JP3900170B2 - Heat-resistant fluorine-containing optical material and optical transmission medium using the same - Google Patents

Description

  The present invention relates to a fluorine-containing optical material having excellent heat resistance in addition to optical characteristics. The optical material of the present invention is suitable as a clad material such as a plastic clad optical fiber having, for example, an optical transmission medium, particularly a quartz or optical glass material as a core material.

  2. Description of the Related Art In recent years, various sensors, signal processing devices, lighting, and the like aimed at upgrading, automation, and safety have been used for communication inside and outside an automobile. As a result, an increase in the amount of signal processing and an accompanying increase in the size of the electric wire cable occur, resulting in a problem of inhibiting the weight reduction of the vehicle body.

  In order to solve such a problem, it is desired to use an optical fiber capable of realizing multiplexing and high-speed communication instead of the electric cable.

  However, these LAN communication cables for vehicles (for in-vehicle LAN) are required to have heat resistance at high temperatures such as the engine room and the ceiling, and the distance from the vehicle design requirement is increased. Therefore, an optical fiber for automobiles that has both heat resistance and signal transmission capability is required.

  These optical fibers include all-glass optical fibers that use quartz or optical glass materials for both the core and cladding materials, all-plastic optical fibers that use plastic materials for both the core and cladding materials, and quartz or optical glass systems for the core materials. A plastic clad optical fiber using a material and a plastic material as a clad material is known.

  Although all glass-based optical fibers have excellent heat resistance but are expensive and inferior in flexibility, attempts have been made to provide heat resistance to all plastic optical fibers and plastic clad optical fibers.

  For all plastic optical fibers, polymethyl methacrylate (PMMA) is used as a core material because of its excellent transparency and high refractive index. And as a clad material, since the copolymer of a low refractive index is given at a high glass transition temperature (Tg), the copolymer which uses hexafluoro neopentyl methacrylate (6FNPM) as a copolymerization component is proposed ( Patent Document 1, Patent Document 2, Patent Document 3).

  However, the copolymer obtained by using 6FNPM as a copolymerization component has a limit in the effects of high Tg and low refractive index in the combination of monomers described in those patent documents.

  For example, Patent Document 1 describes an optical material made of a copolymer of 6FNPM and methyl methacrylate (MMA) in a 50/50 (weight ratio) (27/73 (molar ratio)), which has a refractive index. Patent Document 2 describes an optical material made of a copolymer of 6FNPM and MMA 90/10 (weight ratio) (77/23 (molar ratio)). Inferior. Furthermore, Patent Document 3 only describes a copolymer having 6FNPM up to 20 mol%.

  Further, these 6FNPM copolymers do not have a cured portion and are molded as a thermoplastic resin by melt extrusion or the like.

  As a plastic clad optical fiber, for example, in Patent Document 4, a composition comprising a fluoroalkyl ester of (meth) acrylic acid, a bifunctional acrylate as a crosslinkable monomer, and a photopolymerization initiator is photocured to obtain a clad material. Patent Document 5 discloses a technique using a fluoroalkyl ester of α-fluoroacrylic acid.

  However, many of the examples of the fluoroalkyl group of the fluoroalkyl ester are linear alkyl groups, and do not satisfy the balance between high Tg, low refractive index, mechanical strength, transparency, and core material adhesion.

For example, in Patent Document 4, a monomer having a long-chain fluoroalkyl group of CH ₂ ═CHCOOC ₂ H ₄ C ₈ F ₁₇ is a monomer having a short-chain fluoroalkyl group of CH ₂ ═CHCOOCH ₂ C ₂ F _5. Achieves a lower refractive index than the body. However, since the long-chain fluoroalkyl group exhibits crystallinity when it becomes a polymer, transparency as a clad may be lowered, and Tg is also low at 50-60 ° C. for the long-chain fluoroalkyl group portion. Therefore, the Tg of the entire polymer molecule obtained is lowered, and there is room for improvement in terms of heat resistance.

  In Patent Document 4, 1,1-dimethyl-2,2,3,3-tetrafluoropropyl acrylate, 1,1-dimethyl-2,2,3,3,4,4, are further exemplified as monomers. Fluoroalkyl acrylates having side chains such as 5,5-octafluoropentyl acrylate and 1,1-dimethyl-2,2,3,4,4,4-hexafluorobutyl acrylate are also described. If it is designed to increase the refractive index, it will be difficult to lower the refractive index, and if it is attempted to lower the refractive index, it will be difficult to increase the Tg, and it will be difficult to simultaneously achieve a high Tg and a low refractive index.

  Patent Document 6 discloses an ultraviolet curable resin for clad of an optical fiber comprising 2- (perfluorooctyl) ethyl acrylate, hexafluoroisopropyl acrylate, trimethylolpropane triacrylate, a photopolymerization initiator and γ-mercaptopropyltrimethoxysilane. A composition is disclosed. However, although this can obtain a cured product having a low refractive index, Tg cannot be increased, which is insufficient in terms of heat resistance.

  In addition, there is a proposal to introduce a component having an alicyclic hydrocarbon group or an aromatic ring in the molecule in order to increase Tg (Patent Document 7), but mechanical strength ( Flexibility).

JP 63-33405 A JP 59-1518 JP-A-61-36307 JP 63-43104 A JP-A 63-208805 JP-A-8-248242 JP-A-5-222136

  As a result of intensive studies, the present inventors have satisfied a high level of well-balanced high Tg, low refractive index, mechanical strength, and transparency, which have not been conventionally found, by combining specific monomers. It came to invent the heat resistant fluorine-containing optical material.

  In particular, the present inventors have found that the present invention is useful as a clad material for a plastic optical fiber made of an optical material that can be used in a high temperature environment required in an automobile engine room and has low bending loss.

That is, the first of the present invention is the formula (M-1):
-[M]-[N]-[A]-(M-1)
[Where:
The structural unit M is represented by the formula (1):

(Wherein X ¹ is at least one selected from the group consisting of H, CH ₃ , F, Cl and CF ₃ ; Rf ¹ and Rf ² are the same or different, and a perfluoroalkyl group having 1 to 5 carbon atoms; R ¹ is a structural unit derived from at least one monomer represented by a hydrocarbon group having 1 to 5 carbon atoms in which part or all of the hydrogen atoms may be substituted with fluorine atoms,
The structural unit N is represented by the formula (2):

Wherein X ² and X ³ are the same or different and are at least one selected from the group consisting of H, CH ₃ , F, Cl and CF ₃ ; n is an integer from 1 to 6, for example from 1 to 3; ² is a structural unit derived from at least one monomer represented by a (n + 1) -valent organic group having 1 to 50 carbon atoms, such as 1 to 30 carbon atoms,
The structural unit A is represented by a structural unit derived from at least one other monomer copolymerizable with the monomers of the formula (1) and the formula (2)], and the structural unit M is 1 to 99 mol%. Further, the present invention relates to a heat-resistant fluorine-containing optical material comprising a structural unit M-1 containing 1 to 99 mol% of structural unit N and 0 to 98 mol% of structural unit A, and comprising a polymer cured product having a glass transition temperature of 100 ° C. or higher. .

  The second of the present invention is an optical transmission medium using the above-mentioned heat-resistant fluorine-containing optical material, in particular, a plastic comprising a quartz-based or optical glass-based core and a clad made of the above-mentioned heat-resistant fluorine-containing optical material. The present invention relates to a clad optical fiber.

  Such an optical fiber is suitable as a plastic optical fiber for LAN mounted on a vehicle.

  The third of the present invention is (I) Formula (1):

(Wherein X ¹ is at least one selected from the group consisting of H, CH ₃ , F, Cl and CF ₃ ; Rf ¹ and Rf ² are the same or different, and a perfluoroalkyl group having 1 to 5 carbon atoms; R ¹ represents at least one monomer represented by a hydrocarbon group having 1 to 5 carbon atoms which may be substituted with a fluorine atom;
(II) Formula (2):

Wherein X ² and X ³ are the same or different and are at least one selected from the group consisting of H, CH ₃ , F, Cl and CF ₃ ; n is an integer from 1 to 6, for example from 1 to 3; ² is at least one monomer represented by an (n + 1) -valent organic group having 1 to 50 carbon atoms, such as 1 to 30 carbon atoms;
(III) at least one other monomer copolymerizable with the monomers of the formula (1) and the formula (2); and (IV) a polymerization initiator, and the monomer in all the monomers The present invention relates to a curable composition in which the proportions of (I), monomer (II) and monomer (III) are 1 to 99 mol%, 1 to 99 mol% and 0 to 98 mol%, respectively.

  4th of this invention is related with the manufacturing method of the medium for optical transmission characterized by hardening after applying the 3rd curable composition of this invention to quartz or optical glass.

  The heat-resistant fluorine-containing optical material of the present invention is a material having a balance of high Tg, low refractive index, good flexibility, and low cost that could not be achieved in the past, and is a clad for heat-resistant plastic clad optical fibers. It is extremely effective as a material, particularly as a plastic clad optical fiber for vehicle use.

  The polymer cured product constituting the first heat-resistant fluorine-containing optical material of the present invention will be described.

First, the polymer cured product has the formula (M-1):
-[M]-[N]-[A]-(M-1)
It consists of the structural unit shown by However, the structural unit M, the structural unit N, and the structural unit A are bonded at random, and the structural unit N forms a crosslinking unit.

  The structural unit M which is an essential component in the structural unit M-1 is represented by the formula (1):

(Wherein X ¹ , Rf ¹ , Rf ² and R ¹ are the same as above), which is a structural unit derived from a fluoroacrylate derivative containing a branched fluoroalkyl group, having a high Tg and a low refractive index, Furthermore, it contributes to imparting an appropriate mechanical strength.

As the structural unit M, X ¹ is H, CH ₃ , F, CF ₃ or Cl, in particular CH ₃ , F, further CH ₃ , and Rf ¹ and Rf ² are the same or different, 5 perfluoroalkyl groups, specifically CF ₃ , CF ₂ CF ₃ , CF ₂ CF ₂ CF ₃ , CF ₂ CF ₂ CF ₂ CF ₃ , CF ₂ CF ₂ CF ₂ CF ₂ CF ₃ , especially CF ₃ , R ¹ is an optionally substituted hydrocarbon group having 1 to 5 carbon atoms, specifically CH ₃ , CH ₂ CH ₃ , CH ₂ CH ₂ CH ₃ , CH ₂ CH ₂ CH ₂ CH ₃ , CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ CF ₂ CF ₃ , especially CH ₃ is preferred.

Non-limiting specific monomers that give structural unit M include hexafluoroneopentyl methacrylate (6FNPM: X ¹ = CH ₃ , Rf ¹ = Rf ² = CF ₃ , R ¹ = CH ₃ ), hexafluoroneo Pentyl α-fluoroacrylate (6FNPF: X ¹ = F, Rf ¹ = Rf ² = CF ₃ , R ¹ = CH ₃ ), 2,2-bistrifluoromethylbutyl methacrylate (X ¹ = CH ₃ , Rf ¹ = Rf ² = CF ₃ , R ¹ = CH ₂ CH ₃ ), 2,2-bistrifluoromethylbutyl α-fluoroacrylate (X ¹ = F, Rf ¹ = Rf ² = CF ₃ , R ¹ = CH ₂ CH ₃ ),

(X ¹ = CH ₃ , Rf ¹ = CF ₃ , Rf ² = CF ₃ , R ¹ = CH ₂ CF ₃ )
Can be illustrated. Of these, 6FNPM and 6FNPF are preferable from the viewpoint of excellent heat resistance and easy synthesis, and 6FNPM is particularly preferable.

  Content of the structural unit M in the structural unit M-1 is 1-99 mol%, and a preferable minimum is 5 mol%, Furthermore, 10 mol%. When the content of the structural unit M decreases, the transparency decreases and the heat resistance (Tg) tends to decrease. A preferable upper limit is 85 mol%, and further 70 mol%, and when it increases, flexibility tends to decrease.

  The structural unit N is represented by the formula (2):

(Wherein R ² , X ² , X ³ and n are the same as described above), which is a structural unit derived from a polyfunctional acrylate, which causes a crosslinking reaction by active energy rays, and has a heat resistance (high resistance to the cured product). Tg) and mechanical strength are imparted.

In the structural unit N, X ² and X ³ are preferably H, CH ₃ , F, CF ₃ or Cl, particularly CH ₃ , F, and further CH ₃ .

R ² is a structural unit containing a urethane bond and / or a structural unit containing an aromatic unit and / or a structural unit containing an alicyclic structure, which gives flexibility and increases Tg. Preferably, it is a structural unit containing a phenyl group which may contain a fluorine atom or a derivative thereof from the viewpoint of increasing Tg, and also contains a cyclohexyl group or a derivative thereof which may contain a fluorine atom. A structural unit containing a structural unit or an alicyclic hydrocarbon group having a polycyclic structure which may contain a fluorine atom or a derivative thereof is preferable from the viewpoint of increasing Tg.

R ² may not be substituted with a fluorine atom, but the refractive index can be lowered and the transparency in the near-infrared region can be increased by using the one substituted with a fluorine atom.

n is an integer of 1 to 6, for example, 1 to 3, and when n is 2 or 3, the acrylate moiety is bonded to an intermediate position of R ² in addition to the molecular end.

Specific examples of R ² are exemplified by -O-R ² -O- forms, but is not limited thereto.

(1) Alkylene unit:
For example,
(1-1) Formula:
_{-O (CH 2) n - (} CF 2) m - (C (CH 3)) p -O- (n + m + p = 1~30) unit represented by can be exemplified.

Specific examples are:
-OCH ₂ CH ₂ O-,
_{-OCH 2 CH (CH 3) O-} ,
_{-OCH 2 CH 2 CH (CH 3} ) O-,
-O (CH _{2) 4} O-,
-O (CH _{2) 6} O-,
_{-O (CH 2) 2 (CF} 2) 2 (CH 2) 2 O-,
_{-O (CH 2) 2 (CF} 2) 4 (CH 2) 2 O-,
_{-OCH 2 C (CH 3) 2} CH 2 O- and the like.

(2) Units containing aromatic units (Bz):
For example,
(2-1) Formula:

(Wherein R ⁵ and R ⁶ are the same or different and the alkyl group having 1 to 5 carbon atoms or the fluorine-containing alkyl group having 1 to 5 carbon atoms; Z ¹ and Z ² are the same or different and each represents an alkyl group, A unit containing a moiety represented by a fluorine alkyl group, a functional group or a halogen atom; p and q are the same or different, and an integer of 1 to 4, or (2-2) Formula:

(Wherein R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same or different, and an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms; Z ³ is an alkyl group or a fluorinated alkyl group) And a unit containing a moiety represented by a group, a functional group, or a halogen atom; p is an integer of 1 to 4.

As a specific example of (2-1),
_{-OBz-C (CH 3) 2} -BzO-,
_{-OBz-C (CF 3) 2} -BzO-,
_{-OCH 2 CH (OH) CH 2} O-Bz-C (CH 3) 2 -Bz-O-CH 2 CH (OH) CH 2 O-,
_{-OCH 2 CH (OH) CH 2} O-Bz-C (CF 3) 2 -Bz-O-CH 2 CH (OH) CH 2 O-,
_{- (OCH 2 CH 2) n} O-Bz-C (CH 3) 2 -Bz-O- (CH 2 CH 2 O) m -,
_{- (OCH 2 CH 2) n} O-Bz-C (CF 3) 2 -Bz-O- (CH 2 CH 2 O) m -
As a specific example of (2-2),
—O—C (CF ₃ ) ₂ —Bz—C (CF ₃ ) ₂ —O—
Etc.

In the formula, Bz is an alkyl group, a fluorine-containing alkyl group, a divalent benzene ring which may be substituted with a functional group or a halogen atom, and n and m are 0 or ² to prevent R ² from exceeding 30 carbon atoms. It is an integer of 1 or more.

(3) Units containing alicyclic hydrocarbon units (cHx):
For example,
(3-1) Formula:

(Wherein R ⁵ and R ⁶ are the same or different and the alkyl group having 1 to 5 carbon atoms or the fluorine-containing alkyl group having 1 to 5 carbon atoms; Z ¹ and Z ² are the same or different and each represents an alkyl group, A unit containing a moiety represented by a fluorine alkyl group, a functional group or a halogen atom; p and q are the same or different, and an integer of 1 to 4, or (3-2) formula:

(Wherein R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same or different, and an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms; Z ³ is an alkyl group or a fluorinated alkyl group) And a unit containing a moiety represented by a group, a functional group, or a halogen atom; p is an integer of 1 to 4.

As a specific example of (3-1),
_{-O-cHx-C (CH 3} ) 2 -cHx-O-,
_{-O-cHx-C (CF 3} ) 2 -cHx-O-,
_{-OCH 2 CH (OH) CH 2} O-cHx-C (CH 3) 2 -cHx-O-CH 2 CH (OH) CH 2 O-,
_{-OCH 2 CH (OH) CH 2} O-cHx-C (CF 3) 2 -cHx-O-CH 2 CH (OH) CH 2 O-,
_{- (OCH 2 CH 2) n} O-cHx-C (CH 3) 2 -cHx-O- (CH 2 CH 2 O) m -,
_{- (OCH 2 CH 2) n} O-cHx-C (CF 3) 2 -cHx-O- (CH 2 CH 2 O) m -
As a specific example of (3-2),
_{-O-C (CF 3) 2} -cHx-C (CF 3) 2 -O-
Etc.

In the formula, cHx is an alkyl group, a fluorine-containing alkyl group, a divalent cyclohexane ring which may be substituted with a functional group or a halogen atom, and n and m are 0 or ² to prevent R ² from exceeding 30 carbon atoms. It is an integer of 1 or more.

(4) Units containing multiple rings (NB):
For example,
(4-1) Formula:

(Wherein R ⁵ and R ⁶ are the same or different and the alkyl group having 1 to 5 carbon atoms or the fluorine-containing alkyl group having 1 to 5 carbon atoms; Z ¹ and Z ² are the same or different and each represents an alkyl group, A unit containing a moiety represented by a fluorine alkyl group, a functional group or a halogen atom; p and q are the same or different and an integer of 1 to 4, or a formula (4-2):

(Wherein R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same or different, and an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms; Z ³ is an alkyl group or a fluorinated alkyl group) And a unit containing a moiety represented by a group, a functional group, or a halogen atom; p is an integer of 1 to 4.

As a specific example of (4-1),
_{-O-NB-C (CH 3} ) 2 -NB-O-,
_{-O-NB-C (CF 3} ) 2 -NB-O-,
_{-OCH 2 CH (OH) CH 2} O-NB-C (CH 3) 2 -NB-O-CH 2 CH (OH) CH 2 O-,
_{-OCH 2 CH (OH) CH 2} O-NB-C (CF 3) 2 -NB-O-CH 2 CH (OH) CH 2 O-,
_{- (OCH 2 CH 2) n} O-NB-C (CH 3) 2 -NB-O- (CH 2 CH 2 O) m -,
_{- (OCH 2 CH 2) n} O-NB-C (CF 3) 2 -NB-O- (CH 2 CH 2 O) m -
As a specific example of (4-2),
_{-O-C (CF 3) 2} -NB-C (CF 3) 2 -O-
Etc.

In the formula, NB is an alkyl group, a fluorine-containing alkyl group, a divalent norbornene ring optionally substituted with a functional group or a halogen atom, and n and m are 0 or ² to prevent R ² from exceeding 30 carbon atoms. It is an integer of 1 or more.

(5) Units containing urethane bonds

(6) Example of n = 2 to 3 (polyfunctional)

  Although the following can be illustrated as a specific example of the monomer shown by Formula (2), It is not limited to these.

The R ² in the polyfunctional acrylate monomer represented by the formula (2) that gives the structural unit N is summarized as follows from a slightly different viewpoint. In the following description of R ² , there is a description that overlaps with the description so far, but from the viewpoint of organization, the description will be made without any duplication.

R ² is an (n1 + 1) -valent organic group having 1 to 50 carbon atoms, specifically,
(1) a (n1 + 1) -valent organic group optionally having a linear or branched ether bond,
(2) a (n1 + 1) -valent organic group having an aromatic ring structure,
(3) an (n1 + 1) -valent organic group having an aliphatic cyclic (monocyclic or polycyclic) structure,
(4) (n1 + 1) -valent organic group containing a urethane bond and the like, and in these organic groups, a part or all of hydrogen atoms forming a carbon-hydrogen bond may be substituted with a fluorine atom. Good.

First, preferred embodiments of R ² will be described with specific examples.

(1) A (n1 + 1) -valent organic group which may have a linear or branched ether bond:
As a thing (bifunctional acrylate) of n1 = 1 in Formula (2) which shows the said polyfunctional acrylate, for example, Formula (R2-1):
_{- (CH 2) p1 - (} CF 2) p2 - (C (CH 3)) p3 - (R2-1)
The organic group shown by (In formula, p1 + p2 + p3 = 1-30) can be illustrated.

As a specific example,
-CH ₂ CH ₂ -,
_{-CH 2 CH (CH 3) -} ,
_{-CH 2 CH 2 CH (CH 3} ) -,
- (CH _{2) 4} -,
- (CH _{2) 6} -,
_{- (CH 2) 2 (CF} 2) 2 (CH 2) 2 -,
_{- (CH 2) 2 (CF} 2) 4 (CH 2) 2 -,
_{- (CH 2) 2 (CF} 2) 6 (CH 2) 2 -,
_{-CH 2 C (CH 3) 2} CH 2 -
Etc.

  Formula (R2-1-1):

(Wherein, p1, p2, and p3 are the same as those in the formula (R2-1)).

  More specifically,

Etc. are preferred.

  Other formulas (R2-1-2) and (R2-1-3):

(Wherein p4 is 0 or an integer of 1 to 20, Z ¹⁵ , Z ¹⁶ and Z ¹⁷ are the same or different and H or CH ₃ ).

  Moreover, as a thing of n1 = 2 or more (trifunctional or more), Formula (R2-2):

(Wherein p5 is 0 or an integer of 1 to 5).

  In particular,

Etc.

  Further, as other than the formula (R2-2), for example,

Etc.

  Moreover, as a thing containing a fluorine-containing alkylene group, Formula (R2-3), (R2-4):

(Wherein p6 and p8 are the same or different, an integer of 1 to 10; p7 is an integer of 1 to 30).

  In particular,

Etc. are preferred.

A divalent or higher-valent organic group composed of these exemplified linear or branched alkylene groups as R ² is preferable in that it can impart flexibility and elasticity to the polymer. Further, when introducing a fluorine atom, it can be introduced at a high content, which is advantageous in terms of transparency and a low refractive index.

(2) (n1 + 1) -valent organic group containing an aromatic ring structure:
For example, the formula (R2-5):

(Wherein R ²¹ and R ²² are the same or different and an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms; Z ²¹ and Z ²² are the same or different and have 1 to A divalent organic compound having a moiety represented by 5 alkyl group, a fluorine-containing alkyl group having 1 to 5 carbon atoms, a functional group, a hydrogen atom or a halogen atom; and r1 and r2 are the same or different and are integers of 1 to 4) Group,
Or formula (R2-6):

(In the formula, R ²³ , R ²⁴ , R ²⁵ and R ²⁶ are the same or different, and an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms; Z ²³ has 1 to 5 carbon atoms; And a divalent organic group including a moiety represented by an alkyl group, a fluorine-containing alkyl group having 1 to 5 carbon atoms, a functional group, a hydrogen atom or a halogen atom; r3 is an integer of 1 to 4.

  In addition, the bivalent organic group containing the site | part represented by following formula (R2-7)-(R2-11) is mention | raise | lifted.

Formula (R2-7):

Formula (R2-8):

Formula (R2-9)

Formula (R2-10):

Formula (R2-11):

In the above formula, R ²⁷ , R ²⁸ , R ²⁹ and R ³⁰ are the same or different, and an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms; R ³¹ and R ³² are the same or Different, an alkyl group having 1 to 5 carbon atoms, a fluorinated alkyl group having 1 to 5 carbon atoms, a hydrogen atom; Z ²⁴ , Z ²⁵ and Z ²⁶ are the same or different and an alkyl group having 1 to 5 carbon atoms, 1 to 5 fluorine-containing alkyl group, functional group, hydrogen atom or halogen atom; r4 and r5 are the same or different; an integer of 1 to 4; r6 is an integer of 1 to 2; r7 and r8 are the same or different; It is an integer of 1 to 3, and even if they have the same sign, different groups and integers can be taken if the formulas are different.

  As a specific example of the formula (R2-5),

(Wherein, r4, r5 are the same or different, an integer from 1 to ^{10; Z 21, Z 22, r1} , r2 are the same as the formula (R2-5)) and the like preferably.

  As a specific example of (R2-6),

(Wherein, Z ²³ and r3 are the same as those in the above formula (R2-6)).

  As a specific example of the formula (R2-7),

(Wherein, Z ²⁴ , Z ²⁵ , r4 and r5 are the same as those in the above formula (R2-7)).

  As a specific example of the formula (R2-8),

(Wherein, Z ²⁴ and r6 are the same as those in the above formula (R2-8)).

  As a specific example of the formula (R2-9),

(Wherein, Z ²⁴ , Z ²⁵ , r4 and r5 are the same as those in the above formula (R2-9)).

  As a specific example of the formula (R2-10),

(Wherein, Z ²⁴ , Z ²⁵ , r7 and r8 are the same as those in the above formula (R2-10)).

  As a specific example of the formula (R2-11),

(Wherein, Z ²⁴ , Z ²⁵ , Z ²⁶ , r6, r7 and r8 are the same as those in the above formula (R2-11)).

Specific examples of Z ²¹ , Z ²² , Z ²³ , Z ²⁴ , Z ²⁵ and Z ²⁶ include a hydrogen atom, a fluorine atom, and a methyl group.

  These divalent or higher-valent organic groups having an aromatic cyclic structure are preferable in terms of excellent heat resistance and mechanical properties, and can set a high glass transition point, and as a result, an optical material having high heat resistance can be obtained. preferable.

  Among these, those having a fluorine atom are preferable in terms of high transparency in a wide wavelength band including light in the near infrared region. Further, introduction of fluorine atoms is preferable because it effectively acts in reducing the refractive index.

(3) (n1 + 1) -valent organic group having an aliphatic cyclic (monocyclic or polycyclic) structure:
Specifically, the formula (R2-12):

(Wherein, unlike R ³³ and R ³⁴ are the same or a fluorine-containing alkyl group of 1 to 5 alkyl group or a C1-5 carbon; Z ²⁷ and Z ²⁸ are the same or different, 1 to carbon atoms A divalent organic compound having a moiety represented by 5 alkyl group, fluorine-containing alkyl group having 1 to 5 carbon atoms, functional group, hydrogen atom or halogen atom; s1 and s2 are the same or different and are integers of 1 to 4) Group or formula (R2-13):

(In the formula, R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ are the same or different, and an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms; Z ²⁹ has 1 to 5 carbon atoms; And a divalent organic group including a moiety represented by an alkyl group, a fluorine-containing alkyl group having 1 to 5 carbon atoms, a functional group, a hydrogen atom or a halogen atom; s3 is an integer of 1 to 4.

  In addition, the bivalent organic group containing the site | part represented by following formula (R2-14)-(R2-18) is mention | raise | lifted.

Formula (R2-14):

Formula (R2-15):

Formula (R2-16):

Formula (R2-17):

Formula (R2-18):

In the above formula, R ³⁹ , R ⁴⁰ , R ⁴¹ and R ⁴² are the same or different, and an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms; R ⁴³ and R ⁴⁴ are the same or Different, an alkyl group having 1 to 5 carbon atoms, a fluorine-containing alkyl group having 1 to 5 carbon atoms, a hydrogen atom; Z ³⁰ , Z ³¹ and Z ³² may be the same or different, and an alkyl group having 1 to 5 carbon atoms and a carbon number 1 to 5 fluorine-containing alkyl groups, functional groups, hydrogen atoms or halogen atoms; s4 and s5 are the same or different; an integer of 1 to 4; s6 is an integer of 1 to 2; s7 and s8 are the same or different; It is an integer of 1 to 3, and even if they have the same sign, different groups and integers can be taken if the formulas are different.

  As a specific example of the formula (R2-12),

(Wherein, s4, s5 are the same or different, an integer from 1 to ^{10; Z 27, Z 28, s1} , s2 is the formula (R2-12) and the same)
Etc. are preferred.

  As a specific example of (R2-13),

(In formula, Z < ²⁹ >, s3 is the same as said Formula (R2-13)), etc. are mentioned preferably.

  As a specific example of the formula (R2-14),

(Wherein, Z ³⁰ , Z ³¹ , s4 and s5 are the same as those in the above formula (R2-14)).

  As a specific example of the formula (R2-15),

(In the formula, Z ³⁰ and s6 are the same as those in the formula (R2-15)).

  As a specific example of the formula (R2-16),

(Wherein, Z ³⁰ , Z ³¹ , s4 and s5 are the same as those in the above formula (R2-16)).

  As a specific example of the formula (R2-17),

(Wherein, Z ³⁰ , Z ³¹ , s7 and s8 are the same as those in the above formula (R2-17)).

  As a specific example of the formula (R2-18),

(Wherein, Z ³⁰ , Z ³¹ , Z ³² , s6, s7 and s8 are the same as those in the above formula (R2-18)).

Specific examples of Z ²⁷ , Z ²⁸ , Z ²⁹ , Z ³⁰ , Z ³¹ and Z ³² include a hydrogen atom, a fluorine atom, and a methyl group.

  These divalent or higher-valent organic groups having an aliphatic cyclic structure are preferable in that the glass transition temperature can be set high, and the heat resistance and mechanical properties are excellent. Moreover, it is preferable at a point with high transparency with respect to ultraviolet light, and also preferable at the point which is excellent also in ultraviolet-ray resistance.

  Among them, those having a fluorine atom are preferable because they are highly transparent to light in the near infrared region and high in transparency over a wide wavelength band. Further, introduction of fluorine atoms is preferable because it effectively acts in reducing the refractive index.

(4) (n1 + 1) -valent organic group containing a urethane bond Specifically,

And organic groups such as

Although R ² has been mainly described above, specific examples of the polyfunctional acrylate represented by the formula (2) include the following.

Preferred are polyfunctional acrylate compounds such as

  Content of the structural unit N in the structural unit M-1 is 1-99 mol%, and a preferable minimum is 2 mol%, Furthermore, 5 mol%. When the content of the structural unit N decreases, the heat resistance tends to decrease. A preferable upper limit is 80 mol%, and further 70 mol%, and when it increases, flexibility tends to decrease.

The structural unit A which is an optional component in the formula (M-1) of the present invention is
Formula (3):

Wherein X ⁴ is at least one selected from the group consisting of H, CH ₃ , F, Cl and CF ₃ ; R ³ is a monovalent hydrocarbon group having 6 to 30 carbon atoms and containing an aromatic ring; However, a structural unit A-1 derived from at least one of the monomers represented by the above, wherein some or all of the hydrogen atoms in R ³ may be substituted with fluorine atoms;
Formula (4):

Wherein X ⁵ is at least one selected from the group consisting of H, CH ₃ , F, Cl and CF ₃ ; R ⁴ is a monovalent hydrocarbon having 3 to 30 carbon atoms and having an alicyclic hydrocarbon moiety. A structural unit A-2 derived from at least one monomer represented by the following formula: wherein a part or all of hydrogen atoms in R ⁴ may be substituted with fluorine atoms; 1) to at least one selected from the group consisting of structural units A-3 derived from monomers copolymerizable with the monomers shown in (4),
It is a structural unit containing 1 to 98 mol% of the structural unit A-1 and the structural unit A-2 in the structural unit M-1 and 0 to 97 mol% of the structural unit A-3 to improve heat resistance. In view of increasing the mechanical strength.

  By introducing the structural unit A-1 derived from the monomer of the formula (3), further heat resistance, mechanical properties, low water absorption can be imparted, and the refractive index can be adjusted.

In particular, the structural unit derived from methacrylate in which X ⁴ is CH ₃ in the structural unit A-1 is preferable in that the heat resistance, transparency, and the function of adjusting the refractive index can be more effectively imparted.

In addition, when the structural unit A-1 is a structural unit derived from α-fluoroacrylate in which X ⁴ is a fluorine atom, it is preferable in that heat resistance and mechanical strength, particularly bending strength, and flexibility can be imparted. .

Further, R ³ in the structural unit A-1 is a phenyl group which may contain a fluorine atom or a derivative thereof, particularly a structural unit derived from at least one monomer selected from phenyl methacrylate and phenyl-α-fluoroacrylate. When it is, it is preferable at the point which can provide further heat resistance and low water absorption.

  As a specific example of the structural unit A-1,

Wherein X ⁴ is H, F, Cl, CH ₃ or CF ₃ ; R ^1f , R ^2f , R ^3f , R ^4f and R ^5f are the same or different and are substituted with H, F, Cl or a halogen atom An optionally substituted alkyl group having 1 to 14 carbon atoms; R ^6f represents a bond or an alkylene group having 1 to 6 carbon atoms which may have a branched chain, and the like.

Are preferred.

  Of these, phenyl methacrylate and phenyl α-methacrylate are preferable in terms of improving heat resistance.

  The structural unit A-2 having an alicyclic hydrocarbon moiety represented by the formula (4) imparts heat resistance (high Tg), mechanical strength, particularly heat resistance to the polymer cured product.

R ⁴ forming the side chain in the formula (4) is an organic group having 3 to 30 carbon atoms, and has an alicyclic hydrocarbon moiety therein.

  The alicyclic hydrocarbon moiety may be a monocyclic hydrocarbon moiety, a polycyclic hydrocarbon moiety, or a hydrocarbon moiety including both.

When the alicyclic hydrocarbon moiety includes a monocyclic hydrocarbon moiety, R ⁴ is preferably an organic group having 7 or more carbon atoms, whereby heat resistance can be more effectively imparted.

In particular, R ⁴ is preferably an organic group containing a hydrocarbon moiety having a polycyclic structure, and can impart heat resistance and transparency more effectively.

Specifically, R ⁴ in the case of containing a monocyclic hydrocarbon moiety is
(1) an organic group having a cyclopentyl group and a derivative thereof,
(2) an organic group having a cyclohexyl group and a derivative thereof,
(3) an organic group having a perhydrobiphenyl group and a derivative thereof,
(4) an organic group having spiro [4,4] nonane and derivatives thereof,
(5) Preferred examples include organic groups having spiro [4,5] decane and derivatives thereof, and some examples thereof include

Etc.

  In addition, hydrogen atoms of these exemplified hydrocarbon groups may be substituted with an alkyl group having 1 to 5 carbon atoms, a fluorine atom, or a functional group.

R ⁴ in the case of containing a hydrocarbon moiety having a multicyclic structure is specifically,
(6) an organic group having adamantane and its derivatives,
(7) an organic group having norbornane and its derivatives,
(8) an organic group having perhydroanthracene and derivatives thereof,
(9) an organic group having perhydronaphthalene and derivatives thereof,
(10) Organic groups having tricyclo [5.2.1.0 ^2,6 ] decane and its derivatives, and the like.

Etc.

  In addition, hydrogen atoms of these exemplified hydrocarbon groups may be substituted with an alkyl group having 1 to 5 carbon atoms, a fluorine atom, or a functional group.

Further, among these organic groups containing a hydrocarbon moiety of a polycyclic structure, those containing adamantane and derivatives thereof, norbornane and derivatives thereof, tricyclo [5.2.1.0 ^2,6 ] decane and derivatives thereof are preferable. Can particularly effectively impart heat resistance and transparency to the polymer.

Specifically, the monomer represented by the formula (4) capable of forming a structural unit having a hydrocarbon moiety having an alicyclic structure as the structural unit A-2 is at least one side selected from the above R ^4. Examples of the acrylic monomer having a chain structure include the following.

(I) A monomer having an organic group containing norbornane represented by the following formula and derivatives thereof in the side chain:

(Wherein X ⁵ is H, F, Cl, CH ₃ or CF ₃ ; R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a , R ^7a , R ^8a , R ^9a and R ^10a are the same. Or an alkyl group which may be substituted with H, F, Cl or a halogen atom having 1 to 14 carbon atoms; R ^11a is an alkylene group having 1 to 6 carbon atoms which may contain a bond or a branched chain N is 0 or an integer of 1 to 2).

  More specifically,

Etc.

(II) A monomer having an organic group containing adamantane represented by the following formula and derivatives thereof in the side chain:

Or

(Wherein X ⁵ is H, F, Cl, CH ₃ or CF ₃ ; R ^1b and R ^2b are substituents bonded to the ring, and CH ₃ , C ₂ H ₅ or OH; R ^4b and R ^5b are An alkylene group having 1 to 6 carbon atoms which may have a bond or a branched chain; R ^3b is H, CH ₃ or C ₂ H ₅ ; n is 0 or an integer of 1 or 2).

  More specifically,

Etc.

(III) A monomer having an organic group containing tricyclo [5.2.1.0 ^2,6 ] decane and its derivative represented by the following formula in the side chain:

(Wherein, X ⁵ is H, F, Cl, CH ₃ or _{^{CF 3; R 1c, R 2c}} , R 3c, R 4c, R 5c, R 6c, R 7c, R 8c, R 9c, R 10c, R ^11c , ^R12c , ^R13c , ^R14c and ^R15c are the same or different and each is an alkyl group having 1 to 14 carbon atoms which may be substituted with H, F, Cl or a halogen atom; ^R16c is a bond or a branch An alkylene group having 1 to 6 carbon atoms which may contain a chain),
Or

(Wherein X ⁵ is H, F, Cl, CH ₃ or CF ₃ ; R ^1d , R ^2d , R ^3d , R ^4d , R ^5d , R ^6d , R ^7d , R ^8d , R ^9d , R ^10d , R ^11d, R ^12d and R ^13d are the same or different, H, F, an alkyl group of Cl or a halogen atom carbon atoms and optionally substituted with 1 to 14; R ^14d is also contain a bond or branched A good alkylene group having 1 to 6 carbon atoms.

  More specifically,

Etc.

Among these, R ⁴ in the structural unit A-2 is a cyclohexyl group that may contain a fluorine atom or a derivative thereof, or an alicyclic hydrocarbon group that has a multicyclic structure that may contain a fluorine atom, or A derivative is preferable from the viewpoint of increasing Tg and improving mechanical strength.

  The structural units A-1 and A-2 are optional components, but when introduced, the structural unit M-1 is preferably contained in a total of 1 to 98 mol%. The preferred upper limit (total) is 50 mol%, more preferably 30 mol%, and the preferred lower limit is 2 mol%, further 5 mol%.

  As the monomer forming the structural unit A-3 in the structural unit A of the present invention, a monomer having a chain hydrocarbon group in the side chain (however, the monomer represented by the formula (1) is Preferably).

  As a specific example,

(In the formula, n represents an integer of 1 to 6, m represents an integer of 0 to 29, and Y represents H or F; R ^1e , R ^2e , and R ^3e are the same or different, and H, C 1 to 29 An alkyl group optionally containing an ether bond or a fluorine-containing alkyl group optionally containing an ether bond having 1 to 29 carbon atoms)
Etc.

  More specifically,

Among them, methacrylic acid, α-fluoroacrylic acid, acrylic acid, methyl methacrylate (MMA), and methyl-α-fluoroacrylate are preferable because they are excellent in improving transparency, heat resistance, and mechanical strength. In particular, MMA is excellent in improving optical characteristics and mechanical characteristics.

  Examples of other suitable structural unit A-3 include structural units that improve adhesion to a substrate (an inorganic substrate such as quartz or optical glass, an organic substrate, etc.). For example, in order to improve adhesion to an inorganic base material, a structural unit derived from a monomer having a functional group such as a hydroxyl group, a silanol group, an amino group, or a cyano group, particularly an acrylic monomer is preferable.

  Examples of the structural unit A-3 include glycidyl group-containing monomers.

  The structural unit A-3 is 97 mol% at the maximum in the structural unit M-1, preferably 1 mol% or more and 50 mol% or less, and more preferably 30 mol% or less.

  In the present invention, the polymer cured product has the structural unit M-1 by mixing the above-mentioned monomers, optionally oligomers thereof, and curing by irradiation with active energy rays. In other words, once a monomer is polymerized into a curable polymer, and then the curable polymer is not cured, it is a polymer directly cured from the monomer, like an epoxy resin or an unsaturated polyester. Is to be manufactured.

  In the present invention, the monomer of formula (1) is a liquid at room temperature, and the monomer of formula (2) is a viscous liquid or solid at room temperature. In addition, the monomer giving the structural unit A may be liquid at room temperature or may be solid. These are compositions having a uniform composition that can be applied or molded. The monomer of formula (1) acts as a diluent (reactive diluent) on the monomer of formula (2), but a monomer that gives structural unit A is further added as a reactive diluent. Alternatively, other compounds may be added separately as mere viscosity modifiers. However, the addition amount is in a range not impairing the effect intended by the present invention.

  For example, when an optical material is formed by coating, it is desirable that the viscosity of the coating composition is 100 to 10,000 cps in order to make workability and film thickness thin and uniform. In the case of increasing the viscosity, the above monomers may be oligomerized or polymerized, or other oligomers or polymers that do not impair the intended effect of the present invention may be used. When these are polymerizable compounds, they become the structural unit A-3 of the polymer cured product of the present invention.

  As such other polymers, amorphous fluorine-containing polymers having a fluorine content of 25% by weight or more shown below can be preferably used. Specifically, for example, the amorphous fluorine-containing polymer (D) exemplified in the specification of Japanese Patent Application No. 2003-364751 can be exemplified.

(D-1) An amorphous fluorine-containing acrylic polymer having a fluorine content of 25% by weight or more, which is a polymer obtained by polymerizing only an acrylic monomer.

  Specifically, as the acrylic monomer, the formula (D-1-1):

(In the formula, X ⁶ is H, F, Cl, CH ₃ or CF ₃ ; R ¹¹ is a saturated hydrocarbon group in which part or all of the hydrogen atoms having 1 to 30 carbon atoms may be substituted with fluorine. ^At least one of ⁶ and R ¹¹ contains a fluorine atom). X ⁶ is preferably a fluorine atom from the viewpoint that the fluorine-containing acrylic polymer (D) has good fluorine content, heat resistance (high glass transition temperature), and transparency in the near infrared region.

As preferred R ¹¹ ,
(1) a saturated hydrocarbon group in which some or all of the hydrogen atoms containing an alkylene ether bond may be fluorine-substituted,
(2) a saturated hydrocarbon group in which some or all of the hydrogen atoms including a branched structure may be fluorine-substituted,
(3) an aromatic hydrocarbon group in which some or all of the hydrogen atoms optionally having heteroatoms may be fluorine-substituted,
(4) an aliphatic monocyclic structure in which some or all of the hydrogen atoms optionally having heteroatoms may be fluorine-substituted,
(5) An aliphatic polycyclic structure in which some or all of the hydrogen atoms optionally having heteroatoms may be fluorine-substituted.

(D-2) A polymer obtained by polymerizing a fluorine-containing allyl ether monomer, and an amorphous fluorine-containing allyl ether polymer having a fluorine content of 25% by weight or more.

  The polymer (D-2) is disclosed in WO95 / 33782, WO02 / 18457, WO02 / 73255, etc.

  Although the polymer (D-2) has a high fluorine content, the polymer (D-2) is amorphous and has a very high solubility in the fluorine-containing monomer that gives the structural unit (A). Further, for example, it is possible to easily provide a curing site capable of reacting with the fluorine-containing acrylic monomer that gives the structural unit (A-1), such as a carbon-carbon double bond, at the end of the side chain. In addition, if there is a cured part that can react with the fluorine-containing acrylic monomer, the cured product will form an overall network, so that the cured product has even better performance such as solvent resistance, low linear expansion coefficient, and heat resistance. Is expressed.

(D-3) An amorphous fluorine-containing cyclic polymer having a fluorine content of 25% by weight or more having a cyclic structure in the main chain.

The polymer (D-3) is preferable in that the glass transition temperature is very high and the heat resistance of the cured product is increased. Examples of such a polymer (D-3) include a polymer having an aliphatic cyclic structural unit having fluorine and a polymer having a non-fluorinated alicyclic monomer structural unit.
(D-3-1) Aliphatic cyclic structural unit having fluorine:
By introducing this structural unit, transparency in the near infrared region can be further increased, and an amorphous fluorine-containing cyclic polymer (D-3) having a high glass transition temperature can be obtained, and the hardness of the cured product can be further increased. Is preferable in that it can be expected.
(D-3-2) Non-fluorinated alicyclic monomer structural unit:
Moreover, the amorphous fluoropolymer containing the non-fluorine-based alicyclic monomer structural unit (D-3-2) can achieve a higher glass transition temperature and higher hardness of the cured product.

(D-4) An amorphous fluorine-containing copolymer comprising a fluorine-containing olefin and a hydrocarbon vinyl ether and having a fluorine content of 25% by weight or more.

(D-5) A non-crystalline fluorine-containing polystyrene-based polymer obtained by polymerizing a fluorine-containing polystyrene-based monomer and having a fluorine content of 25% by weight or more.

(D-6) An amorphous vinylidene fluoride copolymer having a fluorine content of 25% by weight or more, which is a vinylidene fluoride copolymer.

  The amorphous vinylidene fluoride copolymer (D-6) is preferably a copolymer of vinylidene fluoride and one or more of other monomers copolymerizable therewith.

  Representative examples of other monomers include tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, vinyl fluoride, hexafluoropropylene, pentafluoropropylene, hexafluoroisobutene, perfluorocyclobutene, perfluoro (methylcyclohexane). Propylene), perfluoroallene, perfluoroalkyl vinyl ethers (eg, perfluoromethyl vinyl ether, perfluoropropyl vinyl ether, etc.), perfluorovinylacetic acid or its ester, perfluorovinyl ether sulfonic acid, perfluorodienes, ethylene, propylene, vinyl Examples include acetic acid or its ester. The content of other monomers is not particularly limited, but it is preferably 10 to 60% by weight and copolymerized so that the fluorine content is 25% by weight or more.

  As the amorphous vinylidene fluoride copolymer, vinylidene fluoride / hexafluoropropylene (85 to 60/15 to 40 mol% ratio) copolymer, vinylidene fluoride / hexafluoropropylene / tetrafluoroethylene (84 to 20 / 15 to 40/1 to 40 mol% ratio) is preferable from the viewpoint of excellent solubility in the fluorinated monomer that gives the structural unit (A) and compatibility of the cured product.

  The polymer (D-6) is particularly preferable in that it is excellent in transparency in the visible region and gives impact resistance to the cured product.

  The upper limit of the number average molecular weight of the amorphous polymer (D) is 500,000, preferably 100,000, particularly preferably 50,000 from the viewpoint of solubility in other components and compatibility. Although a minimum in particular is not restrict | limited, From the same viewpoint, it is preferable that it is an oligomer which is a quantifier, and is specifically 300, Preferably it is 500.

In addition, the refractive index can be usually adjusted by appropriately selecting the type and amount of the structural unit M, the structural unit N, and further the structural unit A. In addition, as a refractive index adjusting component, a low molecular weight can be used as necessary. A compound may be added. Specific examples thereof include benzyl-n-butyl phthalate (refractive index: 1.575), 1-methoxyphenyl-1-phenylethane (refractive index: 1.571), benzyl benzoate (refractive index: 1.75). 568), bromobenzene (refractive index: 1.557), o-dichlorobenzene (refractive index: 1.551), m-dichlorobenzene (refractive index: 1.543), 1,2'-dibromoethane (refractive index). : 1.538), 3-phenyl-1-propanol (refractive index: 1.532), diphenyl phthalate _{(C 6 H 4 (COOC 6} H 5) 2), triphenylphosphine ((C ₆ H _{5) 3} P), dibenzyl phosphate ((C ₆ H ₅ CH ₂ O) ₂ PHO ₂ ), 4,4′-dibromobenzyl, 4,4′-dibromobiphenyl, 2,4′-dibromoacetophenone, 3 ′, 4'-jiku Roasetofenon, 3,4-dichloroaniline, 2,4-dibromo aniline, compounds such as 2,6-dibromo aniline 1,4-dibromo-benzene.

  As other additives, known additives may be appropriately used according to the application and required characteristics. Examples of other additives include a leveling agent and an antioxidant.

  The polymer cured product constituting the heat-resistant fluorine-containing optical material of the present invention is a composition obtained by blending the above monomers in a predetermined amount, and further adding a polymerization initiator and other additives as necessary. Can be produced by initiating a curing reaction after molding or applying to the substrate.

  As a method for inducing a curing reaction, a known method such as a method of irradiating active energy rays or a method of adding a compound (radical polymerization initiator or the like) for initiating radical polymerization and heating, for example, can be employed.

  First, a method of irradiating active energy rays will be described.

  Examples of active energy rays include electromagnetic waves in a wavelength region of 350 nm or less, that is, ultraviolet rays, X rays, γ rays, and other electron beams, and preferably ultraviolet rays are used. In order to efficiently cure the monomer by irradiating active energy rays, an active energy ray curing initiator is usually used.

  An active energy ray curing initiator generates radicals and cations only when exposed to active energy rays, and acts as a catalyst for initiating polymerization (curing reaction) of a polymerizable carbon-carbon double bond of a monomer. In general, those that generate radicals and cations with ultraviolet light, particularly those that generate radicals, are generally used.

  The active energy ray curing initiator in the present invention includes the type of carbon-carbon double bond (radical reactive or cationic reactive) of the monomer, the type of active energy ray used (wavelength region, etc.), and irradiation. As an initiator for curing the monomer having a radical-reactive carbon-carbon double bond using an active energy ray in the ultraviolet region, for example, the following can be exemplified. .

Acetophenone acetophenone, chloroacetophenone, diethoxyacetophenone, hydroxyacetophenone, α-aminoacetophenone, etc.

Benzoin benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal, etc.

Benzophenone benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, hydroxy-propylbenzophenone, acrylated benzophenone, Michler's ketone, etc.

Thioxanthones Thioxanthone, Chlorothioxanthone, Methylthioxanthone, Diethylthioxanthone, Dimethylthioxanthone, etc.

Other benzyl, α-acyl oxime ester, acyl phosphine oxide, glyoxy ester, 3-ketocoumarin, 2-ethylanthraquinone, camphorquinone, anthraquinone, etc.

  Moreover, you may add well-known photoinitiator adjuvants, such as amines, sulfones, and sulfines, as needed.

  Moreover, the following can be illustrated as an initiator which hardens this monomer which has a cation reactive carbon-carbon double bond.

Onium salt iodonium salt, sulfonium salt, phosphonium salt, diazonium salt, ammonium salt, pyridinium salt, etc.

Sulfone compounds β-ketoesters, β-sulfonylsulfones and their α-diazo compounds, etc.

Sulfonic acid esters Alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, imino sulfonates, etc.

Other sulfonimide compounds, diazomethane compounds, etc.

  The amount of the active energy ray curing initiator is usually preferably 0.1 to 10% by weight based on the total amount of monomers.

  Moreover, as a method for adding a compound for initiating radical polymerization, for example, a method for generating radicals using a known radical polymerization initiator is preferred.

  As radical polymerization initiators, peroxides, azo initiators, and the like can be used.

  Examples of peroxides include n-propyl peroxydicarbonate, i-propyl peroxydicarbonate, n-butyl peroxydicarbonate, t-butyl peroxydicarbonate, and bis (4-t-butylcyclohexyl) peroxy. Peroxydicarbonates such as dicarbonate; α, α′-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecano Nate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylper Oxypivalate, 1,1,3,3-tetra Tylbutyl peroxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanate, t-butyl Peroxy-2-ethylhexanonate, t-butylperoxyisobutyrate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethyl Hexanonate, t-butyl peroxylaurate, 2,5-dimethyl-2,5-bis (m-toluoyl peroxy) hexane, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2- Ethyl hexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl Chill-2,5-bis (benzoyl) hexane, t-butyl peroxyacetate, t-butyl peroxy-m-toluate and peroxybenzoate mixture, t-butyl peroxybenzoate, di-t-butyl peroxyisophthalate, etc. Oxyperesters: isobutyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic acid peroxide, m-toluoyl peroxide, benzoyl peroxide Diacyl peroxides such as oxide; 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis ( -Butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2 -Bis (t-butylperoxy) butane, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, etc. Peroxyketals: α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t-butyl kumi Dialkyls such as ruperoxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 Peroxides; hydroperoxides such as P-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide; Examples include persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate; and other perchloric acids and hydrogen peroxide.

In addition, peroxides having a fluorine atom can also be used. One or two selected from fluorine-containing diacyl peroxides, fluorine-containing peroxydicarbonates, fluorine-containing peroxydiesters, and fluorine-containing dialkyl peroxides. More than species are preferred. Among them, for example, pentafluoropropionoyl peroxide (CF ₃ CF ₂ COO) ₂ , heptafluorobutyryl peroxide (CF ₃ CF ₂ CF ₂ COO) ₂ , 7H-dodecafluoroheptanoyl peroxide (CHF ₂ CF ₂ CF Preferred are difluoroacyl peroxides such as ₂ CF ₂ CF ₂ CF ₂ COO) ₂ .

  Examples of the azo radical polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), and 2,2′-azobis (2-methylvaleronitrile). ), 2,2′-azobis (2-cyclopropylpropionitrile), dimethyl 2,2′-azobisisobutyrate, 2,2′-azobis [2- (hydroxymethyl) propionitrile], 4,4′- And azobis (4-cyanopentenoic acid).

  Among these, peroxydicarbonates, difluoroacyl peroxides, oxyperesters, persulfates and the like are preferable as the radical polymerization initiator.

  The lower limit of the amount of radical polymerization initiator used is 0.0001 mol, preferably 0.01 mol, more preferably 0.03 mol, and particularly preferably 0.001 mol, with respect to 1 mol in total of all monomers used. The upper limit is 0.9 mol, preferably 0.5 mol, more preferably 0.1 mol, and particularly preferably 0.08 mol.

  The molecular weight of the heat-resistant fluorine-containing optical material of the present invention cannot be specified because it takes a crosslinked structure with the polyfunctional acrylate of formula (2) (structural unit N).

  The heat-resistant fluorine-containing optical material of the present invention has a heat resistance of 100 ° C. or higher as a glass transition temperature Tg. Further, by selecting each monomer component, it is possible to set Tg to 105 ° C. or higher, further 110 ° C. or higher, 120 ° C. or higher, and 130 ° C. or higher. In order to increase Tg, for example, a ring structure may be introduced into the structural unit N.

  The glass transition temperature Tg defined in the present invention is determined by using a DSC (Differential Scanning Calorimeter) to increase 1st run to 200 ° C. at a rate of temperature increase of 10 ° C./min, maintain at 200 ° C. for 1 minute, and then a temperature decrease rate of 10 ° C. Is cooled to 25 ° C./min, and then the midpoint of the endothermic curve of 2nd run obtained at a heating rate of 10 ° C./min is employed.

  The heat-resistant fluorine-containing optical material of the present invention has a heat resistance of 180 ° C. or higher as the thermal decomposition temperature Td. Furthermore, Td can be set to 200 ° C. or higher, and further 230 ° C. or higher by selecting each monomer component.

  As the thermal decomposition temperature Td, a temperature when a weight is reduced by 0.1% by weight by using a thermobalance (TGA) and heating from room temperature at a heating rate of 10 ° C./min at room temperature is adopted.

  The heat-resistant fluorine-containing optical material of the present invention is amorphous as a whole because the structural unit M forms an amorphous polymer, although it depends on the selection of the structural unit A. Amorphous is advantageous in that it has excellent transparency and can reduce transmission loss in an optical transmission medium such as an optical fiber.

  Here, the term “amorphous” means that an endothermic peak based on melting is not substantially observed when the DSC analysis is carried out at 2nd run under a temperature rising rate of 10 ° C./min, or the heat of fusion is 1 J / g. The following properties are shown.

Furthermore, the heat-resistant fluorine-containing optical material of the present invention can have a refractive index of 1.44 or less. To further lower the refractive index, for example, 1.42 or less, use a fluorine-substituted ^one as R ¹ of the structural unit M, use one having a fluoroalkyl group as the structural unit A, and further refracting if necessary. This can be achieved by adding a rate adjusting component.

  The refractive index is a value measured with an Abbe refractometer at 25 ° C. using sodium D line as a light source.

  The heat-resistant fluorine-containing optical material of the present invention is highly transparent to light in the visible region, and particularly highly transparent to light having a wavelength of 650 nm (more preferably 850 nm). From this viewpoint, the heat-resistant fluorine-containing optical material of the present invention preferably has a light transmittance of 650 nm (or 850 nm) wavelength light of 90% or more, more preferably 92% or more, and particularly 94% or more.

  The light transmittance is a value measured using a self-recording spectrophotometer (U-3310 (trade name) manufactured by Hitachi, Ltd.).

  The optical material of the present invention is different from conventional optical materials in that it is excellent in flexibility. Flexibility is an important requirement for flexible devices such as optical fibers, optical interconnections, and flexible circuits.

  Flexibility is achieved by encapsulating the monomer together with an initiator in a glass tube with an inner diameter of 1 mm, irradiating active energy rays such as ultraviolet rays, and taking out the polymerized and cured product from the glass tube to produce a fiber with a diameter of 1 mm. This fiber is wound around a round steel bar having a different radius under an environment of 25 ° C., and the radius of the round bar when the copolymer fiber is cracked is evaluated. In the present invention, round bars having a radius of 6 mm, 10 mm, 15 mm, 20 mm, and 30 mm are used.

  The flexibility of the heat-resistant fluorine-containing optical material of the present invention is 15 mm (round bar radius) or more. After satisfying the above characteristics, the flexibility is 10 mm or less, and the composition is further adjusted to 6 mm (round). Even if it is wound around a round bar having a radius of less than (rod radius), that is, a radius of 6 mm, it does not crack.

  In addition, the optical material of the present invention exhibits excellent properties in characteristics such as the thermal decomposition temperature Td. These are shown in the examples.

  The optical material of the present invention is useful as a material for various optical devices, for example, an optical transmission medium (second of the present invention). In particular, cladding material of plastic clad optical fiber whose core material is quartz or optical glass, cladding material of all plastic optical fiber whose core material is plastic, anti-reflection coating material, lens material, optical waveguide material, prism material, optical window Optical materials such as materials, optical storage disk materials, nonlinear optical elements, hologram materials, photolithographic materials, sealing member materials, and optical devices including cured products obtained by curing these materials, etc. Can be used.

  Particularly, since it has the characteristics of heat resistance, low refractive index and excellent flexibility, optical fiber cladding material, especially optical fiber whose core material is quartz or optical glass, that is, plastic clad optical fiber. It is suitable as a cladding material.

  A plastic clad optical fiber having quartz or optical glass as a core material and the optical material of the present invention as a clad material has high Tg, high heat resistance and excellent flexibility in addition to the characteristics as an optical fiber. It is particularly useful as an optical fiber disposed in a narrow space below.

  For example, in a light guide, heat resistance is required when a plastic clad optical fiber is laid close to a halogen light source. In sensor applications, heat resistance is required when detecting a part where the atmosphere is hot, such as detection of headlight illumination of a car or positioning sensor of a melt press. The same applies to sensors for industrial robots. In optical communication applications, heat resistance of 100 ° C. or higher is required when wiring to an engine room, a car ceiling, an installed panel, or the like that becomes high temperature in an in-vehicle LAN. The same applies when mounted on an aircraft. For plastic clad optical fiber wiring in factory automation (FA) applications, heat resistance is required when exposed to high temperature environments. Further, even when used outdoors or indoors, heat resistance is required for an environment where there is no normal air conditioning equipment such as a switchboard room on a building roof or a communication base station. The heat-resistant fluorine-containing optical material of the present invention can be effectively used for these applications.

In order to form the heat-resistant fluorine-containing optical material of the present invention on a core material, for example, a core material made of quartz or optical glass, for example, the monomer composition is formed by a method such as a die coating method or a spray coating method. A plastic clad optical fiber can be manufactured by applying to a core material and irradiating the core material with an active energy ray such as ultraviolet rays and curing to form a clad material. The amount of light irradiation is usually 10 to 5000 mJ / cm ² . The diameter of the core is usually 10 to 1000 μm. The thickness of the clad is usually 1 to 100 μm, preferably 5 to 50 μm.

  The present invention also provides (I) Formula (1):

(Wherein X ¹ is at least one selected from the group consisting of H, CH ₃ , F, Cl and CF ₃ ; Rf ¹ and Rf ² are the same or different, and a perfluoroalkyl group having 1 to 5 carbon atoms; R ¹ represents at least one monomer represented by a hydrocarbon group having 1 to 5 carbon atoms which may be substituted with a fluorine atom;
(II) Formula (2):

Wherein X ² and X ³ are the same or different and are at least one selected from the group consisting of H, CH ₃ , F, Cl and CF ₃ ; n is an integer from 1 to 6, for example from 1 to 3; ² is at least one monomer represented by an (n + 1) -valent organic group having 1 to 50 carbon atoms, such as 1 to 30 carbon atoms;
(III) at least one other monomer copolymerizable with the monomers of the formula (1) and the formula (2); and (IV) a polymerization initiator, and the monomer in all the monomers (I), a curable composition in which the monomer (II) and the monomer (III) occupy 1 to 99 mol%, 1 to 99 mol% and 0 to 98 mol%, respectively Regarding 3).

  Monomer component (I) represented by formula (1), monomer component (II) represented by formula (2) and optional monomer component (III) In the heat-resistant fluorine-containing optical material of the first invention, all of ()) described as the structural units M, N, and A are adopted as they are, including specific examples.

  As the polymerization initiator (IV), those described above as the active energy ray curing initiator and the radical polymerization initiator can be employed as they are, including specific examples.

  The combination of component (I), component (II), component (III) and component (IV) and their amounts are the same as those described in the heat-resistant fluorine-containing optical material of the first invention, including specific examples. Adopted.

  Examples of the material for the sealing member include light emitting diodes (LEDs), EL elements, nonlinear optical elements, photorefractive elements, light emitting elements such as photonic crystals, light receiving elements, wavelength conversion elements, optical add / drop elements, optical cross connect elements, Examples include materials used for packages (encapsulation) and surface mounting of optical functional elements such as modulators.

  The optical device encapsulated with the material of the present invention has an extremely high moisture resistance reliability due to the polymer component containing the polymer component in addition to the excellent moisture resistance derived from the fluorine-containing polymer in the encapsulated portion. have. It is also a material having both excellent transparency and heat resistance in the wavelength band to be used.

  These sealed light elements are used in various places, but non-limiting examples include high-mount stop lamps, meter panels, mobile phone backlights, light sources for remote control devices for various electrical products, etc. Light-emitting elements such as: auto-focusing of cameras, light-receiving elements for optical pickups for CD / DVD, and the like.

  The sealing member material using the material of the present invention is blended with additives such as a photo-oxidizing agent, a curing accelerator, a dye, a modifying agent, a deterioration preventing agent, a release agent, and the like as necessary. It can be produced by combining and kneading by a conventional method in combination with a method and further a melt blending method, and then pulverizing and tableting as necessary.

  Sealing with the material for the sealing member can be performed by a conventional method, and can be performed by filling and molding a portion to be sealed by a known molding method such as a transfer molding method.

  The active energy ray-curable composition of the present invention is particularly suitable for optical applications. In addition, by utilizing the properties of organic polymers obtained by curing, applications other than optical applications such as adhesives, paints, and various moldings are used. It is also useful as a material for producing materials and dental materials.

  Accordingly, the curable composition of the present invention can be blended with various additives for optical applications, pigments, fillers, photocatalysts such as titanium oxide, and the like.

  Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to the following examples.

  First, the compounds (monomers) used in the examples and comparative examples and methods for measuring various properties are shown.

Compound

Measurement Method (1) Viscosity of Composition The viscosity of the composition before curing at 25 ° C. is measured with a B-type viscometer manufactured by Tokyo Keiki Co., Ltd.

(2) Refractive index The said method (25 degreeC). The refractometer used is an Abbe refractometer manufactured by Atago Optical Instruments Co., Ltd.

(3) Glass transition temperature (Tg)
Said method. The differential scanning calorimeter used is a differential scanning calorimeter manufactured by Seiko Electronics Corporation.

(4) Thermal decomposition temperature (Td)
Using a TGA-50 type thermobalance manufactured by Shimadzu Corporation, the temperature at which weight reduction starts is measured at a heating rate of 10 ° C./min.

(5) Light transmittance (T)
A film having a thickness of about 1 mm of a cured fluorine-containing organic polymer is sandwiched between quartz glass plates, and using a self-recording spectrophotometer (U-3310 (trade name) manufactured by Hitachi, Ltd.), transmittance at wavelengths of 650 nm and 850 nm. Measure.

(6) Flexibility (F)
Said method. (A fibrous sample is wound once around a steel round bar having a different radius under an environment of 25 ° C., and evaluated by the radius of the round bar when the copolymer fiber is cracked. In the present invention, the round bar is evaluated. (6 mm, 10 mm, 15 mm, 20 mm, and 30 mm radii are used.)

(7) Transmission loss The transmission loss at a wavelength of 650 nm at an incident NA = 0.1 is measured with an optical power meter (ML9001A manufactured by Anritsu Co., Ltd., detector MA9411A) by a cutback method of 25m-5m.

Example 1
The following monomer mixture was prepared.
6FNPF 50 parts by weight FB-DFA 20 parts by weight Cyclohexyl α-F acrylate 10 parts by weight UR-DMA 20 parts by weight

  To this monomer mixture, 0.1% by weight of 2-hydroxy-2-methylpropiophenone was added as an active energy ray curing initiator to prepare an active energy ray curable composition.

This curable composition was coated on an aluminum foil using an applicator so that the film thickness was about 100 μm, and the resulting film was cured by irradiating with ultraviolet rays at an intensity of 1000 mJ / cm ² U using a high-pressure mercury lamp. Then, the aluminum foil was dissolved with dilute hydrochloric acid to obtain a sample film.

  The sample film was examined for refractive index, glass transition temperature, thermal decomposition temperature, and light transmittance. The results are shown in Table 1.

  The flexibility was evaluated by preparing a fibrous sample having a diameter of 1 mm by the above-described manufacturing method.

Example 2
A monomer mixture having the following composition was prepared.
6FNPM 50 parts by weight 8FF 10 parts by weight FB-DFA 20 parts by weight UR-DMA 20 parts by weight

  An active energy ray-curable resin composition was prepared in the same manner as in Example 1 except that this monomer mixture was used, and various physical properties were measured in the same manner as in Example 1. The results are shown in Table 1.

Example 3
A monomer mixture having the following composition was prepared.
6FNPF 60 parts by weight 8FM 20 parts by weight FB-GMA 20 parts by weight

  An active energy ray-curable resin composition was prepared in the same manner as in Example 1 except that this monomer mixture was used, and various physical properties were measured in the same manner as in Example 1. The results are shown in Table 1.

Example 4
A monomer mixture having the following composition was prepared.
6 FNPM 50 parts by weight 8 FM 10 parts by weight BisF-GMA 10 parts by weight FC-DFA 10 parts by weight UR-DMA 20 parts by weight

  An active energy ray-curable resin composition was prepared in the same manner as in Example 1 except that this monomer mixture was used, and various physical properties were measured in the same manner as in Example 1. The results are shown in Table 1.

Example 5
A monomer mixture having the following composition was prepared.
6FNPF 40 parts by weight 8FF 20 parts by weight FB-DFA 20 parts by weight FC-GMA 20 parts by weight

  An active energy ray-curable resin composition was prepared in the same manner as in Example 1 except that this monomer mixture was used, and various physical properties were measured in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1
A monomer mixture having the following composition was prepared.
17 FMA 40 parts by weight Bis-GMA 30 parts by weight UR-DMA 30 parts by weight

  An active energy ray-curable resin composition was prepared in the same manner as in Example 1 except that this monomer mixture was used, and various physical properties were measured in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2
A monomer mixture having the following composition was prepared.
17 FMA 50 parts by weight 8FF 10 parts by weight FB-DFA 20 parts by weight UR-DMA 20 parts by weight

  An active energy ray-curable resin composition was prepared in the same manner as in Example 1 except that this monomer mixture was used, and various physical properties were measured in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 3
A monomer mixture having the following composition was prepared.
17 FMA 60 parts by weight 8 FM 20 parts by weight FB-GMA 20 parts by weight

  An active energy ray-curable resin composition was prepared in the same manner as in Example 1 except that this monomer mixture was used, and various physical properties were measured in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 4
A monomer and polymer mixture having the following composition was prepared.
Monomer shown in Formula (10) 25 parts by weight Monomer shown in Formula (11) 15 parts by weight Polymer shown in Formula (12) 60 parts by weight

An active energy ray-curable resin composition was prepared in the same manner as in Example 1 except that this mixture was used, and various physical properties were measured in the same manner as in Example 1. The results are shown in Table 1.
Formula (10):

Formula (11):

Formula (12):

  dcP = dicyclopentanyl group, NB = norbornene group, x: y: z = 1: 8: 1, molecular weight = about 10,000

Example 6
The curable composition of Example 1 was uniformly applied to a quartz core (refractive index: 1.46) having a diameter of 200 μm (film thickness: about 20 μm), and cured by irradiating with ultraviolet rays in the same manner as in Example 1.

  The initial transmission loss at a wavelength of 650 nm and the transmission loss after a heat resistance test (held at 125 ° C. for 24 hours) of the obtained plastic clad optical fiber were measured. The results are shown in Table 2.

Comparative Example 5
A plastic clad optical fiber was prepared in the same manner as in Example 6 except that the curable composition of Comparative Example 2 was used, and the transmission loss of the obtained optical fiber and the transmission loss after the heat test were measured in the same manner as in Example 6. did. The results are shown in Table 2.

Example 7
A monomer mixture having the following composition was prepared.
6FNPM 15 parts by weight FB-GMA 20 parts by weight 8FM 32 parts by weight MMA 25 parts by weight

  Further, 8 parts by weight of an 8FM polymer having a number average molecular weight of 80,000 was dissolved in this mixture.

  An active energy ray-curable resin composition was prepared in the same manner as in Example 1 except that the obtained mixture was used, and various physical properties were measured in the same manner as in Example 1. The results are shown in Table 3.

Example 8
A monomer mixture having the following composition was prepared.
6FNPM 15 parts by weight FB-GMA 20 parts by weight 8FF 32 parts by weight MMA 25 parts by weight

  Further, 8 parts by weight of an 8FF polymer having a number average molecular weight of 80,000 was dissolved in this mixture.

  An active energy ray-curable resin composition was prepared in the same manner as in Example 1 except that the obtained mixture was used, and various physical properties were measured in the same manner as in Example 1. The results are shown in Table 3.

Claims (12)

Formula (M-1):
-[M]-[N]-[A]-(M-1)
[Where:
The structural unit M is represented by the formula (1):

(Wherein X ¹ is at least one selected from the group consisting of H, CH ₃ , F, Cl and CF ₃ ; Rf ¹ and Rf ² are the same or different, and a perfluoroalkyl group having 1 to 5 carbon atoms; R ¹ is a structural unit derived from at least one monomer represented by a hydrocarbon group having 1 to 5 carbon atoms in which part or all of the hydrogen atoms may be substituted with fluorine atoms,
The structural unit N is represented by the formula (2):

Wherein X ² and X ³ are the same or different and are at least one selected from the group consisting of H, CH ₃ , F, Cl and CF ₃ ; R ² contains a fluorine atom, and
Formula (R2-5):

(Wherein R ²¹ and R ²² are the same or different and an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms; Z ²¹ and Z ²² are the same or different and have 1 to A divalent organic compound having a moiety represented by 5 alkyl group, a fluorine-containing alkyl group having 1 to 5 carbon atoms, a functional group, a hydrogen atom or a halogen atom; and r1 and r2 are the same or different and are integers of 1 to 4) Group,
Formula (R2-6):

(In the formula, R ²³ , R ²⁴ , R ²⁵ and R ²⁶ are the same or different, and an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms ; Z ²³ has 1 to 5 carbon atoms ; A divalent organic group containing a site represented by an alkyl group, a fluorine-containing alkyl group having 1 to 5 carbon atoms, a functional group, a hydrogen atom or a halogen atom; r3 is an integer of 1 to 4,
Formula (R2-12):

(Wherein, unlike R ³³ and R ³⁴ are the same or a fluorine-containing alkyl group of 1 to 5 alkyl group or a C1-5 carbon; Z ²⁷ and Z ²⁸ are the same or different, 1 to carbon atoms A divalent organic compound having a moiety represented by 5 alkyl group, fluorine-containing alkyl group having 1 to 5 carbon atoms, functional group, hydrogen atom or halogen atom; s1 and s2 are the same or different and are integers of 1 to 4) Group,
Or
Formula (R2-13):

(In the formula, R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ are the same or different, and an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms ; Z ²⁹ has 1 to 5 carbon atoms ; An alkyl group, a fluorine-containing alkyl group having 1 to 5 carbon atoms, a functional group, a hydrogen atom or a halogen atom; s3 is a divalent organic group containing a site represented by an integer of 1 to 4) A structural unit derived from at least one species,
The structural unit A is represented by a structural unit derived from at least one other monomer copolymerizable with the monomers of the formula (1) and the formula (2)], and the structural unit M is 1 to 99 mol%. A heat-resistant fluorine-containing optical material comprising a structural unit M-1 containing 1 to 99 mol% of the structural unit N and 0 to 98 mol% of the structural unit A, and comprising a polymer cured product having a glass transition temperature of 100 ° C. or higher. The structural unit A is represented by the formula (3):

Wherein X ⁴ is at least one selected from the group consisting of H, CH ₃ , F, Cl and CF ₃ ; R ³ is a monovalent hydrocarbon group having 6 to 30 carbon atoms and containing an aromatic ring; However, a structural unit A-1 derived from at least one of the monomers represented by the above, wherein some or all of the hydrogen atoms in R ³ may be substituted with fluorine atoms;
Formula (4):

Wherein X ⁵ is at least one selected from the group consisting of H, CH ₃ , F, Cl and CF ₃ ; R ⁴ is a monovalent hydrocarbon having 3 to 30 carbon atoms and having an alicyclic hydrocarbon moiety. A structural unit A-2 derived from at least one monomer represented by the following formula: wherein a part or all of hydrogen atoms in R ⁴ may be substituted with fluorine atoms; Structural units A-3 derived from monomers copolymerizable with the monomers respectively represented by 1) to (4)
At least one selected from the group consisting of:
Heat of claim 1 Symbol placement 1 to 98 mol% combined structural unit A-1 and the structural unit A-2 in the structural unit M-1 and the structural unit A-3 is a structural unit containing 0 to 97 mol% Fluorinated optical material. The heat-resistant fluorine-containing fluorine-containing compound according to claim 2 , wherein at least one of the structural units A-1 is a phenyl group in which a part or all of hydrogen atoms in R ³ may be substituted with fluorine atoms, or a derivative thereof. Optical material. The heat-resistant fluorine-containing fluorine-containing compound according to claim 2 , wherein at least one of the structural units A-2 is a cyclohexyl group or a derivative thereof in which R ⁴ may be partially or entirely substituted with a fluorine atom. Optical material. At least one of the structural units A-2 is an alicyclic hydrocarbon group or a derivative thereof having a multicyclic structure in which R ⁴ may have some or all of hydrogen atoms substituted with fluorine atoms. The heat-resistant fluorine-containing optical material according to claim 2 . The heat-resistant fluorine-containing optical material according to any one of claims 1 to 5 , wherein the polymer cured product has a refractive index of 1.44 or less. Optical transmission medium made by using a heat-resistant fluorine-containing optical material of any of claims 1-6. A plastic clad optical fiber comprising a quartz or optical glass core and a clad made of the heat-resistant fluorine-containing optical material according to any one of claims 1 to 6 . The plastic clad optical fiber according to claim 8, which is a plastic optical fiber for LAN mounted on a vehicle. (I) Formula (1):

(Wherein X ¹ is at least one selected from the group consisting of H, CH ₃ , F, Cl and CF ₃ ; Rf ¹ and Rf ² are the same or different, and a perfluoroalkyl group having 1 to 5 carbon atoms; R ¹ is at least one monomer represented by a hydrocarbon group having 1 to 5 carbon atoms in which part or all of the hydrogen atoms may be substituted with fluorine atoms,
(II) Formula (2):

Wherein X ² and X ³ are the same or different and are at least one selected from the group consisting of H, CH ₃ , F, Cl and CF ₃ ; R ² contains a fluorine atom, and
Formula (R2-5):

(Wherein R ²¹ and R ²² are the same or different and an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms; Z ²¹ and Z ²² are the same or different and have 1 to A divalent organic compound having a moiety represented by 5 alkyl group, a fluorine-containing alkyl group having 1 to 5 carbon atoms, a functional group, a hydrogen atom or a halogen atom; and r1 and r2 are the same or different and are integers of 1 to 4) Group,
Formula (R2-6):

(In the formula, R ²³ , R ²⁴ , R ²⁵ and R ²⁶ are the same or different, and an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms ; Z ²³ has 1 to 5 carbon atoms ; A divalent organic group containing a site represented by an alkyl group, a fluorine-containing alkyl group having 1 to 5 carbon atoms, a functional group, a hydrogen atom or a halogen atom; r3 is an integer of 1 to 4,
Formula (R2-12):

(Wherein, unlike R ³³ and R ³⁴ are the same or a fluorine-containing alkyl group of 1 to 5 alkyl group or a C1-5 carbon; Z ²⁷ and Z ²⁸ are the same or different, 1 to carbon atoms A divalent organic compound having a moiety represented by 5 alkyl group, fluorine-containing alkyl group having 1 to 5 carbon atoms, functional group, hydrogen atom or halogen atom; s1 and s2 are the same or different and are integers of 1 to 4) Group,
Or
Formula (R2-13):

(In the formula, R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ are the same or different, and an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms ; Z ²⁹ has 1 to 5 carbon atoms ; An alkyl group, a fluorine-containing alkyl group having 1 to 5 carbon atoms, a functional group, a hydrogen atom or a halogen atom; s3 is a divalent organic group containing a site represented by an integer of 1 to 4) At least one;
(III) at least one other monomer copolymerizable with the monomers of the formula (1) and the formula (2); and (IV) a polymerization initiator, and the monomer in all the monomers A curable composition in which the proportions of (I), monomer (II) and monomer (III) are 1 to 99 mol%, 1 to 99 mol% and 0 to 98 mol%, respectively. The curable composition according to claim 10 which is active energy ray curable. A method for producing an optical transmission medium, wherein the curable composition according to claim 10 or 11 is applied to quartz or optical glass and then cured.