WO2006082845A1

WO2006082845A1 - Curable composition and optical member obtained by curing same

Info

Publication number: WO2006082845A1
Application number: PCT/JP2006/301652
Authority: WO
Inventors: Yoshito Tanaka; Yuzo Komatsu; Yoshito Ando
Original assignee: Daikin Industries, Ltd.
Priority date: 2005-02-04
Filing date: 2006-02-01
Publication date: 2006-08-10
Also published as: JP5169213B2; JPWO2006082845A1

Abstract

Disclosed is a curable composition containing a multifunctional fluorine-containing compound (I) represented by the following general formula (1): (1) (wherein X1s may be the same as or different from one another and respectively represent at least one selected from the group consisting of H, CH3, F Cl and CF3; n represents an integer of 2-7; R1s may be the same as or different from one another and respectively represent a bonding hand or a divalent organic group having 1-50 carbon atoms wherein some or all of the hydrogen atoms may be substituted by fluorine atoms; and R2 represents an n-valent organic group having 1-50 carbon atoms wherein some or all of the hydrogen atoms may be substituted by fluorine atoms), and a curing initiator (II). The multifunctional fluorine-containing compound (I) is also characterized in that (1) the fluorine content thereof is not less than 40% by mass; (2) the viscosity at 35°C is not more than 100,000 mPa·s; and (3) a cured product thereof has a glass transition temperature of not less than 70°C. This curable composition enables to obtain an optical member such as an optical waveguide with high fluorine content which has high heat resistance and high transparency without using a solvent.

Description

Curable composition and optical member obtained by curing the same

Technical field

[0001] The present invention relates to a curable composition capable of providing an optical material having a high fluorine content and high heat resistance and high transparency without using a solvent, for example, an optical waveguide.

Background art

In recent years, organic materials that can be mass-produced with good processability in circuit creation have attracted attention as optical waveguide materials.

[0003] Among them, various fluorine-based materials have been proposed because fluorine-based materials are transparent to light in the near-infrared region, which is a communication wavelength band. By using these materials, it is possible to fabricate organic optical waveguides with low optical signal loss. However, in order to realize organic optical waveguides with even lower loss, materials with further improved transparency can be used. Is desired

[0004] As fluorine-based organic materials for optical waveguides, fluorine-containing polyimide materials (JP-A-2-281037) and fluorine-containing acrylic polymers (JP-A 2000-81520) are known. .

[0005] By the way, in order to cover the optical waveguide, the polymer and Z or polymer are dissolved in an organic solvent, and a thin film (core layer, clad layer) is formed by a method such as spin coating, dipping or casting. In general, a processing method of appropriately curing is taken.

However, in molding using such an organic solvent, when forming the core layer, the surface of the previously formed cladding layer is dissolved by the organic solvent and mixed with each other. Due to the mixing, the interface of the core Z-cladding becomes non-uniform and the optical signal loss increases significantly. In addition, after forming each layer, it is necessary to volatilize the organic solvent in the film forming the layer by drying or the like, but the light in the near-infrared region is still emitted by the organic solvent remaining in the film in minute amounts. Another problem is that transparency in the near-infrared region decreases due to absorption and scattering. In addition, microvoids resulting from the evaporation of the organic solvent remaining in the film may cause light scattering, leading to a decrease in transparency in the near infrared region. . In particular, residual organic solvents and microvoids significantly reduce the transparency in the near-infrared region, so that the optical waveguide loss is greatly increased.

[0007] In order to solve such a problem, it has been proposed to use a curable composition comprising an acrylic monomer and a fluorine-containing acrylic polymer (Japanese Patent Laid-Open No. 5-9043).

JP-A-5-9043 discloses a fluorinated polymer obtained by polymerizing a fluorinated curable monomer containing a fluorinated alkyl group having 5 or less carbon atoms as an essential component, and a fluorinated alkyl group. A curable composition comprising a fluorine-containing curable monomer containing a polyfunctional monomer containing two or more (meth) attalyloyl groups in the molecule, and a fluorine-based curable monomer. For the purpose of further improving the fluorine content, a monomer containing a linear fluoroalkyl group having a high fluorine content is used in the ester part. And

However, such a fluorinated monomer may cause the liquid composition itself to become cloudy because the solubility of the fluorinated polymer is low. Even if a uniform liquid composition can be formed, even if a cured product obtained becomes cloudy or even a transparent cured product is obtained, the fluorine-containing polymer and the fluorine content are high by heating. When the phase separation from the linear fluoroalkyl group occurs and the cloudiness occurs, the transparency is lowered. Furthermore, even in the cured product, crystallization of linear fluoroalkyl groups proceeds, resulting in white turbidity due to recrystallization at high temperatures, and transparency of the cured product in the near-infrared region. There is a problem that decreases.

A liquid material having a high fluorine content that can be used as a raw material for optical materials has been proposed in JP-A-1-216948. This liquid material is a fluorine-containing polyether compound having two chain-like (meth) atalyloyl groups, and its crosslinked product exhibits an elastomeric shape and has a low glass transition temperature.

[0011] Further, JP-A-63-101409 describes a liquid polyfunctional fluorine-containing compound which contains an aromatic hydrocarbon structure and gives a cured product having a high glass transition temperature. The thing has low transparency in the near infrared region where the fluorine content is low.

[0012] Further, a compound having a high fluorine content that gives a cured product having a high glass transition temperature, which has been known so far, is a solid compound and is dissolved in an organic solvent or dissolved in a liquid comonomer. Let To produce a cured product. However, according to the study by the present inventors, there is a limit to the solubility when used by dissolving in a liquid copolymer, and many compounds having a high fluorine content cannot be dissolved. There is a limit to improving the content rate.

Disclosure of the invention

[0013] Thus, in order to give a cured product with a high fluorine content (excellent transparency) and a high glass transition temperature (excellent heat resistance), the raw material has a high fluorine content and It is necessary to be liquid at room temperature, and curable compositions containing fluorine-containing compounds that satisfy these requirements are known.

[0014] The present invention can obtain a cured product by forming a liquid composition without using an organic solvent, and even if the cured product has a high fluorine content, the transparency and heat resistance of the cured product can be obtained. It aims at providing the curable composition which can improve property.

[0015] Still another object of the present invention is to provide an optical waveguide using the composition.

That is, the present invention relates to

(I) Formula (1):

[0017] [Chemical 1]

X ¹

I

—— ( _R i _ o-C-C = CH ₂ ) _n (1)

O

[0018] (where X ¹ is the same or different, and a group force consisting of H, CH, F, CI and CF is also selected)

3 3

At least one; n is an integer of 2 to 7; R ¹ is the same or different, and a bond or a part or all of hydrogen atoms having 1 to 50 carbon atoms may be substituted with a fluorine atom. An organic group; R ² may be a fluorine atom in which some or all of the hydrogen atoms having 1 to 50 carbon atoms may be substituted with an n-valent organic group; provided that at least one of X ¹ , R ¹ and R ² is (Including fluorine atoms)

(1) Fluorine content is 40 mass% or more,

(2) viscosity at 35 ° C is 100, OOOmPa'sec or less, and

(3) The glass transition temperature of the cured product of the compound represented by formula (1) is 70 ° C or higher.

A polyfunctional fluorine-containing compound, and (II) Curing initiator

The present invention relates to a curable composition (first invention).

In the polyfunctional fluorine-containing compound (I) represented by the formula (1), at least one of R ¹ is a divalent fluorine-containing organic compound in which a part or all of hydrogen atoms are substituted with fluorine atoms. In addition, a fluorine-containing organic group having a monovalent fluorine-containing organic group in the side chain is preferred because it has a high fluorine content and can form a liquid composition.

[0020] In addition, in the polyfunctional fluorine-containing compound (I) represented by the formula (1), R ² may have a hetero atom! /, Or may be a portion of an aromatic hydrocarbon structure or Partial force of the aliphatic cyclic hydrocarbon structure which may have a tera atom An n-valent organic group containing at least one selected portion is also preferable for improving the heat resistance of the cured product .

[0021] The curable composition of the present invention may further contain a monofunctional acrylate, preferably a monofunctional fluorine-containing acrylate.

[0022] The monofunctional fluorine-containing acrylate includes a monofunctional fluorine-containing fluorine having a fluorine content of 10% by mass or more and a glass transition temperature of a cured product of the monofunctional fluorine-containing acrylate. Atallate is preferable in that the heat resistance of the cured product is improved and the fluorine content is high, that is, it is transparent over a wide wavelength range (ultraviolet region to near infrared region). Furthermore, from the viewpoint of good compatibility with the polyfunctional fluorine-containing compound (I), preferred is the formula (2):

[0023] [Chemical 2]

[Wherein X ² is at least one selected from the group force consisting of H, CH, F, CI and CF; R ³ is R ⁴

3 3

And / or R ⁵ and

R ⁴ is the formula (1-1):

[0025] [Chemical 3]

-40CF ₂ -H-OCF ₂ CFZH ^-OCF ₂ CF ₂ CF ₂ ^-(OCH ₂ CF ₂ CF ₂ HT (1 — 1) [0026] (where Z is F or CF; ml, m2, m3 , M4 is 0 or an integer from 1 to 10, provided that

Three

ml + m2 + m3 + m4 is an integer of 1 to 10) R ⁵ is the formula (1 2):

[0027] [Chemical 4]

Rf ²

-CH ^ C-Rf ¹ (i-2)

R S

(Wherein Rf ¹ and Rf ² are the same or different, and a perfluoroalkyl group having 1 to 5 carbon atoms; R ⁶ is a hydrogen atom partially or entirely substituted with a fluorine atom; And a fluorine-containing alkyl group containing a moiety represented by a hydrocarbon group having 1 to 5 carbon atoms)

1 type or 2 types or more of monofunctional fluorine-containing acrylates represented by these.

[0029] The content of the curing initiator (II) is preferably 0.01% by mass or more and 10% by mass or less.

[0030] When the monofunctional fluorine-containing acrylate is blended, 10 to 80 parts by mass is blended with 100 parts by mass of the polyfunctional fluorine-containing compound (I). It is preferable in terms of improvement and less shrinkage during curing.

[0031] It is desirable that the curable composition of the present invention is also liquid. The viscosity at 35 ° C is preferably 10 to: LO, 00 OmPa 'seconds.

[0032] The second invention of the present invention relates to a cured product obtained by curing the curable composition of the present invention.

[0033] This cured product preferably has a fluorine content power of 0% by mass or more, a heat resistance point force that is preferable from the viewpoint of excellent transparency, and a glass transition temperature of 100 ° C or higher.

[0034] The third invention of the present invention is an optical material having a cured product force of the second invention and an optical waveguide having a core part and a clad part force, wherein at least one of the core part and the clad part is the second part. The present invention relates to an optical waveguide characterized in that the cured product of the invention is obtained.

[0035] The fourth invention of the present invention relates to a novel polyfunctional fluorine-containing compound represented by the formula (3).

Equation (3):

[0036] [Chemical 5] X ³

R ^ (: R No O— C— C = CH ₂ ) _n (3)

O

[0037] (wherein X ³ is the same or different and a group force consisting of H, CH, F, CI and CF is also selected)

3 3

At least one; n is an integer of 2 to 7; R ⁷ is the same force or different, and a bond or a part or all of hydrogen atoms having 1 to 50 carbon atoms may be substituted with a fluorine atom. Organic group; R ⁸ may be a part of or all of hydrogen atoms having 1 to 50 carbon atoms substituted by fluorine atoms, or a V ヽ n-valent organic group having hetero atoms. An aromatic hydrocarbon structure site or a heteroatom, but an aliphatic cyclic hydrocarbon structure site force, an organic group containing at least one selected site; provided that at least R ⁷ One is the formula (4):

[0038] [Chemical 6] ^ _ ^ c II ₂ ~ 7 ~ ―ri ri and II ₉ ~) ~ ~, 4)

'I

R f ³

[0039] (wherein Rf ³ is a fluorine-containing alkyl group having 1 to 19 carbon atoms; z, X and y are the same or different and 0 or 1). A polyfunctional fluorine-containing compound represented by:

[0040] Examples of the polyfunctional fluorine-containing compound represented by the formula (3) include

(1) Fluorine content is 40 mass% or more,

(2) viscosity at 35 ° C is 100, OOOmPa'sec or less, and

(3) The glass transition temperature of the cured product of the compound represented by formula (3) is 70 ° C or higher.

The polyfunctional fluorine-containing compound is preferred.

[0041] The fifth invention of the present invention relates to a curable composition comprising the novel polyfunctional fluorine-containing compound (1-1) represented by the formula (3) and a curing initiator (II).

[0042] The curable composition of the fifth invention may further contain the above monofunctional acrylate, preferably a monofunctional fluorine-containing acrylate.

[0043] Further, a cured product obtained by curing the composition of the fifth invention, an optical material comprising the cured product, and an optical waveguide having a core part and a clad part force, the core part and the clad The present invention also relates to an optical waveguide characterized in that at least one of the parts has a cured product force obtained by curing the composition of the fifth invention.

Brief Description of Drawings

FIG. 1 is a schematic cross-sectional view of the structure of an optical waveguide device.

FIG. 2 is a block diagram of a manufacturing process of an optical waveguide device.

FIG. 3 is a schematic flowchart of an optical system used to measure the emission intensity at 1550 nm in the present invention. BEST MODE FOR CARRYING OUT THE INVENTION

[0045] First, the formula (1) used in the curable composition of the present invention:

[0046] [Chemical 7]

X ¹

I

—— (RO— C— C = CH ₂ ) _n (1)

O

[0047] (In the formula, X ¹ is the same or different, and a group force consisting of H, CH, F, CI and CF is selected.

3 3

(1) Fluorine content is 40 mass% or more,

(2) viscosity at 35 ° C is 100, OOOmPa'sec or less, and

The polyfunctional fluorine-containing compound (I) will be described.

[0048] In Formula (1), X ¹ is the same or different and is a group consisting of H, CH, F, CI and CF

3 3

At least one selected from the group consisting of a (meth) atallyloyl group or a halogen-containing (meth) attalyl group. X ¹ is preferably F or CH because it has excellent heat resistance of the cured product.

3 In particular, when the fluorine content is increased, F is also preferred for the point force. [0049] The polyfunctional fluorine-containing compound represented by the formula (1) is a polyfunctional fluorine-containing compound having n of 2 to 7, that is, 2 to 7 (meth) atalyloyl groups or halogen-containing (meth) atalyloyl groups . n is preferably 2 to 4, more preferably 2 or 3, from the viewpoint of good storage stability.

[0050] R ¹ may be the same force or different, and a bond or a hydrogen atom having 1 to 50 carbon atoms, preferably 1 to 30 carbon atoms may be partially or entirely substituted with a fluorine atom. It is an organic group, and acts as a spacer that connects the n-valent organic group R ² and the attalyloyl group. If R ² has the required fluorine content, it may simply be a bond.

[0051] R ¹ is preferably a fluorine-containing organic group in which some or all of the hydrogen atoms are substituted with fluorine atoms, and the point of increasing the fluorine content is also preferable.

[0052] In particular, a divalent fluorine-containing organic group having a monovalent fluorine-containing organic group in the side chain is preferred from the viewpoint that a liquid composition can be formed with a high fluorine content. The monovalent fluorine-containing organic group forming the side chain has a fluorine content of 50% by mass or more, more preferably 60% by mass or more, and particularly 70% by mass or more. Point power to increase the fluorine content is preferable. . The upper limit is the fluorine content of the perfluoro organic group.

[0053] R ¹ is preferred to have the structure represented by formula (5):

[0054] [Chemical 8]

〇 ^ ~ c II c II ~ kc II ₂ (5)

I

R f ⁴

[0055] (wherein Rf ⁴ is a fluorine-containing organic group having 1 to 19 carbon atoms; z, X and y are the same or different, 0 or l; q is an integer of 1 to 10) It is preferable that the fluorine-containing organic group is 2 to 50 in order to increase the fluorine content and lower the viscosity.

[0056] Specifically,

[0057] [Chemical 9] z "― θ H 22-CH ^-CH 1 ₂ 2""-j J ~ q (5 ^— 1)

R f ⁴

H f

h-fO ^ CH ^ C H -4- (5-2)

R f

E ~ ΌΊ CH— CH ₉ 2 · ~ ϊ J q

R f ⁴ CH-+ (5-4)

R f ⁴

(5 5)

[0058] (where Rf ⁴ and q are the same as in formula (5))

The formulas (5-2) and (5-3) are preferred because they are particularly easy to synthesize and easily become liquid compositions. q is preferably 1 or 2 from the viewpoint of improving the heat resistance of the cured product.

[0059] Rf ⁴ is a monovalent fluorine-containing organic group having 119 carbon atoms, and is preferably a fluorine-containing hydrocarbon group, more preferably a fluorine-containing aliphatic hydrocarbon group, from the viewpoint of good compatibility with other solvents. It is.

[0060] More specifically, F (CF) (CH)-(CF) CF (CH)-(CF) CF (CF) (C

2 n 2 m 3 2 2 m 3 2 2 n

H) ― H (CF) (CH) ― F (CF) (CF CH) (CH) ― (CF) CF (CF) (C

2 m 2 n 2 m 2 n 2 2 1 2 m 3 2 2 n

F CH) (CH) One, H (CF) (CF CH) (CH) One,

2 2 1 2 m 2 n 2 2 1 2 m

[0061] [Chemical 10] F 2 CCF-(CH 2) m-

CF ₂ ,

HF C One C F- (CH ₂ ) _m G 2 ^^^ ^ ^ G 2

CF ₂

[0062] (In the formula, n, m and 1 are the same or different and are integers from 0 to 12. However, not all of them are 0)

Etc.

[0063] More specifically, F (CF) -CH—, F (CF) — CH—, F (CF) — CH—, (C

2 2 2 2 4 2 2 6 2

F) CF-CH, (CF) CF (CF) CH—, H (CF) CH—, F (CF) (CF

3 2 2 3 2 2 4 2 2 4 2 2 4 2

CH) —CH— and the like can be preferably exemplified.

2 2 2

Among these, F (CF) —CH— and (CF) CF—CH— are preferred because the cured product has good heat resistance and excellent compatibility with other solvents.

2 4 2 3 2 2

[0065] There are n (= 2 to 7) R ^{1 s} , which may be the same or different. However, it is more advantageous in terms of synthesis if they are the same.

[0066] R ² which is an n-valent organic group may be an organic group in which some or all of the hydrogen atoms having 1 to 50 carbon atoms are substituted with fluorine atoms.

[0067] Specifically,

(1) n-valent chain-like organic group containing tertiary or quaternary carbon,

(2) an n-valent organic group having an aromatic cyclic structure,

(3) an n-valent organic group having an aliphatic cyclic (monocyclic or polycyclic) structure,

In these organic groups, a part or all of hydrogen atoms forming a carbon-hydrogen bond may be substituted with a fluorine atom.

[0068] First, each preferred U and mode of R ² will be described with specific examples.

(1) n-valent chain organic group containing tertiary or quaternary carbon:

Preferably, the aliphatic hydrocarbon group having 3 to 8 carbon atoms improves the heat resistance of the cured product. The preferred valence n is also easy to synthesize and has good storage stability.

[0069] As the divalent chain organic group containing tertiary carbon,

[0070] [Chemical 11]

-CH-CH- -CH-CH-

CH ₃ C II 3 CF ₃ CF ₃

[0071] and the like.

[0072] As the divalent chain organic group containing a quaternary carbon,

[0073] [Chemical 12]

C H C F C F

CH 2 C CH ₂ CH ₂ C CH ₂ CH ₂ C CH.

CH CH

[0074] and the like.

[0075] Examples of the trivalent chain organic group containing tertiary carbon include

[0076] [Chemical 13]

― C 丄 I― し 11― し n ₉ ―

I I

CH 3 CH _2-

[0077] and the like.

[0078] As the trivalent chain organic group containing a quaternary carbon,

[0079] [Chemical 14]

CH _2- … ¹ ^

CH ₂ —

[0080] and the like.

[0081] As the tetravalent chain organic group containing tertiary carbon,

[0082] [Chemical 15] CII ₂ CH 1 C II ₂ CH 1 C II ₂

CH ₂ C II ₂

[0083] and the like.

[0084] As a tetravalent chain organic group containing a quaternary carbon,

[0085] [Chemical 16]

²²

— CH ₂ — C— CH ₂ —

1

C T T _

Γ .1 2

[0086] and the like.

[0087] (2) An n-valent organic group containing an aromatic ring structure:

For example, the formula (R1— 1):

[0088] [Chemical 17]

[0089] (wherein R ²¹ and R ²² are the same force 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 An alkyl group having 1 to 5 carbon atoms, a fluorine-containing alkyl group having 1 to 5 carbon atoms, a functional group, a hydrogen atom or a halogen atom; rl and r2 are the same or different and include a moiety represented by an integer of 1 to 4) Bivalent organic base,

Or the formula (R1—2):

[0090] [Chemical 18]

[0091] (wherein 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 is a carbon number; A divalent organic group having a moiety represented by the following formula: 1-5 alkyl group, fluorine-containing alkyl group having 1-5 carbon atoms, functional group, hydrogen atom or halogen atom; r3 is an integer of 1-4.

[0092] In addition, divalent organic groups containing the sites represented by the following formulas (R1-3) to (R1-7) are also included.

Formula (R1-3):

[0093] [Chemical 19]

[0094] Formula (R1-4):

[0095] [Chemical 20]

[0096] Formula (R1—5)

[0097] [Chemical 21]

[0098] Formula (R1-6):

[0099] [Chemical 22]

[0100] Formula (Rl-7):

[0101] [Chemical 23]

[0102] In the above formula, R ²⁷ , R ²⁸ , R ²⁹ and R ³ ° 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 force 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 force or different and have 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; r4 and r5 are the same force or different, an integer of 1 to 4; r6 is an integer of 1 to 2; r7 and r8 Are the same or different and are integers of 1 to 3, and even if they have the same sign, different formulas or integers can be used as long as the formulas are different.

[0103] As a specific example of the formula (R1-1),

[0104] [Chemical 24]

[S2 ^] [SOTO]

ST

ZS9TOC / 900Zdf / X3d 8 丽 900 OAV

H 2 ₂ CH-i ~ n

-CH _{2 2} CH † 7i

[Wherein r4 and r5 are the same or different and are integers of 1 to 10; Z, rl, and r2 are the same as the above formula (Rl

-Same as 1)).

[0107] As a specific example of (R1-2),

[0108] [Chemical 26]

[0109] (wherein Z ²³ and r3 are the same as those in the above formula (Rl-2)).

[0110] As a specific example of the formula (R1-3),

[0111] [Chemical 27]

CH ₃

[0112] (wherein Z ²⁴ , Z ²⁵ , r4 and r5 are the same as those in the above formula (Rl-3)) are preferred.

[0113] As a specific example of the formula (R1-4),

[0114] [Chemical 28]

[0115] and the like are preferable.

[0116] Specific examples of the formula (Rl-5) include [0117] [Chemical 29]

[0118] (wherein Z ²⁴ Z ²⁵ r4 and r5 are the same as those in the above formula (Rl-5)) are preferred.

[0119] As a specific example of the formula (R1-6),

[0120] [Chemical 30]

ΙΖ

ZS9T0C / 900Zdf / X3d 8 丽 900 OAV

[0122] (wherein Z ²⁴ , T r7 and r8 are the same as those in the above formula (Rl-6)) are preferred.

[0123] As a specific example of the formula (R1-7),

[0124] [Chemical 32]

-CH ₂

HOCHCH, 0-

CH.

C ~ OCH ₂ CHOH CF,

3]

U.

CH ₃

[0126] (wherein Z ^M , Z ^A Z ^z r6, r7 and r8 are the same as those in the above formula (Rl-7)) are preferred.

[0127]

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

[0128] These divalent or higher-valent organic groups having an aromatic ring structure can set a glass transition point that is preferable in terms of excellent heat resistance and mechanical properties, and as a result, optical materials having high heat resistance. Is preferable in that it is obtained.

[0129] Among them, 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. [0130] (3) n-valent organic group having an aliphatic cyclic (monocyclic or polycyclic) structure:

Specifically, the formula (R1-8):

[0131] [Chemical 34]

[0132] (wherein R ³³ and R ³⁴ are the same force or different, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms; Z ²⁷ and Z ²⁸ 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 functional group, a hydrogen atom or a halogen atom; si and s2 are the same or different and include a moiety represented by an integer of 1 to 4) Divalent organic group or formula (R1-9):

[0133] [Chemical 35]

[Wherein 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 fluorine-containing alkyl group having 1 to 5 carbon atoms; Z ²⁹ is a carbon number A divalent organic group having a moiety represented by the following formula: 1-5 alkyl group, fluorine-containing alkyl group having 1-5 carbon atoms, functional group, hydrogen atom or halogen atom; s3 is an integer of 1-4.

In addition, divalent organic groups including the sites represented by the following formulas (R1-10) to (R1-14) are listed.

Formula (R1—10):

[0136] [Chemical 36]

[0141] Formula (Rl

[0142] [Chemical 39]

[0143] Formula (Rl— 14)

[0144] [Chemical 40]

[0145] In the above formula, R ³⁹ , R ⁴ °, R ⁴¹ and R ⁴² are the same force or different, and an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms; and R ⁴⁴ are the same Power or different, charcoal

'5 alkyl group, fluorine-containing alkyl group having 1 to 5 carbon atoms, hydrogen atom; °, and Ζ ³同じ the same or different, alkyl group having 1 to 5 carbon atoms, fluorine-containing carbon atom having 1 to 5 carbon atoms Alkyl group, functional group, hydrogen atom or halogen atom; 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, an integer of 1 to 3 Even with the same sign, different groups and integers can be used as long as the expressions are different.

[0146] As a specific example of the formula (R1-8),

[0147] [Chemical 41]

2]

[0149] (wherein s4 and s5 are the same or different, an integer of 10; Z ²⁷

sl s2 is the above formula (Rl

Same as 8)

Etc. are preferred.

[0150] As a specific example of (R1-9),

[0151] [Chemical 43]

[0152] (In the formula, T s3 is the same as in the above formula (Rl-9)).

[0153] As a specific example of the formula (R1-10),

[0154] [Chemical 44]

[0155] (In the formula, Z ³ °, Z ³¹ , s4 and s5 are the same as those in the above formula (Rl-10)).

[0156] As a specific example of the formula (R1-11),

[0157] [Chemical 45]

[0158] and the like are preferable.

[0159] Specific examples of the formula (Rl-12) include [0160] [Chemical 46]

[0161] (wherein Z ³ °, s4 and s5 are the same as those in the above formula (Rl-12)) are preferred.

[0162] As a specific example of the formula (R1-13),

[0163] [Chemical 47]

[0164] [Chemical 48]

— CH

HOCHCH ₂ 0

One CH ₂

[0165] (wherein, Ζ ^Α Ζ ^ό s7 and s8 are the same as those in the above formula (Rl-13)) and the like [0166] Specific examples of the formula (R1-14) include

[0167] [Chemical 49]

[Oe ^] [8910]

9t

ZS9T0C / 900Zdf / X3d 8 丽 900 OAV

n

[0169] (wherein Z T T s6, s7 and s8 are the same as those in the above formula (Rl-14)).

[0170] Specific examples of Z ²⁹ , Z ³ °, Z ³¹ and Z ³² include a hydrogen atom, a fluorine atom, and a methyl group.

[0171] These divalent or higher-valent organic groups having an aliphatic cyclic structure are preferred in that they can be set at a high glass transition temperature and are excellent in heat resistance and mechanical properties. In addition, it is preferable in terms of high transparency with respect to ultraviolet light and high in ultraviolet resistance.

[0172] Among them, those having a fluorine atom are preferable because they have high transparency over a wide wavelength band that is highly transparent to light in the near infrared region. Also, the introduction of fluorine atoms is preferred because it works more effectively in reducing the refractive index. [0173] The polyfunctional fluorine-containing compound (I) used in the curable composition of the present invention must satisfy the following three physical properties.

(1) The fluorine content is 40% by mass or more.

(2) Viscosity at 35 ° C is 100, OOOmPa's or less.

[0174] Each physical property will be described.

(1) The fluorine content is 40% by mass or more.

When used as an optical material, if the fluorine content of the cured product is not high, the transparency in the near-infrared region will not improve unless it is, for example, 40% by mass or more. Therefore, the fluorine content of the polyfunctional fluorine-containing compound (I) that is the raw material must also be high. Therefore, it is necessary to increase the fluorine content of the polyfunctional fluorine-containing compound (I) as a raw material.

[0175] When the preferable fluorine content is 50% by mass or more, further 60% by mass or more, particularly 70% by mass or more, a cured product having particularly excellent transparency is obtained. The upper limit is about 76% by mass.

[0176] (2) The viscosity at 35 ° C is 100, OOOmPa'sec or less.

As described above, in order to process an optical material such as an optical waveguide, a processing method in which a thin film (core layer or cladding layer) is formed by a method such as spin coating, dip, or casting, and is appropriately cured is generally used. Is taken. From the viewpoint of workability, the curable composition of the present invention that does not use an organic solvent needs to be liquid around room temperature (35 ° C).

[0177] The preferred viscosity is less than 10, OOOmPa ', more preferably less than 1, OOOmPa', particularly less than 500 mPa · sec, and the lower limit is about lOmPa · sec.

[0178] (3) The glass transition temperature Tg of the cured product of the compound represented by formula (1) is 70 ° C or higher.

“The cured product of the compound represented by the formula (1)” refers to 100 parts by mass of the compound represented by the formula (1) by adding the curing initiator (II) in an amount to be completely cured, This refers to a product that has been completely cured. “Completely cured” means a cured product after curing when the peak strength of the carbon-carbon double bond by IR measurement of the polyfunctional fluorine-containing compound represented by the formula (1) before curing is 100. This means that the peak intensity of carbon-carbon double bond is 5 or less by IR measurement.

[0179] If the glass transition temperature Tg of the resulting cured product is low, the heat resistance becomes insufficient and Therefore, problems such as deformation occur.

[0180] Preferred Tg is 80 ° C or higher, further 90 ° C or higher, particularly 100 ° C or higher, and the upper limit is about 30 ° C.

[0181] Specific examples of the polyfunctional fluorine-containing compound (I) used in the present invention are illustrated below, but are not limited thereto.

[0182] In the present invention, the polyfunctional fluorine-containing compound (I) satisfying these three requirements is selected from the polyfunctional fluorine-containing compounds represented by the formula (1). The method can be easily carried out by those skilled in the art according to the measurement method described later.

[0183] As a specific example,

H _

[0184] [Chemical 51]

F CH ₃ o

CH _? = C— COO— CH ₇ — CH— 0— CH Ku C— CH 0— CH— CH _S

CH ₂ CH CH ₂

I I

C 6 F l:

F CH

o F

o c =

CH: ： C—COO CH—CH o C 1 O CH. ■ CH—OC— C = CH,

1 "!! 1 c F l '

CH, CH ₂ O

I c

C ₆ F

CH, CH p

I

CH ₇ = C— COO— CH. CH-O-• C CH— CH OC ™ C = CH,

I i

CH ₂ H CH: O

I

C _S F, ₇

[0185] [Chemical 52] cl

CH = CF F

)

n

F CF CH-> O

(CFJ _n F

(n = 4, 6 or 8)

[0186] [Chemical 53]

(n = 4, 6 or 8)

[0187] [Chemical 54]

[0188] [Chemical 55] CF

CH ₂ = CF_COO— CH-C — O— C

I

(CF ₂ ) _n F

(n = 4, 6 or 8) 56] CF,

CF.

CH ₂ = C F-COO-CH-CH ₂ -0-C

i ICQ— CH- CH "-" OC "-" CF ^{: = ::} CH _?, CH ₂ CF

I CH ₂ O

CF (CF ₃ ) ₂ IH ₃

[0190] [Chemical 57]

(n = 4, 6 or 8)

[0191] and so on.

[0192] The curable composition of the present invention comprises a curing initiator in addition to the polyfunctional fluorine-containing compound (I).

(II) is included as essential.

[0193] The curing initiator (II) is preferably blended in an amount of 0.01% by mass to 10% by mass.

[0194] As the curing initiator (II), the activity used in the curing method of irradiating active energy rays Examples thereof include an energy ray curing initiator (II 1) and a radical polymerization initiator (II 2) used in a curing method by radical polymerization.

[0195] The active energy ray curing initiator (II 1) generates radical cations only when exposed to active energy rays, and polymerizes monomeric polymerizable carbon-carbon double bonds ( In general, those that generate radicals and cations with ultraviolet light, particularly those that generate radicals, are generally used.

[0196] Examples of the active energy rays include electromagnetic waves in a wavelength region of 350 nm or less, that is, electron rays as well as ultraviolet rays, X rays, and γ rays, and preferably ultraviolet rays are used. Although the curing reaction occurs only by irradiation with an active energy line, an active energy ray curing initiator is usually used in order to cure the polyfunctional fluorine-containing compound efficiently.

[0197] The active energy ray curing initiator (II-1) in the present invention includes the type of the carbon-carbon double bond of the compound (whether it is radical reactive cationic or cationic reactive), and the type of active energy ray used ( (Wavelength region, etc.) and irradiation intensity, etc., which are appropriately selected. In general, as an initiator for curing a compound having a radical-reactive carbon-carbon double bond using an active energy ray in the ultraviolet region, for example, Can be illustrated.

[0198] (Acetophenone series)

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

[0199] (Benzoin series)

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

[0200] (Benzophenone series)

Benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenolbenzoneone, hydroxybenzophenone, hydroxy-propinolevenzophenone, talinorenobenzophenone, Michler's ketone, etc.

[0201] (Thixanthones)

Thioxanthone, Black mouth thixanthone, Methylthioxanthone, Jetylthioxanthone, Dimethylthioxanthone, etc. [0202] (Others)

Benzyl, a-siloxime ester, acyl-phosphine oxide, glyoxet steal, 3-ketocoumarin, 2-ethyl anthraquinone, camphorquinone, anthraquinone, etc.

[0203] If necessary, add a known photoinitiator such as amines, sulfones and sulfines.

[0204] Examples of the initiator for curing the compound having a cation-reactive carbon-carbon double bond include the following.

[0205] (Onium salt)

Yordonium salt, sulfo-um salt, phospho-um salt, diazo-um salt, ammonium salt, pyridinium salt, etc.

[0206] (Sulfone compound)

β-keto esters, 13 sulfonyl sulfones and their α diazo compounds, etc.

[0207] (Sulfonic acid esters)

Alkyl sulfonate, haloalkyl sulfonate, aryl sulfonate, imino sulfonate, etc.

[0208] (Others)

Sulfonimide compounds, diazomethane compounds, etc.

[0209] The amount of the active energy ray curing initiator (II 1) is usually 0.1% by mass, preferably 0.2% by mass, more preferably 0%, based on the total amount of the compound having a functional group. 3 mass%, particularly preferably 0.5 mass%, and the upper limit is 15 mass%, preferably 10 mass%, more preferably 8 mass%, particularly preferably 7 mass%.

[0210] Next, the radical polymerization initiator (II 2) will be described.

[0211] As a method for initiating radical polymerization, for example, a method in which a radical is generated by heating using a known radical polymerization initiator is preferable.

[0212] As the radical polymerization initiator (II 2), known peroxides, azo initiators and the like can be used.

[0213] The amount of the radical polymerization initiator (II 2) is usually based on the total amount of the compound having a functional group, The lower limit is 0.01% by mass, preferably 0.05% by mass, more preferably 0.1% by mass, particularly preferably 0.5% by mass, and the upper limit is 10% by mass, preferably 7% by mass, and more. The content is preferably 5% by mass, particularly preferably 3% by mass.

[0214] The curable composition of the present invention may further contain a monofunctional acrylate (A).

[0215] The monofunctional acrylate (A) may be a monofunctional fluorine-containing acrylate or a monofunctional non-fluorinated acrylate.

[0216] The blending amount is preferably such that the fluorine content of the cured product is 0% by mass or more when it is a cured product, regardless of whether it is fluorine-containing or non-fluorinated.

[0217] As the monofunctional acrylate, the formula (6):

[0218] [Chemical 58]

CH ₂ = CX ⁴ II

o

[0219] (wherein X ⁴ is H, F, Cl, CH or CF; R ⁹ is a part of a hydrogen atom having 1 to 30 carbon atoms or

3 3

Is a saturated hydrocarbon group which may contain an ether bond which may be all fluorine-substituted. However, at least one of X ⁴ and R ⁹ contains a fluorine atom). Fluorine content higher instrument heat resistance of the resulting cured product (high glass transition temperature), the viewpoint force X ⁴ and transparency in the near infrared region is satisfactory fluorine atom is preferred.

[0220] Preferred R ⁹ is

(A1) Some or all of the hydrogen atoms containing an alkylene ether bond are fluorine-substituted! , May! /, Saturated hydrocarbon group,

(A2) Some or all of the hydrogen atoms containing a branched structure may be substituted with fluorine !, saturated hydrocarbon groups,

(A3) an aromatic hydrocarbon group which has a heteroatom and part or all of the hydrogen atoms may be fluorine-substituted,

(A4) an aliphatic monocyclic structure having a hetero atom, and part or all of the hydrogen atoms may be fluorine-substituted,

(A5) having a heteroatom, part or all of the hydrogen atoms may be fluorine-substituted Aliphatic double ring structure

It is. The above-described effect is remarkably exhibited when the acrylate component containing these structures (A1) to (A5) in the ester portion is present in the polymer.

[0221] Particularly preferably, R ⁹ contains a fluorine atom, and a structure containing an even larger number of fluorine atoms (high fluorine content) is preferred.

[0222] From this point of view, the fluorine-containing hydrocarbon group of the above (A1) to (A5) in which part or all of the hydrogen atoms are replaced by fluorine atoms, particularly perfluoroalkylene ether groups, perfluoroaromatic carbons. Those containing hydrogen groups, perfluoroaliphatic monocyclic structures, and perfluoroaliphatic bicyclic structures are preferred. A specific example will be described later.

[0223] A fluorine-containing alkyl group, particularly a perfluoroalkyl group containing a perfluoroalkyl group having 1 to 10 carbon atoms is preferably a perfluoroalkyl group having 1 to 5 carbon atoms. Especially preferred to include. A perfluoroalkyl group having an excessively large number of carbon atoms is not preferable because the obtained cured product is easily crystallized or becomes white turbid, resulting in a decrease in transparency.

[0224] The monofunctional fluorine-containing acrylate has a fluorine content of 10% by mass or more, and a cured product of the monofunctional fluorine-containing acrylate has a glass transition temperature of 50 ° C or more. It is excellent and preferable in that it does not reduce the heat resistance of the cured product.

[0225] The fluorine content is preferably 10% by mass or more, more preferably 30% by mass or more, and the upper limit is when all the hydrogen atoms are replaced with fluorine atoms.

[0226] The glass transition temperature of the cured product is preferably 50 ° C or higher, more preferably 70 ° C or higher, especially 100 ° C.

The upper limit is about 200 ° C.

[0227] Next, specific examples of R ⁹ will be described individually.

(A1) Some or all of the hydrogen atoms containing an alkylene ether bond are fluorine-substituted! , May! /, Saturated hydrocarbon group:

This alkylene ether group is preferable in that the fluorine content of the cured product can be increased, the solubility in the multifunctional fluorine-containing compound (I) can be increased, and a uniform liquid composition can be easily obtained. .

[0228] The alkylene ether group preferably has 2 or more and 25 or less, particularly 10 or less carbon atoms. . If the carbon number is too large, the hardness and mechanical properties of the cured product may be lowered, which is not preferable.

[0229] Preferred examples of the monofunctional attalylate containing (A1) include those represented by the formula (7):

[0230] [Chemical 59]

X ⁵

^CH = 丫

COR ¹⁰⁾

II

0

[0231] (where X ⁵ is at least one selected from the group force consisting of H, CH, F, CI and CF; R ^1Q is

3 3

Formula (1 1):

[0232] [Chemical 60]

-40CF ₂ -H-OCF ₂ CFZH ^-OCF ₂ CF ₂ CF ₂ ^-(OCH ₂ CF ₂ CF ₂ HT (1— 1)

[Wherein Z is F or CF; ml, m2, m3, m4 are 0 or an integer of 1 to 10, provided that

Three

ml + m2 + m3 + m4 is preferably a monofunctional fluorine-containing acrylate (al-1) represented by a fluorine-containing alkyl group containing a moiety represented by 1) to 10).

[0234] The feature of the monofunctional fluorine-containing acrylate (al-1) is that in the general formula (2), R ³ has a specific ester moiety having a fluorine-containing alkylene ether structure R ^1Q , and these ester moieties By using this, it is possible to ensure excellent solubility and uniformity of the curable composition of the present invention, and good compatibility and transparency after curing.

[0235] This specific monofunctional fluorine-containing acrylate (al 1) and specific polyfunctional fluorine-containing compound (I)

By selecting (polyfunctional fluorine-containing compound of formula (1)) and making it a curable composition, in the cured product after curing, the heat resistance (high glass transition temperature), mechanical strength, When the amorphous fluoropolymer (C) described later is used, as a result of the improved hardness and the phase separation being suppressed by the polyfunctional fluorine-containing compound (I) having a crosslinked structure, the polymer (C) and As a result, the transparency of the near-infrared region due to white turbidity caused by insufficient compatibility can be eliminated.

[0236] Further, partial crystallization in the cured product is also suppressed by the cured product having a cross-linked structure, and the reduction in transparency in the near-infrared region such as cloudiness due to crystallization can be solved. [0237] Further, the monofunctional fluorine-containing acrylate (al-1) has a lower viscosity than an acrylate having a linear fluoroalkyl group in the ester portion, and the viscosity of the composition can be reduced. Therefore, it is excellent in workability. In addition, since these monofunctional fluorine-containing acrylates (al-1) have low volatility, the composition of the liquid composition changes due to volatilization of the acrylate (al-1) component during the molding process, and the cured product When physical properties such as refractive index change, there is no problem. In addition, since it is highly compatible with the polyfunctional fluorine-containing compound (I) and the fluorine-containing acrylic polymer (C) even after curing, there is no problem when it becomes cloudy or undergoes phase separation by heating. In addition, the hardened material obtained has a characteristic that it exhibits amorphousness despite the high fluorine content.

[0238] Examples of R ^1Q constituting the ester moiety of formula (7) include, but are not limited to, the following.

(1-3):

[0239] [Chemical 61]

— CH ₂ CF ~ KCF ₂ CF

F ₃ CF ₃

(Where m5 is an integer from 1 to 5)

[0240] (1-4):

[0241] [Chemical 62] g 11 ^ 1

(Where m6 is an integer of 1 6)

[0242] (1-5):

[0243] [Chemical 63]

(Where m7 is an integer of 1 8)

[0244] (1-6):

[0245] [Chemical 64] CH ₂ CF _2- (OCF ₂ CF _2- ^ F

(Where m8 is an integer from 1 to 8)

[0246] (1-7):

[0247] [Chemical 65]

H _{2 2} P ₄ ~)

(Where m9 is an integer of 1 7)

[0248] (1-8):

[0249] [Chemical 66]

-CH ₂ CF ₂ ^ OCH ₂ CF ₂ CF _2- ^ F

(Where m 10 is an integer of 1 8)

[0250] Among these, high fluorine content, solubility of fluorinated acrylic polymer (C), compatibility with fluorinated acrylic polymer (C) after curing, transparency of cured product in near infrared region From the viewpoint that is favorable, a particularly preferred structure is represented by the formula (13):

[0251] [Chemical 67]

[0252] (where m5 is an integer of 15).

[0253] Among them, the heat resistance (high glass transition temperature) of the cured product and the viewpoint of mechanical strength, m5 is 1 3 force, and m5 is most preferably 1.

[0254] X ² in the formula (2) is excellent in the polymerization reactivity of the monofunctional fluorine-containing acrylate (al-1), the transparency of the cured product in the near infrared region, and the heat resistance (high glass transition temperature). Viewpoint power of being Fluorine Nuclear S Most preferable.

[0255] Examples of the non-limiting monofunctional fluorine-containing acrylate (al-1) containing R ^1Q include the following.

(la): [0256] [Chemical 68]

CHF

(Where m5 is an integer from 1 to 5)

(No Jl

C-0-CH ₂ CF- OCF ₂ CF ^ F il II

O CF ₃ CF ₃

(Where m5 is an integer from 1 to 5)

CH ₂ = CH

(Where 1115 is an integer from 1 to 5)

[0257] (lb):

[0258] [Chemical 69]

CH ₂ = CF

(Where m6 is an integer between! And 6)

CH., = CC 1

"i

C— O— C ₃ H _S C F- 0 CF ₂ CFO CF ₃ CF ₃

(Where m6 is an integer from 1 to 6) [0259] (lc):

[0260] [Chemical 70]

CH ₂ = CF

CO ~ CH ₂ CF- 3CF ₃ ) _{-i; rT} F

O CF ₃

(Where m7 is an integer from 1 to 8)

CH, = CCH

C— O— CH ₂ CF "OC F ₂ ) ~ ^ F

tl '

O C F

(Where πι7 is an integer from 1 to 8)

[0261] (Id):

[0262] [Chemical 71]

And One day

co -CH ₂ CF ₂ -OCF ₂ CF ₂ Hrr ₈ F

II

o

(Where m8 is an integer from 1 to 8)

CH, = CCH

(Where m8 is an integer from 1 to 8)

[0263] (le):

[0264] [Chemical 72] T

C-0-CH ₂ C ₂ F 0CF ₂ CF ₂ CF ₂ H ^ F

O

(Where m9 is an integer from 1 to 7),

CH CH ₃

C- CH ₂ C ₂ F OCF ₂ CF ₂ CF ₂ H ^

o

(Where m9 is an integer from 1 to 7)

[0265] (If):

[0266] [Chemical 73] and n 2 CF

I

_{_{C-0CH 2 CF ^ 0CH 2}} CF 2 CF 2 - 7TT F

II

Yes

(Where ml 0 is an integer from 1 to 8),

CH ₂ = CCH ₃

C-0 "-CH _g CF ^ 0CH ₂ CF ₂ CF ₂ ) _{ml ()} F

O

(Where m 10 is an integer from 1 to 8)

[0267] Of these, R ^{1Q represented} by the formula (1-3), particularly a fluorine-containing acrylate (la-1) having R ^{1Q of} m5 = 1:

[0268] [Chemical 74]

CH ₂ = CF

I

C-0-CH ₂ CFOCF ₂ CF ₂ (la— 1)

O CF ₃ CF [0269] U, most preferred from the viewpoints of solubility of 1S fluorine-containing acrylic polymer (C), compatibility with fluorine-containing acrylic polymer (C) after curing, and transparency of the cured product in the near infrared region.

(A2) Some or all of the hydrogen atoms containing a branched structure may be substituted with fluorine! / Saturated hydrocarbon group:

By including a branched structure, solubility in the polyfunctional fluorine-containing compound (I) is improved, it is easy to obtain a uniform liquid composition, and the heat resistance (high glass transition temperature) of the cured product can be increased. .

[0270] Specific examples of R ⁹ include the following.

(A2—1) Formula (1 2)

[0271] [Chemical 75]

[0272] (wherein Rf ¹ and Rf ² are the same or different, and a perfluoroalkyl group having 1 to 5 carbon atoms)

R ⁶ is a fluorine-containing tertiary alkyl structure represented by a hydrocarbon group having 1 to 5 carbon atoms in which some or all of the hydrogen atoms may be substituted with fluorine atoms)

By including a branched structure at the ester site, in addition to the above-mentioned effects, particularly the cured product is imparted with heat resistance (high glass transition temperature) and appropriate mechanical strength and hardness.

[0273] Rf ¹ and Rf ² are the same or different perfluoroalkyl groups having 1 to 5 carbon atoms, specifically, ί CF, CF CF, CF CF CF, CF CF CF CF, CF CF CF CF with CF

There are 3 2 3 2 2 3 2 2 2 3 2 2 2 2 3, and CF is particularly preferable from the viewpoint of good compatibility and good heat resistance (glass transition temperature) of the cured product.

Three

[0274] R ⁶ is a hydrocarbon group having 1 to 5 carbon atoms which may be substituted with a fluorine atom. Specifically, CH, CH CH, CH CH CH, CH CH CH CH, CH CH CH CH CH , C

3 2 3 2 2 3 2 2 2 3 2 2 2 2 3

H CF, CH CH CF, CH CF CF, especially compatibility and heat resistance of cured products

2 3 2 2 3 2 2 3

The strength of the viewpoint that the lath transition temperature is good is also CH Rf ² and R ⁶

When the number of carbon atoms in each of the carbon atoms is 6 or more, the branched chain is crystallized and the transparency of the cured product is immediately reduced. [0275] Specific examples of atalylate having a fluorine-containing tertiary alkyl structure include hexafluoroneopentyl methacrylate (6FNPM: X ⁴ = CH, Rf ^ Rf ^ CF, R ⁶ = CH

3 3 3

), Hexafluoroneopentyl α-Fluoroatalylate (6FNPF: X ⁴ = F, Rf ^{1 =} Rf 2 = CF, R ⁶ = 3CH), 2, 2-bistrifluoromethylbutyl metatalylate (X ⁴ = CH, R

3 3 3 f ^ Rf ^ CF, R ⁶ = CH 2 CH 2), 2, 2—bistrifluoromethylbutyl α-fluoroa

3 2 "

Tally rate (X ⁴ = F, Rf ^ Rf ^: CF, R. = CH CH)

[0276] [Chem 76] Les 2 5

C Η ₂ = CC Η

C 2 5

CH. = C F

O C H One C One C F

CH.

CF

CH ₂ = CCH

1

c one o CH, -C-CF

II

o

CH ₂ CF 3

[0277] and the like. Of these, from the point of excellent heat resistance of cured products and easy synthesis

Hexafluoroneopentyl metatalylate (6FNPM),

[0278] [Chemical 77]

[0279] Hexafluoroneopentyl a Fluoroatalylate (6FNPF)

[0280] [Chemical 78]

[0281] Especially when heat resistance is required when processing an optical device using an optical waveguide, or when an optical device using an optical waveguide is used in a car or in an FA application at high temperatures In the case of 6FNPF, the heat resistance of the cured product (high glass transition temperature) and high transparency in the near infrared region are preferable.

[0282] (A2-2)

[0283] [Chemical 79]

[In the formula, Rf ⁵ and Rf ⁶ are the same or different, and a perfluoroalkyl group having 1 to 5 carbon atoms; R ¹¹ represents a hydrogen atom partially or entirely substituted with a fluorine atom. A good hydrocarbon group having 1 to 5 carbon atoms, H or F; n is an integer of 1 to 6; m is an integer of 1 to 6)

More specifically,

[0285] [Chemical 80]

C F

-CH (C F ^ -TC— C F

2 ¹ 5

Or

CF

-(C ₂ H ₄ ^ — (CF ₂ ^ C— C ₃ F ₇

CF ₃

[0286].

[0287] Specific examples of the fluorine-containing acrylate include the following.

[0288] [Chemical 81]

(In the formula, X ⁶ is at least one selected from the group consisting of H, CH ₃ , F, C 1 and CF ₃ , Rf ⁵ , R i R ", n and m are the same as in formula (A2-2))

[0289] Specifically,

[0290] [Chemical 82]

F

Or

C F

CH. = CC H ..

C-O ^ C ₂ H ₄ ) — CF -C ₃ F ₇

¾ CIF 3 [0291].

[0292] (A2-3)

[0293] [Chemical 83]

R f ⁶

I

— C-one R f ⁵

( ^Where R f ⁵ R f ^fi and R ⁿ are the same as in formula (A 2− 2))

[0294] More specifically,

[0295] [Chemical 84]

C ί 3

Η

Or

CF ₃

I

— C— CF ₃

[0296].

[0297] Specific examples of the fluorine-containing acrylate include the following.

[0298] [Chemical 85]

[0299] (where X ⁶ Rf ⁵ Rf ⁶ R ¹¹ is the same as above)

[0300] Specifically, Hexafluoroisopropyl a fluoroatarylate (HFIPF)

[0301] [Chemical 86]

CH ₂ = CF ^{CF 3}

Γ ¹ 3

[0302] or

Hexafluoroisopropyl methacrylate (HFIPM)

[0303] [Chemical 87]

CH ₂ = C CH ₃ ? ¹³

I I

C— 0— C— C F,

H or

[0304].

[0305] Among these, 6FNPM, 6FNPF, hexafluoroisopropyl metatalylate (HFIP M), xafluoroisopropyl α-fluoro attalate (HFIPF) is the metathermal property of the cured product (high glass transition temperature) From the viewpoint of good transparency in the near-infrared region. Among them, 6FNPF and HFIPF have good solubility in polyfunctional fluorine-containing compounds (I), making it easier to obtain a uniform liquid composition, heat resistance of the cured product (high glass transition temperature), and near infrared region. Is most preferable from the viewpoint of good transparency.

[0306] (A3) An aromatic hydrocarbon group which has a heteroatom and may have part or all of the hydrogen atoms substituted with fluorine:

This aromatic hydrocarbon group is preferable in terms of good heat resistance (high glass transition temperature). Special In addition, those in which part or all of the hydrogen atoms in the structure are substituted with fluorine atoms are further excellent in transparency in the near-infrared region.

[0307] Specific examples of R ⁹ include the following.

(A3-1)

[0308] [Chemical 88]

[Wherein R is the same or different, and F, C, or an optionally substituted alkyl group having 1 to 14 carbon atoms; R ¹³ has a bond or a branched chain. An optionally substituted alkylene group having 1 to 6 carbon atoms; a is an integer of 1 to 5; provided that any one of R ¹² and R ¹³ has a fluorine atom.

[0310] More specifically,

[0311] [Chemical 89]

[0312]

[0313] Specific examples of the fluorine-containing acrylate include the following:

[0314] [Chemical 90]

[0315] Perfluorophenol α-Fluoroatalylate

[0316] [Chemical 91]

[0317] Perfluorophenol methacrylate

[0318] [Chem 92]

[0319] is preferred.

[0320] Among these, perfluorophenol methacrylate and perfluorophenol a-fluoroatalylate improve heat resistance (high glass transition temperature) and transparency in the near-infrared region. This is preferable.

[0321] (A4) Aliphatic monocyclic structure having a heteroatom and part or all of the hydrogen atoms may be fluorine-substituted:

This aliphatic monocyclic structure is preferable in terms of good heat resistance (high glass transition temperature). In particular Those in which some or all of the hydrogen atoms in the structure are substituted with fluorine atoms are also excellent in transparency in the near infrared region.

[0322] Specific examples of R ⁹ include, but are not limited to, the following.

(A4- 1)

[0323] [Chemical 93]

[0324] (wherein R is the same or different, and F, C, or a halogen atom may be substituted with an alkyl group having 1 to 14 carbon atoms; R ¹⁵ has a bond or a branched chain. An optionally substituted alkylene group having 1 to 6 carbon atoms; b is an integer of 1 to 5; provided that one of R "and R ¹⁵ has a fluorine atom)

[0325] More specifically,

[0326] [Chemical 94]

[0327].

[0328] (A4-2) Those having an aliphatic cyclic hydrocarbon structure having one or two of the following monocyclic structures are also preferred.

[0329] [Chemical 95]

[0330] Specific examples of the fluorine-containing acrylate include the following.

[0331] [Chemical 96]

[0332] (A5) An aliphatic polycyclic structure having a heteroatom, and part or all of the hydrogen atoms may be substituted with fluorine:

This aliphatic polycyclic structure is preferable in terms of good heat resistance (high glass transition temperature). In particular

Those in which some or all of the hydrogen atoms in the structure are substituted with fluorine atoms are also excellent in transparency in the near-infrared region.

[0333] Specific examples of R ⁹ include the following.

(A5-1) adamantane and its derivatives,

(A5 2) norbornane and its derivatives,

(A5 3) perhydroanthracene and its derivatives,

(A5-4) perhydronaphthalene and its derivatives,

(A5- 5) tricyclo [5.2.2 1.0 ^2, ^6] decane and its derivatives

As examples of some of them,

[0334] [Chemical 97]

[0335] and so on.

[0336] In these examples, at least one hydrogen atom of the hydrocarbon group is substituted with a fluorine-containing alkyl group having 1 to 5 carbon atoms or a fluorine atom.

[0337] Further, among these organic groups containing a hydrocarbon moiety of a polycyclic structure, those containing adamantane and its derivatives, norbornane and its derivatives are preferred, particularly those having heat resistance (high glass transition temperature) and near red. Transparency in the outer region can be effectively imparted to the cured product.

[0338] Specific examples of the fluorine-containing acrylate include the following.

(a5-l) Monomer having adamantane represented by the following formula and its derivative in the side chain

[0339] [Chemical 98]

Or

[Wherein X ⁷ is H, F, Cl, CH or CF; R ^lb,! T ^b is a substituent bonded to the ring, and CH

3 3 3

, CH or OH; R ^4b and R ^{5b each} have a bond or a branched chain and have 1 to 6 carbon atoms

twenty five

An alkylene group; R ^3b is H, CH or CH; n is 0 or an integer of 1 to 2. However, eventually

3 2 5

Force substituents contain fluorine atoms).

[0341] More specifically,

[0342] [Chemical 99]

[0343] and so on.

[A344] (a5-2) Atallate having norbornane and its derivative represented by the following formula in the side chain:

[0345] [Chemical 100]

[Wherein X ⁸ is H, F, Cl, CH or CF; R ^la , R ^2a , R ^3a , R ^½ , R ^5a , R ^6a , R ^7a , R ^S R ^9a * 5

3 3

And R ^1Qa are the same or different, and H, F, C, or C 1-14 substituted with a halogen atom may be an alkyl group; ^RUa contains a bond or a branched chain, and Also, an alkylene group having 1 to 6 carbon atoms; n is 0 or an integer of 1 to 2. However, any substituent contains a fluorine atom).

[0347] More specifically,

[0348] [Chemical 101]

[0349] and so on.

[0350] The monofunctional fluorine-containing acrylate is an optional component. The compounding ratio is 10 parts by mass or more, further 20 parts by mass or more, especially 30 parts by mass with respect to 100 parts by mass of the polyfunctional fluorine-containing compound (1). It is preferable that the viscosity of the liquid composition is adjusted to an appropriate range. . The upper limit is 80 parts by mass, further 50 parts by mass, especially 40 parts by mass from the viewpoint of not reducing the heat resistance of the cured product and reducing shrinkage during curing.

[0351] Examples of the monofunctional non-fluorinated attalylate include compounds in which X ⁴ and R ⁹ in formula (6) do not contain a fluorine atom. The blending amount is an amount that does not greatly reduce the fluorine content of the cured product (for example, the fluorine content does not fall below 40% by mass).

[0352] Non-limiting specific examples of monofunctional non-fluorinated acrylates include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate. N-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, and other aliphatic ester (meth) acrylates; Examples thereof include (meth) acrylate, adamantyl (meth) acrylate, and dimethyladamantyl (meth) acrylate.

[0353] In addition to the polyfunctional fluorine-containing compound (I), the polyfunctional fluorine-containing compound (B) other than the polyfunctional fluorine-containing compound (I) is added to the curable composition of the present invention. Anyway.

[0354] Examples of other polyfunctional fluorine-containing compounds (B) include those represented by the formula (8):

[0355] [Chemical 102]

[0356] (wherein X ⁹ and X ^1Q are the same or different, from the group consisting of H, CH, F, CI and CF

3 3

At least one selected. n is an integer of 1 to 6, for example, 1 to 3; R ¹⁶ is a 1 to 50 carbon atom, for example, a 3 to 50 hydrogen atom, part or all of which may be substituted with a fluorine atom (n + 1) A polyfunctional fluorine-containing compound represented by:

[0357] In the formula (8), it is preferable that X ⁹ and X ^1Q are fluorine atoms in that the reactivity of the polyfunctional fluorine-containing compound is good and the heat resistance of the resulting cured product is improved ( High glass transition temperature). Moreover, it is preferable at the point which the transparency in the near-infrared area | region of the hardened | cured material with high fluorine content also becomes high.

[0358] In the formula (8), R ¹⁶ may be an (n + 1) -valent organic compound in which a part or all of hydrogen atoms having 1 to 50 carbon atoms, for example 3 to 50 carbon atoms, are substituted with fluorine atoms. It is a group. Part of the hydrogen atom Alternatively, when all of them are substituted with fluorine atoms, the transparency of the obtained cured product in the near infrared region is improved.

[0359] Further, the organic group R ¹⁶ has, in its structure, (B-1) a portion of an aromatic hydrocarbon structure which may have a heteroatom, and (B-2) a heteroatom. ! /, May! /, At least one part selected from a part of an aliphatic monocyclic structure, or (B—3) has a heteroatom! /, May! /, Part of an aliphatic polycyclic structure It is preferred to be an organic group containing a species site. By including these cyclic structures, the heat resistance of the resulting cured product is improved (high glass transition temperature).

[0360] This polyfunctional fluorine-containing compound (B) has both the effect of improving the heat resistance of the cured product and the effect of improving the mechanical strength of the cured product. Furthermore, by containing a fluorine atom, it contributes to the improvement of the fluorine content and the transparency in the near infrared region of the cured product. In addition, the heat resistance of the cured product due to the cyclic structure at the polyfunctional site can be improved by introducing a small amount of cyclic structure compared to the case of fluorine-containing acrylic acrylate having a cyclic structure at the monofunctional talylate site. Improvement of heat resistance (high glass transition temperature) can be realized. Moreover, the reason is unknown. Force shrinkage can also be reduced by having a cyclic structure at the polyfunctional site.

[0361] R ¹⁶ is an (n + 1) -valent organic group having 1 to 50 carbon atoms, specifically,

(1) having a linear or branched ether bond, (n + 1) valent organic group,

(2) an (n + 1) -valent organic group having an aromatic ring structure,

(3) an (n + 1) -valent organic group having an aliphatic cyclic (monocyclic or polycyclic) structure,

(4) (n + 1) -valent organic group containing urethane bond

In these organic groups, a part or all of the hydrogen atoms forming a carbon monohydrogen bond may be substituted with a fluorine atom.

[0362] First, each of the good or of the R ^16, Tsu the embodiment, Te will be described with reference to specific examples.

(1) (n + 1) -valent organic group having a linear or branched ether bond: n = 1 in formula (8) showing the polyfunctional acrylate (2 As the sensory acrylate,

Formula (R2— 1):

One (CH) — (CF) — (C (CH)) — (R2-1)

2 pi 2 p2 3 p3

An organic group represented by (wherein pi + p2 + p3 = 1 to 30) can be exemplified. [0363] As a specific example,

CH CH

twenty two

CH CH (CH) —

twenty three

CH CH CH (CH) —

2 2 3

"(CH)

twenty four

-(CH)

2 6

-(CH) (CF) (CH)

2 2 2 2 2 2

-(CH) (CF) (CH)

2 2 2 4 2 2

-(CH) (CF) (CH)

2 2 2 6 2 2

-CHC (CH) CH

2 3 2 2

Etc.

[0364] Also, the formula (R2-1-1):

[0365] [Chemical 103]

— CH ₂ CH _2-

II CHCHaQ-eCHa) _pl (CF ₂ ) _p2 (CH ₂ i ~ ^ OCH ₂ CH (R2— 1— 1)

OH OH

[0366] (wherein, pl, p2, and p3 are the same as those in the above formula (R2-1)).

[0367] More specifically,

[0368] [Chemical 104]

— CH 2 CH ₂ ^—

i I

HOCHCH ₂ OCH ₂ CH ₂ OCH ₂ CHOH,

― CH 2 CH 3 CH 2 ^—

I i I

HOCHCH ₂ OCH ₂ CHOCH ₃ CHOH,

Shi! ! Ni ni I

HOCHCH ₂ OCHr CF ₂ CH ₂ OCH ₂ CHOH,

— Jn (C

™ Shi H ―

II ²

HOCHCH ₂ OCH ₂ CH "<CF ₂ -)- ₄ CH ₂ CH ₂ OCH ₂ CHOH, one CH ₂ CH ₂ —

I I

HOCHCH ₂ OCH ₂ CH ^ CF ₂ ^ ~ ₆ CH ₂ CH ₂ OCH ₂ CHOH,

— CvVf 2 and T XI 2

_{_{HOCHCH 2 OCH 2 CH - (CF}} 2 - 8 CH 2 CH 2 OCH 2 CHOH

[0369] and the like are preferable.

[0370] Other formulas (R2 — 1 2), (R2 — 1 3):

[0371] [Chemical 105] Z ¹ Z ² Z ³

1 I I

CHCH2- OCHCH ₂ "r iOCHCH _2- (R 2-1-2)

— CH ₂ Z ¹ Z ² Z ³ CH ₂ —

ί I I I I

HOCHCH ₂ OCHCH ₃ ^ fOCHCH2 ^-OCHCH20CH ₂ CHOH

(R 2-1-3)

[0372] (wherein p4 is 0 or an integer of 1 to 20,)

And so on.

[0373] In addition, n = 2 or more (trifunctional or more) has the formula (R2-2):

[0374] [Chem 106]

(R 2-2)

[Wherein p5 is 0 or an integer of 1 to 5].

[0376] Specifically,

[0377] [Chemical 107]

CH ₂ —

1

-CH ₂ CCH,-

I

[0378] and the like.

[0379] Further, as other than the formula (R2-2), for example,

[0380] [Chemical 108] Rl 2―

i

Then ig then Jrl then Jrl ₂

CH _2-

CH ₂ -CH _? -

I I

CH ₃ CH ₂ CCH ₂ OCH ₂ CCH ₂ CH ₃

CHt ₂ — iiH ₂一

[0381] and the like.

[0382] Further, as a compound containing a fluorine-containing alkylene group, the formula (R2-3), (R2-4):

[0383] [Chem 109]

-CH ₂ CH _2-

— CH ~ CH ₂ ) pa (CF ₂ ) p7 (CH ^ TT CH— (R2— 3),

— CH ₂ CH ₂ --CHCHaQ ^ CHa) p6 (CF ₂ ) _P 7 (CH ^ irsOCHaCH- (R 2-4)

[Wherein p6 and p8 are the same or different and are integers of 1 to 10; p7 is an integer of 1 to 30].

[0385] Specifically,

[0386] [Chem 110]

I I

― CHCH CF _2- ) — ₂ CH ₂ CH-, ~ CH 2 and H ₂ —

I ί

CHCH CF ₂ CH ₂ CH—, ~ CH ₂ CH _2-

-CHCH CF _{2 6} CH ₂ 0H-,

,

,

— CH ₂ CH 2 ^—

I!

-CHCH ₂ OCH ₂ CHi ~ CF ₂ -^- ₂ CH ₂ CH ₂ OCH ₂ CH-,

-CH ₂ CH ₂ —

I!

_{_{_{-CHCH 2 OCH 2 CHi- (CF 2}}} - 4 CH 2 CH 2 OCH 2 CH-,

,

— CH ₂ CH _2-

I _f I

-CHCH ₂ OCH ₂ CHr- CFj-7CH ₂ CH ₂ OCH ₂ CH-

[0387] and the like are preferable.

[0388] These exemplified linear or branched alkylene group divalent or higher organic groups as R ¹⁶ are preferred in that they 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 low refractive index. [0389] (2) (n + 1) -valent organic group containing aromatic ring structure:

For example, the formula (R2—5):

[0390] [Chem 111]

[0391] (wherein R ²¹ and R ²² are the same force 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 carbon An alkyl group having 1 to 5 carbon atoms, a fluorine-containing alkyl group having 1 to 5 carbon atoms, a functional group, a hydrogen atom or a halogen atom; rl and r2 are the same or different and include a moiety represented by an integer of 1 to 4) Bivalent organic base,

Or the formula (R2—6):

[0392] [Chem 112]

[0393] (wherein R ²³ , R ²⁴ , R ²⁵ and R ²⁶ are the same or different and are each an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms; Z ²³ is a carbon number A divalent organic group having a moiety represented by the following formula: 1-5 alkyl group, fluorine-containing alkyl group having 1-5 carbon atoms, functional group, hydrogen atom or halogen atom; r3 is an integer of 1-4.

[0394] In addition, divalent organic groups containing the sites represented by the following formulas (R2-7) to (R2-11) are listed.

Formula (R2-7):

[0395] [Chem 113] [0396] Formula (R2—8):

[0397] [Chemical 114]

[0398] Formula (R2—9) [0399] [Chemical 115]

[0400] Formula (R2-10):

[0401] [Chem 116]

[0402] Formula (R2-11):

[0403] [Chemical 117] RCRII

(R 2-1 1)

[0404] In the above formula, R ²⁷ ,

R ²⁹ and R ³ ° are the same force or different, alkyl group having 1 to 5 carbon atoms or fluorine-containing alkyl group having 1 to 5 carbon atoms; R ³¹ and R ³² are the same force or different, and alkyl having 1 to 5 carbon atoms Group, a fluorine-containing alkyl group having 1 to 5 carbon atoms, a hydrogen atom; Z ²⁴ , Z ²⁵ and Z ²⁶ may be the same or different, and an alkyl group having 1 to C RRII5 and a fluorine-containing alkyl group having 1 to 5 carbon atoms 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 and are an integer of 1 to 3 Yes, even if they have the same sign, different groups and integers can be taken as long as the expressions are different.

[0405] As a specific example of the formula (R2-5),

[0406] [Chemical 118]

[6Π¾] [LOW]

LL

ZS9T0C / 900Zdf / X3d 8 丽 900 OAV

H 2 ₂ CH-i ~ n

-CH _{2 2} CH † 7i

[0408] (wherein r4 and r5 are the same or different and are integers of 1 to 10; Z, rl and r2 are

— Same as 5)).

[0409] As a specific example of (R2-6),

[0410] [Chemical 120]

[0411] (wherein Z ²³ and r3 are the same as those in formula (R2-6)) are preferred.

[0412] As a specific example of the formula (R2-7),

[0413] [Chemical 121]

CH ₃

[0414] (where

Preferably, r4 and r5 are the same as the above formula (R2-7).

[0415] As a specific example of the formula (R2-8),

[0416] [Chemical 122]

[0417] and the like are preferable.

[0418] Specific examples of the formula (R2-9) include [0419] [Chemical 123]

[0420] (wherein Z ²⁴ Z ²⁵ r4 and r5 are the same as those in the above formula (R2-9)) are preferred.

[0421] As a specific example of the formula (R2-10),

[0422] [Chemical 124]

[0423] [Chemical 125]

[0424] (wherein Z ²⁴ , T r7 and r8 are the same as those in the above formula (R2-10)) are preferred.

[0425] As a specific example of the formula (R2-11),

[0426] [Chemical 126]

-CH ₂

HOCHCH, 0-

CH.

C ~ OCH ₂ CHOH CF,

27]

U.

CH ₃

[0428] (wherein, Z ^M , Z ^A Z ^z r6, r7 and r8 are the same as those in the above formula (R2-11)) are preferred.

[0429]

[0430] These divalent or higher-valent organic groups having an aromatic cyclic structure can set a glass transition point that is preferable in terms of excellent heat resistance and mechanical properties, and as a result, optical materials having high heat resistance. Is preferable in that it is obtained.

[0431] Among them, 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. [0432] (3) (n + 1) -valent organic group having an aliphatic cyclic (monocyclic or polycyclic) structure: Specifically, the formula (R2-12):

[0433] [Chemical 128]

[Wherein R ³³ and R ³⁴ are the same or different, and the alkyl group having 1 to 5 carbon atoms or the fluorinated alkyl group having 1 to 5 carbon atoms; Z ²⁷ and Z ²⁸ are the same or different, and carbon An alkyl group having 1 to 5 carbon atoms, a fluorine-containing alkyl group having 1 to 5 carbon atoms, a functional group, a hydrogen atom or a halogen atom; si and s2 are the same or different and include a moiety represented by an integer of 1 to 4) Divalent organic group or formula (R2-13):

[0435] [Chemical 129]

[0436] ^{^{(wherein, R 35, R 36, R}} 37 and R ³⁸ are the same or different, alkyl group or fluorine-containing alkyl group of 1 to 5 carbon atoms from 1 to 5 carbon atoms; the number of Z ²⁹ is carbon A divalent organic group having a moiety represented by the following formula: 1-5 alkyl group, fluorine-containing alkyl group having 1-5 carbon atoms, functional group, hydrogen atom or halogen atom; s3 is an integer of 1-4.

[0437] In addition, divalent organic groups including the sites represented by the following formulas (R2-14) to (R2-18) are listed.

Formula (R2-14):

[0438] [Chemical 130]

[0445] Formula (R2—18)

[0446] [Chemical 134]

[0447] In the above formulas, R ³⁹ , R ⁴ °, R ⁴¹ and R ⁴² are the same or different and each represents 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 force 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 ³ °, Z ³¹ and Z ³² are the same or different and have 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; s4 and s5 are the same or different, an integer of 1 to 4; s6 is an integer of 1 to 2; s8 is the same or different and is an integer of 1 to 3, and even if it is the same sign, different formulas and integers can be taken if the formulas are different.

[0448] As a specific example of the formula (R2-12),

[0449] [Chemical 135]

36]

[0451] (wherein s4 and s5 are the same or different, an integer of 10; Z ²⁷

sl s2 is the above formula (R2

Same as 12)

Etc. are preferred.

[0452] As a specific example of (R2-13),

[0453] [Chemical 137]

CH CH Z ²⁹ ) S 3

I 丄 3 C H- ioOcCHH ₂ .iCHOH

[0454] (In the formula, Z ²⁹ and s3 are the same as those in the formula (R2-13)).

[0455] As a specific example of the formula (R2-14),

[0456] [Chemical 138]

CH ₃

[0457] (wherein Z ³ °, Z ³¹ , s ⁴ and s ⁵ are the same as in the above formula (R2-14)) and the like, [0458] Specific examples of formula (R2-15) ,

[0459] [Chemical 139]

[0460] and the like are preferable.

[0461] Specific examples of the formula (R2-16) include [0462] [Chemical 140]

[0463] (wherein Z ³ °, s4 and s5 are the same as those in the above formula (R2-16)) are preferred.

[0464] As a specific example of the formula (R2-17),

[0465] [Chem 141]

[0466] [Chemical 142]

HO

[0467] (wherein Z ^3U Z ³¹ s7 and s8 are the same as the above formula (R2-17)) and the like, [0468] Specific examples of the formula (R2-18) include

[0469] [Chemical 1431

[ffl ^ [OLfO

86

ZS9T0C / 900Zdf / X3d 8 丽 900 OAV

n

[0471] (wherein Z T T s6, s7, and s8 are the same as those in the above formula (R2-18)).

[0472] Specific examples of Z ²⁹ , Z ³ °, Z ³¹ and Z ³² include a hydrogen atom, a fluorine atom, and a methyl group.

[0473] These divalent or higher-valent organic groups having an aliphatic cyclic structure are preferred in that they can be set at a high glass transition temperature and are excellent in heat resistance and mechanical properties. In addition, it is preferable in terms of high transparency with respect to ultraviolet light and high in ultraviolet resistance.

[0474] Among them, those having a fluorine atom are preferable because they have high transparency over a wide wavelength band that is highly transparent to light in the near infrared region. Also, the introduction of fluorine atoms is preferred because it works more effectively in reducing the refractive index. [0475] (4) (n + 1) -valent organic group containing urethane bond

In particular,

[0476] [Chemical 145]

CH ₃

And organic groups such as [0477].

[0478] Although R ¹⁶ has been mainly described above, specific examples of the other polyfunctional fluorine-containing compound (B) represented by the formula (8) include the following.

[0479] [Chemical 146]

CH ₂ = H ₂

CH ₂ = CF-CO-CH ₂ -V C-CF = CH ₂

○ o

CH ₃ CH ₃

CH ₂ = i— CC CH ₂ V "OC— = CH ₂

CH ⁼ CF― CO— (-C — OC _ CF = CH ₉

o o,

CH ₂ = CF- -CO- CH ₂ ^-CH ₂ -VOC- CF = CH,

O

147]

CH ₂ = H:

O

F CH ₂ OC-C F = CH ₂

CH. C- ^ OCH CH ₂ 0 (0 = C to CF = CH ₂

O C H ·> O C― C F― \ ^ h

2 II ²

o

148] CH ₃ O CH ₃

CH ₂ = CCOOCH ₂ CH ₂ OC-C = CH ₂

CH ₂ = CCOOC1HCH ₂ -CF ₂ ^ CH ₂ ¾H〇CC = CH ₂ in ₃ O CH ₃

O

CH ₂ = C FCOOCH ₂ CH ₂ OC— CF = CH

I ² I

CH ₂ = C FCOOCHCH ₂ ™ ~ tCF ₂ ^ — ₆ CH ₂ CHO ^ -CF = C

O

149]

150]

[TSI ^] o] D = ¾3

SOT

ZS9T0C / 900Zdf / X3d S178Z80 900Z; OAV —— 广

2

[0485] [Chemical 152]

CF,

CH, = CFCO- OHOOCCF = CH,

O CF _£ CF ₃ O o O

[0486] [Chemical 153]

[0487] [Chemical 154]

ccl

[0488] [Chemical 155]

oo

[0489] [Chemical 156]

[0490] [Chemical 157]

o

[0491] [Chemical 158]

O

CH ₂ = CFCO— CH ₂

CH _? = CFCOCHC 0 CH ₂ OCCF = CH ₂ [0492] [Chemical 159]

A polyfunctional fluorine-containing compound (B) such as [0493] is preferred.

[0494] The amount of other polyfunctional fluorine-containing compound (B) added is up to 30% by mass, preferably up to 20% by mass.

[0495] The curable composition of the present invention may further contain an amorphous fluorine-containing polymer (C) having a fluorine content of 25% by mass or more.

[0496] Here, non-crystalline refers to the fact that an endothermic peak based on melting is not observed when measured under the condition of a temperature increase rate of 10 ° CZ by 2nd run in the DSC analysis described above. Or, it shows the property that the heat of fusion is UZg or less.

[0497] When the fluorine content is 25% by mass or more, it is possible to impart the property of improving the transparency of the obtained cured product in the near-infrared region. Further, since it is amorphous, it is easy to obtain a uniform liquid composition having high solubility in the fluorine-containing compounds (I) and (A). In addition, since there is no scattering due to crystal components, the property of improving the transparency of the cured product in the near infrared region can be imparted. The fluorine content is more preferably 30% by mass or more, further preferably 40% by mass or more, and particularly preferably 50% by mass or more from the viewpoint of good transparency in the near infrared region.

[0498] The number average molecular weight of the fluorine-containing polymer (C) is 500, 000, preferably <100,000, particularly preferably <from the viewpoint of solubility and compatibility with other components. 50,000. The lower limit is not particularly limited, but it is preferable that the oligomer is a quantifier with the same viewpoint power. Specifically, it is ί or 300, preferably ί or 500.

[0499] Next, preferred examples of the amorphous fluorine-containing polymer having a specific fluorine content of 25% by mass or more are exemplified, but the invention is not limited thereto.

(C 1) A polymer obtained by polymerizing only an acrylic monomer, and an amorphous fluorine-containing acrylic polymer having a fluorine content of 25% by mass or more

(C2) A polymer obtained by polymerizing a fluorine-containing aryl ether monomer, and an amorphous fluorine-containing ether ether polymer having a fluorine content of 25% by mass or more

(C3) Amorphous fluorine-containing cyclic polymer having a cyclic structure in the main chain and a fluorine content of 25% by mass or more

(C-4) A copolymer containing fluorinated olefins and hydrocarbon-based vinyl ether, which is an amorphous fluorinated copolymer with a fluorine content of 25% by mass or more.

(C5) A polymer obtained by polymerizing a fluorine-containing polystyrene monomer, and an amorphous fluorine-containing polystyrene polymer having a fluorine content of 25% by mass or more

(C-6) A vinylidene fluoride copolymer, which is an amorphous vinylidene fluoride copolymer having a fluorine content of 25% by mass or more.

[0500] Of these, the structures are preferably (C-1) and (C2), and the most preferred structures are (C — 1). The amorphous fluorine-containing polymer (C) may be a blend of two or more of these polymers.

[0501] Next, (C-1) to (C-3) and (C-6), which are structures of (C), will be described.

(C 1) A polymer obtained by polymerizing only an acrylic monomer, and an amorphous fluorine-containing acrylic polymer having a fluorine content of 25% by mass or more:

By using this polymer (C-1), a curable composition which is a uniform liquid composition with the fluorine-containing compounds (I) and (I) is formed. The polymer (C 1) has a function of adjusting the viscosity of the curable composition, a function of reducing polymerization shrinkage during curing, and a fluorine content of the cured product in combination with the fluorine-containing compound (I) or (Α). Also has a function to raise. In addition, when a shape is imparted with a mold or the like at the time of molding and cured, it also has a function of improving the peelability of the cured product from the mold. [0502] The fluorinated acrylic polymer (C-1) may be a homopolymer or copolymer of a fluorinated acrylate. Further, if the fluorine content is 25% by mass or more, it may be a copolymer of fluorine-containing acrylate and non-fluorine acrylate. Two or more kinds of fluorine-containing acrylic polymers (C-1) may be blended and used.

[0503] Examples of the fluorine-containing acrylate include monofunctional fluorine-containing acrylates containing (A1) to (A5) among the monofunctional acrylates (A).

[0504] Non-fluorinated acrylates that may be copolymerized with fluorinated acrylates are not particularly limited as long as the fluorine content of the fluorinated acrylate-based polymer (C 1) is 25% by mass or more. Not.

[0505] As a non-limiting specific example of the non-fluorinated acrylic monomer, a monofunctional non-fluorinated acrylate can be exemplified among the monofunctional acrylate (A).

[0506] The fluorine content of the fluorine-containing acrylic polymer (C 1) should be 25% by mass or more. The strength is preferable in that the cured product obtained has a high transparency in the near infrared region. 30% by mass or more, more preferably 40% by mass or more, and particularly preferably 50% by mass or more. The upper limit is the fluorine content when all of the hydrogen atoms in each polymer are replaced with fluorine atoms.

[0507] The number-average molecular weight of the fluorine-containing acrylic polymer (C 1) is determined based on the solubility in other components and the compatibility, and the upper limit is ί 500, 000, preferably ί 100 000, particularly preferably ί or 50,000. The lower limit is not particularly limited, but is preferably 300, preferably 500, which is preferably an oligomer having a similar viewpoint power.

[0508] The glass transition temperature of the polymer (C-1) is more preferably 85 ° C or more from the viewpoint of improving the heat resistance of the cured product. More preferably 90 ° C or more. More preferably, it is 95 ° C or higher. Since polymers with these structures have an acrylic polymer backbone, they are essentially well dissolved in the fluorine-containing acrylate component (al-1), resulting in a uniform liquid composition and high compatibility of the cured product. For this reason, the transparency in the near-infrared region without white turbidity is also high.

[0509] (C 2) A polymer obtained by polymerizing a fluorine aryl ether monomer, which is an amorphous fluorine-containing aryl ether polymer having a fluorine content of 25% by mass or more:

Polymer (C 2) is W095Z33782, WO02Zl8457, WO02Z73255 Disclosed in Lett et al.

[0510] The polymer (C 2) is amorphous despite its high fluorine content, and has very high solubility in the fluorine-containing compounds (I) and (A). In addition, for example, a curing site capable of reacting with a fluorine-containing allylate such as a carbon-carbon double bond can be easily provided at the end of the side chain, and there is a curing site capable of reacting with such a fluorine-containing acrylate. For example, since the cured product forms a mutual network as a whole, it exhibits even better cured product performance such as solvent resistance, low linear expansion coefficient, and heat resistance.

[0511] (C 3) Amorphous fluorine-containing cyclic polymer having a cyclic structure in the main chain and a fluorine content of 25% by mass or more:

The polymer (C 3) is preferable in that the cured product having a very high glass transition temperature has high heat resistance. Examples of such a polymer (C 3) include a polymer having an aliphatic cyclic structural unit preferably having fluorine and a polymer having a non-fluorinated alicyclic structural unit.

[0512] (C 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 (C 3) having a high glass transition temperature can be obtained, further increasing the hardness of the cured product. I like it because I can expect it.

[0513] The fluorine-containing aliphatic cyclic structural unit (C 3-1) is represented by the formula (9):

[0514] [Chemical 160]

(CX ^{, 5} X ^1B ) n2

{(CX ⁿ X ¹² ) _nl CX ¹³ CX ^H (CX

I (9)

(0) _n4 (0) _nS

Rf ⁷

[0515] (where X ^U , X ¹² , X ¹⁵ , X ¹⁶ , X ¹⁷ and X ¹⁸ are the same force or different, H or F; X ¹³ and X "are the same or different, H, F, C I'm CF; Rf ⁷ is a fluorinated Al

Three

A xylene group or a fluorine-containing alkylene group having an ether bond of 2 to 10 carbon atoms; n2 is an integer of 0 to 3; nl, n3, n4 and n5 are the same or different and are integers of 0 or 1) Those are preferred.

[0516] For example,

[0517] [Chemical 161]

™ CX ¹³ — CX ¹⁴ G

I I

o o

\ /

[0518] (wherein Rf ⁷ , X ¹³ and X "are the same as those described above).

[0519] Specifically,

[0520] [Chemical 162]

oocll

c

I!

O CF ₂

\ /

CF ₂

CF CX ^l5 X ^m

/ \

-CF ₂ CF CF-)--C FCF C F--i I \ I

O CF ₂ O t ¹ 2

\ /

CF ₂

/ \

-^ CX ⁿ X ¹² -CFCF-CX ⁿ X ¹² CF-C FCF ₂

ISII CF ₂ -0 CF ₂ — O

-CF-CF CF-

I \

O O O

\ /

CF C F

F F

[0521] (wherein X ¹¹ X ¹² X ¹⁵ and X ¹⁶ are the same as above).

[0522] Other fluorine-containing aliphatic cyclic structural units include, for example,

[0523] [Chemical 163]

-CF ₂ -C

0 0

1 I

CF.-CF

I

CF, [0524] and so on.

[0525] (C 3-2) Non-fluorinated alicyclic structural unit:

In addition, an amorphous fluorine-containing polymer containing a non-fluorinated alicyclic structural unit (C 3-2) can increase the glass transition temperature of the cured product and further increase the hardness.

[0526] Specific examples of the non-fluorinated alicyclic structural unit (C 3-2) include

[0527] [Chemical 164]

[0528] (m is an integer of 0 to 3; A, B, C and D are the same or different, such as H, F, Cl, COOH, CH OH or a perfluoroalkyl group having 1 to 5 carbon atoms) Norbornene indicated by

2

Derivatives,

[0529] [Chem 165]

[0530] and the like, and derivatives obtained by introducing a substituent into them.

[0531] (C 6) A vinylidene fluoride copolymer, which is an amorphous vinylidene fluoride copolymer having a fluorine content of 25% by mass or more:

Amorphous biridene fluoride-based copolymers are preferably those obtained by copolymerizing one or two or more of other monomers copolymerizable with bilidene fluoride.

[0532] Typical examples of other monomers include tetrafluoroethylene, black trifluoroethylene, trifnoreo ethylene, vinylphenololide, hexafluororeopropylene, pentafluororeropropylene, hexafluororeoisobutene. Perfluoronorolocyclobutene, perfluoro (methylcyclopropylene), perfluoroallene, perfluoroalkyl butyl ethers (eg perfluoromethyl vinyl ether, perfluoropropyl butyl ether) Perfluorolobule acetic acid or its ester, perfluorolobule Examples thereof include ether sulfonic acids, perfluorogens, ethylene, propylene, bulacetic acid, and esters thereof. The content of other monomers is not particularly limited, but it is preferable to copolymerize such that the fluorine content is in the range of 25% by mass or more, usually 10 to 60% by mass.

Particularly isopropylidene fluoride copolymer, bi - - [0533] bi amorphous benzylidene fluoride Z to hexa full O b propylene (85～60Z15～40 mole ^_0/0 ratio) copolymer, bi - Ridenfu Ruoraido to Ζ Xafluoropropylene Ζtetrafluoroethylene (84-20Ζ15-40 Zl-40 mol% ratio) copolymer strength This is preferred from the viewpoint of excellent solubility and compatibility with fluorine-containing compounds (I) and (Α).

[0534] The polymer (C6) is particularly preferable in that it is excellent in transparency in the visible region and gives impact resistance to the cured product. When the cured product requires rubber elasticity, the glass transition temperature of the polymer (C-6) is usually lower than room temperature. By using the polymer (C-6), the glass transition temperature of the entire cured product can be kept below room temperature. Can and prefer.

[0535] The amorphous fluorine-containing polymer (C) having a fluorine content of 25% by mass or more may have a cured portion. For example, a curing site that can react with a fluorine-containing acrylate, such as a carbon-carbon double bond, can be easily provided at the end of the side chain, and if there is a curing site that can react with such a fluorine-containing acrylate, Since the cured product forms a mutual network as a whole, it exhibits further excellent cured product performance such as solvent resistance, low linear expansion coefficient, and heat resistance.

[0536] From the viewpoint of workability, the preferred viscosity range of the liquid curable composition of the present invention is lOmP a 'less than, more preferably less than 20 mPa', particularly less than 50 mPa ', The range is preferably not more than OOOmPa's, more preferably not more than 8, OOOmPa's.

[0537] Further, it is preferable that the organic solvent is not substantially contained. However, for the purpose of adjusting the viscosity, a solvent or the like may be added within a range without adversely affecting the physical properties of the cured product.

[0538] Also, other compounds may be added separately as simple viscosity modifiers! However, the amount added is in a range that does not impair the effect intended by the present invention.

[0539] For example, when an optical material is formed by coating, it is desirable that the viscosity of the coating composition is 50 to 8, OOOmPa's in order to make the workability and film thickness thin and uniform. To increase the viscosity, increase the ratio of amorphous fluorine-containing polymer (C), polyfunctional fluorine-containing compound (I) or (B).

[0540] Further, the refractive index of the cured product obtained from the composition of the present invention is changed to polyfunctional fluorine-containing compound (I), monofunctional fluorine-containing acrylate (A), fluorine-containing acrylic polymer (C) and Z or others. The polyfunctional fluorine-containing compound (B) can be adjusted by appropriately selecting the type and amount. In addition, a low molecular weight compound may be added as necessary as a refractive index adjusting component. Specific examples of these include benzyl-n-butyl phthalate (refractive index: 1.575), 1 methoxyphenol- 1-phenol (refractive index: 1.571), benzyl benzoate (refractive index: 1.568), Bromobenzene (refractive index: 1.557), o Dichroic benzene (refractive index: 1.55 1), m-dichroic benzene (refractive index: 1.543), 1, 2, -dibromoethane (refractive index: 1) 53 8), 3-phenol- 1-propanol (refractive index: 1.532), di-phthalic acid (CH (

6 4

COOC H)), triphenylphosphine ((C H) P), dibenzyl phosphate ((C H

6 5 2 6 5 3 6

CH O) PHO), 4, 4, —Dibromobenzyl, 4, 4, —Dibromobiphenyl, 2, 4, —

5 2 2 2

Examples include compounds such as dib mouth moacetophenone, 3 ', 4'-dichloroacetophenone, 3,4 dichloroaniline, 2,4 dib mouth moorin, 2,6 dib mouth moain 1,4 dibromobenzene, etc. It is done.

[0541] In the composition of the present invention, known additives may be appropriately used according to the application and required properties. Typical examples of the additive include a leveling agent and an acid and sour prevention agent.

[0542] The second invention of the present invention relates to a cured product obtained by curing the curable composition of the present invention.

[0543] The cured product is obtained by adding a curing initiator (II) or various appropriate additives to the curable composition, and then applying it to, for example, molding or a substrate and irradiating with active energy rays or heating. It can be manufactured from a coconut paste.

[0544] The irradiation dose of the active energy ray may be appropriately selected depending on the type of the active energy ray curing agent used, the thickness of the cured film, and the like! The heating temperature may be appropriately selected depending on the type of radical polymerization initiator used.

[0545] The cured product of the present invention is excellent in heat resistance, transparency, and low refractive index. Furthermore, the curing obtained by using a curable fluorine-containing resin composition prepared without using a solvent. The product is not affected by the residual solvent, and the generation of macrovoids can be greatly reduced. When used as an optical material, light loss can be reduced.

[0546] The physical properties and characteristics of the cured product of the present invention will be described below.

[0547] Since the polyfunctional fluorine-containing compound (I) is used, the molecular weight is a cross-linked structure by itself, and when other components (A), (C), (B), etc. are blended, it is complicated. Because of reaction (crosslinking, graph K IP N structure), it cannot be specified! /.

[0548] The glass transition temperature Tg is preferably set to a force that can be selected within a wide range depending on the composition of 100 ° C or higher. Furthermore, by selecting each component, it is possible to make Tg 120 ° C or higher, 130 ° C or higher, or 150 ° C or higher. In order to increase the Tg, the polyfunctional fluorine-containing compound (I) component may be increased, or a ring structure may be introduced into the fluorine-containing polymer (C) component.

[0549] Thermal decomposition temperature Td is 180 ° C or more, and has excellent heat resistance. Furthermore, Td can be increased to 200 ° C or higher, and further 230 ° C or higher, by selecting each component.

[0550] Since the polyfunctional fluorine-containing compound (I) is used, the cured product of the present invention becomes amorphous as a whole. When the cured product is amorphous, it is advantageous in that it has excellent transparency and can reduce transmission loss in an optical transmission medium such as an optical waveguide or an optical fiber.

[0551] The cured product of the present invention can have a refractive index of 1.44 or less. Lowering the refractive index, for example, to 1.42 or less, can be achieved by increasing the overall fluorine content. Such a low refractive index is advantageous as an optical waveguide, a cladding material for an optical fiber, and an antireflection material.

[0552] The cured product 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 (or 850 nm). From this viewpoint, when the cured product of the present invention is used as an optical material, it is possible to provide a light transmittance of light having a wavelength of 650 nm (or 850 nm) of 90% or more, further 92% or more, particularly 94% or more.

[0553] Furthermore, the cured product of the present invention is highly transparent to light in the near-infrared region, and particularly highly transparent to light having a wavelength of 1310 nm (more preferably 1550 nm). From this point of view, when the cured product of the present invention is used as an optical material, a light transmittance of 1310 nm (or 1550 nm) wavelength light is 90% or more, more preferably 92% or more, and particularly 94% or more. [0554] In order to enhance such optical transparency, the fluorine content is preferably 40% by mass or more, more preferably 45% by mass or more, and particularly preferably 50% by mass or more. The upper limit is when all hydrogen atoms are replaced by fluorine atoms.

[0555] The third invention of the present invention relates to an optical material comprising a cured product of the curable composition. The present invention also relates to an optical waveguide having a core part and a clad part force, wherein at least one of the core part and the clad part is a cured product force of the curable composition of the present invention.

[0556] First, the optical material will be described.

[0557] The cured product of the present invention is transparent as described above, has high heat resistance, and has a high fluorine content. Therefore, it becomes an optical material with a low refractive index. For example, it is useful as an optical transmission medium. 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 including optical materials such as materials, optical storage disk materials, nonlinear optical elements, hologram materials, and photorefractive materials, sealing member materials, and cured products obtained by curing these materials Can be used.

[0558] Examples of the material for the sealing member include light emitting diodes (LEDs), EL elements, nonlinear optical elements, photorefractive elements, photoluminescent crystals, light receiving elements, wavelength conversion elements, optical add / drop elements, Examples include the materials used for optical cross-connect devices, optical functional devices such as modulators (encapsulation), and surface mounting.

[0559] The optical device encapsulated with the material of the present invention has excellent moisture resistance resulting from the fluorine-containing polymer in addition to the excellent moisture resistance derived from the fluorine-containing polymer. It has high humidity resistance. It is also a material that combines excellent transparency and heat resistance in the wavelength band used.

[0560] These encapsulated light elements are used in various locations. Non-limiting examples include high-mount stop lamps, instrument panels, mobile phone backlights, and remote control devices for various electrical products. Light emitting elements such as light sources; camera autofocus And light receiving elements for optical pickups for CDZDVD.

[0561] The sealing member material using the material of the present invention may be blended with additives such as a photo-oxidant, a curing accelerator, a dye, a modifier, a deterioration inhibitor, and a release agent as necessary. It can be produced by combining a dry blend method, a melt blend method, etc., mixing and kneading by a conventional method, pulverizing, and tableting as necessary.

[0562] Sealing with a sealing member material 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.

Next, the optical waveguide will be described. The optical waveguide member is a member constituting an optical waveguide element, and is formed on a substrate. Here, the optical waveguide element is a device in which optical functional elements are connected by an optical waveguide, and the optical waveguide portion is composed of a core portion and a clad portion force. On the other hand, an optical functional element is an element that exhibits effects such as amplification, wavelength conversion, optical multiplexing / demultiplexing, wavelength selection, etc., on optical communication signals. Although it has various forms, it is introduced like optical multiplexing / demultiplexing and optical amplification. There are waveguide-type functional elements. In that case, the functional element is also formed of a core part and a clad part. The optical material of the present invention can be used in any core part and cladding part, and the optical material of the present invention may be used only in the core part or only in the cladding part. Also, various functional compounds such as nonlinear optical materials, fluorescent organic functional organic dyes, photorefractive materials, and the like are included in the optical material of the present invention and used as the core material of the waveguide type functional element. It is also possible. Further, it is more preferable that both the core part and the clad part are obtained by curing the curable fluorine-containing resin composition.

[0564] According to the present invention, an optical waveguide device containing a cured product of the curable composition can also be provided.

[0565] When the optical waveguide element has a core part and a cladding part, the refractive index of the core part must be higher than that of the cladding part, but the difference in refractive index between the core part and the cladding part is 0. Preferably it is 003 or more, more preferably 0.01 or more. Since the material of the present invention is wide and the refractive index can be controlled, the material selection range is wide.

[0566] In the optical waveguide device, the width of the core portion is preferably 1 to 200 m, more preferably 5 to 50 µm. The height of the core part is preferably 5 to 50 μm. The accuracy of the width and height of the core is preferably 5% or less of the average value, more preferably 1% or less.

FIG. 1 illustrates a schematic cross-sectional view of the structure of a typical optical waveguide device. 1 for board, 2 for The core parts 4 and 5 are the cladding parts. The optical waveguide type element that is applied is used to connect the optical functional elements, and the light transmitted from the terminal of one optical functional element passes through the core part 2 of the optical waveguide type element, for example, the core part 2 It propagates to the other optical functional device terminal while repeating total reflection at the interface between the clad part 4 and 5. The form of the optical waveguide type element may take an appropriate form such as a planar type, a strip type, a ridge type, and an embedded type.

[0568] The substrate material of the optical waveguide element is not particularly limited, and any appropriate material such as metal, semiconductor material, ceramic, glass, thermoplastic resin, thermosetting resin, and the like can be used.

[0569] FIG. 2 shows an example of the manufacturing process of the optical waveguide device using the material of the present invention. The optical waveguide element is manufactured by using a photolithography technique. First, as shown in FIG. 2 (a), a clad portion 4 is previously formed on a substrate 1, and a film 3 of the optical material of the present invention for forming a core portion is formed. In forming the film of the optical waveguide material for forming the clad part 4 and the core part, a method of applying the uniform liquid composition by a coating means such as spin coating or casting, a mold There is a method of using. The composition is preferably prepared by filtering through a filter having a pore size of about 0.2 μm, for example.

[0570] The preferred viscosity of the curable composition is generally 10 to: LO, 000 mPa-s, particularly preferably 20 to: LO, OOOmPa's, and more preferably 50 to 8, OOOmPa's. Here, as described above, the viscosity is adjusted with the polymer components (C 1) and (C).

[0571] Next, as shown in Fig. 2 (b), the curable yarn and the composition are irradiated with active energy rays 7 through a mask 6 having a predetermined pattern shape. Thereafter, preliminary firing is performed as necessary. When photocured, the curable composition polymerizes between molecules. As a result, the resin hardness increases, the mechanical strength is improved, and the heat resistance is improved. Since a polyfunctional fluorine-containing compound is used, it becomes insoluble in many other types of solvents, in addition to being insoluble in the solvent dissolved before curing. That is, it functions as a photoresist material. Next, the uncured curable composition is dissolved in a suitable solvent and distilled off to form a core portion 2 having a predetermined pattern shape as shown in FIG. 2 (c). The optical waveguide type element can be used as it is in a form having only the core part 2 formed as described above.However, after the core part 2 is formed, as shown in FIG. Preferably, part 5 is formed. This cladding 5 Is preferably formed by applying the material solution by spin coating, cast coating, roll coating or the like, and spin coating is particularly preferred. Further, the uniform liquid composition of the clad part 5 is preferably prepared by filtering with a filter having a pore diameter of about 0.2 m, for example.

[0572] As the curing method, a known method may be adopted as appropriate. In addition, the photocuring as described above is advantageous because the process is simplified. In addition to the above methods, a new molding method using a curable composition has recently been proposed as a method for forming a waveguide. For example, a stamper molding method for producing an optical waveguide using a fine mold, embossing, and a nanoimprint method via a silicone rubber mold. The curable composition of the present invention can also be applied to these moldings.

[0573] The cured product of the present invention utilizes forces that are particularly suitable for optical applications, and also uses the properties of organic polymers obtained by curing, for applications other than optical applications such as adhesives, paints, various molding materials, It is also useful as a material for producing dental materials and the like.

[0574] Therefore, the curable composition of the present invention includes pigments in addition to various additives for optical applications.

Further, a photocatalyst such as a filler and titanium oxide can be blended.

[0575] The curable composition of the present invention may be further added with a rare earth metal compound (III) to provide a curable composition that gives an optical material having optical functionality.

[0576] In the periodic table, the rare earth element used in the rare earth metal compound (III) is at least one selected from the 17 elemental forces of scandium-um group elements and lanthanoids excluding Kuchiyumu, Among them, erbium (Er), thulium (Tm), praseodymium (Pr), holmium (

Ho), neodymium (Nd), europium (Eu), cerium (Ce), samarium (Sm), dysporium (Dy), terbium (Tb) and the like are preferred.

[0577] From these, the type of rare earth element to be used is selected according to the applications such as light emission, optical amplification and wavelength conversion, and according to the type of light (wavelength) required.

[0578] For example, in the optical amplification application of optical communication using near-infrared light having a wavelength of 1300 to 1550 nm, it is preferable to select from rare earth elements having fluorescence generation ability in the near-infrared region.

[0579] Specific examples include rare earth elements such as prasedium (fluorescence wavelength: 1300 nm), erbium (fluorescence wavelength: 1550 nm), and for optical communication optical amplification applications using near-infrared light with a wavelength of 850 nm. And neodymium (fluorescence wavelength: 850 nm) are preferred. Visible light with a wavelength of 650 nm Europium (fluorescence wavelength: 615nm) is preferred for the optical amplification used in optical communications.

[0580] For use as a light emitting device and a wavelength conversion material, a rare earth element that generates light of a necessary wavelength as fluorescence is selected.

[0581] For light emission applications, for example, it is preferable to select power such as terbium for green light emission (fluorescence wavelength: 532 nm) and europium for red light emission (fluorescence wavelength: 615 nm).

[0582] The rare earth metal compound (III) in the optical functional optical material of the present invention is a rare earth metal complex (in a state where a complex is formed with a ligand) (111-1), an inorganic phosphor (111- 2) Rare earth metal ion (state existing in a normal ionic bond) (ΠΙ-3), and rare earth metal complexes and inorganic phosphors are preferred. Of these, rare earth metal complexes are particularly preferred.

[0583] Each rare earth metal compound will be described below.

[0584] (III-1) Rare earth metal complexes

Rare earth metal complexes are preferred because of their high light emission (amplification) efficiency and excellent dispersibility and compatibility with the multifunctional fluorine-containing compound (I) used in the present invention.

[0585] In other words, a rare earth metal complex usually has one or more ligands coordinated to a rare earth element, and the ligand surrounds the rare earth element compared to the rare earth metal ion. Yes. As a result, in the process where the excited rare earth element emits light, the stored rare earth element energy is prevented from escaping to the surrounding matrix molecules (polymer molecules, etc.), resulting in an increase in emission intensity and luminous efficiency of rare earth metal power. To do.

[0586] The ligand of the rare earth metal complex may be either inorganic or organic as long as it contains an unsaturated bond or the like, such as a π-electron atom (such as a heteroatom). In particular, the polyfunctional fluorine-containing compound used in the present invention is an organic compound having a carbon-carbon double bond, a double bond between carbon-heteroatoms, and a double bond between heteroatoms-heteroatoms. Preferred because of its excellent dispersibility and compatibility with (I).

[0587] Sarasako is a rare-earth metal complex that contains a charge-compensated ligand that forms a cation and forms a coordination bond and an ionic bond with the rare earth metal ion (cation). It is preferable in terms of excellent stability, heat resistance, and ultraviolet resistance.

[0588] Specifically, charge-compensated ligands include, for example, the formula (bl): [0589] [Chemical 166]

(In the formula, Y ² is the same or different, co or o = s = o;

I I

[0590] X ¹¹ includes a hydrogen atom, a deuterium atom, a fluorine atom, a hydrocarbon group having 1 to 20 carbon atoms, and a carbon atom having 1 to 20 carbon atoms in which part or all of the hydrogen atoms are substituted with fluorine atoms. Having a structural unit represented by fluorine or a hydrocarbon group),

Formula (b2):

[0591] [Chemical 167]

[0592] (wherein Υ Υ ² is the same as in formula (bl)),

Formula (b3):

[0593] [Chemical 168]

[0594] [wherein Y ³ is 0, S or N— (where R is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a carbon atom in which part or all of the hydrogen atoms are substituted with fluorine atoms) 1 to 20 fluorine-containing hydrocarbon base force selected) force also selected; Y ⁴ is

[0595] [Chemical 169]

C = 0, 0 = S = 0, S

[0596] (In the formula, R ¹ 'is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a fluorine-containing carbon atom having 1 to 20 carbon atoms in which part or all of the hydrogen atoms are substituted with fluorine atoms. And hydrogen may be further selected to form a ring structure with carbon atoms in C = N; R ² ′ and R ³ ′ may be the same or different and have a carbon number of 1 A hydrocarbon group having 1 to 20 carbon atoms and a hydrocarbon group having 1 to 20 carbon atoms in which some or all of the hydrogen atoms are substituted with fluorine atoms are also selected, and further R ² ′, R ^{3 /} May form a ring structure with a phosphorus atom, and includes those having a structural unit represented by at least one selected from C).

[0597] Specific examples of the ligand having the structure of formula (bl) include the following.

[0598] (bl— 1) Ligand with β-diketone structure

Specifically, the formula (bl— 1):

[0599] [Chemical 170]

[0600] (where

Rb ² is the same or different, and represents a hydrocarbon group having 1 to 20 carbon atoms, a fluorine-containing hydrocarbon group having 1 to 20 carbon atoms in which part or all of the hydrogen atoms are substituted with fluorine atoms, and a heterocyclic structure. Having at least one hydrocarbon group having 1 to 20 carbon atoms; X ¹¹ is the same as the above formula (bl)), and these are luminescent efficiency, amplification efficiency, complex formed and It is preferable in terms of good compatibility with the polyfunctional fluorine-containing compound (I).

[0601] Specifically,

[0602] [Chemical 171]

[0603] can be exemplified, among them

[0604] [Chemical 172]

[0605] is preferred.

[0606] Ligand with (bl -2) β -disulfol structure

Specifically, the formula (bl— 2):

[0607] [Chemical 173]

[0608] (wherein RlA Rb ² is the same as the formula (bl—1); X ¹¹ is the same as the formula (bl)), and these are luminescent efficiency, amplification efficiency, formation In view of good compatibility between the complex and the polyfunctional fluorine-containing compound (I).

[0609] Specifically,

[0610] [Chemical 174]

No

[0611] is an example, among them

[0612] [Chemical 175]

s = =

[0613] is preferred.

[0614] Specific examples of the ligand having the structure of the formula (b2) include the following. [0615] (b2- l) Ligand having a force sulfonylimide structure

Specifically, the formula (b2-1):

[0616] [Chemical 176]

[0617] (wherein Rb R is the same as the above formula (bl-1)), and these are luminescent efficiency, amplification efficiency, complex formed and polyfunctional fluorine-containing compound (I) It is preferable in terms of good compatibility with.

[0618] Specifically,

[0619] [Chemical 177]

[0620] can be illustrated, among them

[0621] [Chemical 178]

[0622] is preferred.

[0623] (b2-2) Ligands having a sulfonimide structure

Specifically, the formula (b2-2):

[0624] [Chemical 179]

[0625] (where

Rb ² is a ligand represented by the above formula (b2−l)), and these have good emission efficiency, amplification efficiency, and compatibility between the complex formed and the polyfunctional fluorine-containing compound (I). Good in terms.

[0626] Specifically,

[0627] [Chemical 180]

[0628] can be shown,

[0629] [Chemification: 81]

[0630] is preferred.

[0631] According to the formulas (bl-l), (bl-2), (1) 2-1) and 0) 2-2-2), 1¾ ¹ and 1¾ ² are at least one of which is hydrogen From the viewpoint of light emission (amplification) efficiency, a fluorine-containing hydrocarbon group having 1 to 20 carbon atoms in which some or all of the atoms are substituted with fluorine atoms.

[0632] Furthermore, in the formulas (bl-1) and (bl-2), X ¹¹ is preferably a deuterium atom or a fluorine atom in terms of light emission (amplification) efficiency.

[0633] Specific examples of the ligand having the structure of the formula (b3) include the following.

[0634] (b3-1) Formula (b3-1):

[Wherein Rb ³ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a fluorine-containing hydrocarbon having 1 to 20 carbon atoms in which part or all of the hydrogen atoms are substituted with fluorine atoms. And at least one hydrocarbon group having 1 to 20 carbon atoms having a heterocyclic structure; Rb ⁴ is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have an ether bond, hydrogen A part of or all of the atoms have an ether bond substituted by a fluorine atom, and may be a fluorine-containing hydrocarbon group; Y ³ is the same as (b3) above) These are preferable in terms of good luminous efficiency, amplification efficiency, and compatibility between the complex formed and the polyfunctional fluorine-containing compound (I).

[0637] Specifically,

[0638] [Chemical 183]

184]

[0640] can be exemplified, among them [0641] [Chemical 185]

[0642] is preferred.

[0643] (b3-2) Formula (b3-2):

[0644] [Chemical 186]

(Wherein Rb ³ and Rb ⁴ are the same as the above formula (b3-1); Y ³ is the same as the above (b3)), and these are the luminous efficiency, amplification efficiency, and the complex formed. Preferred because of its good compatibility with the polyfunctional fluorine-containing compound (I). [0646] Specifically, [0647] [Chemical 187]

[0648] [Chemical 188]

[0649] can be exemplified, among them [0650] [Chemical 189]

[0651] is preferred.

[0652] (b3-3) Formula (b3-3):

[0653] [Chemical 190]

(Wherein Rb ³ and Rb are the same as in the above formula (b3-1); Y ³ and R ² are the same as in the above (b3)), and these are luminescent efficiency, amplification efficiency, formation U, preferred because of good compatibility between the complex and the polyfunctional fluorine-containing compound (I). [0655] Specifically, [0656] [Chemical 191]

[0657] [Chemical 192]

[0658] can be exemplified, among them [0659] [Chemical 193]

opchl

[0660] is preferred.

[0661] In formulas (b3), (b3-1), (b3-2) and (b3-3)! /, Rb ³ is a part or all of hydrogen atoms replaced by fluorine atoms The fluorine-containing hydrocarbon group having 1 to 20 carbon atoms is preferred from the viewpoint of light emission (amplification) efficiency.

[0662] In the formulas (b3) and (b3-3), R ¹ ', R ² ', and R ³ 'each represents a carbon number of 1 to 20 in which part or all of the hydrogen atoms are substituted with fluorine atoms. From the viewpoint of light emission (amplification) efficiency, the fluorine-containing hydrocarbon group is preferred.

[0663] The rare earth metal complex used in the optical functional optical material of the present invention may further be one that has no charge (negative charge) and into which a charge-uncompensated ligand is introduced.

[0664] A charge-uncompensated ligand has no charge in the entire ligand, It has π electron pairs that can be coordinated dynamically,

[0665] [Chemical 194]

[0666] Compound powers having sites such as are usually selected.

[0667] Specifically,

[0668] [Chemical 195]

p s =,

c

s .. c

C ₂ HC _a F

C ₂ HC ₂ F

196]

[0671].

[0672] Among the charge non-compensation type ligands, one in which a fluorine atom is introduced is preferable from the viewpoint of light emission (amplification) efficiency.

[0673] In the rare earth metal complex used in the present invention, at least one kind of ligand selected from the above-mentioned charge-compensated or non-compensated ligand ligand is coordinated to a trivalent rare earth metal ion. If combined, 3 or 4 ligands are preferably coordinated. In the rare earth metal complex, the ligand is composed of only one of the charge-compensated type and the non-charge-compensated type !, but includes both the charge-compensated type and the non-charge-compensated type! / Yes.

[0674] Of these, those containing at least one charge-compensating ligand are preferred, and those having three charge-compensating ligands coordinated are particularly preferred. If necessary, a non-compensated ligand may be introduced as the fourth ligand! / ヽ. Complexes containing these charge-compensated ligands are themselves highly stable and excellent in light emission (amplification) efficiency, and further in dispersibility and compatibility in the polyfunctional fluorine-containing compound (I) used in the present invention. I like it in terms.

[0675] As a result, the optical functional optical material of the present invention is preferable in that it is particularly effective in light emission (amplification) intensity and light emission (amplification) efficiency. [0676] (ΠΙ-2) Inorganic phosphor

Inorganic phosphors are obtained by activating rare earth metals in inorganic salts, and are preferable in terms of high heat resistance.

[0677] As a specific example of the inorganic phosphor,

(1) YAG (yellow luminescent material)

Specifically (YaGdl—a) (AlbGal-b) O Ce ³⁺ etc.

12

(2) YOS (Red light emitting material)

Specifically, Y O S: Er etc.

twenty two

(3) BAM: Eu (Blue light emitting material)

Specifically, (Ba, Mg) Al 2 O: Er, etc.

10 17

(4) SCA (Blue light emitting material)

Specifically (Sr, CaBaMg) (PO) CI: Eu, etc.

10 4 6 2

(5) GN4 (green light emitting material)

ZnS: Cu, A1, etc.

(6) BAM: Eu, Mn (Green light emitting material)

Specifically, (Ba, Mg) Al 2 O: Eu, Mn, etc.

10 17

Phosphors.

[0678] (ΙΠ-3) Rare earth metal ions

In the rare earth metal compound (III) used in the present invention, the rare earth metal ion is usually mixed in the form of a salt with a counter ion capable of ionic bonding with a rare earth metal ion. Rare earth metal cations are generally used as salts of divalent, trivalent or tetravalent metal cations, with no limit on valence.

[0679] Examples of rare earth metal salts include halides such as chlorides, bromides, and iodides of the above-mentioned rare earth elements; salts such as nitrates, perchlorates, bromates, acetates, sulfates, and phosphates. Etc. Further, organic salts of rare earth metals such as organic acid salts and organic sulfonic acid salts may be used. Also, double nitrates, double sulfates and chelate cakes can be used.

[0680] Specific examples of rare earth metal salts include: salt prasedium, prasedium bromide, brazeodium iodide, praseodymium nitrate, prasedium perchlorate, praseodymium bromate Prasedium salts such as sodium acetate, prasedium acetate, prasedium sulfate, and prasedium phosphate; Neodium salts such as neodymium phosphate; europium salts such as europium chloride, europium bromide, europium iodide, europium nitrate, europium perchlorate, europium bromate, europium acetate, europium sulfate, europium phosphate; Erbium, Erpium bromide, Rubium iodide, Erbium nitrate, Erbium perchlorate, Erbium bromate

Erbium salts such as erbium acetate, erbium sulfate, erbium phosphate; terbium chloride, terbium bromide, terbium iodide, terbium nitrate, terbium perchlorate, terbium benzoate, terbium acetate, terbium sulfate, terbium phosphate Terbium salts such as: samarium chloride, samarium bromide, samarium iodide, samarium nitrate, samarium perchlorate, samarium bromate, samarium acetate, samarium sulfate, samarium phosphate, and the like.

[0681] In the optical functional optical material of the present invention, the abundance ratio is (I) is from 1 to 99.99 mass ^_0/0 of the polyfunctional fluorine-containing compound (I) and rare earth metal of compound (III), (111 ) 0.01 to 99 weight ^_0/0 for the (mass% of the ion. rare earth metal compound (III) content is hereinafter the same), a rare earth metal compound to use (III) and the polyfunctional fluorine-containing compound It is appropriately selected depending on the type, use, purpose, etc. of (I).

[0682] When used as an optical communication component such as an optical amplifier or an optical waveguide or a light emitter, the rare earth metal compound content is in the range of 0.01 to 20 mass% from the viewpoint of improving fluorescence intensity. More preferably, it is 0.1 to 15% by mass, and most preferably 0.5 to 10% by mass.

[0683] If the content of the rare earth metal compound (III) is too small, the desired light amplification effect and emission intensity

The target performance such as the wavelength conversion effect is not exhibited.

[0684] On the other hand, if the content of the rare earth metal compound (III) is too large, the dispersibility and compatibility between the rare earth metal compound (III) and the polyfunctional fluorine-containing compound (I) forming the matrix polymer are deteriorated. Therefore, it is not preferable.

[0685] The content of rare earth metal ions burns organic components in an electric furnace at a temperature of about 600 ° C. The ash can be quantified by baking, or quantitatively measured by physical techniques such as X-ray fluorescence analysis.

[0686] In addition to the above-mentioned polyfunctional fluorine-containing compound (I) and rare earth metal compound (III), various additives may be blended in the optical functional optical material of the present invention as necessary. Examples of the additive include a leveling agent, a viscosity modifier, a light stabilizer, an antioxidant, a moisture absorbent, a pigment, a dye, and a reinforcing agent.

[0687] There are no particular restrictions on the method for producing the photofunctional optical material having the multifunctional fluorine-containing compound (I) and rare earth metal compound (III) of the present invention, for example, the multifunctional fluorine-containing compound (I), If necessary, the rare earth metal compound (III) is mixed or dissolved in the monofunctional acrylate of the formula (2) and then polymerized (cured) by a known polymerization method such as a radical polymerization method or an anion polymerization method. It is done.

[0688] More specifically, the polyfunctional fluorine-containing compound (I) and, if necessary, the monofunctional acrylate and the optional monomer (n) of the formula (2) and the rare earth metal compound (III) catalyst. Is prepared, and a polymerization composition to which a polymerization initiator is added as necessary is polymerized (cured) to produce an optical functional optical material.

[0689] Examples of the monomer (n) include acrylate monomers other than the above formulas (1) and (2), (meth) acrylic acids, fluorine-containing (meth) acrylic acids, maleic acid derivatives, etc. It is preferable that the structural unit strength derived from the monomer is also selected. As the acrylate monomer, a (meth) acrylate monomer having a linear or branched alkyl group having 1 to 20 carbon atoms in the side chain, specifically, methyl methacrylate (MMA) is used. , Methyl acrylate (MA), ethyl meta acrylate (EMA), ethino rare acrylate (EA), isopropyl meta acrylate, isopropyl acrylate, butyl meta acrylate, butyl acrylate, hexyl meta acrylate Preferred are rate, hexyl acrylate, octadecyl meta acrylate, octadecyl acrylate and the like.

[0690] In general, the radical polymerization method is preferable in terms of polymerization reactivity and productivity, and high homogeneity of the monomer composition in the polyfunctional fluorine-containing compound (I). .

[0691] For the radical polymerization, a polymerization initiator is not used! /, A thermal radical polymerization method, a thermal polymerization method using a radical polymerization initiator, a photopolymerization method using a photo radical generator, etc. can be used. Of these, a thermal polymerization method using a radical polymerization initiator and a photopolymerization method using a photo radical generator are preferred because they have good polymerization reactivity. Further, the photopolymerization method using a photoradical generator is preferable in producing the optical functional optical material (1) above, particularly in terms of excellent continuous processability.

[0692] The optical functional optical material of the present invention includes, in addition to the above-described light amplifying element and light emitting element, for example, a cover material for a lighting fixture, a knock light for a liquid crystal display, a transparent design case, a display board, and an automotive part. It is useful as a sheet-like illuminant exemplified by wavelength conversion filters, X-ray imaging plates, fiber lasers, photosensitive inks, sensors and the like.

[0693] The optical functional optical material of the present invention can also be used as a sealing member material having optical functionality and an optical device comprising the same.

[0694] The optical device encapsulated with the optical functional optical material of the present invention has excellent moisture resistance and moisture resistance because the sealed portion has excellent moisture resistance and moisture resistance derived from the fluorine-containing polymer. have. Further, the optical functional optical material of the present invention is excellent in transparency over a wide range of ultraviolet power and near infrared, and is particularly useful as a sealing member for optical applications. Furthermore, since the optical functionality of the present invention is combined, it is possible to add added value such as a wavelength conversion function and an optical amplification function, in addition to the normal sealing function.

[0695] Examples of usage of the optical functional sealing member in the present invention include light-emitting elements such as light-emitting diodes (LEDs), EL elements, nonlinear optical elements, photorefractive elements, and photo-tus crystals, and light-receiving elements and wavelength conversions. Examples include optical functional device packages (encapsulation), surface mounting, etc., such as devices, optical add / drop devices, optical cross-connect devices, and modulators. Further, sealing materials (or fillers) for optical members such as lenses for deep ultraviolet microscopes are also included. Encapsulated light elements are used in various places, but non-limiting examples include: light mounts, meter-stop lamps, instrument panels, mobile phone backlights, light sources for remote control devices for various electrical products, etc. Light-emitting elements; autofocus of cameras, light-receiving elements for optical pickups for CDZ DVDs, and the like.

[0696] The fourth invention of the present invention relates to a novel polyfunctional fluorine-containing compound.

[0697] A powerful polyfunctional fluorine-containing compound is represented by the formula (3):

[0698] [Chemical 197] X ³

R ^ (: R No O— C— C = CH ₂ ) _n (3)

O

[0699] (In the formula, X ³ is the same or different and a group force consisting of H, CH, F, CI and CF is selected.

3 3

[0700] [Chemical 198] ^ _ ^ c II ₂ ~ 7 ~ ―ri ri and II ₉ ~) ~ ~, 4)

'I

R f ³

[0701] (wherein Rf ³ is a fluorine-containing alkyl group having 1 to 19 carbon atoms; z, X and y are the same or different, 0 or 1) Is a polyfunctional fluorine-containing compound (I 1).

[0702] As the polyfunctional fluorine-containing compound (I 1) represented by the formula (3),

(1) Fluorine content is 40 mass% or more,

(2) viscosity at 35 ° C is 100, OOOmPa'sec or less, and

The polyfunctional fluorine-containing compound (I 1) is preferred.

[0703] This polyfunctional fluorine-containing compound (I 1) can be synthesized, for example, by the following two-step reaction.

First stage (diol synthesis)

By reacting a fluorine-containing polyhydric alcohol with one or more fluorine-containing epoxy compounds under acidic or basic conditions, the formula (10):

^{^{R 8 - (R 7 OH)}} (10) (Wherein R ⁷ , R ⁸ and n are the same as in formula (3)).

[0704] This reaction is carried out for 0.1 to 600 hours at a reaction temperature of 100 to 200 ° C, with or without a solvent, in the presence or absence of a catalyst.

[0705] When a solvent is used, the solvents used in the acid conditions include methylene chloride, chloroform, dichloroethane, carbon tetrachloride, trichloroethane, tetrachloroethane, hexane, pentane, heptane, octane, Benzene, Toluene, Nitrobenzene, Benzonitrile, Nitromethane, Nitroethane, Acetonitrile, Carbon dioxide, Sulfur dioxide, Ethyl acetate, No, Iodine fluorocarbon (HFC), Hyde mouth fluorocarbon (HCFC), Black mouth fluorocarbon (CFC) And perfluorocarbon (PFC). Examples of catalysts include sulfuric acid, phosphoric acid, perchloric acid, trichloroacetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, methanesulfonic acid, ptoluenesulfonic acid, boron trichloride, boron tribromide, and trifluoride. Boron, trisalt-aluminum, aluminum tribromide, titanium tetrachloride, disalt-magnesium, tin dichloride, tin tetrachloride, disalt-zinc, silicon tetrachloride, methyl trichloride, trisalt Ethylsilane, salt 匕 trimethylsilane, salt 匕 trimethoxysilane, salt 匕 triethoxysilane, tetramethoxysilane, tetraethoxysilane, pentachloride 匕 antimony, antimony pentafluoride, ethylaluminum dichloride, methyl dichloride Aluminum, Jetyl aluminum chloride, Dimethyl aluminum chloride, Triethyl aluminum, Trimethyla Such as Miniumu, and the like. Solvents used under basic conditions include, for example, jetyl ether, diisopropyl ether, dibutyl ether, t-butyl methyl ether, tetrahydrofuran, 1,4 di-dioxane, 1,3-di dioxane, 1,3-dioxolan, dimethoxyethane, Dimethoxymethane, diglyme, triglyme, tetraglyme, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec butanol, t-butanol, octanol, acetone, methyl ethyl ketone, methyl butyl ketone, dimethyl sulfoxide, Single solvent such as sulfolane dimethylformamide, dimethylacetamide, N-methylpyrrolidone, hexane monohydrate, pentane monohydrate, heptane monohydrate, octane monohydrate, benzene monohydrate, toluene monohydrate, nitrobenzene monohydrate Ben Zo-tolyl monohydric, nitromethane monohydric, acetontril monohydric, ethylacetate acetic acid, hydrated fluorocarbon (HFC) —water, nodular fluorocarbon (HCFC) water, chlorofluorocarbon (CFC) water, perfluoro Carbon (PFC) —an immiscible solvent such as water. These solvents can be mixed with jetyl ether, diisopropyl ether, dibutyl ether, t-butyl methyl to control the solubility of the reaction layer and product layer. Ether, tetrahydrofuran, 1,4-dioxane, 1,3-di-oxane, 1,3-dioxolan, dimethoxyethane, dimethoxymethane, diglyme, triglyme, tetraglyme, methanol, ethanol, n-propanol, iso-propanol, _n —Butanol, sec butanol, t-butanol, octanol, acetone, methyl ethyl ketone, methyl butyl ketone, and sulfolane may be added. When a two-layer solvent is used, a phase transfer catalyst can be used. Examples of the catalyst include tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium hydroxide, tetra Methyl ammonium hydrogen sulfate, tetramethyl ammonium sulfate, tetramethyl ammonium phosphate, tetraethyl ammonium chloride, tetraethyl ammonium bromide, tetraethyl ammonium hydroxide, tetraethyl ammonium Hydrogensulfurate, tetraethylammonium acetate, tetraethylammonium phosphate, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetrapropylammonium hydroxide , Tetrapropylammonium acetate, tetrapropylammonium phosphate, salt butyl tetrabutylammonium, tetrabutylammonium bromide, tetrabutylammonium hydroxide, tetrabutylammonium hydrogensulfate, Tetraptyl ammonium acetate, tetrabutyl ammonium phosphate, benzyl trimethyl ammonium chloride, benzyl trimethyl ammonium bromide, benzyl trimethyl ammonium hydroxide, benzyl trimethyl ammonium hydrogen sulfide Art, benzyltrimethylammonium acetate, benzyltrimethylammonium phosphate, benzyltriethyl amine chloride, benzyltriethylamine bromide, benzyltriethylamine ammonium hydroxide, Benzyltriethylammonium hydrogen sulfate, benzyltriethylammonium acetate, benzyltriethylammonium phosphate, benzyltributylammonium chloride, benzyltributylammonium bromide, benzyltributylammonium hydroxide, benzyltributylammonium Um hydrodiene sulfate, benzyltributylammonium acetate, benzyltri Butyl ammonium phosphate, Phenol trimethyl ammonium chloride, Phenol bromide Trimethyl ammonium, Phenol trimethyl ammonium hydroxide, Phenol trimethyl Ammonium hydrogen sulfate, Phenol trimethyl Ammonium acetate, fermtrimethylammonium phosphate, trioctylmethylammonium chloride, trioctylmethylammonium bromide, trioctylmethylammonium hydroxide, trioctylmethylammonium hydrogensulfur Art, Trioctylmethyl ammonium acetate, Trioctylmethyl ammonium phosphate, Trioctyl methyl ammonium chloride, Trioctyl methyl ammonium bromide, Trioctyl methyl ammonium hydroxide, Trioctyl ester Chiluan Mou Muhydrodiene sulfate, trioctyl cetyl anne momuacetate, trioctyl cetyl ammo phosphate and the like are preferred. In this reaction, the base can be used in an equal amount or a catalytic amount, such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, Sodium methoxide, sodium ethoxide, sodium iso-propoxide, sodium n-propoxide, sodium t-butoxide, sodium n-butoxide, sodium sec-butoxide, potassium methoxide, potassium ethoxide, potassium iso-propoxide, potassium n —Propoxide, potassium tert-butoxide, potassium n-butoxide, potassium sec-butoxide, lithium methoxide, lithium ethoxide, lithium iso-propoxide, lithium n-propoxide, lithium tert-butoxy Lithium n-butoxide, lithium sec-butoxide, sodium hydride, potassium hydride, lithium hydride, calcium hydride, sodium naphthalene, methyllithium, ethyllithium, butyllithium, methylmagnesium chloride, methylmagnesium bromide, methylmagnesium Ethylmagnesium chloride, ethylmagnesium bromide, ethylmanzinoremagnesium iodide, phenylmagnesium chloride, phenylmagnesium bromide, phenylmagnesium iodide and the like are used.

[0706] Stage 2 (Esterification)

Obtained fluorine-containing polyhydric alcohol (10) and formula (11):

[0707] [Chemical 199] ON. 3

L- C 1 (.). ..I.)

o

[0708] By reacting an acrylic compound represented by the formula (wherein R ¹⁷ is H, CI, etc .; X ³ is the same as formula (3)) under an acid condition or a base condition, The polyfunctional fluorine-containing compound represented by 3) can be synthesized.

[0709] This latter reaction is carried out with or without a solvent in the presence or absence of a base.

The reaction temperature is 100-200 ° C, and it is preferable to carry out for 0.1-600 hours! /.

[0710] As the solvent, those exemplified in the first step reaction can be adopted.

[0711] Examples of the base include triethylamine, trimethylamine, tripropylamine, toluamine, dibenzylmethylamine, dibenzylethylamine, dimethylamine, jetylamine, dipropylamine, diisopropylamine, dibutylamine, Examples thereof include dibenzylamine, pyrrolidine, piperidine, morpholine, pyridine, N-methylpyridine, and imidazole.

[0712] The powerful new polyfunctional fluorine-containing compound (1-1) can form a curable composition together with the curing initiator (II). Furthermore, if necessary, a monofunctional fluorine-containing acrylate, preferably a monofunctional fluorine-containing acrylate represented by the formula (2) may be blended.

[0713] Similar to the curable composition of the first invention, this curable composition is an optical material having a high fluorine content, such as an optical waveguide, which has high heat resistance and high transparency without using a solvent. In addition to providing a curable composition that can provide the above-described effects, the above-described various effects are exhibited.

[0714] Therefore, the curable composition of the first invention, the cured product of the second invention, the various optical materials of the third invention and the optical waveguide are described in the curable composition of the fifth invention, It is also applied to cured products using various materials, various optical materials, and optical waveguides.

[0715] Various physical properties and characteristics in this specification are measured by the following methods.

[0716] (1) Polymer composition (^ H—NMR ¹⁹ F—NMR, IR) NMR measuring device: BRUKER

iH-NMR measurement conditions: 300 MHz (tetramethylsilane = 0 ppm)

¹⁹ F— NMR measurement conditions: 282 MHz (Trichlorofluoromethane = Oppm)

IR measurement device: PERKIN ELMER Fourier transform infrared spectrophotometer 1760X Measurement conditions: measured at room temperature

[0717] (2) Fluorine content (F)

Sample lOmg is burned by the oxygen flask combustion method, the decomposition gas is absorbed into 20 ml of deionized water, and the fluorine ion concentration in the absorption liquid is measured by the fluorine selective electrode method (fluorine ion meter, model 901 manufactured by Olion). The value obtained by this is adopted (mass%).

[0718] (3) Viscosity (35 ° C)

Using an E-type viscometer manufactured by Toki Sangyo Co., Ltd. that conforms to JIS K7117-2, measure the viscosity at 35 ° C (mPa's).

[0719] (4) Glass transition temperature (Tg)

Using a DSC (Differential Scanning Calorimeter), the cured product produced by the following method was raised to 200 ° C with a 1st run temperature increase rate of 10 ° CZ, maintained at 200 ° C for 1 minute, and then a temperature decrease rate of 10 ° Cool to 25 ° C in CZ minutes, and then adopt the midpoint of the endothermic curve of the 2nd run obtained at a heating rate of 10 ° CZ.

[0720] (Manufacture of cured product)

2-hydroxy 2-methylpropiophenone as a curing initiator for polyfunctional fluorine-containing compounds. Add 5% by weight to prepare a curable composition. Next, using an applicator on the aluminum foil, it was applied to a film thickness of about 100 / zm, using a high-pressure mercury lamp on the film, and irradiating it with ultraviolet light at an intensity of 1500 mjZcm ² U. Melt to make a cured film. This cured film is further post-cured in an electric furnace at 70 ° C for 6 hours, and then completely cured to obtain a completely cured product (complete curing is achieved by reducing the C = C peak strength force or less by IR analysis). Check).

[0721] (5) Thermal decomposition temperature (Td)

Using a thermobalance (TGA), heat from room temperature at a temperature increase rate of 10 ° CZ at room temperature, and use the temperature at which the weight has decreased by 0.1% by mass. [0722] (6) Amorphous

Amorphous means that in the DSC analysis used to measure Tg, the endothermic peak based on melting was not observed when the temperature was increased by 10 ° CZ for 2nd run, or the heat of fusion was UZg. The following properties are shown.

[0723] (7) Refractive index (n)

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

[0724] (8) Light transmittance (visible light region)

Use a value obtained by measuring the spectral transmittance curve of a sample (cured film) approximately 100 m thick at a wavelength of 300 to 800 nm using a self-recording spectrophotometer (U-3310 (trade name) manufactured by Hitachi, Ltd.). .

[0725] (9) Light transmittance (near infrared region)

As the light transmittance, a value measured using a weak absorption spectrum measuring apparatus (MAC-1 (trade name) manufactured by JASCO Corporation) is adopted.

[0726] (10) Measurement of emission intensity of Eu complex-containing sample

Using a fluorescence spectrophotometer equipped with an integrating sphere (Fluorescence Spectrophotometer F-4010 manufactured by HITACHI), measure the emission spectrum of each sample, compare the peak areas of specific wavelengths, and measure the relative emission intensity.

[0727] (11) Measurement of luminescence intensity of Er complex-containing samples

Measure with the optical system shown in Fig. 3. In FIG. 3, reference numeral 10 denotes a sample to be measured, which is arranged in the integrating sphere 11. The laser light (1480 nm) generated in the integrating sphere 11 by the wavelength tunable laser generator 12 is guided to the integrating sphere 11 by the optical fiber 13, and the emission intensity at 1550 nm, which generates the sample force, is measured by the optical power meter 14.

[0728] The tunable laser generator used was 81480A made by Agilent 'Technology, the optical power meters were ML9001A and MA9711A made by Anritsu, and the integrating sphere was IS-040 made by Labsphere. -SL.

Example

[0729] Next, the present invention will be specifically described according to examples. It is not limited to only.

[0730] Synthesis Reference Example 1 (Synthesis of Diol A)

1,3 bis (1, 1, 1, 3, 3, 3 hexafluoro-2-hydroxypropyl) benzene (41.0 g, lOOmmol) and 3 perfluorinated hexyl 1,2 epoxypropane (113 g, 300 mmol) in a 500 ml flask ) And dissolved in toluene (100 g). Subsequently, 5N-sodium hydroxide aqueous solution (10 ml, 50 mmol), benzyltrimethylammonium chloride (0.92 g, 5. Ommol) and triglyme (50 g) were sequentially prepared, and then stirred at a temperature of 100 ° C. for 120 hours.

[0731] The reaction solution was poured into 1N-hydrochloric acid aqueous solution (500 ml), the organic phase was separated, and C HC1 F (HCFC

3 2 5

225), and dried over MgSO. The solvent was distilled off.

Four

[0732] Using silica gel column chromatography (made by MERCK: Silica gel 60 (0. 063— 0.20 Omm) (trade name)), purification was performed with hexane acetate ethyl acetate (10: 1) mixed solvent, The reaction product was isolated (92.4 g, 80 mmol, 80% yield).

[0733] investigated the reaction product ¹ 'F- NMR and ¹ H- NMR, wherein:

[0734] [Chemical 200]

[0735] It was confirmed that this was a diol compound (hereinafter referred to as “diol A”).

[0736] ¹⁹ F-NMR (CD COCD): δ —69.5 (3F), — 69.8 (3F), — 70.0 (3F), — 73.8 (3F), — 80.1 (6

3 3

F), -111.9 (4F), -120.7 (4F), — 121.8 (4F), -122.6 (4F), -125.2 (4F)

'H-NMR (CD COCD): δ 2.56 (4H), 3.77 (4H), 4.51 (2H), 5.02 (2H), 7.63-8.50 (4

3 3

H)

[0737] Example 1 (Synthesis of diatalylate B)

Diol A (29.0 g, 25 mmol) synthesized in Synthesis Reference Example 1 was placed in a 300 ml three-necked flask and dissolved in HCFC225 (150 ml). Under a nitrogen atmosphere, the reactor was cooled to 4 ° C, and triethylamine (6. lg, 60 mmol) was added dropwise over 10 minutes, and then the reactor was stirred at room temperature for 30 minutes. The reactor is then cooled to 4 ° C, and F-acrylic acid chloride (6.5 g, 60 mmo 1) was added dropwise over 30 minutes. The reactor was then stirred at room temperature for 3 hours.

[0738] The reaction solution was poured into a 1N-hydrochloric acid aqueous solution (200 ml), the organic phase was separated, extracted with HCFC225, dried over MgSO, and the solvent was distilled off. For silica gel column chromatography

Four

The reaction product was isolated by developing with hexane ethyl acetate (24: 1) and purification, and the reaction product was isolated (30.2 g, 23 mmol, 92% yield).

[0739] The reaction product was investigated by ¹⁹ F-NMR and ¹ H-NMR and represented by the formula:

[0740] [Chemical 201]

[0741] di a F Atari rate Lee匕合product represented by (hereinafter referred to as "Jiatarireto B") was Make that ₀

[0742] ¹⁹ F-NMR (CD COCD): δ —69.4 (6F), — 70.5 (6F), — 80.3 (6F), — 112.3 (4F), -117.4

3 3

(2F), -120.9 (4F), -122.1 (4F), -122.8 (4F), -125.4 (4F)

^J H-NMR (CD COCD): δ 2.54 (4H), 3.77 (4H), 5.28 (2H), 5.44 (2H), 5.48 (2H), 7.

3 3

63-8.52 (4H)

[0743] Example 2 (Synthesis of diatalylate C)

Diol A (29.0 g, 25 mmol) synthesized in Synthesis Reference Example 1 was placed in a 300 ml three-necked flask and dissolved in HCFC225 (150 ml). Under a nitrogen atmosphere, the reactor was cooled to 4 ° C, and triethylamine (6. lg, 60 mmol) was added dropwise over 10 minutes, and then the reactor was stirred at room temperature for 30 minutes. Thereafter, the reactor was cooled to 4 ° C., and methacrylic acid chloride (6.5 g, 60 mmol) was added dropwise over 30 minutes. The reactor was then stirred at room temperature for 4 hours.

[0744] The reaction solution was poured into 1N-hydrochloric acid aqueous solution (200 ml), the organic phase was separated, extracted with HCFC225, dried over MgSO, and the solvent was distilled off. For silica gel column chromatography

Four

The reaction product was isolated by developing with hexane ethyl acetate (24: 1) and purification, and the reaction product was isolated (31.2 g, 24 mmol, 96% yield).

[0745] The reaction product was examined by ¹⁹ F-NMR and ¹ H-NMR, and represented by the formula: [0746] [Chemical 202]

[0747] was confirmed to be a dimethacrylate compound (hereinafter referred to as “diatalylate C”).

[0748] ¹⁹ F-NMR (CD COCD): δ —69.2 (6F), -70.2 (6F), — 80.0 (6F), — 112.5 (4F), — 121.1

3 3

(4F), -121.2 (4F), — 121.9 (4F), — 123.8 (4F)

'H-NMR (CD COCD): δ 1.96 (6H), 2.54 (4H), 3.77 (4H), 5.59 (2H), 5.64 (2H), 5.

3 3

98 (2H), 7.63-8.52 (4H)

[0749] Synthesis Reference Example 2 (Synthesis of Diol D)

In a 500 ml flask, 1,3 bis (1,1,1,3,3,3 hexafluoro-2-hydroxypropyl) benzene (41.0 g, lOOmmol) and 3 perfluorobutyl—1,2 epoxy propane (82 8 g, 300 mmol) was added and dissolved in toluene (lOOg). Subsequently, 5N-sodium hydroxide aqueous solution (10 ml, 50 mmol), benzyltrimethylammonium chloride (0.92 g, 5. Ommol) and triglyme (50 g) were sequentially prepared, and then stirred at a temperature of 100 ° C. for 120 hours.

[0750] The reaction solution was poured into a 1N-hydrochloric acid aqueous solution (500 ml), the organic phase was separated, extracted with HCFC225, dried over MgSO, and the solvent was distilled off.

Four

[0751] Using silica gel column chromatography, the reaction product was isolated by developing with a mixed solvent of hexyl acetate (10: 1) and purification, and the reaction product was isolated (82.9 g, 86 mmol, yield 86%).

[0752] investigated the reaction product ¹ 'F- NMR and ¹ H- NMR, wherein:

[0753] [Chemical 203]

[0754] was confirmed to be a dioli compound (hereinafter referred to as “diol D”). [0755] F-NMR (CD COCD): δ —69.5 (6F), — 70.0 (6F), — 80.3 (6F), — 111.8 (4F), — 123.5

3 3

(4F), -124.9 (4F)

1H-NMR (CD COCD): δ 2.56 (4H), 3.78 (4H), 4.53 (2H), 5.02 (2H), 7.65-8.30 (4

3 3

H)

[0756] Example 3 (Synthesis of diatalylate E)

Diol D (24. lg, 25 mmol) synthesized in Synthesis Reference Example 2 was placed in a 300 ml three-necked flask and dissolved in HCFC225 (150 ml). Under a nitrogen atmosphere, the reactor was cooled to 4 ° C, and triethylamine (6. lg, 60 mmol) was added dropwise over 10 minutes, and then the reactor was stirred at room temperature for 30 minutes. Thereafter, the reactor was cooled to 4 ° C., and F-acrylic acid chloride (6.5 g, 60 mmo 1) was added dropwise over 30 minutes. The reactor was then stirred at room temperature for 5 hours.

[0757] The reaction solution was poured into a 1N-hydrochloric acid aqueous solution (200 ml), the organic phase was separated, extracted with HCFC225, dried over MgSO, and the solvent was distilled off. For silica gel column chromatography

Four

The reaction product was isolated after developing with hexane ethyl acetate (24: 1) and purification (27.7 g, 25 mmol, yield> 99%).

[0758] investigated the reaction product ¹ 'F- NMR and ¹ H- NMR, wherein:

[0759] [Chemical 204]

[0760] di a F- Atari rate Lee匕合product represented by (hereinafter referred to as "Jiatarireto E") was Make that ₀

[0761] ¹⁹ F-NMR (CD COCD): δ —69.0 (6F), -70.2 (6F), — 81.0 (6F), -112.2 (4F), — 117.3

3 3

(2F), -123.3 (4F), -124.9 (4F)

'H-NMR (CD COCD): δ 2.53 (4H), 3.80 (4H), 5.60 (2H), 5.74 (2H), 5.82 (2H), 7.

3 3

50-8.28 (4H)

[0762] Example 4 (Synthesis of diatalylate F)

Diol D (24.lg, 25mmol) synthesized in Synthesis Reference Example 2 was placed in a 300ml three-necked flask. The sample was dissolved in HCFC225 (150 ml). Under a nitrogen atmosphere, the reactor was cooled to 4 ° C, and triethylamine (6. lg, 60 mmol) was added dropwise over 10 minutes, and then the reactor was stirred at room temperature for 30 minutes. Thereafter, the reactor was cooled to 4 ° C., and methacrylic acid chloride (6.5 g, 60 mmol) was added dropwise over 30 minutes. The reactor was then stirred at room temperature for 4 hours.

[0763] The reaction solution was poured into a 1N-hydrochloric acid aqueous solution (200 ml), the organic phase was separated, extracted with HCFC225, dried over MgSO, and the solvent was evaporated. For silica gel column chromatography

Four

The reaction product was isolated by developing with hexane ethyl acetate (24: 1) and purification, and the reaction product was isolated (26.3 g, 24 mmol, yield 98%).

[0764] ^{1 of} this reaction product. F- examined by NMR and ¹ H- NMR, wherein:

[0765] [Chemical 205]

[0766] was confirmed to be a dimethacrylate compound (hereinafter referred to as “diatalylate F”).

[0767] ¹⁹ F-NMR (CD COCD): δ —68.7 (6F), — 70.1 (6F), — 81.3 (6F), -112.7 (4F), — 123.3

3 3

(4F), -124.5 (4F)

'H-NMR (CD COCD): δ 1.95 (6H), 2.53 (4H), 3.80 (4H), 5.64 (2H), 5.74 (2H), 6.

3 3

08 (2H), 7.63-8.52 (4H)

[0768] Synthesis Reference Example 3 (Synthesis of Diol G)

In a 500 ml flask, add 1,3 bis (1, 1, 1, 3, 3, 3 hexafluoro-2-hydroxypropyl) benzene (41.0 g, lOOmmol) and 3 perfluoroisopropyl-1,2-epoxypropane ( 67.8 g (300 mmol) was added and dissolved in toluene (100 g). Next, 5 N aqueous sodium hydroxide solution (10 ml, 50 mmol), benzyltrimethylammonium chloride (0.92 g, 5. Ommol), and triglyme (50 g) were sequentially added, followed by stirring at 100 ° C for 120 hours. .

[0769] The reaction solution was poured into a 1N aqueous hydrochloric acid solution (500 ml), the organic phase was separated, and HCFC225 was used. After extraction and drying with MgSO, the solvent was distilled off.

Four

[0770] Using silica gel column chromatography, the reaction product was isolated by developing with a mixed solvent of hexyl acetate (10: 1) and purification, and the reaction product was isolated (68.0 g, 79 mmol, yield 79%).

[0771] The reaction product was investigated by ¹⁹ F-NMR and ¹ H-NMR and represented by the formula:

[0772] [Chemical 206]

[0773] was confirmed to be a diol compound (hereinafter referred to as “diol G” t).

[0774] ¹⁹ F-NMR (CD COCD): δ —69.0 (6F), — 70.6 (6F), — 75.9 (12F), — 184.4 (2F)

3 3

1H-NMR (CD COCD): δ 2.93 (4H), 4.02 (4H), 4.43 (2H), 4.96 (2H), 7.83-7.99 (4

3 3

H)

[0775] Example 5 (Synthesis of diatalylate H)

Diol G (24. lg, 25 mmol) synthesized in Synthesis Reference Example 3 was placed in a 300 ml three-necked flask and dissolved in HCFC225 (150 ml). Under a nitrogen atmosphere, the reactor was cooled to 4 ° C, and triethylamine (6. lg, 60 mmol) was added dropwise over 10 minutes, and then the reactor was stirred at room temperature for 30 minutes. Thereafter, the reactor was cooled to 4 ° C., and F-acrylic acid chloride (6.5 g, 60 mmo 1) was added dropwise over 30 minutes. The reactor was then stirred at room temperature for 8 hours.

[0776] The reaction solution was poured into a 1N-hydrochloric acid aqueous solution (200 ml), the organic phase was separated, extracted with HCFC225, dried over MgSO, and the solvent was distilled off. For silica gel column chromatography

Four

The reaction product was isolated by developing with hexane ethyl acetate (20: 1) and purification, and the reaction product was isolated (22.0 g, 22 mmol, 88% yield).

[0777] The reaction product was examined by ¹⁹ F-NMR and ¹ H-NMR and represented by the formula:

[0778] [Chemical 207]

[0779] It was confirmed that it was a di-A F-atetalito toy compound (hereinafter referred to as “diatalylate Η”).

[0780] ¹⁹ F-NMR (CD COCD): δ —69.1 (6F), — 70.5 (6F), — 76.0 (12F), — 117.3 (2F), — 184.6

3 3

(2F)

1H-NMR (CD COCD): δ 2.90 (4H), 4.03 (4H), 5.60 (2H), 5.76 (2H), 5.84 (2H), 7.

3 3

85-8.00 (4H)

[0781] Synthesis Reference Example 4 (Synthesis of Diol I)

Neopentyl glycol (15.6 g, 150 mmol) was placed in a 500 ml three-necked flask, and HCF C225 (200 g) was added thereto and then dissolved at 50 ° C. in a nitrogen atmosphere. Then, the fluorine trifluoride-deethyl ether complex (1.90 ml, 13. Ommol) was stirred for 20 minutes, and then 3 -perfluorohexyl 1,2 epoxypropane (113 g, 300 mmol) was added in 2 parts. Dripping over time. The mixture was stirred at 50 ° C for 5 hours, and the disappearance of the 3 perfluorinated hexyl-1,2 epoxy bread was confirmed by gas chromatography to complete the reaction.

[0782] The reaction solution was poured into water (500 ml), the organic phase was separated, extracted with HCFC225, MgSO

After drying with 4, the solvent was distilled off to obtain a reaction product (126 g, 147 mmol, yield 98%).

[0783] The reaction product was investigated by ¹⁹ F-NMR and ¹ H-NMR and represented by the formula:

[0784] [Chemical 208]

[0785] was confirmed to be a diol compound (hereinafter referred to as “diol I” t).

[0786] ¹⁹ F-NMR (CD COCD): δ —79.1 (6F), — 110.3 (4F), — 119.0 (4F), — 120.3 (4F), — 121.

3 3

4 (4F), -122.9 (4F)

'H-NMR (CD COCD): δ 1.05 (6H), 2.20-2.40 (4H), 3.31-3.70 (8H), 4.24 (2H)

3 3

[0787] Example 6 (Synthesis of diatalylate J)

Diol 1 (48.8 g, 50 mmol) synthesized in Synthesis Reference Example 4 was placed in a 300 ml three-necked flask and dissolved in HCFC225 (300 ml). Under a nitrogen atmosphere, the reactor was cooled to 4 ° C and triethylamine (12. lg, 120 mmol) was added dropwise over 15 minutes, and then the reactor was stirred at room temperature for 30 minutes. Stir for a while. Thereafter, the reactor was cooled to 4 ° C., and F-acrylic acid chloride (13. Og, 120 mmol) was added dropwise over 30 minutes. The reactor was then stirred at room temperature for 7 hours.

[0788] The reaction solution was poured into a 1N-hydrochloric acid aqueous solution (500 ml), the organic phase was separated, extracted with HCFC225, dried over MgSO, and the solvent was distilled off. For silica gel column chromatography

Four

The reaction product was isolated by developing with hexane ethyl acetate (30: 1) and purification, and the reaction product was isolated (44.0 g, 44 mmol, 87% yield).

[0789] The reaction product was examined by ¹⁹ F-NMR and ¹ H-NMR, and the formula:

[0790] [Chemical 209]

[0791] It is confirmed that it is a di-F—atre relay toy compound (hereinafter referred to as “Jiatallate J”).

[0792] ¹⁹ F-NMR (CD COCD): δ —79.1 (6F), — 110.3 (4F), — 119.0 (4F), — 120.3 (4F), — 121.

3 3

4 (4F), -122.9 (4F)

'H-NMR (CD COCD): δ 1.05 (6H), 2.20—2.40 (4H), 3.31—3.70 (8H), 4.97 (2H), 5.

3 3

58 (2H), 5.73 (2H)

[0793] Synthesis Reference Example 5 (Synthesis of diol ジオール)

Add 4, 4 (hexafluoroisopropylidene) diphenol (33.6 g, 1 OOmmol) and 3 perfluorohexyl 1,2 epoxypropane (113 g, 300 mmo 1) to a 500 ml flask and dissolve in toluene (100 g) I let you. Next, 5N-sodium hydroxide aqueous solution (10 ml, 50 mmol), benzyltrimethylammonium chloride (0.92 g, 5. Ommol), and triglyme (50 g) were added sequentially, and then at a temperature of 100 ° C for 48 hours. Stir.

[0794] The reaction solution was poured into a 1N-hydrochloric acid aqueous solution (500 ml), the organic phase was separated, extracted with HCFC225, dried over MgSO, and the solvent was distilled off.

Four

[0795] Using silica gel column chromatography, the reaction product was isolated by developing with ethyl hexane monoacetate (8: 1) mixed solvent for purification, and the reaction product was isolated (77.4 g, 71 mmol, 71% yield).

[0796] The reaction product was examined by ¹⁹ F-NMR and ¹ H-NMR and represented by the formula: [0797] [Chemical 210]

[0798] It was confirmed that this was a diol compound (hereinafter referred to as "diol K").

[0799] ¹⁹ F-NMR (CD COCD): δ —64.5 (6F), — 79.8 (6F), — 111.3 (4F), — 120.5 (4F), -122.2

3 3

(4F), -123.9 (4F), — 125.1 (4F)

1H-NMR (CD COCD): δ 2.56 (4H), 3.77 (4H), 4.51 (2H), 5.02 (2H), 7.43—8.60 (8

3 3

H)

[0800] Example 7 (Synthesis of Diatalylate L)

Diol K (27.2 g, 25 mmol) synthesized in Synthesis Reference Example 5 was placed in a 300 ml three-necked flask and dissolved in HCFC225 (150 ml). Under a nitrogen atmosphere, the reactor was cooled to 4 ° C, and triethylamine (6. lg, 60 mmol) was added dropwise over 10 minutes, and then the reactor was stirred at room temperature for 30 minutes. Thereafter, the reactor was cooled to 4 ° C., and F-acrylic acid chloride (6.5 g, 60 mmo 1) was added dropwise over 30 minutes. The reactor was then stirred at room temperature for 6 hours.

[0801] The reaction solution was poured into a 1N-hydrochloric acid aqueous solution (200 ml), the organic phase was separated, extracted with HCFC225, dried over MgSO, and the solvent was distilled off. For silica gel column chromatography

Four

The reaction product was isolated by developing with hexane ethyl acetate (14: 1) and purification, and the reaction product was isolated (25.8 g, 21 mmol, 83% yield).

[0802] The reaction product was examined by ¹⁹ F-NMR and ¹ H-NMR and represented by the formula:

[0803] [Chemical 211]

[0804] It is confirmed that it is a di-a talato toy compound (hereinafter referred to as “diatalate L”).

[0805] F-NMR (CD COCD): δ —65.2 (6F), — 80.1 (6F), — 112.0 (4F), — 120.4 (4F), -122.6 (4F), -124.2 (4F), -125.5 (4F)

1H-NMR (CD COCD): δ 2.53 (4H), 3.79 (4H), 5.59 (2H), 5.74 (2H), 5.86 (2H), 7.

3 3

45-8.59 (4H)

[0806] Example 8

The viscosity of diatalylate synthesized in Examples 1 to 7, the glass transition temperature Tg of the cured product, the fluorine content, and the refractive index were measured. The results are shown in Table 1.

[0807] [Table 1]

table 1

[0808] Reference examples (physical properties of diathalate described in JP-A-63-101409)

The physical properties (glass transition temperature, fluorine content and properties) of diatalylate specifically described in JP-A-63-101409 were examined and were as follows.

[0809] (AF-GA)

[0810] [Chem 212]

Fluorine content: 19% by mass

Glass transition temperature: 9 3 ° C

Property: Liquid

[0811] (AF-GMA)

[0812] [Chemical 213] CC

CH = C C = CH

H H

c-0-c-c-c-o- -o-c-c-c-o-c

II H, I H, H I H II

O ² OH ² OH O Fluorine content: 1 8% by mass

Glass transition temperature: 90 ° C

Property: Liquid

[0813] (FB-GA)

[0814] [Chemical 214]

cccll

FF

Fluorine content: 3 4% by mass

Glass transition temperature: 8 6 ° C

Property: Liquid

[0815] (FB-GMA)

[0816] [Chemical 215]

Fluorine content: 33% by mass

Glass transition temperature: 94 ° C

Property: Liquid

[0817] (DO-GA)

[0818] [Chemical 216]

Fluorine content: 3 7 mass c

Glass transition temperature: 39 ° C

Property: Liquid

[0819] (DO-GMA)

[0820] [Chemical 217]

Fluorine content: 35% by mass

Glass transition temperature: 37 ° C

Property: Liquid

[0821] Example 9 (Evaluation of physical properties of composition)

50 parts by weight of diatalylate B obtained in Example 1 as a polyfunctional fluorine-containing compound, and hexafluoroneopentyl α-fluoroatalylate (6FNP-F) as monofunctional fluorine-containing allylate:

[0822] [Chemical 218]

[0823] was added in an amount of 50 parts by weight, and 0.1% by weight of 2-hydroxy-2-methylpropiophenone as an active energy ray curing initiator was added thereto to prepare the liquid curable fluorine-containing resin composition of the present invention. did.

[0824] The viscosity of the composition before curing at 35 ° C was measured, and the appearance of the liquid composition was visually evaluated. The results are shown in Table 2. ◯: Transparent and uniform, and the transmittance of light at 550 nm is 80% or more. Δ: Partly cloudy (gel-like material) is observed.

X: Opaque and cloudy.

[0825] Next, an applicator was used on the aluminum foil so that the film thickness was about 100 m. The coating was irradiated with ultraviolet light at a strength of 1500 mjZcm ² U using a high-pressure mercury lamp, and the aluminum foil was then diluted with dilute hydrochloric acid. The sample film was melted.

[0826] Refractive index (n), glass transition temperature (Tg), thermal decomposition temperature (Td) of sample film (after curing)

, Fluorine content (F), light transmittance visible (633nm) (T (633)), light transmittance near infrared (1310nm

) (T (1310)) was examined.

[0827] The appearance was visually evaluated.

◯: Transparent and uniform.

Δ: Some cloudiness is observed.

X: Opaque and cloudy.

[0828] The results are shown in Table 2.

[0829] Example 10

50 parts by weight of dichlore KJ obtained in Example 6 as a polyfunctional fluorine-containing compound, and 50 parts by weight of hexafluoroneopentyl α-fluoroatarylate (6FNP-F) as monofunctional fluorine-containing acrylate The active energy ray-curable fluorine-containing resin composition was obtained in the same manner as in Example 9 except that the various physical properties were measured in the same manner as in Example 9. The results are shown in Table 2.

[0830] Example 11

60 parts by weight of ditalylate soot obtained in Example 1 as a polyfunctional fluorine-containing compound, and 2 perfluoropropoxy 2, 3, 3, 3-tetrafluoro-orthopropyl α-fluoroatari as monofunctional fluorine-containing allylate Rate (6FOnl— F):

[0831] [Chemical 219] H— G

C -CH -CF-O-CFjCF-F

II ² I ² 1

0 CF ₃ CF ₃ [0832] containing 20 parts by weight of fluorine, and 20 parts by weight of methyl methacrylate (MMA) as a monomer was used in the same manner as in Example 9, except that the active energy ray-curable fluorine-containing film was used. A fat composition was obtained, and various physical properties were measured in the same manner as in Example 9. The results are shown in Table 2.

[0833] Example 12

60 parts by weight of diatalylate C obtained in Example 2 as a polyfunctional fluorine-containing compound, 20 parts by weight of hexafluoroneopentyl α-fluoroatarylate (6FNP-F) as a monofunctional fluorine-containing allylate, An active energy ray-curable fluorine-containing resin composition was obtained in the same manner as in Example 9 except that 20 parts by weight of methyl metatalylate (ΜΜΑ) was used as a monomer not containing fluorine, and various physical properties were carried out. Measurement was performed in the same manner as in Example 9. The results are shown in Table 2.

[0834] Example 13

50 parts by weight of ditalylate soot obtained in Example 5 as a polyfunctional fluorine-containing compound, and 30 parts by weight of hexafluoroneopentyl α-fluoroatalylate (6FNP-F) as monofunctional fluorine-containing acrylate. Xafluoroisopropyl a fluoroatarolate (H FIP-F):

[0835] [Chemical 220]

I

GH 3

C-0-C-H

0 CF „

An active energy ray-curable fluorine-containing resin composition was obtained in the same manner as in Example 9 except that 20 parts by weight of [0836] was used, and various physical properties were measured in the same manner as in Example 9. The results are shown in Table 2.

[0837] Example 14

50 parts by weight of ditalylate H obtained in Example 5 as a polyfunctional fluorine-containing compound and 45 parts by weight of hexafluoroneopentyl α-fluoroatarylate (6FNP-F) as monofunctional fluorine-containing acrylate. An active energy ray-curable fluorine-containing resin composition was obtained in the same manner as in Example 9 except that 5 parts by weight of polymethylmetatalylate (ΡΜΜΑ: number average molecular weight: about 90,000) was used as a polymer. Physical properties were measured in the same manner as in Example 9. The results are shown in Table 2. [0838] Example 15

50 parts by weight of ditalylate L obtained in Example 7 as a polyfunctional fluorine-containing compound, and 50 parts by weight of hexafluoroneopentyl α-fluoroatarylate (6FNP-F) as monofunctional fluorine-containing acrylate The active energy ray-curable fluorine-containing resin composition was obtained in the same manner as in Example 9 except that the various physical properties were measured in the same manner as in Example 9. The results are shown in Table 2.

[0839] Comparative Example 1

1, 4 Bis (hexafluoroisopropyl _α -fluoroacryl) benzene (FB—DFA) as a polyfunctional fluorine-containing compound as a curable fluorine-containing resin composition:

[0840] [Chem 221]

An active energy ray-curable fluorine-containing resin composition was prepared in the same manner as in Example 1 except that 50 parts by weight of [0841] was used. However, the solid FB-DFA could not be dissolved at room temperature and was uniform. I couldn't make a good film.

[0842] Comparative Example 2

1, 4 Bis (hexafluoroisopropyl _α -fluoroacryl) benzene (FB—GMA) as polyfunctional fluorine-containing compound as curable fluorine-containing resin composition

[0843] [Chemical 222]

[0844] An active energy ray-curable fluorine-containing resin composition was prepared in the same manner as in Example 1 except that 50 parts by weight was used, and various physical properties were measured in the same manner as in Example 1. The results are shown in Table 2.

[0845] [Table 2]

Example 16

From the results of the above examples, the curable fluorine-containing resin composition of Example 9 (refractive index after curing: 1.386) was used as the cladding, and the curable fluorine-containing resin composition of Example 12 (after curing). Refractive index of 1.415) is used to form a core Z-clad type optical waveguide. [0847] Therefore, the curable fluorine-containing resin composition obtained in Example 9 was filtered with a 0.5 μm filter, and then spun onto a silicon wafer for 10 seconds at a rotation speed of 200 rpm and then for 30 seconds at a rotation speed of 500 rpm. Coated. A high pressure mercury lamp was used to irradiate ultraviolet rays with an intensity of 1500 mjZcm ² U to obtain a cladding layer having a thickness of about 15 m on the silicon substrate. Next, after filtering the curable fluorine-containing resin composition of Example 12 through a 0.5 μm filter, it was applied on the previous cladding layer for 10 seconds at 500 rpm for 30 seconds at lOOOrpm for 30 seconds. Spin coated.

[0848] Next, light was irradiated through a photomask to cure the core film. Thereafter, the uncured portion of the core film was washed away with a solvent and processed into a linear rectangular pattern having a length of 50 mm, a width of 8 / ζ πι, and a height of 8 m. After processing, the clad part was coated on the core part according to the process described in accordance with Fig. 2 to produce an optical waveguide.

[0849] Next, the transmission loss of the obtained optical waveguide was measured by the cut-back method, and it was 0.880 dBZcm or less at a wavelength of 633, 0.75 dB / cm at a wavelength of 850, and 0.80 dBZcm at a wavelength of 1310. As a result, the light in the communication wavelength band from visible light to near-infrared light was successfully transmitted.

[0850] Table 3 shows the change in transmission loss (dBZcm) after the endurance test after holding for 168 hours in a thermostat of 85 ° C and 85% humidity.

[0851] [Table 3]

Table 3

[0852] Synthesis Reference Example 6 (Preparation of Er (CF COCHCOCF))

3 3 3

Into a 100 ml glass flask are charged 2.lg (5 mmol) of europium acetate tetrahydrate, 3.0 g (20 mmol) of hexafluoroacetylacetone and 50 ml of pure water, and stirred at 25 ° C for 3 days. did.

[0853] Next, the precipitated solid was taken out by filtration, washed with water, and recrystallized with a water-methanol mixed solvent to obtain white crystals (yield 50%). [0854] This crystal was analyzed by IR analysis, NMR and ¹⁹ F—NMR analysis, and the desired complex, Er (CF C

Three

OCHCOCF).

3 3

[0855] The obtained white crystals were estimated to be dihydrate by Tg measurement.

[0856] Example 17 (Production of optical functional optical material)

The formula synthesized in Example 6 into a cylindrical heat-resistant glass tube with an inner diameter of 4 mm and a length of 200 mm sealed on one side:

[0857] [Chemical 223]

C ₆ F ₁₃ -CH CH-0 9 ^H 3

V CH ₂ OCOCF = CH ₂

CH ₂ = CFC0 ₂ H ₂ C

CH, 0-CHCH ₂ -C ₆ F 13

[0858] 2.0 g of diatalylate J represented by the rare earth metal complex obtained in Synthesis Reference Example 6: Er (CF C

Three

0.020 g of OCHCOCF), and azobisisobutyrate as a radical polymerization initiator

3 3

When 0.002 g of ril (AIBN) was added and mixed, a clear homogeneous solution was obtained.

[0859] Then, the heat-resistant glass tube containing the mixed composition was immersed in liquid nitrogen and cooled, and then sufficiently deaerated with a vacuum pump, and then sealed.

[0860] Heating was performed at 60 ° C for 12 hours, and the heat-resistant glass tube was pulverized to obtain a cylindrical transparent solid composed of ditalylate J and erbium complex (III).

[0861] Example 18 (Production of optical functional optical material)

A cylindrical heat-resistant glass tube with an inner diameter of 4 mm and a length of 200 mm sealed on one side, 0.32 g of digilate J, formula:

[0862] [Chemical 224]

C H 3

I I

CH ₂ = C— COO— CH ₂ C— CH ₃

I

CF ₃

[0863] 2.0 g of hexafluoroneopentyl metatalylate, Rare earth metal complex obtained in Synthesis Reference Example 6: 0.020 g of Er (CF COCHCOCF), and radical polymerization initiator

3 3 3

As a result, when 0.002 g of azobisisobuty-mouth-tolyl (AIBN) was added and mixed, a transparent homogeneous solution was obtained. [0864] Then, the heat-resistant glass tube containing the mixed composition was immersed in liquid nitrogen, cooled, and sufficiently deaerated with a vacuum pump, and then sealed.

[0865] Heating was performed at 60 ° C for 12 hours, and the heat-resistant glass tube was pulverized to obtain a columnar transparent solid material comprising diatalylate J, hexafluoroneopentylmethacrylate and erbium complex (in) force.

[0866] Example 19 (Production of optical functional optical material)

Example, except that 2.Og of methylmetatalate, 0.32 g of diatalylate J, 0.020 g of Er (CF COCHCOCF) obtained in Synthesis Reference Example 6, and 0.002 g of AIBN were used.

3 3 3

A polymerization reaction was carried out in the same manner as in 17 to obtain a solid comprising a polyfunctional fluorine-containing compound and erbium complex (III).

[0867] Comparative Example 3 (Production of optical functional optical material for comparison)

2. Og of methyl metatalylate, 0.0 of Er (CF COCHCOCF) obtained in Synthesis Reference Example 6

3 3 3

A polymerization reaction was carried out in the same manner as in Example 17 except that 20 g and 0.002 g of AIBN were used. V, a solid having polymethylmetatalylate and erbium complex (III) strength was obtained.

[0868] Test Example 1

The obtained erbium complex-containing solid was examined for the following physical properties. The results are shown in Table 4.

[0869] (12) Measurement of fluorine content in cured polyfunctional fluorine-containing compound

(12-1) Synthesis of cured products of polyfunctional fluorine-containing compounds

In Examples 17 to 19 and Comparative Example 3, the erbium complex Er (CF COCHCOCF)

3 Perform the polymerization reaction in the same way except that 3 was not added, and combine the corresponding cured products.

Three

Made.

[0870] (12-2) Measurement of fluorine content

For each of the obtained cured products, the fluorine content (% by mass) was measured by the aforementioned oxygen flask combustion method.

[0871] (13) Content of rare earth metal complex

In Examples 17 to 19 and Comparative Example 3, the amount (mass%) of metal (ion) with respect to the entire optical functional optical material was calculated from the amount of rare earth metal complex used. [0872] (14) Appearance

The transparency of each of the talate polymer obtained in Examples 1 to 19 and Comparative Example 3 and the cylindrical solid material having erbium complex strength was evaluated by visual observation according to the following criteria.

○: Completely transparent without precipitation of rare earth metal complex in the composition

X: Precipitation of rare earth metal complex is observed, causing turbidity

[0873] (15) Relative emission intensity at 1550 nm wavelength

Cylindrical solids having the aterylate polymer and erbium complex force obtained in Examples 17 to 19 and Comparative Example 3 were cut into 3 cm in the height direction, and both end faces were optically polished.

[0874] The above sample was set in a fluorescence spectrophotometer equipped with an integrating sphere shown in Fig. 3, and a fixed amount of 1480 nm wavelength light was irradiated as an excitation wavelength, and the emission intensity at 1550 nm of the emission spectrum was measured.

[0875] In the emission spectrum, the relative emission peak intensity ratio of each sample when the emission peak intensity of 155 Onm of the polymethylmetatalate solid sample of Comparative Example 3 was set to 100 was calculated at 1550 nm. The relative emission intensity was used.

[0876] [Table 4] Table 4

Industrial applicability

According to the present invention, it is possible to provide a curable composition capable of providing an optical material having a high fluorine content, which has high heat resistance and high transparency without using a solvent, for example, an optical waveguide. The various effects described above are exhibited.

Claims

Claim [1] (I) Formula (1) [Chemical 1] X 1 I —— (R is OC-C = CH,) n (1) II o (where X1 is the same or different and H Group force consisting of CH, F, CI and CF 3 3 At least one selected; n is an integer of 2 to 7; R1 is the same force or different and is a bond or part of a hydrogen atom having 1 to 50 carbon atoms Or a divalent organic group in which all may be substituted with fluorine atoms; R2 is an n-valent organic group in which some or all of the hydrogen atoms having 1 to 50 carbon atoms may be substituted with fluorine atoms; Provided that at least one of X1, R1 and R2 contains a fluorine atom)

(1) Fluorine content is 40 mass% or more,

(2) viscosity at 35 ° C is 100, OOOmPa'sec or less, and

A polyfunctional fluorine-containing compound, and

(II) Curing initiator

A curable composition comprising:

[2] In the polyfunctional fluorine-containing compound (I) represented by the formula (1), a divalent fluorine-containing organic compound in which at least one of R ¹ is partially or entirely substituted with fluorine atoms. The curable composition according to claim 1, which is a group.

[3] In the polyfunctional fluorine-containing compound (I) represented by the formula (1), the divalent fluorine-containing organic group is a fluorine-containing organic group having a monovalent fluorine-containing organic group in the side chain. 2. The curable composition according to item 2 of the above.

[4] In the polyfunctional fluorine-containing compound (I) represented by the above formula (1), R ² has a hetero atom !, but may have a portion of an aromatic hydrocarbon structure or a hetero atom. The curing according to any one of claims 1 to 3, which is an n-valent organic group containing at least one site selected from the partial force of the aliphatic cyclic hydrocarbon structure. Sex composition.

[5] The curable composition according to any one of claims 1 to 4, further comprising a monofunctional fluorine-containing acrylate.

[6] The range according to claim 5, wherein the monofunctional fluorine-containing acrylate has a fluorine content of 10% by mass or more and the glass transition temperature of the cured product of the monofunctional fluorine-containing acrylate is 50 ° C or higher. The curable composition as described.

[7] The monofunctional fluorine-containing acrylate is represented by the formula (2):

[Chemical 2]

(Where X ² is at least one selected from the group force consisting of H, CH, F, CI and CF; R ³ is R ⁴

3 3

And / or R ⁵ and

R ⁴ is the formula (1-1):

[Chemical 3]

-0CF ₂ ) _mt (OCF ₂ CFZ) _mi (OCF ₂ CF ₂ CF ₂ ) _mg (OCHaCFaCFa rT (1 — 1) (where Z is F or CF; ml, m2, m3, m4 is 0 or 1 ~ An integer of 10. However,

Three

ml + m2 + m3 + m4 is an integer from 1 to 10)

R ⁵ is the formula (1 2):

[Chemical 4]

(Wherein Rf ¹ and Rf ² are the same or different, and a perfluoroalkyl group having 1 to 5 carbon atoms; R ⁶ may be substituted or partially substituted with fluorine atoms for a hydrogen atom; A fluorine-containing alkyl group containing a moiety represented by a hydrocarbon group having 1 to 5 carbon atoms)

7. The curable composition according to claim 6, which is one or more monofunctional fluorine-containing acrylates represented by the formula:

[8] The curable composition according to any one of claims 1 to 7, wherein the curing initiator (II) is blended in an amount of 0.01% by mass to 10% by mass.

[9] The monofunctional fluorine-containing acrylate is 1 to 100 parts by mass of the polyfunctional fluorine-containing compound (I).

The curable composition according to any one of claims 5 to 8, wherein 0 to 80 parts by mass are blended.

[10] The curable composition according to any one of claims 1 to 9, wherein the viscosity of the composition at 35 ° C is 10 to 10, OOOmPa 'seconds.

[11] (I 1) Equation (3):

[Chemical 5]

X ³

, 'NO- ™ rJ RI) _n

o

(In the formula, X ³ is the same or different, and a group force consisting of H, CH, F, CI and CF is selected.

3 3

[Chemical 6] ^ Q _ c I I ~ ― C I I― C I I ") ~" ~ ~ ~~ (4

'I

R f ³

(Wherein Rf ³ is a fluorine-containing alkyl group having 1 to 19 carbon atoms; z, X and y are the same or different, 0 or 1), and is a fluorine-containing organic group having 2 to 20 carbon atoms ) A polyfunctional fluorine-containing compound represented by

(II) Curing initiator

A curable composition comprising:

[12] The curable composition according to claim 11, further comprising a monofunctional fluorine-containing acrylate.

13. The monofunctional fluorine-containing allylate has a fluorine content of 10% by mass or more, and the glass transition temperature of the cured product of the monofunctional fluorine-containing acrylate is 50 ° C. or more. The curable composition as described.

[14] The monofunctional fluorine-containing acrylate is represented by the formula (2):

[Chemical 2]

3 3

And / or R ⁵ and

R ⁴ is the formula (1-1):

[Chemical 3]

Three

ml + m2 + m3 + m4 is an integer from 1 to 10)

R ⁵ is the formula (1 2):

[Chemical 4]

14. The curable composition according to claim 13, which is one or more monofunctional fluorine-containing acrylates represented by:

[15] The curable composition according to any one of claims 11 to 14, wherein the curing initiator (II) is blended in an amount of 0.01% by mass to 10% by mass.

[16] The monofunctional fluorine-containing acrylate is 1 to 100 parts by mass of the polyfunctional fluorine-containing compound (I).

16. The curable composition according to any one of claims 12 to 15, wherein 0 to 80 parts by mass is blended.

[17] A cured product obtained by curing the curable composition according to any one of claims 1 to 16.

18. The cured product according to claim 17, wherein the fluorine content is 40% by mass or more.

[19] The cured product according to claim 17 or 18, wherein the glass transition temperature is 100 ° C or higher.

[20] An optical material having a cured product force according to any one of claims 17 to 19.

[21] An optical waveguide comprising a core part and a clad part, wherein at least one of the core part and the clad part comprises the cured product according to any one of claims 17 to 19.

[22] Equation (3):

[Chemical 5]

X ³

R ^ (: R No O— C— C = CH ₂ ) _n (3)

O

(In the formula, X ³ is the same or different and a group force consisting of H, CH, F, CI and CF is selected.

3 3

[Chemical 6]

—— (o— ₇ ~~ c II ₂ ^-^ c II ~ 6 c II _2- ^ —— (4)

'I

R f ³ (Wherein Rf ³ is a fluorine-containing alkyl group having 1 to 19 carbon atoms; z, X and y are the same or different, 0 or 1), and is a fluorine-containing organic group having 2 to 20 carbon atoms The polyfunctional fluorine-containing compound represented by this.

The polyfunctional fluorine-containing compound represented by the formula (3) is

(1) Fluorine content is 40 mass% or more,

(2) viscosity at 35 ° C is 100, OOOmPa'sec or less, and

The polyfunctional fluorine-containing compound according to claim 22, which is