JP2013181140A - Optical resin composition, cured matter, optical part, sealant for semiconductor light-emitting device, optical lens, optical adhesive, optical sealing agent and optical waveguide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optical resin composition formable of cured matter with a low refractive index, excellent in terms of hardness, light resistance and heat discoloration resistance, furthermore excellent in terms of transparency.SOLUTION: This optical resin composition includes, for example, a compound MA31 and a compound FA-14.

Description

  The present invention relates to an optical resin composition, a cured product formed using the optical resin composition, an optical component, a sealing agent for a semiconductor light emitting device, an optical lens, an optical adhesive, an optical sealing agent, an optical Related to the waveguide.

A resin composition containing a fluorine-containing compound is used for various applications. However, it may be used for optical applications because it has a low refractive index.
For example, Patent Document 1 discloses a fluorine-containing polyfunctional monomer capable of forming a polymer thin film suitable as an antireflection film.

JP 2006-028280 A

  The fluorine-containing polyfunctional monomer described in Patent Document 1 is for forming a polymer thin film. However, in the case where a thicker film is formed using the fluorine-containing polyfunctional monomer, the viewpoint of transparency It turns out that there is room for improvement. Especially for optical components such as encapsulants for semiconductor light-emitting devices, optical lenses, optical adhesives, optical sealants, and optical waveguides, the transparency of the cured product is important, so a more transparent cured product is provided. A resin composition that can be used is required. Further, when considering optical applications, in addition to transparency, it is required to have a low refractive index and be excellent in terms of hardness, light resistance, and heat-resistant colorability. Furthermore, since a cured product giving the most suitable refractive index is required depending on the application, a composition capable of adjusting the refractive index is required.

  Therefore, the object of the present invention is to form a cured product that has a low refractive index, is excellent in terms of hardness, light resistance, and heat-resistant colorability, is excellent in terms of transparency, and can provide an optimum refractive index. It is providing the optical resin composition which can do. Another object of the present invention is to provide a cured product, an optical component, a sealant for a semiconductor light emitting device, an optical lens, an optical adhesive, an optical sealant, and an optical waveguide formed using the optical resin composition. To do.

  As a result of intensive studies in view of the above circumstances, the inventors of the present invention have a low refractive index when a resin composition having a specific compound having a fluorine-containing core part and another specific fluorine-containing compound is used. The present inventors have found that it is possible to form a cured product that is excellent from the viewpoints of hardness, light resistance, and heat-resistant colorability, excellent from the viewpoint of transparency, and capable of giving an optimum refractive index. Furthermore, since the fluorine content of the composition was high, an effect of being excellent in releasability from the mold when producing an optical component by mold molding was also obtained.

  That is, the present invention is as follows.

[1]
An optical resin composition comprising a fluorine-containing compound represented by the following general formula (1) and a fluorine-containing compound represented by the following general formula (12) or (13).

In general formula (1), a represents an integer of 3 to 8, b represents an integer of 0 to 3, c represents an integer of 0 to 10, d and e each independently represents 0 or 1, r represents 0 or 1, Y represents a group represented by the following general formula (2), (3), (4) or (5), an allyl group, or a vinyl group, and L ₁ represents the following general formula ( 6) or a group represented by (7), L ₂ and L ₃ each independently represent a group represented by the following general formula (8), (9), (10) or (11) , Rf ₁ represents a (a + b) -valent, may contain an etheric oxygen atom, a linear, branched or cyclic saturated perfluoroalkyl group having 3 to 20 carbon atoms, Rf ₂ is etheric oxygen atoms may contain, represents a monovalent perfluoroalkyl group or a fluorine atom, linear or branched C1-5, Rf ₃ is It may contain ether oxygen atoms, a straight, branched or cyclic, monovalent perfluoroalkyl group of 3 to 100 carbon atoms.

In general formula (2), X represents a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group, or a hydroxyl group.
In the general formulas (3), (4) and (5), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a carbon atom which may have a hydrogen atom or a substituent. A linear or branched monovalent alkyl group having a number of 1 to 5 is represented.
In general formula (5), k represents 1 or 2.
In general formulas (6) and (7), m represents an integer of 0 to 10.
In general formula (8), (9), (10), (11), n represents the integer of 0-10.
In the general formula (7), Y represents a group represented by the general formula (2), (3), (4) or (5), an allyl group, or a vinyl group.

In General Formula (12), f represents an integer of 0 to 5, g represents 0 or 1, and Y represents a group represented by General Formula (2), (3), (4), or (5). , An allyl group, or a vinyl group, L ₄ represents a group represented by the general formula (6) or (7), or the following general formula (14) or (15), and Rf ₄ represents an etheric oxygen A linear, branched or cyclic monovalent polyfluoroalkyl group having 1 to 100 carbon atoms which may contain an atom is represented.
In general formula (13), h and i each independently represent an integer of 1 to 5, Y is a group represented by general formula (2), (3), (4) or (5), or an allyl group. Or L ₄ represents a group represented by the general formula (6) or (7) or the following general formula (14) or (15), and Rf ₅ represents an etheric oxygen. A linear, branched or cyclic divalent perfluoroalkyl group having 1 to 100 carbon atoms which may contain an atom is represented.

In general formula (14), m represents an integer of 0 to 10.
In the general formula (15), Y represents a group represented by the general formula (2), (3), (4) or (5), an allyl group, or a vinyl group.
[2]
[1] The content of the fluorine-containing compound represented by the general formula (1) is 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the total solid content of the optical resin composition. An optical resin composition.
[3]
The optical resin composition according to [1] or [2], wherein a fluorine atom content of the fluorine-containing compound represented by the general formula (12) or (13) is 30% by mass or more and 75% by mass or less.
[4]
The optical resin composition according to any one of [1] to [3], wherein (a + b) in the general formula (1) is an integer of 3 to 8.
[5]
The optical resin composition according to any one of [1] to [4], wherein d and e in the general formula (1) are 1.
[6]
The fluorine-containing compound represented by the general formula (1) is a fluorine-containing compound represented by the following general formula (17), and the fluorine-containing compound represented by the general formula (12) or (13) is The optical resin composition according to any one of [1] to [5], which is a fluorine-containing compound represented by the general formula (18) or (19).

In general formula (17), a represents an integer of 3 to 8, b represents an integer of 0 to 3, c represents an integer of 0 to 10, Y represents the general formulas (2), (3), (4) or (5) represents a group, an allyl group, or a vinyl group, L ₁ represents a group represented by the general formula (6) or (7), and Rf ₁ represents an (a + b) value. Represents a linear, branched or cyclic saturated perfluoroalkyl group having 3 to 20 carbon atoms which may contain an etheric oxygen atom, and Rf ₂ may contain an etheric oxygen atom. 1 to 5 linear or branched monovalent perfluoroalkyl group or fluorine atom, Rf ₆ having at least one trifluoromethyl group, which may contain an etheric oxygen atom, carbon number 3 to 100 linear, branched or cyclic monovalent perfluoroalkyl groups are represented.

In general formula (18), f represents an integer of 0 to 5, Y represents a group represented by general formula (2), (3), (4) or (5), an allyl group, or a vinyl group. Rf ₇ represents a linear or branched monovalent polyfluoroalkyl group having 1 to 100 carbon atoms, which may contain an etheric oxygen atom, and has at least one trifluoromethyl group.
In general formula (19), h and i each independently represent an integer of 1 to 5, Y is a group represented by the general formula (2), (3), (4) or (5), or an allyl group Or Rf ₈ represents a linear or branched divalent perfluoroalkyl group having 1 to 100 carbon atoms, which may contain an etheric oxygen atom.
[7]
The optical resin composition according to any one of [1] to [6], wherein a in the general formula (1) or (17) is 4 and b is 0.
[8]
The optical resin composition according to any one of [1] to [7], wherein Rf ₁ in the general formula (1) or (17) is a group selected from the following f- ₁ to f-14.

Wherein * _{Y-L 1 -O-CH 2} - (CF 2) c - [CF (Rf 2)] r - (O) d -L 2 - or _{Rf 3 - (O) e -L} 3 - Represents the position to be combined.
[9]
Furthermore, the optical resin composition of any one of [1]-[8] containing the non-fluorine compound represented by following General formula (16).

In general formula (16), j represents an integer of 1 to 6, and Y represents a group represented by the following general formula (21), (3), (4) or (5), an allyl group, or a vinyl group. L ₅ represents a group represented by the following general formula (6), (7), (14) or (15), and R ₇ has 1 to 1 carbon atoms which may have a hydrogen atom or a substituent. 20 linear, branched or cyclic j-valent organic groups are represented.

In General Formula (21), X ¹ represents a hydrogen atom, a chlorine atom, a methyl group, a trifluoromethyl group, or a hydroxyl group.
In the general formulas (3), (4) and (5), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a carbon atom which may have a hydrogen atom or a substituent. A linear or branched monovalent alkyl group having a number of 1 to 5 is represented.
In general formula (5), k represents 1 or 2.
In general formulas (6), (7), and (14), m represents an integer of 0 to 10.
In the general formulas (7) and (15), Y represents a group represented by the general formula (21), (3), (4) or (5), an allyl group, or a vinyl group.
[10]
The optical resin composition according to any one of [1] to [9], wherein the refractive index after curing is 1.35 or more and less than 1.45.
[11]
Hardened | cured material formed by hardening | curing the optical resin composition of any one of [1]-[10].
[12]
[1] An optical component using the optical resin composition according to any one of [10].
[13]
[1] A sealing agent for a semiconductor light emitting device, comprising the optical resin composition according to any one of [10].
[14]
[1] An optical lens using the optical resin composition according to any one of [10].
[15]
[1]-[10] An optical adhesive comprising the optical resin composition according to any one of [10].
[16]
[1] An optical sealing agent comprising the optical resin composition according to any one of [10].
[17]
An optical waveguide using the optical resin composition according to any one of [1] to [10].

  According to the present invention, a cured product having a low refractive index, excellent in terms of hardness, light resistance, and heat-resistant colorability, excellent in terms of transparency, and capable of giving an optimum refractive index is formed. The optical resin composition which can be provided can be provided. Moreover, the hardened | cured material formed using this optical resin composition, an optical component, the sealing agent for semiconductor light-emitting devices, an optical lens, the optical adhesive agent, the optical sealing agent, and an optical waveguide can be provided.

The optical resin composition of the present invention contains a fluorine-containing compound represented by the following general formula (1) and a fluorine-containing compound represented by the following general formula (12) or (13).
The compounds represented by general formula (1), general formula (12), and general formula (13) are described in detail below.

<Compound represented by the general formula (1)>
The compound represented by the general formula (1) used in the present invention is mainly composed of a plurality of fluorine atoms and carbon atoms (however, oxygen atoms may be partly included), and does not substantially participate in polymerization. 3 groups having radical polymerizability, cationic polymerizability, or condensation polymerizability via an atomic group (hereinafter also referred to as “fluorine-containing core”) and a linking group such as an ester bond or an ether bond. This is a fluorine-containing compound having the above polymerizable group.

In general formula (1), a represents an integer of 3 to 8, b represents an integer of 0 to 3, c represents an integer of 0 to 10, d and e each independently represents 0 or 1, r represents 0 or 1, Y represents a group represented by the following general formula (2), (3), (4) or (5), an allyl group, or a vinyl group, and L ₁ represents the following general formula ( 6) or a group represented by (7), L ₂ and L ₃ each independently represent a group represented by the following general formula (8), (9), (10) or (11) , Rf ₁ represents a (a + b) -valent, may contain an etheric oxygen atom, a linear, branched or cyclic saturated perfluoroalkyl group having 3 to 20 carbon atoms, Rf ₂ is etheric oxygen atoms may contain, represents a monovalent perfluoroalkyl group or a fluorine atom, linear or branched C1-5, Rf ₃ is It may contain ether oxygen atoms, a straight, branched or cyclic, monovalent perfluoroalkyl group of 3 to 100 carbon atoms.

In general formula (2), X represents a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group, or a hydroxyl group.
In the general formulas (3), (4) and (5), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a carbon atom which may have a hydrogen atom or a substituent. A linear or branched monovalent alkyl group having a number of 1 to 5 is represented.
In general formula (5), k represents 1 or 2.
In general formulas (6) and (7), m represents an integer of 0 to 10.
In general formula (8), (9), (10), (11), n represents the integer of 0-10.
In the general formula (7), Y represents a group represented by the general formula (2), (3), (4) or (5), an allyl group, or a vinyl group.

  In general formula (1), a represents an integer of 3 to 8. a is preferably an integer of 3 to 6, more preferably an integer of 3 to 5, and even more preferably 3 or 4 from the viewpoint of availability of raw materials and ease of production.

  In general formula (1), b represents an integer of 0 to 3. From the viewpoint of ease of production, b is preferably an integer of 0 to 2, and more preferably 0 or 1.

  In general formula (1), a + b represents an integer of 3 to 11. a + b is preferably an integer of 3 to 8, more preferably an integer of 3 to 6, and even more preferably 3 or 4, from the viewpoint of the balance between availability of raw materials and ease of production. .

  In general formula (1), it is preferable that a is 4 and b is 0 from a compatible viewpoint with the other component in a composition.

  In general formula (1), c represents an integer of 0 to 10. c is preferably an integer of 0 to 6, more preferably an integer of 0 to 3, further preferably 0 or 1, and still more preferably 1.

  In general formula (1), d represents 0 or 1. d is preferably 1 from the viewpoint of transparency.

  In general formula (1), e represents 0 or 1. e is preferably 1.

  In general formula (1), r represents 0 or 1. r is preferably 1 from the viewpoint of transparency.

  It is preferable that at least one of d and r is 1 from the viewpoint of transparency. When d and r are 0 simultaneously, m in the general formula (6) or (7) is preferably 1 to 10 from the viewpoint of transparency.

  In general formula (2), X represents a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group or a hydroxyl group, and is a hydrogen atom, a fluorine atom or a methyl group from the viewpoint of availability of raw materials. Are preferable, and a hydrogen atom is preferable.

In general formulas (3) to (5), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each independently have 1 to 5 carbon atoms which may have a hydrogen atom or a substituent. Represents a linear or branched monovalent alkyl group. Examples of the substituent when the alkyl group has a substituent include a fluorine atom, an alkoxyl group, and a hydroxyl group.
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom.

  In general formula (5), k represents 1 or 2. k is preferably 1.

  Y in the general formula (1) is preferably a group represented by the general formula (2) or the general formula (3) or an allyl group from the viewpoint of refractive index and curability.

  Y in the general formula (1) may be the same or different from each other, but is preferably the same from the viewpoint of production suitability. When mutually different, it is preferable at the point which can produce harder hardened | cured material by combining two or more types of hardening processes.

In the general formulas (6) and (7), m represents an integer of 0 to 10, and from the viewpoint of ease of production, m is preferably 0 to 4, more preferably 0 or 1. More preferably, it is 0. When m is 0, L ₁ is a single bond.

In the general formulas (8), (9), (10) and (11), n represents an integer of 0 to 10, and from the viewpoint of availability of raw materials, n is preferably 0 to 4, and 0 or 1 is more preferable, and 0 is still more preferable. When n is 0, it represents that L ₂ and L ₃ are single bonds.

In the general formula (1), Rf ₁ constitutes a “fluorine-containing core part” and has a (a + b) -valent, C3-C20 linear, branched or cyclic group which may contain an etheric oxygen atom. Represents a saturated perfluoroalkyl group.
The perfluoroalkyl group is an alkyl group in which substantially all hydrogen atoms are substituted with fluorine atoms, and is a group having no substituent such as a hydroxyl group, a carboxyl group, or a nitro group.
Rf ₁ is preferably a (a + b) -valent branched or cyclic saturated perfluoroalkyl group having 3 to 19 carbon atoms which may contain an etheric oxygen atom, more preferably an (a + b) -valent. A branched or cyclic saturated perfluoroalkyl group having 4 to 14 carbon atoms, which may contain an etheric oxygen atom. Preferable examples of the “fluorine-containing core portion” represented by Rf ₁ include the following specific examples.

Wherein * _{Y-L 1 -O-CH 2} - (CF 2) c - [CF (Rf 2)] r - (O) d -L 2 - or _{Rf 3 - (O) e -L} 3 - Represents the position to be combined.

Rf ₁ is the above f-1, f-2, f-4, f-5, f-6, f-8, f-10, f-11 or f-12 from the viewpoint of availability of raw material. Preferably f-5, f-8, or f-11, and most preferably f-8.

In the general formula (1), Rf ₂ represents an etheric oxygen atom may include, monovalent perfluoroalkyl group or a fluorine atom, linear or branched C1-5. Examples of perfluoroalkyl groups include
CF _3- ,
CF ₃ CF _2- ,
CF ₃ (CF ₂ ) ₃ −,
(CF ₃ ) ₂ CF−,
CF ₃ CF ₂ OCF ₂ CF _2- ,
CF ₃ CF ₂ OCF ₂ CF ₂ OCF ₂ −,
(CF ₃ ) ₂ CFO (CF ₂ ) ₂ −
Etc.
Rf ₂ is preferably CF ₃ — or a fluorine atom, and more preferably a fluorine atom.

In the general formula (1), Rf ₃ may contain an etheric oxygen atom, a straight, branched or cyclic, monovalent perfluoroalkyl group of 3 to 100 carbon atoms.
Rf ₃ is preferably a perfluoroalkyl group having 3 to 60 carbon atoms which may contain an etheric oxygen atom, and is a perfluoroalkyl group having 4 to 40 carbon atoms which may contain an etheric oxygen atom. It is more preferable.
When the carbon number of Rf ₃ is within the above range, the curability is excellent when the carbon number is small, and the low refractive index property is excellent when the carbon number is large, and the releasability is improved.
Specific examples of Rf ₃ are shown below.
In the following examples, x and y represent an integer combination such that the number of carbon atoms in Rf ₃ satisfies ₃ to 100. x is preferably 1 to 40, and more preferably 3 to 20. y is preferably 1 to 40, and more preferably 3 to 20.

CF ₃ (CF ₂ ) _5- ,
(CF ₃ ) ₂ CFOCF ₂ CF _2- ,
CF ₃ (OCF ₂ CF ₂ ) ₄ −,
_{CF 3 (OCF 2) x (} OCF 2 CF 2) y -,
_{CF 3 (OCF 2 CF 2 CF} 2) x -,
_{CF 3 CF 2 CF 2 (OCF} (CF 3) CF 2) 4 -,
CF ₃ CF ₂ OCF ₂ CF _2- ,
_{CF 3 CF 2 (OCF 2 CF} 2) 4 -,
CF ₃ CF ₂ (OCF ₂ CF ₂ ) _6- ,

_{CF 3 (CF 2) 3 -} , CF 3 (CF 2) 7 -,
CF ₃ CF ₂ OCF ₂ CF ₂ OCF ₂ −,
CF ₃ CF ₂ OCF ₂ CF ₂ OCF ₂ CF _2- ,
CF ₃ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ OCF _2- ,
_{CF 3 CF 2 OCF 2 CF 2} OCF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 -,
CF ₃ CF ₂ CF ₂ OCF _2- ,
CF ₃ CF ₂ CF ₂ OCF ₂ CF _2- ,
_{CF 3 CF 2 CF 2 OCF (} CF 3) -,
_{CF 3 CF 2 CF 2 OCF (} CF 3) CF 2 -,
_{CF 3 CF 2 CF 2 OCF (} CF 3) CF 2 OCF 2 CF 2 -,
_{CF 3 CF 2 CF 2 OCF (} CF 3) CF 2 OCF (CF 3) -,
_{CF 3 CF 2 CF 2 OCF (} CF 3) CF 2 OCF (CF 3) CF 2 -

  The compound represented by the general formula (1) preferably has a fluorine content of 32% by mass or more, more preferably 35% by mass or more, and still more preferably 40% by mass from the viewpoint of low refractive index. % Or more.

  The fluorine-containing compound represented by the general formula (1) is preferably a fluorine-containing compound represented by the following general formula (17).

In general formula (17), a represents an integer of 3 to 8, b represents an integer of 0 to 3, c represents an integer of 0 to 10, Y represents the general formulas (2), (3), (4) or (5) represents a group, an allyl group, or a vinyl group, L ₁ represents a group represented by the general formula (6) or (7), and Rf ₁ represents an (a + b) value. Represents a linear, branched or cyclic saturated perfluoroalkyl group having 3 to 20 carbon atoms which may contain an etheric oxygen atom, and Rf ₂ may contain an etheric oxygen atom. 1 to 5 linear or branched monovalent perfluoroalkyl group or fluorine atom, Rf ₆ having at least one trifluoromethyl group, which may contain an etheric oxygen atom, carbon number 3 to 100 linear, branched or cyclic monovalent perfluoroalkyl groups are represented.

In the general formula (17), specific examples and preferred ranges of a, b, c, Y, L ₁ , Rf ₁ , Rf ₂ are a, b, c, Y, L ₁ in the general formula (1), The same as Rf ₁ and Rf ₂ .

In the general formula (17), Rf ₆ is a linear, branched or cyclic monovalent peroxy group having 3 to 100 carbon atoms, which may contain an etheric oxygen atom, having at least one trifluoromethyl group. Represents a fluoroalkyl group.
Rf ₆ is preferably a C 3-60 perfluoroalkyl group having at least one trifluoromethyl group, which may contain an etheric oxygen atom, and an ether having at least one trifluoromethyl group It is more preferably a perfluoroalkyl group having 4 to 40 carbon atoms which may contain a reactive oxygen atom.
Specific examples and preferred ranges of Rf ₆ are the same as the specific examples and preferred ranges of Rf ₃ in the general formula (1).

  Although the specific example of a compound represented by General formula (1) below is given, this invention is not limited by these. As a specific example, only structures in which all Y in the same molecule are the same are listed. However, when Y is different from each other as described above, a favorable effect may be obtained, and this does not exclude any structure with different Y in the same molecule. In the following specific example compounds, x and y each independently represents an integer of 1 to 40. n1, n2, n3, and n4 each independently represents an integer of 0 to 10.

  Among the above specific examples, MA1, MA2, MA3, MA4, MA5, MA6, MA7, MA9, MA12, MA13, MA14, MA17, MA23, MA24, MA30, MA31, MA32, MA33, MA35, MA36, MA37, MA38 , ME1, ME2, ME3, ME4, ME5, ME6, ME7, ME12, ME13, ME14, ME17, ME23, ME24, ME29, ME30, ME31, ME32, ME33, ME35, ME36, ME37, ME39, ME40 are preferred, and MA1 MA3, MA6, MA17, MA30, MA31, MA33, ME1, ME6, ME17, ME29, ME33, ME39 are more preferable, MA30, MA31, MA33, ME29, ME33, ME39 are more preferable, A31, ME29 is most preferable.

  As a method for producing these fluorine-containing polyfunctional monomers, a compound having an ester bond, a dialkoxy group and / or a halogen atom, preferably a compound having an ester bond, is preferably substantially liquid-phase fluorinated. A method in which three or more polymerizable groups are introduced after all hydrogen atoms have been replaced with fluorine atoms is preferred. Liquid phase fluorination is described, for example, in US Pat. No. 5,093,432.

The compound subjected to liquid phase fluorination is required to be dissolved in a fluorine-based solvent used for liquid phase fluorination or to be liquid, but there is no particular limitation other than that. From the viewpoint of such solubility and reactivity, a compound containing fluorine in advance may be used. A compound having an ester bond, a dialkoxy group, and / or a halogen atom is preferable because it can serve as a reaction point when a polymerizable group is introduced after liquid phase fluorination.
By introducing fluorine atoms by liquid phase fluorination, it is possible to extremely increase the fluorine content of the portion other than the polymerizable group introduced later.

  The fluorine-containing compound represented by the general formula (1) contained in the optical resin composition of the present invention may be one type or two or more types.

<Compound represented by formula (12) or (13)>
The compound represented by formula (12) or (13) contained in the optical resin composition of the present invention will be described.

In general formula (12), f represents an integer of 0 to 5, g represents 0 or 1, and Y represents a group represented by the following general formula (2), (3), (4) or (5). , An allyl group, or a vinyl group, L ₄ represents a group represented by the following general formula (6), (7), (14), or (15), and Rf ₄ contains an etheric oxygen atom. Or a linear, branched or cyclic monovalent polyfluoroalkyl group having 1 to 100 carbon atoms.
In General Formula (13), h and i each independently represent an integer of 1 to 5, Y is a group represented by the following General Formula (2), (3), (4) or (5), or an allyl group Or a vinyl group, L ₄ each independently represents a group represented by the following general formula (6), (7), (14), or (15), and Rf ₅ may contain an etheric oxygen atom. It represents a linear, branched or cyclic divalent perfluoroalkyl group having 1 to 100 carbon atoms.

In general formula (2), X represents a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group, or a hydroxyl group.
In the general formulas (3), (4) and (5), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a carbon atom which may have a hydrogen atom or a substituent. A linear or branched monovalent alkyl group having a number of 1 to 5 is represented.
In general formula (5), k represents 1 or 2.
In general formulas (6), (7), and (14), m represents an integer of 0 to 10.
In the general formulas (7) and (15), Y represents a group represented by the general formula (2), (3), (4) or (5), an allyl group, or a vinyl group.

  In general formula (12), f represents the integer of 0-5. f is preferably an integer of 0 to 3, and more preferably an integer of 0 to 2.

  In general formula (12), g represents 0 or 1. g is preferably 1.

In general formula (12), Y represents a group represented by the above general formula (2), (3), (4) or (5), an allyl group, or a vinyl group.
Y in general formula (12) is synonymous with Y in general formula (1). Y in the general formula (12) is preferably a group represented by the general formula (2) or the general formula (3) from the viewpoint of refractive index and curability.

In General Formula (12), L ₄ represents a group represented by the above General Formula (6), (7), (14) or (15) (where m represents an integer of 0 to 10). Y in the general formula (15) has the same meaning as Y in the general formula (12), and preferred groups are also the same. m is preferably 0 to 4, more preferably 0 or 1, and still more preferably 0. That is, L ₄ is preferably a single bond.

In General Formula (12), Rf ₄ represents a linear, branched or cyclic monovalent polyfluoroalkyl group having 1 to 100 carbon atoms which may contain an etheric oxygen atom.
The polyfluoroalkyl group in the present invention is a perfluoroalkyl group in which one fluorine atom or 20% or less of the total fluorine atoms is replaced by a hydrogen atom, and preferably one of the fluorine atoms is a hydrogen atom. Represents a substituted group.
Rf ₄ is preferably a linear or branched polyfluoroalkyl group having 1 to 50 carbon atoms which may contain an etheric oxygen atom, and may contain an etheric oxygen atom. More preferably, it is a linear or branched polyfluoroalkyl group having from 20 to 20, and may contain an etheric oxygen atom, and is a linear or branched polyfluoroalkyl having 1 to 10 carbon atoms More preferably, it is a group.
Specific examples of Rf ₄ are shown below.
Incidentally, z in the following examples, the number of carbons in Rf ₄ represents an integer of combinations satisfying 1-100. z becomes like this. Preferably it is 0-20, More preferably, it is 1-10.

CF ₃ −,
C ₂ F _5- ,
CF ₃ (CF ₂ ) ₂ −,
(CF ₃ ) ₂ CH—
CF ₃ (CF ₂ ) ₃ −,
(CF ₃ ) ₂ CFCF _2- ,
(CF ₃ ) ₃ C-,
C ₄ F _9- ,
H _{(CF 2)} 4 -,
C ₅ F _11- ,
(CF ₃ CF ₂ ) ₂ CH—,
C ₆ F _13- ,
H (CF ₂ ) _6- ,
_{CF 3 CF 2 O (CF 2} CF 2 O) z CF 2 -,
_{(CF 3) 3 CO (CF} 2 CF 2 O) z CF 2 -,
_{(CF 3) 2 CFO (CF} 2 CF 2 CF 2 O) z CF 2 CF 2 -,
_{CF 3 O (CF 2 CF 2} CF 2 O) z CF 2 CF 2 -,
_{CF 3 CF 2 CF 2 O (} CF (CF 3) CF 2 O) z CF (CF 3) -,
_{CF 3 (CF 2) 7 -} ,
_{HCF 2 (CF 2) 7 -} ,
CF ₃ CF ₂ OCF ₂ CF ₂ OCF ₂ CF _2- ,
_{CF 3 CF 2 OCF 2 CF 2} OCHFCF 2 -,
_{CF 3 CF 2 OCF 2 CF 2} OCF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 -,
CF ₃ CF ₂ CF ₂ OCF _2- ,
CF ₃ CF ₂ CF ₂ OCF ₂ CF ₂ −
_{CF 3 CF 2 CF 2 OCF (} CF 3) -,
_{CF 3 CF 2 CF 2 OCF (} CF 3) CF 2 -,
_{CF 3 CF 2 CF 2 OCF (} CF 3) CF 2 OCF 2 CF 2 -,
_{CF 3 CF 2 CF 2 OCF (} CF 3) CF 2 OCF (CF 3) CF 2 -,
CF ₃ CF ₂ CF ₂ O [CF (CF ₃ ) CF ₂ O] _z CF (CF ₃ ) −

  In general formula (13), h and i each independently represent an integer of 1 to 5. h and i are each independently preferably an integer of 1 to 3, more preferably 1 or 2, and still more preferably 1.

  Y in the general formula (13) has the same meaning as Y in the general formula (12), and preferred groups are also the same.

_{L 4} in the general formula (13) has the same meaning as _{L 4} in the formula (12), which is also the same preferable groups.

In General Formula (13), Rf ₅ represents a linear, branched or cyclic divalent perfluoroalkyl group having 1 to 100 carbon atoms which may contain an etheric oxygen atom.
Rf ₅ is preferably a divalent perfluoroalkyl group which may contain a linear etheric oxygen atom having 2 to 90 carbon atoms, and a linear etheric oxygen atom having 6 to 80 carbon atoms. More preferably, it may be a divalent perfluoroalkyl group.
Specific examples of Rf ₅ are shown below.
In addition, p and q in the following example represent the combination of integers in which the carbon number in Rf ₅ satisfies 1 to 100. p is preferably 1 to 40, and more preferably 3 to 20. q is preferably 1 to 40, more preferably 3 to 20.

_{-CF 2 O- (CF 2 CF 2} O) p -CF 2 -,
_{-CF 2 O- (CF 2 CF 2} CF 2 O) p -CF 2 -,
_{-CF 2 O- (CF 2 CF 2} CF 2 CF 2 O) p -CF 2 -,
_{-CF 2 O- (CF 2 CF 2} O) p (CF 2 O) q -CF 2 -,
- _{(CF 2) 2} -,
- _{(CF 2)} 4 -,
- _{(CF 2)} 6 -,
- _{(CF 2)} 8 -,
- _{(CF 2) 10} -,
_{- (CF 3) CF [OCF} 2 CF (CF 3)] OCF 2 (CF 2) 4 CF 2 O [CF (CF 3) CF 2 O] CF (CF 3) -,
_{-CF 2 CF 2 OCF 2 (CF} 3) CF [OCF 2 CF (CF 3)] OCF 2 -,
_{- (CF 2) 4 CF 2} O [CF (CF 3) CF 2 O] CF (CF 3) CF 2 OCF 2 CF 2 -

  The fluorine-containing compound represented by the general formula (12) or (13) is preferably a fluorine-containing compound represented by the following general formula (18) or (19).

In general formula (18), f represents an integer of 0 to 5, Y represents a group represented by general formula (2), (3), (4) or (5), an allyl group, or a vinyl group. Rf ₇ represents a linear or branched monovalent polyfluoroalkyl group having 1 to 100 carbon atoms, which may contain an etheric oxygen atom, and has at least one trifluoromethyl group.
In general formula (19), h and i each independently represent an integer of 1 to 5, Y is a group represented by the general formula (2), (3), (4) or (5), or an allyl group Or Rf ₈ represents a linear or branched divalent perfluoroalkyl group having 1 to 100 carbon atoms, which may contain an etheric oxygen atom.

  In general formulas (18) and (19), specific examples and preferred ranges of f, Y, h and i are the same as those in f, Y, h and i in general formula (12) or (13).

In General Formula (18), Rf ₇ is a linear or branched monovalent polyfluoroalkyl having 1 to 100 carbon atoms, which may contain an etheric oxygen atom, having at least one trifluoromethyl group. Represents a group.
Rf ₇ has at least one trifluoromethyl group, may contain an etheric oxygen atom, has 1 to 50 carbon atoms, or a linear polyfluoro having a trifluoromethyl group as a branched chain It is preferably an alkyl group, has at least one trifluoromethyl group, may contain an etheric oxygen atom, has 1 to 20 carbon atoms, is linear, or has a trifluoromethyl group as a branched chain More preferably, it is a polyfluoroalkyl group in the form of a ring.
Specific examples and preferred ranges of Rf ₇ are the same as those of Rf ₄ in the general formula (12).
Specific examples of Rf ₇ are shown below.
In addition, z1 in the following example represents the combination of the integers in which the carbon number in Rf ₇ satisfies 1 to 100. z1 becomes like this. Preferably it is 0-20, More preferably, it is 1-10.

CF ₃ −,
C ₂ F _5- ,
CF ₃ (CF ₂ ) ₂ −,
(CF ₃ ) ₂ CH—
CF ₃ (CF ₂ ) ₃ −,
(CF ₃ ) ₂ CFCF _2- ,
(CF ₃ ) ₃ C-,
C ₄ F _9- ,
C ₅ F _11- ,
C ₆ F _13- ,
_{CF 3 CF 2 O (CF 2} CF 2 O) z1 CF 2 -,
_{(CF 3) 3 CO (CF} 2 CF 2 O) z1 CF 2 -,
_{(CF 3) 2 CFO (CF} 2 CF 2 CF 2 O) z1 CF 2 CF 2 -,
_{CF 3 O (CF 2 CF 2} CF 2 O) z1 CF 2 CF 2 -,
_{CF 3 CF 2 CF 2 O (} CF (CF 3) CF 2 O) z1 CF (CF 3) -,
_{CF 3 (CF 2) 7 -} ,
CF ₃ CF ₂ OCF ₂ CF ₂ OCF ₂ CF _2- ,
_{CF 3 CF 2 OCF 2 CF 2} OCHFCF 2 -,
_{CF 3 CF 2 OCF 2 CF 2} OCF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 -,
CF ₃ CF ₂ CF ₂ OCF _2- ,
CF ₃ CF ₂ CF ₂ OCF ₂ CF ₂ −
_{CF 3 CF 2 CF 2 OCF (} CF 3) -,
_{CF 3 CF 2 CF 2 OCF (} CF 3) CF 2 -,
_{CF 3 CF 2 CF 2 OCF (} CF 3) CF 2 OCF 2 CF 2 -,
_{CF 3 CF 2 CF 2 OCF (} CF 3) CF 2 OCF (CF 3) CF 2 -,
CF ₃ CF ₂ CF ₂ O [CF (CF ₃ ) CF ₂ O] _z1 CF (CF ₃ ) −

In General Formula (19), Rf ₈ represents a linear or branched divalent perfluoroalkyl group having 1 to 100 carbon atoms which may contain an etheric oxygen atom.
Specific examples and preferred ranges of Rf ₉ are the same as those of Rf ₅ in the general formula (13).

  The compound represented by the general formula (12) or (13) preferably has a fluorine atom content of 30% by mass or more and 75% by mass or less, more preferably 32% by mass from the viewpoint of refractive index and curability. It is 67 mass% or less, More preferably, it is 33 mass% or more and 60 mass% or less.

  Although the specific example of a compound represented by General formula (12) or (13) below is given, this invention is not limited by these. Z in the following specific example compounds represents an integer of 0 to 20, and p and q each independently represents an integer of 1 to 40.

  Among the above specific examples, FA-1, FA-2, FA-3, FA-7, FA-8, FA-10, FA-12, FA-13, FA-14, FA-16, FA-17. , FA-20, FA-21, FA-26, FA-27, FA-28, FE-1, FE-4, FE-7, FE-8, FE-10, FE-12, FE-13, FE -14, FE-16, FE-17, FE-20, FE-21, FE-26, FE-27, FE-28 are preferred, FA-1, FA-2, FA-8, FA-14, FA -17, FA-21, FA-26, FA-28, FE-1, FE-8, FE-14, FE-17, FE-21, FE-26, and FE-28 are more preferred, FA-1. FA-2, FA-8, FA-14, FA-26, FE-1, FE-8, FE-14, FE More preferably 26, FA-1, FA-2, FE-1 is most preferred.

  The compound represented by the general formula (12) or (13) may be obtained commercially or may be produced by synthesis. In the case of synthesis, there is no particular limitation on the synthesis method, and it is known by a known method, for example, a method by dehydration condensation of a commercially available fluorinated alcohol compound and acrylic acid, or a substitution reaction with epichlorohydrin. Can be synthesized.

  The fluorine-containing compound represented by the general formula (12) or (13) contained in the optical resin composition of the present invention may be only one type or two or more types.

<Optical resin composition>
The optical resin composition of the present invention contains at least one fluorine-containing compound represented by the above general formula (1) and a fluorine-containing compound represented by the above general formula (12) or (13). .
The optical resin composition of the present invention is represented by the fluorine-containing compound represented by the general formula (1) having a perfluoroalkyl group or a polyfluoroalkyl group as a main part, and the general formula (12) or (13). A composition containing a fluorine-containing compound as a main component.
Since the fluorine-containing compound contained in the optical resin composition of the present invention has a high fluorine content, it forms a cured product having a low refractive index.
In the optical resin composition of the present invention, since the proportion of the partial structure other than the perfluoroalkyl group or the polyfluoroalkyl group is low in light resistance and / or heat resistance colorability, the optical resin composition has a low light resistance and heat resistance colorability. Forms an excellent cured product.
The optical resin composition of the present invention is a polyfunctional compound represented by the general formula (1) in which the monofunctional or low functional fluorine-containing compound represented by the general formula (12) or (13) has a high crosslinkable group density. By polymerizing together with the fluorine-containing compound, a cured product that is excellent in terms of hardness cross-linked in a network is formed. When the fluorine-containing compound represented by the general formula (1) is cured alone, the network-like cross-linking density becomes too high, resulting in optical anisotropy due to curing shrinkage, and as a result, Although the transparency is lowered, the optical anisotropy is achieved by appropriately reducing the crosslinking density and reducing the shrinkage of curing by curing together with the fluorine-containing compound represented by the general formula (12) or (13). This is considered to result in the formation of a cured product that is excellent in terms of transparency.

In the optical resin composition, the content of the fluorine-containing compound represented by the general formula (1) is from 0.01 to the total solid content of the optical resin composition from the viewpoint of a balance between hardness and transparency. It is preferably 90% by mass, more preferably 0.1 to 70% by mass, and further preferably 1 to 50% by mass.
Moreover, the fluorine-containing compound represented by General formula (12) or (13) is 10-99. With respect to the fluorine-containing compound represented by General formula (1) from a viewpoint of the balance of hardness and transparency. It is preferably 99% by mass, more preferably 30 to 99.9% by mass, and even more preferably 50 to 99% by mass.

  In the optical resin composition of the present invention, the content ratio of the fluorine-containing compound represented by the general formula (1) and the fluorine-containing compound represented by the general formula (12) or (13) is a mass ratio of ( The fluorine-containing compound represented by the general formula (1) / (the fluorine-containing compound represented by the general formula (12) or (13)) is preferably 0.0001 to 9, preferably 0.001 to 2. .33 is more preferable, and 0.01 to 1 is still more preferable. When the ratio of (fluorine-containing compound represented by general formula (1)) / (fluorine-containing compound represented by general formula (12) or (13)) is 0.0001 or more, the crosslinking density is increased and curing is performed. It is preferable for the reason that the hardness of the product is increased, and is preferably 9 or less for the reason that the transparency of the cured product is increased by relaxation of the curing shrinkage.

  In the optical resin composition of the present invention, the fluorine-containing compound represented by the general formula (1) is a fluorine-containing compound represented by the general formula (17), and the general formula (12) or (13 ) Is preferably a fluorine-containing compound represented by the general formula (18) or (19).

  As the compound represented by the general formula (1), a fluorine-containing compound in which b in the general formula (1) is 0 (preferably MA30, MA31, MA32, MA33, MA35, MA36, MA37, MA38, ME29, ME30, ME31, ME32, ME33, ME35, ME36, ME37, ME39, and ME40, and most preferably, when MA31 and ME29 are used, the fluorine-containing compound represented by the general formula (12) or (13) is FA- 1, FA-2, FA-3, FA-7, FA-8, FA-10, FA-12, FA-13, FA-14, FA-16, FA-17, FA-20, FA-21, FA-26, FA-27, FA-28, FE-1, FE-4, FE-7, FE-8, FE-10, FE-12, FE-13, FE-14, FE-16, F -17, FE-20, FE-21, FE-26, FE-27, and FE-28 are preferable, and FA-1, FA-2, FA-14, FA-21, FE-1, and FE-14 are particularly preferable. In this embodiment, (the fluorine-containing compound represented by the general formula (1)) / (the fluorine-containing compound represented by the general formula (12) or (13)) is 0.0001 to 2 in mass ratio. Is preferable, 0.01-1 is more preferable, and 0.01-0.9 is still more preferable.

  As the compound represented by the general formula (1), a fluorine-containing compound in which b in the general formula (1) is 1 to 3 (preferably MA1, MA2, MA3, MA4, MA5, MA6, MA7, MA9, MA12 , MA13, MA14, MA17, MA23, MA24, ME1, ME2, ME3, ME4, ME5, ME6, ME7, ME12, ME13, ME14, ME17, ME23, ME24, most preferably MA1, MA6, ME1, ME6 were used. In this case, as the fluorine-containing compound represented by the general formula (12) or (13), FA-1, FA-2, FA-3, FA-7, FA-8, FA-10, FA-12, FA -13, FA-14, FA-16, FA-17, FA-20, FA-21, FA-26, FA-27, FA-28, FE-1, FE-4, FE-7, E-8, FE-10, FE-12, FE-13, FE-14, FE-16, FE-17, FE-20, FE-21, FE-26, FE-27, and FE-28 are preferred, FA-1, FA-2, FA-14, FE-1, FE-14, and FE-26 are particularly preferable.In this embodiment, (fluorinated compound represented by general formula (1)) / (general formula ( 12) or the fluorine-containing compound represented by (13)) is preferably from 0.001 to 9, more preferably from 0.01 to 2.33, and more preferably from 0.05 to 1 in terms of mass ratio. More preferably.

<Non-fluorine compound>
The optical resin composition of the present invention preferably further contains a non-fluorine compound represented by the following general formula (16) from the viewpoint of adjusting the refractive index of the cured product and promoting the curing.

In general formula (16), j represents an integer of 1 to 6, and Y represents a group represented by the following general formula (21), (3), (4) or (5), an allyl group, or a vinyl group. L ₅ represents a group represented by the following general formula (6), (7), (14) or (15), and R ₇ has 1 to 1 carbon atoms which may have a hydrogen atom or a substituent. 20 linear, branched or cyclic j-valent organic groups are represented.

In General Formula (21), X ¹ represents a hydrogen atom, a chlorine atom, a methyl group, a trifluoromethyl group, or a hydroxyl group.
In the general formulas (3), (4) and (5), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a carbon atom which may have a hydrogen atom or a substituent. A linear or branched monovalent alkyl group having a number of 1 to 5 is represented.
In general formula (5), k represents 1 or 2.
In general formulas (6), (7), and (14), m represents an integer of 0 to 10.
In the general formulas (7) and (15), Y represents a group represented by the general formula (21), (3), (4) or (5), an allyl group, or a vinyl group.

  In general formula (16), j represents the integer of 1-6. j is preferably an integer of 1 to 4. When j is 1 or 2, the refractive index of the cured product can be adjusted by adjusting the content ratio of the non-fluorine compound represented by the general formula (16). When j is 3 or 4, the content ratio It is possible to increase the hardness of the cured product by adjusting.

  In the general formula (16), Y represents a group represented by the above general formula (21), (3), (4) or (5), an allyl group, or a vinyl group.

In general formula (21), X ¹ is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

  General formula (3)-(5) is synonymous with general formula (3)-(5) which Y in General formula (1) can take.

  Y in the general formula (16) is preferably a group represented by the general formula (21) or the general formula (3) from the viewpoint of material availability.

In General Formula (16), L ₅ has the same meaning as L ₄ in General Formula (12), and preferred groups are also the same.

In General Formula (16), R ₇ represents a hydrogen atom or a linear, branched or cyclic j-valent organic group having 1 to 20 carbon atoms which may have a substituent. The organic group is not particularly limited, and examples thereof include a linear or branched alkyl group, a skeleton obtained by removing a hydroxyl group from dipentaerythritol, pentaerythritol, and ditrimethylolpropane. Examples of the substituent when the organic group has a substituent include an alkyl group, a hydroxyl group, and a chlorine atom.

  Specific examples of the non-fluorine compound represented by the general formula (16) include methyl (meth) acrylate, ethyl (meth) acrylate, diethylene glycol di (meth) acrylate, glycidyl methyl ether, glycidyl phenyl ether, diethylene glycol. Diglycidyl ether, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra A glycidyl ether etc. are mentioned.

  It is preferable to contain 1-30 mass% of non-fluorine compounds represented by the said General formula (16) with respect to the fluorine-containing compound represented by General formula (1) from a viewpoint of refractive index.

<Polymerization initiator>
The optical resin composition of the present invention preferably further contains a polymerization initiator. Examples of the polymerization initiator include a thermal polymerization initiator that initiates polymerization by heat and a photopolymerization initiator that initiates polymerization by light. The polymerization initiator to be used is not particularly limited, but is preferably a radical photopolymerization initiator, a cationic photopolymerization initiator, or a thermal radical polymerization initiator.

Photoinitiators include photoradical polymerization initiators that initiate light polymerization by generating radicals by absorbing light, and photocationic polymerization initiators that initiate polymerization reaction by absorbing light and generating cations. There is an agent.
Examples of the radical photopolymerization initiator include 2-hydroxy-2-methyl-1-phenylpropan-1-one (manufactured by BASF Japan Ltd., Darocur 1173), 1-hydroxycyclohexyl phenyl ketone (BASF Japan Ltd.). Irgacure 184), benzyl dimethyl ketal (Irgacure 651, manufactured by BASF Japan Ltd.), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (BASF Japan) (Irgacure 907), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (BASF Japan, Irgacure 369), 2,4-diethyl Preferred example of thioxanthone (Nippon Kayaku Co., Ltd., Kayacure DETX) It is possible to mention to.
The cationic photopolymerization initiator, for example, ^{_{[CH 3 -ph-I + -ph}} -CH- (CH 3) 2] [PF 6 -] ( although, ph represents a 1,4-phenylene group) is preferred, ^{_{[CH 3 -ph-I + -ph}} -CH- (CH 3) 2] [PF 6 -] ( although, ph is a 1,4-phenylene group show a) 3 propylene carbonate: a mixture of 1 (BASF Japan An example is Irgacure 250 manufactured by Co., Ltd. Other preferred examples include dimethyl-4-methylphenylsulfonium trifluoromethanesulfonate (manufactured by Wako Pure Chemical Industries, Ltd., WPAG-336).
As a photocationic polymerization initiator, a sulfonium salt compound or an iodonium salt compound is preferable.
As the thermal polymerization initiator, an organic or inorganic peroxide thermal polymerization initiator or an azo compound thermal polymerization initiator is preferably used.
Examples of organic oxide thermal polymerization initiators include ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, acetylacetone peroxide, cyclohexanone peroxide, and methylcyclohexanone peroxide; 1,1,3,3-tetramethyl Hydroperoxides such as butyl hydroperoxide, cumene hydroperoxide and t-butyl hydroperoxide; diisobutyryl peroxide, bis-3,5,5-trimethylhexanol peroxide, lauroyl peroxide, benzoyl peroxide and m -Diacyl peroxides such as toluylbenzoyl peroxide; dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butyl peroxide) Oxy) hexane, 1,3-bis (t-butylperoxyisopropyl) hexane, t-butylcumyl peroxide, di-t-butyl peroxide and 2,5-dimethyl-2,5-di (t-butylperoxy) Dialkyl peroxides such as hexene; 1,1-di (t-butylperoxy-3,5,5-trimethyl) cyclohexane, 1,1-di-t-butylperoxycyclohexane and 2,2-di (t-butyl) Peroxyketals such as peroxy) butane; 1,1,3,3-tetramethylbutylperoxyneodicarbonate, α-cumylperoxyneodicarbonate, t-butylperoxyneodicarbonate, t-hexylperoxypivalate, t-butyl Peroxypivalate, 1,1,3,3-tetramethylbut Tylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, di-t-butylperoxyhexahydro Terephthalate, 1,1,3,3-tetramethylbutylperoxy-3,5,5-trimethylhexanate, t-amylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-3,5 Alkyl peresters such as 5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate and dibutylperoxytrimethyladipate; di-3-methoxybutylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, bis ( , 1-butylcyclohexaoxydicarbonate), diisopropyloxydicarbonate, t-amylperoxyisopropyl carbonate, t-butylperoxyisopropyl carbonate, t-butylperoxy-2-ethylhexyl carbonate and 1,6-bis (t-butylperoxy) Preferred examples include peroxycarbonates such as carboxy) hexane; 1,1-bis (t-hexylperoxy) cyclohexane and (4-t-butylcyclohexyl) peroxydicarbonate.
As the azo compound thermal polymerization initiator, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile) ), 1,1′-azobis-1-cyclohexanecarbonitrile, dimethyl-2,2′-azobisisobutyrate, 4,4′-azobis-4-cyanovaleric acid, 2,2′-azobis- ( 2-Amidinopropane) dihydrochloride (see JP 2010-189471 A) and the like can be given as preferred examples.
These may be used alone or in combination of two or more. 0.1-50 mass% is preferable with respect to the total amount of the polymeric compound in the optical resin composition, and, as for the quantity of a photoinitiator, 1-10 mass% is more preferable.

<Solvent>
The optical resin composition of the present invention preferably does not contain a solvent, but may contain a solvent in order to improve moldability and coatability. Solvents include ketones such as acetone and 2-butanone, alcohols such as methanol, ethanol and isopropanol; esters such as ethyl acetate and butyl acetate; hydrocarbons such as hexane, nonafluorobutyl methyl ether (Sumitomo 3M ( Fluorine-containing compounds such as Nobec HFE-7100), dichloropentafluoropropane (Asahi Glass Co., Ltd., Asahi Clin AK-225; a mixture of CF ₃ CF ₂ CHCl ₂ and CClF ₂ CF ₂ CHClF) Is preferred. These may be used alone or in combination of two or more. The solid content concentration in the solution is preferably 0.01 to 50% by mass, more preferably 0.1 to 10% by mass.

  Other optical resin compositions include photosensitizers, polymerization inhibitors, phosphors, light stabilizers, heat stabilizers, antioxidants, resins, resins having functional groups, resin oligomers, metal particles, inorganics. Particles, particulate organic matter, fibrous matter and the like may be included.

<Hardened product and optical component>
The optical resin composition of the present invention can be cured to form a cured product.
The cured product obtained by curing the optical resin composition of the present invention has a low refractive index, is excellent in terms of hardness, light resistance, and heat-resistant colorability, and is excellent in terms of transparency, and thus is suitable as an optical component. .
The cured product obtained by curing the optical resin composition of the present invention preferably has a refractive index of 1.35 or more and less than 1.45, and more preferably 1.37 or more and less than 1.44.

  The optical resin composition of the present invention can be made into a cured product by being cured after being poured into a mold to be molded or formed into a desired shape by coating on a substrate.

The molding method of the cured product is not particularly limited, such as potting (dispensing), printing, coating, injection molding, blow molding, press molding, transfer molding, and insert molding.
When coating on a base material, it is preferable to dry after coating on the base material. As a coating method, methods such as spin coating, dip coating, wire bar coating, blade coating, and roll coating can be employed. The application is preferably performed at room temperature or under heating. Moreover, it is preferable that the base material after application | coating is dried in air | atmosphere or nitrogen stream. The drying is preferably performed at room temperature. When drying is performed under heating, it is preferable to appropriately change the temperature and time depending on the heat resistance of the base material.
When a flexible substrate such as a plastic substrate is used as a base material, an exposure machine is installed between a plurality of rolls installed so that a roll-to-roll method (Roll to Roll method) can be performed, and a plurality of rolls. By performing light irradiation on the substrate, a treated substrate can be obtained with high throughput.

As a curing method, for example, photocuring, thermal curing, or a combination of photocuring and thermal curing can be performed.
In the case of photocuring, it is preferable to irradiate a part or all of the surface of the resin composition coated on the mold or injected onto the substrate. The light used for light irradiation is preferably light having a wavelength of 200 nm or more, and more preferably light having a wavelength of 300 nm or more. Moreover, light with a wavelength of 380 nm or less is preferable, and light with a wavelength of 365 nm or less is more preferable. Light having a wavelength of 200 nm or more has an advantage that there is little possibility of decomposing the substrate. Moreover, the photoinitiator which starts superposition | polymerization by light irradiation with a wavelength of 380 nm or less is easy to obtain, and a light source is also cheap. The irradiation time can be appropriately changed according to the wavelength of light, the intensity of light, the type of light source, the type of composition, the content of the polymerization initiator, and the like. In the case of an ultra high pressure mercury lamp, irradiation may be performed at ² to 100 mW / cm ² for 5 to 360 seconds. In general, in the case of a high-pressure mercury lamp, irradiation can be performed in a shorter time than an ultra-high pressure mercury lamp.

  Light sources include low-pressure mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, xenon lamps, sodium lamps, gas lasers such as nitrogen, liquid lasers of organic dye solutions, solid-state lasers containing rare earth ions in inorganic single crystals, etc. Can be mentioned. Further, as a light source other than the laser from which monochromatic light is obtained, light having a specific wavelength obtained by extracting a broadband line spectrum or continuous spectrum using an optical filter such as a bandpass filter or a cutoff filter may be used. When irradiating a large area at once, a high pressure mercury lamp or an ultra high pressure mercury lamp is preferable as the light source.

For UV irradiation dose as the amount of light, usually 100~5000mJ / cm ² or so, preferably 1000~4000mJ / cm ^2.

  The atmosphere for light irradiation can be arbitrarily selected. For example, in order to avoid curing inhibition due to oxygen, light irradiation can be performed in an inert gas atmosphere such as a nitrogen gas atmosphere. Examples of the inert gas include a gas selected from nitrogen, argon, helium, carbon dioxide, and the like, and nitrogen gas is most preferable because it can be obtained at a low cost.

In the case of thermosetting, the curing temperature is usually about 50 to 200 ° C, preferably 100 to 180 ° C.
Setting it to 50 ° C. or higher does not cause curing failure, and setting it to 200 ° C. or less prevents coloring and the like from occurring.
The curing time varies depending on the fluorine-containing compound and polymerization initiator used, but is preferably 0.01 to 6 hours.
Post-heating may be performed after the light irradiation, and it is preferably performed at 70 to 200 ° C. for 0.01 to 12 hours.

  The cured product obtained by curing the resin composition of the present invention is excellent in heat resistance and transparency, and the total light transmittance is preferably 85% or more, more preferably 90% or more.

  The kind of the optical component of the present invention is not particularly limited. In particular, it can be suitably used as an optical component utilizing the excellent optical properties of the cured resin composition, particularly as an optical component that transmits light (so-called passive optical component). Examples of the optical functional device provided with such an optical component include optical semiconductors (LEDs, etc.), flat panel displays (organic EL elements, etc.), electronic circuits, resins for optical circuits (optical waveguides) (sealing agents, adhesives). , Clad / core material), optical communication members such as optical communication lenses and optical films. In particular, it is suitable for a sealing agent for semiconductor light emitting devices (LED, etc.), an optical lens, an optical adhesive, an optical sealing agent, and an optical waveguide.

  For this reason, the resin composition of the present invention is a semiconductor element / integrated circuit (IC, etc.), an individual semiconductor (diode, transistor, thermistor, etc.), LED (LED lamp, chip LED, light receiving element, optical semiconductor lens), Sensors (temperature sensors, optical sensors, magnetic sensors), passive components (high-frequency devices, resistors, capacitors, etc.), mechanical components (connectors, switches, relays, etc.), automotive components (circuit systems, control systems, sensors, lamp seals) Etc.), adhesives (optical components, optical discs, pickup lenses), etc., and also for optical films and the like for surface coating.

The structure as a sealant for optical semiconductors (LEDs, etc.) can be applied to a device such as a shell type or surface mount (SMT) type, and is in good contact with a semiconductor such as GaN formed on a metal or polyamide. It can also be used by dispersing a fluorescent dye such as YAG.
Further, it can be used for a surface coating agent of a bullet type LED, a lens of an SMT type LED, and the like.
The organic EL device has a structure in which an anode / hole injection layer / light emitting layer / electron injection layer / cathode are sequentially provided on a transparent substrate such as general glass or transparent resin. It can be applied to an EL element.
In order to provide gas barrier properties to an adhesive for covering a resin film coated with a metal can, a metal sheet, or SiN as an organic EL element sealing material, or to the resin composition of the present invention It is also possible to directly seal the EL element by dispersing an inorganic filler or the like.
As a display method, it can be applied to the mainstream bottom emission type at present. The effect of heat resistance and heat can be utilized.
The configuration used in an optical circuit can be applied to a single-mode or multi-mode thermo-optic switch, arrayed waveguide grating, multiplexer / demultiplexer, wavelength tunable filter, or optical fiber core material or cladding material.
Further, the present invention can be applied to a microlens array for condensing light in a waveguide or a mirror of a MEMS type optical switch.
Moreover, it is applicable also to the pigment | dye binder etc. of a photoelectric conversion element.

  The optical component using the cured product of the present invention is suitably used for a lens substrate. The lens substrate manufactured using the method for manufacturing a semi-cured product and the method for manufacturing a cured product of the present invention preferably has a low refractive index, and has both transparency, heat-resistant coloring property, and light weight, and optical characteristics. Is excellent. Moreover, it is possible to arbitrarily adjust the refractive index of the lens substrate by appropriately adjusting the type of the fluorine-containing compound and / or the non-fluorine compound constituting the optical resin composition.

  When the lens substrate is used as a lens, the lens substrate itself may be used alone as a lens, or may be used as a lens with a film or a frame added thereto. The type and shape of the lens using the lens substrate are not particularly limited. The lens substrate is, for example, a spectacle lens, an optical device lens, an optoelectronic lens, a laser lens, a pickup lens, an in-vehicle camera lens, a portable camera lens, a digital camera lens, an OHP lens, or a microlens. It is used for an array, and a wafer level lens array (Japanese Patent No. 3926380, International Publication No. 2008/102648, Japanese Patent No. 4226061, Japanese Patent No. 4226067, etc.).

  Examples that specifically illustrate the present invention are given below, but the present invention is not limited thereto.

[Synthesis Example 1] Synthesis of Compound MA1

(Synthesis Example 1-1) Synthesis of Compound MA1-A Compound (MA1-A) was synthesized with reference to a method described in non-patent literature (J. Org. Chem. Vol. 55, 1990, page 6368). .
In a reactor equipped with a distiller, 136 g (1.00 mol) of pentaerythritol (manufactured by Wako Pure Chemical Industries, Ltd.), 100 mL of toluene, triethyl orthoformate (manufactured by Wako Pure Chemical Industries, Ltd.) 183 mL (1.00 mol) ), Taking 0.50 g of p-toluenesulfonic acid monohydrate, gradually raising the reactor temperature to 100 ° C. while removing the distilled ethanol, allowing the reaction to proceed for 12 hours, and further reacting at 125 ° C. for 1 hour. It was. After completion of the reaction, low-boiling components were distilled off under reduced pressure at 50 ° C., and the resulting product was dried to obtain a white solid.
To the reactor, 26.4 g (0.470 mol) of potassium hydroxide and 160 mL of dimethyl sulfoxide were added, and 16.0 g (0.100 mol) of the white solid was added while stirring at room temperature, and then 20.0 g of 1-bromohexane ( 0.121 mol) was added and allowed to react for 30 minutes. The reaction solution was added to 1.5 L of water, and this was extracted twice with 200 mL of ethyl acetate. The obtained organic layer was washed with water and dried, and then the low boiling point product was distilled off to obtain a white solid.
This white solid was dissolved in 70 mL of methanol, and then added with 250 mL of 0.01 mol / L hydrochloric acid, reacted at room temperature for 2 hours, and then added with 9.3 g of sodium bicarbonate and stirred at room temperature for 1 hour. After distilling off the solvent under reduced pressure from the obtained reaction liquid, 125 mL of methanol was added and stirred for 12 hours, then insoluble matters were filtered off, and the solvent was distilled off from the obtained filtrate to obtain colorless oily compound MA1. -A was obtained. Yield 18.5 g (83% yield).

(Synthesis example 1-2) Synthesis | combination of compound MA1-B Compound MA1-B was synthesize | combined with reference to the method as described in a patent document (Unexamined-Japanese-Patent No. 2009-149595).
In 40 mL of toluene, 17.6 g (0.080 mol) of the compound MA1-A, 13.4 g of 40 wt% potassium hydroxide aqueous solution, and 0.10 g of benzyltrimethylammonium chloride are taken and stirred at 15 to 20 ° C. while stirring in a water bath. Acrylonitrile (13.2 g, 0.249 mol) was added dropwise over 3 hours. 50 mL of toluene was added to the pale yellow reaction liquid and the phases were separated, and the resulting organic layer was washed with 5 wt% saline, dilute hydrochloric acid, and further 5 wt% saline. After drying over sodium sulfate, the solid was filtered and the solvent was distilled off under reduced pressure to obtain pale yellow oily compound MA1-B. Yield 28.5 g (94% yield).

(Synthesis Example 1-3) Synthesis of Compound MA1-C Compound MA1-C was synthesized with reference to a method described in non-patent literature (J. Fluorine Chem., 2004, No. 125, page 749).
25.0 g (0.066 mol) of the compound MA1-B was added to 125 mL of dehydrated methanol. While stirring at room temperature, hydrogen chloride gas was slowly poured to saturation, and the reaction was continued for 6 hours under heating and refluxing conditions while circulating chlorine gas. After circulating nitrogen gas, the solvent was distilled off, and the residue was dissolved in 200 mL of ethyl acetate and washed with saturated aqueous sodium hydrogen carbonate, water, and saturated brine. After drying over sodium sulfate, the solid was filtered and the solvent was distilled off under reduced pressure to obtain pale yellow oily compound MA1-B. Further purification by column chromatography (developing solvent: hexane / ethyl acetate = 5/1 to 1/1) gave colorless oily compound MA1-C. Yield 24.3 g (77% yield).

(Synthesis example 1-4) Synthesis | combination of compound MA1-D Cyclopentyl methyl ether 150mL, ethanol 20mL, MA1-C 20.0g (0.042mol) is taken, sodium borohydride 5.7g is added to this, and it is in an ice-water bath. While stirring, the solution of calcium chloride dihydrate 16.5g in 70 mL of ethanol was slowly added dropwise and allowed to stir for 1 hour. The mixture was heated to 50 ° C., then 17.7 mL of concentrated hydrochloric acid was added and stirred for 1 hour, and further neutralized with an aqueous sodium hydroxide solution, and the resulting solid was filtered off. After the solvent was distilled off from the obtained filtrate, 100 mL of methanol was added to the residue, and then the solvent was distilled off again to obtain colorless oily compound MA1-D. Yield 16.3 g (99% yield). This was purified by column chromatography and used in the next step.

(Synthesis Example 1-5) Synthesis of Compound MA1-E 16.3 g (0.041 mol) of MA1-D and 14.8 mL of pyridine were added to 200 mL of ethyl acetate, and H (CF ₂ ) ₆ COCl 66 was stirred at room temperature. 0.7 g (0.137 mol, manufactured by Daikin Industries, Ltd.) was added and stirred for 4 hours. Hexane 100mL was added to this, and it wash | cleaned by dilute hydrochloric acid, salt solution, sodium hydrogen carbonate solution, and also salt solution. After drying over sodium sulfate, the solid was filtered and the solvent was removed in vacuo to give colorless oily compound MA1-E. Yield 51.3 g (90% yield).

(Synthesis example 1-6) The synthesis | combination of compound MA1-F The process of compound MA1-F-compound MA1 was synthesize | combined with reference to the method as described in a patent document (Unexamined-Japanese-Patent No. 2010-53084).
In a 500 mL fluororesin container equipped with a raw material supply port, a fluorine supply port, a helium gas supply port and an exhaust port connected to a fluorine trap via a reflux device cooled with dry ice, 300 mL of FC-72 solvent (Sumitomo 30.6) and 70.6 g of sodium fluoride were taken, and helium gas was blown at an internal temperature of 10 ° C. at a flow rate of 100 mL / min for 30 minutes. Next, 20% F ₂ /80% N ₂ mixed gas (fluorine gas) was blown in at a flow rate of 100 mL / min for 30 minutes, and then the fluorine gas flow rate was increased to 250 mL / min and the compound MA1-E 27.6 g ( 0.020 mol) and 4.0 g (0.021 mol) of hexafluorobenzene were added at an internal temperature of 10 to 15 ° C. over 8.5 hours. The flow rate of fluorine gas was reduced to 100 mL / min, a solution of 2.0 g of hexafluorobenzene in 5 mL of FC-72 was added over 1 hour, and fluorine gas was further circulated at 100 mL / min for 15 minutes. After replacing the inside of the reaction vessel with helium gas, the solid was filtered off. The obtained filtrate was added to a methanol 100 mL dispersion of 20 g of sodium fluoride and stirred at room temperature for 1 hour, and then the solvent was distilled off under reduced pressure. To the residue, 100 mL of HFE-7100 (manufactured by Sumitomo 3M Limited) was added and dissolved, and washed with aqueous sodium bicarbonate. After drying over magnesium sulfate, the solid was filtered off and the solvent was distilled off. The obtained residue was distilled under reduced pressure to obtain colorless oily compound MA1-F. Yield 13.9 g (65% yield).

(Synthesis Example 1-7) Synthesis of Compound MA1-G In an ice-water bath, 2.7 g (0.071 mol) of sodium borohydride was added to 120 mL of anhydrous THF and stirred in a nitrogen atmosphere. While adjusting at an internal temperature of 10 to 20 ° C., a solution of 20.4 g (0.019 mol) of compound MA1-F in 30 mL of anhydrous THF was added dropwise and stirred as it was for 1 hour, and further stirred at room temperature for 3 hours. 25 mL of 3 mol / L hydrochloric acid was added to bring the pH to 1, followed by stirring for 1 hour. Next, 60 mL of saturated brine and 60 mL of ethyl acetate were added, and the separated organic layer was washed with aqueous sodium bicarbonate and brine, dried over magnesium sulfate, the solid was filtered off, and the solvent was distilled off to remove colorless oil. Compound MA1-G was obtained. Yield 18.0 g (96% yield). This was purified by column chromatography and used in the next step.

(Synthesis Example 1-8) Synthesis of Compound MA1 To 500 mL of acetonitrile, 88.9 g (0.090 mol) of Compound MA1-G and 186.3 g of potassium carbonate were taken, and 60.8 g (0 .672 mol) was added dropwise and then allowed to stir at room temperature for 5 hours. 120 mL of ethyl acetate and 120 mL of hexane were added to the reaction solution, and 135 mL of 64 wt% sulfuric acid was added dropwise at an internal temperature of 10 ° C. or lower, and the precipitated solid was separated by filtration. The obtained filtrate was washed with brine, aqueous sodium bicarbonate, and saturated brine, and then the solvent was distilled off to obtain a crude product. This was purified by column chromatography (developing solvent: hexane / ethyl acetate = 6/1 to 3/1) to obtain colorless oily compound MA1. Yield 56.9 g (55% yield).

[Synthesis Example 2] Synthesis of Compound MA6

(Synthesis Example 2-1) Synthesis of Compound MA6-A Compound (MA6-A) was synthesized with reference to the method described in non-patent literature (J. Org. Chem. 55, 1990, 6368). .
In a reactor equipped with a distiller, 136 g (1.00 mol) of pentaerythritol (manufactured by Wako Pure Chemical Industries, Ltd.), 100 mL of toluene, triethyl orthoformate (manufactured by Wako Pure Chemical Industries, Ltd.) 183 mL (1.00 mol) ), Taking 0.50 g of p-toluenesulfonic acid monohydrate, gradually raising the reactor temperature to 100 ° C. while removing the distilled ethanol, allowing the reaction to proceed for 12 hours, and further reacting at 125 ° C. for 1 hour. It was. After completion of the reaction, low-boiling components were distilled off under reduced pressure at 50 ° C., and the resulting product was dried to obtain a white solid.
To the reactor, 26.4 g (0.470 mol) of potassium hydroxide and 160 mL of dimethyl sulfoxide were added, and 16.0 g (0.100 mol) of the white solid was added while stirring in an ice-water bath, and then trifluoromethanesulfonic acid-1 88.4 g (0.130 mol) of-(1H, 1H-perfluoro-3,6,9-trioxatridecyl) was added and allowed to react for 30 minutes. The reaction solution was added to 1.5 L of water, and this was extracted twice with 200 mL of ethyl acetate. The obtained organic layer was washed with water and dried, and then the low boiling point was distilled off to obtain a slightly yellow oil. .
This oily substance was dispersed in 100 mL of methanol, 250 mL of 0.01 mol / L hydrochloric acid was added and reacted at room temperature for 2 hours, and then 9.3 g of sodium bicarbonate was added and stirred at room temperature for 1 hour. After the solvent was distilled off from the obtained reaction solution under reduced pressure, 125 mL of methanol was added and the mixture was stirred for 12 hours, then insoluble matter was filtered off, and the solvent was distilled off from the obtained filtrate to give a slightly yellow oil. Obtained. Further, this was purified by column chromatography to obtain a colorless oily compound ME6-A. Yield 36.0 g (54% yield).

(Synthesis Example 2-2) Synthesis of Compound MA6-G The step of synthesizing Compound MA6-B to Compound MA6 was performed in the same manner as in Synthesis Example 1 to obtain Compound MA6.

[Synthesis Example 3] Synthesis of Compound MA15

(Synthesis Example 3-1) Synthesis of Compound MA15-C MA15-C is a known method using 1,2,4,5-benzenetetracarboxylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) as a starting material. They were combined and synthesized according to the above synthesis route. MA15-C was purified by column chromatography and used in the next step.

(Synthesis Example 3-2) Synthesis of Compound MA15 The step of synthesizing Compound MA15 was performed in the same manner as in Synthesis Example 1 to obtain Compound MA15.

[Synthesis Example 4] Synthesis of Compound MA17

(Synthesis Example 4-1) Synthesis of Compound MA17-A 254 g (1.00 mol) of dipentaerythritol (manufactured by Wako Pure Chemical Industries, Ltd.), 200 mL of toluene, and 252 g of acetophenone were attached to a reactor equipped with a Dean-Stark distiller. (2.10 mol), taking 1.0 g of p-toluenesulfonic acid monohydrate, gradually raising the reactor temperature to reflux conditions until a defined amount of water is obtained in the Dean-Stark still The reaction was performed for 12 hours. After completion of the reaction, the low-boiling components were distilled off under reduced pressure, and the resulting product was dried to obtain a white solid.
To the reactor, 26.4 g (0.470 mol) of potassium hydroxide and 160 mL of dimethyl sulfoxide were added, and 45.9 g (0.100 mol) of the white solid was added while stirring in an ice-water bath, and then converted into methanesulfonic acid ester. Polyethylene glycol monomethyl ether (manufactured by Wako Pure Chemical Industries, Ltd., average molecular weight 350, average value of x = 7.6) 90.3 g (0.210 mol) was added and reacted as it was for 60 minutes. The reaction solution was added to 1.5 L of water, and this was extracted twice with 150 mL of ethyl acetate. The obtained organic layer was washed with water and dried, and then the low boiling point product was distilled off to obtain a slightly yellow oil. .
This oily substance was dispersed in 100 mL of methanol, 250 mL of 0.01 mol / L hydrochloric acid was added and reacted at room temperature for 2 hours, and then 9.3 g of sodium bicarbonate was added and stirred at room temperature for 1 hour. After the solvent was distilled off from the obtained reaction solution under reduced pressure, 125 mL of methanol was added and allowed to stir for 12 hours. Then, insoluble matters were filtered off, and the solvent was distilled off from the obtained filtrate to give a slightly yellow oily substance. Compound MA17-A was obtained. Yield 66.8 g (70% yield).

(Synthesis example 4-2) The synthesis | combination of compound MA17-C The process of synthesize | combining compound MA17-B and compound MA17-C was performed like the synthesis example 1, and compound MA17-C was obtained.

(Synthesis example 4-3) The synthesis | combination of compound MA17-D The process of compound MA17-D was synthesize | combined with reference to the method as described in a patent document (Unexamined-Japanese-Patent No. 2010-53084).
In a 300 mL fluororesin container equipped with a raw material supply port, a fluorine supply port, a helium gas supply port and an exhaust port connected to a fluorine trap via a reflux device cooled to 20 ° C., 200 mL of halocarbon 1.8 oil (Halocarbon Products Corporation) was taken, and helium gas was blown at an internal temperature of 30 ° C. at a flow rate of 100 mL / min for 30 minutes. Next, 20% F2 / 80% N2 mixed gas (fluorine gas) was blown in at a flow rate of 100 mL / min for 30 minutes, and then the fluorine gas flow rate was increased to 250 mL / min, and 16.0 g of compound MA17-C (0.0. 0124 mol), 0.80 g (0.043 mol) of hexafluorobenzene, and 30 mL of halocarbon 1.8 oil were added at an internal temperature of 30 to 40 ° C. over 20 hours. The fluorine gas flow rate was lowered to 100 mL / min, a 1.0 mL halocarbon 1.8 oil 5 mL solution of hexafluorobenzene was added over 1 hour, and fluorine gas was further circulated at 100 mL / min for 15 minutes. After replacing the inside of the reaction vessel with helium gas, the reaction solution was added to a methanol 100 mL dispersion of 20 g of sodium fluoride and stirred at room temperature for 1 hour, and then the solvent was distilled off under reduced pressure. To the residue, 100 mL of HFE-7100 (manufactured by Sumitomo 3M Co., Ltd.) was added and dissolved, washed with aqueous sodium bicarbonate, dried over magnesium sulfate, and then the solvent was distilled off. The obtained residue was distilled under reduced pressure to obtain colorless oily compound MA17-D. Yield 13.9 g (65% yield).

(Synthesis Example 4-4) Synthesis of Compound MA17 The step of synthesizing Compound MA17-D to Compound MA17 was performed in the same manner as in Synthesis Example 1 to obtain Compound MA17.

[Synthesis Example 5] Synthesis of Compound MA31

(Synthesis Example 5-1) Synthesis of Compound MA31-E The step of synthesizing Compound MA31-A to Compound MA31-E was performed in the same manner as in Synthesis Example 1 to obtain Compound MA31-E.

(Synthesis Example 5-2) Synthesis of Compound MA31 580 mL of THF was placed in a reactor, 20.7 g (0.548 mol) of sodium borohydride was added in an ice-water bath under a nitrogen atmosphere, and 140 mL of water was further added and stirred. It was. While adjusting the internal temperature at 10 to 20 ° C., a solution of compound MA31-D 100 g (0.110 mol) in THF 25 mL was added dropwise, and the mixture was stirred as it was for 30 minutes, and then stirred at 20 ° C. for 3 hours. After setting the internal temperature to 10 ° C., 120 mL of 6 mol / L hydrochloric acid was added to adjust the pH to 1, and then 250 mL of brine was added and stirred for 1 hour. Next, 280 mL of ethyl acetate was added, and the separated organic layer was washed 4 times with brine. This solution was directly used in the next step.
The organic layer, 500 mL of n-hexane, 50 g of pyridine, 170 mL of water, and 133 g of sodium bicarbonate were taken in the reactor and stirred in an ice-water bath. To this was added dropwise 160 g (1.26 mol) of 3-chloropropionic acid chloride over 1.5 hours, and the mixture was stirred as it was for 3.5 hours. After the internal temperature was raised to 25 ° C., 600 mL of 10% aqueous potassium carbonate solution was added. And stirred for 1 hour. The organic layer was separated from this, washed with 10% aqueous potassium carbonate solution, 2 mol / L hydrochloric acid, and further with brine, and dried over magnesium sulfate. This solution was directly used in the next step.
The organic layer, 0.05 g of 4-methoxyphenol, and 81.8 g (0.808 mol) of triethylamine were taken in a reactor and stirred at 50 ° C. for 4 hours. The mixture was allowed to cool to room temperature, washed with 400 mL of 2 mol / L hydrochloric acid, aqueous sodium hydrogen carbonate, and brine, dried over magnesium sulfate, added with 40 g of activated alumina, stirred for 30 minutes, and then the solid was filtered off. After adding 0.05 g of 4-methoxyphenol to the obtained filtrate, the solvent was distilled off to obtain compound MA31 as a slightly yellow oil. Yield 92.5 g (83% yield). This was purified by column chromatography and used for composition preparation.

[Synthesis Example 6] Synthesis of compounds MA33, MA34, MA35, MA36, and MA37

  Compounds MA33, MA34, and MA37 are dipentaerythritol (manufactured by Tokyo Chemical Industry Co., Ltd.), glycerol (manufactured by Wako Pure Chemical Industries, Ltd.), ditrimethylolpropane (manufactured by Sigma Aldrich Japan Co., Ltd.), respectively. As a starting material in the same manner as in Synthesis Example 5. Compounds MA35 and MA36 are respectively 1,3,5-benzenetricarboxylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) and 1,2,4,5-benzenetetracarboxylic acid (manufactured by Wako Pure Chemical Industries, Ltd.). ) Was used in the same manner as in Synthesis Example 3 and Synthesis Example 5.

[Synthesis Example 7] Synthesis of Compound ME1

(Synthesis example 7-1) Synthesis | combination of compound ME1-G The process of synthesize | combining compound ME1-A-compound ME1-G was performed like the synthesis example 1. FIG.

(Synthesis Example 7-2) Synthesis of Compound ME1 While taking 2.00 g (0.05 mol) of sodium hydroxide and 4.63 g (0.05 mol) of epichlorohydrin in a reactor, stirring at 50 ° C. in a nitrogen atmosphere. Then, 9.88 g (0.01 mol) of ME1-G was slowly added and allowed to stir for 3 hours. After allowing to cool to room temperature, the precipitated solid was filtered off, and low-boiling substances were distilled off under reduced pressure. Then, 200 mL of ethyl acetate and 100 mL of water were added for liquid separation, and the resulting organic layer was dried over sodium sulfate. And the solvent was distilled off to obtain the crude product. This was purified by column chromatography to obtain a colorless oily compound ME1. Yield 4.05 g (41% yield).

[Synthesis Example 8] Synthesis of Compound ME6

Synthesis Example 8-1 Synthesis of Compound ME6-A

The compound (ME6-A) was synthesized with reference to the method described in non-patent literature (J. Org. Chem. Vol. 55, 1990, page 6368).

In a reactor equipped with a distiller, 136 g (1.00 mol) of pentaerythritol (manufactured by Wako Pure Chemical Industries, Ltd.), 100 mL of toluene, triethyl orthoformate (manufactured by Wako Pure Chemical Industries, Ltd.) 183 mL (1.00 mol) ), Taking 0.50 g of p-toluenesulfonic acid monohydrate, gradually raising the reactor temperature to 100 ° C. while removing the distilled ethanol, allowing the reaction to proceed for 12 hours, and further reacting at 125 ° C. for 1 hour. It was. After completion of the reaction, low-boiling components were distilled off under reduced pressure at 50 ° C., and the resulting product was dried to obtain a white solid.
To the reactor, 26.4 g (0.470 mol) of potassium hydroxide and 160 mL of dimethyl sulfoxide were added, and 16.0 g (0.100 mol) of the white solid was added while stirring in an ice-water bath, and then trifluoromethanesulfonic acid-1 88.4 g (0.130 mol) of-(1H, 1H-perfluoro-3,6,9-trioxatridecyl) was added and allowed to react for 30 minutes. The reaction solution was added to 1.5 L of water, and this was extracted twice with 200 mL of ethyl acetate. The obtained organic layer was washed with water and dried, and then the low boiling point was distilled off to obtain a slightly yellow oil. .
This oily substance was dispersed in 100 mL of methanol, 250 mL of 0.01 mol / L hydrochloric acid was added and reacted at room temperature for 2 hours, and then 9.3 g of sodium bicarbonate was added and stirred at room temperature for 1 hour. After the solvent was distilled off from the obtained reaction solution under reduced pressure, 125 mL of methanol was added and the mixture was stirred for 12 hours, then insoluble matter was filtered off, and the solvent was distilled off from the obtained filtrate to give a slightly yellow oil. Obtained. Further, this was purified by column chromatography to obtain a colorless oily compound ME6-A. Yield 36.0 g (54% yield).

(Synthesis Example 8-2) Synthesis of Compound ME6-G The steps of synthesizing Compound ME6-B to Compound ME6-G were performed in the same manner as in Synthesis Example 1.

(Synthesis Example 8-3) Synthesis of Compound ME6 The step of synthesizing Compound ME6 was performed in the same manner as in Synthesis Example 6-2. The obtained product was purified by column chromatography and used for composition preparation.

[Synthesis Example 9] Synthesis of Compound ME31

(Synthesis Example 9-1) Synthesis of Compound ME31-F The steps of synthesizing Compound ME31-A to Compound ME31-F were performed in the same manner as in Synthesis Example 4.

(Synthesis Example 9-2) Synthesis of Compound ME31 The step of synthesizing Compound ME31 was performed in the same manner as Synthesis Example 6-2. The obtained product was purified by column chromatography and used for composition preparation.

<Preparation of optical resin composition>
[Examples 1 to 20, Comparative Examples 1 to 6]
In a sample bottle, the fluorine-containing compound represented by the general formula (1), the fluorine-containing compound represented by the general formula (12) or (13), and a photopolymerization initiator are taken, and the general formula (16 ) Was added, and the mixture was sufficiently stirred to obtain a uniform solution. Tables 1 to 3 show a list of the prepared optical resin compositions.
Polymerization initiator A: IRGACURE184, manufactured by BASF Japan Ltd.
Polymerization initiator B: WPAG-336, manufactured by Wako Pure Chemical Industries, Ltd.
Polymerization initiator C: Perbutyl O, manufactured by NOF Corporation.
FA-1: acrylic acid-2,2,2-trifluoroethyl, manufactured by Kanto Chemical Co., Inc.
FA-2: Fluorester, manufactured by Tosoh F-Tech Co., Ltd.
FA-14: Acrylic acid-2- (perfluorohexyl) ethyl, manufactured by Daikin Industries, Ltd.
FA-21: CF ₃ CF ₂ CF ₂ O [CF (CF ₃ ) CF ₂ O] ₃ CF (CF ₃ ) CH ₂ OH (manufactured by Synquest Laboratories, Inc.) was acrylated according to a known method. A thing was used.
FA-26: HOCH ₂ (CF ₂ ) ₆ CH ₂ OH (manufactured by Daikin Industries, Ltd.) was used after acrylate formation according to a known method.
FA-28: Fluorolink D10-H (average molecular weight 700, fluorine atom content 61%, manufactured by Solvay Solexis) and acrylated according to a known method was used.
FE-14: 2- (perfluorohexyl) ethanol (manufactured by Daikin Industries, Ltd.) obtained by glycidyl etherification according to a known method was used.
_FE-26: HOCH ₂ a _{(CF 2) 6 CH 2 OH} ( Daikin Industries Co., Ltd.), was used as the glycidyl etherification according to known methods.
DPHA: dipentaerythritol hexaacrylate, manufactured by Daicel-Cytec Corporation.
MMA: methyl methacrylate, manufactured by Tokyo Chemical Industry Co., Ltd. DEDG: diethylene glycol diglycidyl ether, manufactured by Kyoeisha Chemical Co., Ltd.

[Comparative Examples 7 and 8]
Optical resin composition as in Examples 1 to 20, except that BPAF-GMA (Comparative Example 7) and BPAF-G (Comparative Example 8) were used instead of the compound represented by the general formula (1). Was prepared.
BPAF-GMA:

  BPAF-G:

<Production of cured product by photocuring>
The optical resin composition is poured into a transparent glass mold having a diameter of 10 mm and a thickness of 1 mm, and irradiated with 15 mW / cm ² of ultraviolet rays for 180 seconds using Execute 3000 (manufactured by HOYA Co., Ltd.). A 1 mm cured product was produced. The releasability from the glass mold of the cured product composed of the composition of the present invention, that is, ease of removal, is compared with a cured product composed of a non-fluorine compound, for example, a cured product composed of the composition of Comparative Example 1 or Comparative Example 5. And it was excellent.

<Production of cured product by thermal curing>
The optical resin composition was sandwiched between glass plates, and heat cured at 70 ° C. for 30 minutes, 130 ° C. for 30 minutes, and 150 ° C. for 5 hours to produce a cured product having a thickness of 1 mm.

<Production of cured product by photocuring and thermal curing>
By sandwiching the optical resin composition between glass plates, irradiating with 15 mW / cm ² ultraviolet rays for 20 seconds using Execute 3000 (manufactured by HOYA), and then heating at 200 ° C. for 5 minutes using a hot plate A cured product having a thickness of 1 mm was produced.
In addition, the hardening method in each Example and a comparative example was described in Tables 1-3.

<Transparency evaluation>
The transmittance of the cured product was measured using a spectrophotometer (U-3400, manufactured by Hitachi, Ltd.), and the transmittance of 450 nm was used as an index of transparency. The case where the transmittance at 450 nm is 90% or more is “◎”, the case where it is 85% or more and less than 90% is “◯”, and the case where it is less than 85% is “x”. In addition, about the hardened | cured material from which transparency evaluation was set to "x", evaluation of refractive index, light resistance, and heat-resistant coloring property was not implemented.

<Refractive index measurement>
The refractive index at 589 nm of the cured product was measured using an Abbe refractometer (manufactured by Atago Co., Ltd.).

<Hardness test>
As an index of scratch resistance, pencil hardness was evaluated with reference to the test method described in JIS K5600. Using a 2H test pencil specified in JIS S6006, the test was carried out under a load of 1 kg and evaluated as follows.
○: No scratches are observed in 5 evaluations.
Δ: 1 or 2 scratches in 5 evaluations ×: 3 or more scratches in 5 evaluations

<Light resistance test>
The sample was irradiated with light for 200 hours under the conditions of 90 mW / cm ² , 63 ° C., and 50% humidity using an I-super UV tester W151 manufactured by Iwasaki Electric Co., Ltd. Subsequently, the transmittance at 450 nm was measured, and a case where the change was less than 20% was indicated as “◯”, and a case where the change was 20% or more was indicated as “x”.

<Heat resistant colorability test>
The sample was heated at 150 ° C. for 300 hours under air atmosphere. Subsequently, the transmittance at 450 nm was measured, and a case where the change was less than 20% was indicated as “◯”, and a case where the change was 20% or more was indicated as “x”.

  In Comparative Example 1, the cured product was clouded by curing shrinkage, and thus the transmittance was evaluated as “x”. In Comparative Example 3, since the FA-14 and DPHA were not compatible, the cured product became opaque and the transmittance was evaluated as “x”. In Comparative Example 5 and Comparative Example 6, the refractive index of the cured product exceeded the preferable range in the present invention (from 1.35 to less than 1.45), and showed high measurement results.

Claims (17)

An optical resin composition comprising a fluorine-containing compound represented by the following general formula (1) and a fluorine-containing compound represented by the following general formula (12) or (13).

In general formula (1), a represents an integer of 3 to 8, b represents an integer of 0 to 3, c represents an integer of 0 to 10, d and e each independently represents 0 or 1, r represents 0 or 1, Y represents a group represented by the following general formula (2), (3), (4) or (5), an allyl group, or a vinyl group, and L ₁ represents the following general formula ( 6) or a group represented by (7), L ₂ and L ₃ each independently represent a group represented by the following general formula (8), (9), (10) or (11) , Rf ₁ represents a (a + b) -valent, may contain an etheric oxygen atom, a linear, branched or cyclic saturated perfluoroalkyl group having 3 to 20 carbon atoms, Rf ₂ is etheric oxygen atoms may contain, represents a monovalent perfluoroalkyl group or a fluorine atom, linear or branched C1-5, Rf ₃ is It may contain ether oxygen atoms, a straight, branched or cyclic, monovalent perfluoroalkyl group of 3 to 100 carbon atoms.

In general formula (2), X represents a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group, or a hydroxyl group.
In the general formulas (3), (4) and (5), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a carbon atom which may have a hydrogen atom or a substituent. A linear or branched monovalent alkyl group having a number of 1 to 5 is represented.
In general formula (5), k represents 1 or 2.
In general formulas (6) and (7), m represents an integer of 0 to 10.
In general formula (8), (9), (10), (11), n represents the integer of 0-10.
In the general formula (7), Y represents a group represented by the general formula (2), (3), (4) or (5), an allyl group, or a vinyl group.

In General Formula (12), f represents an integer of 0 to 5, g represents 0 or 1, and Y represents a group represented by General Formula (2), (3), (4), or (5). , An allyl group, or a vinyl group, L ₄ represents a group represented by the general formula (6) or (7), or the following general formula (14) or (15), and Rf ₄ represents an etheric oxygen A linear, branched or cyclic monovalent polyfluoroalkyl group having 1 to 100 carbon atoms which may contain an atom is represented.
In general formula (13), h and i each independently represent an integer of 1 to 5, Y is a group represented by general formula (2), (3), (4) or (5), or an allyl group. Or L ₄ represents a group represented by the general formula (6) or (7) or the following general formula (14) or (15), and Rf ₅ represents an etheric oxygen. A linear, branched or cyclic divalent perfluoroalkyl group having 1 to 100 carbon atoms which may contain an atom is represented.

In general formula (14), m represents an integer of 0 to 10.
In the general formula (15), Y represents a group represented by the general formula (2), (3), (4) or (5), an allyl group, or a vinyl group.   The content rate of the fluorine-containing compound represented by the said General formula (1) is 1 mass part or more and 50 mass parts or less with respect to 100 mass parts of total solid of an optical resin composition. An optical resin composition.   The optical resin composition according to claim 1 or 2, wherein a fluorine atom content of the fluorine-containing compound represented by the general formula (12) or (13) is 30% by mass or more and 75% by mass or less.   The optical resin composition according to any one of claims 1 to 3, wherein (a + b) in the general formula (1) is an integer of 3 to 8.   D and e in the said General formula (1) are 1, The optical resin composition of any one of Claims 1-4. The fluorine-containing compound represented by the general formula (1) is a fluorine-containing compound represented by the following general formula (17), and the fluorine-containing compound represented by the general formula (12) or (13) is The optical resin composition according to any one of claims 1 to 5, which is a fluorine-containing compound represented by the general formula (18) or (19).

In general formula (17), a represents an integer of 3 to 8, b represents an integer of 0 to 3, c represents an integer of 0 to 10, Y represents the general formulas (2), (3), (4) or (5) represents a group, an allyl group, or a vinyl group, L ₁ represents a group represented by the general formula (6) or (7), and Rf ₁ represents an (a + b) value. Represents a linear, branched or cyclic saturated perfluoroalkyl group having 3 to 20 carbon atoms which may contain an etheric oxygen atom, and Rf ₂ may contain an etheric oxygen atom. 1 to 5 linear or branched monovalent perfluoroalkyl group or fluorine atom, Rf ₆ having at least one trifluoromethyl group, which may contain an etheric oxygen atom, carbon number 3 to 100 linear, branched or cyclic monovalent perfluoroalkyl groups are represented.

In general formula (18), f represents an integer of 0 to 5, Y represents a group represented by general formula (2), (3), (4) or (5), an allyl group, or a vinyl group. Rf ₇ represents a linear or branched monovalent polyfluoroalkyl group having 1 to 100 carbon atoms, which may contain an etheric oxygen atom, and has at least one trifluoromethyl group.
In general formula (19), h and i each independently represent an integer of 1 to 5, Y is a group represented by the general formula (2), (3), (4) or (5), or an allyl group Or Rf ₈ represents a linear or branched divalent perfluoroalkyl group having 1 to 100 carbon atoms, which may contain an etheric oxygen atom.   The optical resin composition according to claim 1, wherein a in the general formula (1) or (17) is 4 and b is 0. The optical resin composition according to any one of claims 1 to 7, wherein Rf1 in the general formula (1) or (17) is a group selected from the following f- ₁ to f-14.

Wherein * _{Y-L 1 -O-CH 2} - (CF 2) c - [CF (Rf 2)] r - (O) d -L 2 - or _{Rf 3 - (O) e -L} 3 - Represents the position to be combined. Furthermore, the optical resin composition of any one of Claims 1-8 containing the non-fluorine compound represented by following General formula (16).

In general formula (16), j represents an integer of 1 to 6, and Y represents a group represented by the following general formula (21), (3), (4) or (5), an allyl group, or a vinyl group. L ₅ represents a group represented by the following general formula (6), (7), (14) or (15), and R ₇ has 1 to 1 carbon atoms which may have a hydrogen atom or a substituent. 20 linear, branched or cyclic j-valent organic groups are represented.

In General Formula (21), X ¹ represents a hydrogen atom, a chlorine atom, a methyl group, a trifluoromethyl group, or a hydroxyl group.
In the general formulas (3), (4) and (5), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a carbon atom which may have a hydrogen atom or a substituent. A linear or branched monovalent alkyl group having a number of 1 to 5 is represented.
In general formula (5), k represents 1 or 2.
In general formulas (6), (7), and (14), m represents an integer of 0 to 10.
In the general formulas (7) and (15), Y represents a group represented by the general formula (21), (3), (4) or (5), an allyl group, or a vinyl group.   The optical resin composition according to any one of claims 1 to 9, wherein the refractive index after curing is 1.35 or more and less than 1.45.   Hardened | cured material formed by hardening | curing the optical resin composition of any one of Claims 1-10.   The optical component which uses the resin composition for optics of any one of Claims 1-10.   The sealing agent for semiconductor light-emitting devices which uses the optical resin composition of any one of Claims 1-10.   The optical lens which uses the resin composition for optics of any one of Claims 1-10.   The optical adhesive agent using the optical resin composition of any one of Claims 1-10.   The optical sealing agent formed using the optical resin composition of any one of Claims 1-10.   An optical waveguide using the optical resin composition according to claim 1.