthesis of reaction intermediate)
In a 200 mL three-necked flask equipped with a reflux tube, 8.4 g of perfluoro-1,3-adamantanediol obtained in Production Example 1, 22.4 g of 3-chloro-1,2-propanediol, 28 mL of dioxane, potassium carbonate 8.4 g and 1.6 g of potassium iodide were added. The oil bath was heated and stirred for 4 hours under reflux of dioxane. After cooling to room temperature, the inorganic salt was removed and the filtrate was concentrated. The concentrate was diluted with ethyl acetate, washed 3 times with a 3% by mass aqueous K ₃ PO ₄ solution, and once with saturated brine. The organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain the desired product represented by the following formula (yield 75%, 8.5 g).

-Nuclear magnetic resonance spectrum (solvent: acetonitrile-d) JNM-ECA500 manufactured by JEOL Ltd.
[ ¹ H-NMR (500 MHz)]: 2.84-2.90 (m, 1H), 3.27-3.34 (m, 1H), 3.48-3.58 (m, 2H), 3 79-3.84 (m, 1H), 4.16-4.20 (m, 1H), 4.25-4.30 (m, 1H)
[ ¹³ C-NMR (125 MHz)]: 63.11, 71.45, 73.69
[ ¹⁹ F-NMR (465 MHz, internal standard BTF: −64 ppm)]: −11.58, −118.86, −122.58, −222.48

[Example 2] Synthesis of perfluoro-1,3-bis (2,3-diacryloyloxy-1-propoxy) adamantane In a 200 mL three-necked flask, perfluoro-1,3-3 obtained in Example 2 was added. Bis (2,3-dihydroxypropoxy) adamantane (5.9 g) was dissolved in chloroform (50 mL) and triethylamine (7 mL) and cooled to 0 ° C. Next, 4 mL of acrylic acid chloride was dropped and stirred at 0 ° C. for 30 minutes. Further, 4 mL of 7 mL of triethylamine acrylic acid chloride was added and stirred at 0 ° C. for 30 minutes.
Saturated saline and chloroform were added to the reaction mixture, and the product was extracted with chloroform three times. The collected organic layers were each washed once with a 2N hydrochloric acid aqueous solution, a saturated sodium hydrogen carbonate aqueous solution, and a saturated saline solution. The organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain the desired product represented by the following formula (yield 99%, 7.8 g).

-Nuclear magnetic resonance spectrum (solvent: acetonitrile-d) JNM-ECA500 manufactured by JEOL Ltd.
[ ¹ H-NMR (500 MHz)]: 4.60-4.67 (m, 1H), 4.70-4.75 (m, 1H), 4.76-4.83 (m, 2H), 5 .70-5.80 (m, 1H), 6.20-6.28 (m, 2H), 6.39-6.50 (m, 2H), 6.62-6.73 (m, 2H)
[ ¹³ C-NMR (125 MHz)]: 61.01, 62.43, 70.48, 128.72, 128.76, 132.35, 132.73, 165.92, 166.33
[ ¹⁹ F-NMR (465 MHz, internal standard BTF: −64 ppm)]: −114.97, −118.93, −122.51, −222.42,

-Gas chromatograph-mass spectrometry (GC-MS): EI (Shimadzu Corporation GCMS-QP2010)
784 (M ⁺ , 0.01%), 756 (0.14%), 713 (0.21%), 586 (1.54%), 169 (4.5%), 55 (100%)

[Example 3]
2% by mass of benzoin isobutyl ether as a photopolymerization initiator was added to the perfluoro-1,3-bis (2,3-diacryloyloxy-1-propoxy) adamantane obtained in Example 2 and mixed well, followed by vacuum degassing did. This resin composition was poured into a glass cell and irradiated with a mercury lamp at 1000 mJ / cm ² to obtain a cured product having a thickness of 1 mm.
The physical properties of the obtained cured product are shown in Table 1.

[Comparative Example 1]
The perfluoro-1,3-bis (2,3-diaacryloyloxy-1-propoxy) adamantane of Example 3 was changed to perfluoro-1,3-bis (acryloyloxyethoxy) adamantane represented by the following formula: A curing reaction was carried out in the same manner except that.
The physical properties of the obtained cured product are shown in Table 1.

  The resin composition containing a fluorine adamantane derivative having three or more functional groups of the present invention is excellent in low refractive index, heat resistance and scratch resistance, and particularly provides a cured product having improved surface hardness. As described above, since the cured product of the present invention has excellent characteristics, an antireflection film, an optical fiber, an optical waveguide, a volume hologram, a hologram memory material, a coating material, a nanoimprint monomer, a surface modifier, an industrial tube material, and a seal. It is useful for materials and solid polymer fuel cell electrolyte membranes.

Claims (16)

A fluorine-containing adamantane derivative represented by the following general formula (I).

[In formula (I), G ¹ represents a single bond, a hetero atom or a divalent group containing a hetero atom, and R ¹ and R ² are each independently a hydrogen atom; substituted with a halogen atom or a hydroxyl group. An aliphatic hydrocarbon group that may contain an oxygen atom; and an organic group represented by the following formula (I-1), wherein X ¹ represents a hydroxyl group and 1 type chosen from groups represented by following formula (I-2)-(I-4) is shown. a is an integer of 1 to 4, b is an integer of 10 to 15, and a + b = 16. c is an integer of 1 to 10, and d is an integer of 1 to 10. A plurality of G ¹ , R ¹ , R ² and X ¹ may be the same or different from each other, and a plurality of c and d may be the same or different from each other.

[In formula (I-1), G ² represents a single bond, a hetero atom or a divalent group containing a hetero atom, and R ³ and R ⁴ are each independently a hydrogen atom; substituted with a halogen atom or a hydroxyl group. An aliphatic hydrocarbon group that may be present; and an aliphatic hydrocarbon group that may contain an oxygen atom. X ¹ is the same as defined above. e is 0 or an integer of 1 to 10, and f is 0 or an integer of 1 to 10. A plurality of G ² , R ³ , R ⁴ and X ¹ may be the same or different from each other, and a plurality of e and f may be the same or different from each other. ]

[In the formula (I-2), R ⁵ represents one selected from a hydrogen atom, a methyl group and a trifluoromethyl group. In formula (I-4), R ⁶ represents a hydrocarbon group having 1 to 5 carbon atoms. ]
However, the general formula (I) satisfies any of the following (1) to (3).
(1) When a = 1, at least ^two of R ¹ and R ² are organic groups represented by the formula (I-1), and three or more of X ¹ are represented by the formula (I-2) ) To (I-4).
(2) When a = 2, at least one of the plurality of R ¹ and R ² is an organic group represented by the formula (I-1), and three or more of X ¹ are represented by the formula (I -2) to (I-4) are selected from the groups represented by (I-4).
(3) When a = 3 or 4, three or more of X ¹ are one selected from the groups represented by the formulas (I-2) to (I-4). ]   In the said general formula (I), it is a = 2, The fluorine-containing adamantane derivative of Claim 1 characterized by the above-mentioned. The fluorine-containing adamantane derivative according to claim 1, wherein d = 1 and G ¹ is a single bond in the general formula (I). The fluorine-containing adamantane derivative according to claim 1, wherein at least one of X ^{1 in} the general formula (I) is the formula (I-2).   In said general formula (I), it is c = 3, The fluorine-containing adamantane derivative in any one of Claims 1-4. A fluorine-containing adamantane derivative represented by the following general formula (II).

[In Formula (II), G ¹ represents a single bond, a hetero atom or a divalent group containing a hetero atom, and R ⁷ and R ⁸ are each independently a hydrogen atom; substituted with a halogen atom or a hydroxyl group. An aliphatic hydrocarbon group which may contain an oxygen atom; and an organic group represented by the following formula (II-1). a is an integer of 1 to 4, b is an integer of 10 to 15, and a + b = 16. c is an integer of 1 to 10, and d is an integer of 1 to 10. A plurality of G ¹ , R ⁷ and R ⁸ may be the same or different from each other, and a plurality of c and d may be the same or different from each other.

[In formula (II-1), G ² represents a single bond, a hetero atom or a divalent group containing a hetero atom, and R ³ and R ⁴ are each independently a hydrogen atom; substituted with a halogen atom or a hydroxyl group. 1 type chosen from the aliphatic hydrocarbon group which may contain; and the aliphatic hydrocarbon group which may contain an oxygen atom. e is 0 or an integer of 1 to 10, and f is 0 or an integer of 1 to 10. A plurality of G ² , R ⁵ and R ⁶ may be the same or different from each other, and a plurality of e and f may be the same or different from each other. ]
However, the general formula (II) satisfies any of the following (4) to (6).
(4) When a = 1, at least two of R ⁷ and R ⁸ are organic groups represented by the formula (II-1).
(5) When a = 2, at least one of the plurality of R ⁷ and R ⁸ is an organic group represented by the formula (II-1).
(6) When a = 3 or 4, R ⁷ and R ⁸ may not be an organic group represented by the formula (II-1). ]   The fluorine-containing adamantane derivative according to claim 6, wherein a = 2 in the general formula (II). The fluorine-containing adamantane derivative according to claim 6 or 7, wherein in the general formula (II), d = 1 and G ¹ is a single bond.   The fluorine-containing adamantane derivative according to any one of claims 6 to 8, wherein c = 3 in the general formula (II). The fluorine-containing adamantane derivative (II) according to any one of claims 6 to 9 is reacted with a hydroxyl group-reactive compound having a group represented by the following formulas (II-2) to (II-4). The manufacturing method of fluorine-containing adamantane derivative (I) as described in 1 above.

[In formula (II-2), R ⁵ represents one selected from a hydrogen atom, a methyl group and a trifluoromethyl group. In formula (II-4), R ⁶ represents a hydrocarbon group having 1 to 5 carbon atoms. ]   After reacting at least one hydroxyl group in the fluorine-containing adamantane derivative (II) according to any one of claims 6 to 9 with a glycidyl group-containing hydroxyl group-reactive compound, (meth) acrylic anhydride is reacted, The method for producing a fluorinated adamantane derivative (I) according to claim 1, wherein a group represented by the formula (I-2) is introduced.   10. The fluorine-containing adamantane derivative having a hydroxyl group selected from perfluoroadamantane monool, perfluoroadamantanediol, perfluoroadamantane triol, and perfluoroadamantane tetraol and a halogen-containing alcohol compound are reacted. Of producing a fluorine-containing adamantane derivative (II).   A resin composition comprising the fluorine-containing adamantane derivative (I) according to claim 1.   The resin composition according to claim 13, comprising a thermal polymerization initiator and / or a photopolymerization initiator.   Hardened | cured material formed by hardening | curing the resin composition of Claim 13 or 14.   An antireflection film using the fluorine-containing adamantane derivative (I) according to claim 1 or the cured product according to claim 15.