JP2006002129A - Curable fluorine-containing resin composition and optical member obtained by curing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable fluorine-containing resin composition, capable of obtaining a liquid state composition without using an organic solvent and obtaining a cured product, and also improving the transparency and heat resistance of the cured product even if the cured product has a high fluorine content. <P>SOLUTION: This curable fluorine-containing resin composition consists of a fluorine-containing acrylic monomer having a fluorine-containing alkylene ether structure or fluorine-containing tert-alkyl structure in its ester part, an amorphous fluorine-containing polymer having ≥25 mass% fluorine content and further if necessary a polyfunctional fluorine-containing monomer, and is homogeneous liquid form. The cured product of the same, and optical member are also provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a curable fluorinated resin composition capable of providing an optical material having high heat resistance and high transparency, such as an optical waveguide, without using a solvent.

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

  Among these, since fluorine-based materials are transparent to light in the near-infrared region, which is a communication wavelength band, various fluorine-based materials have been proposed. If these materials are used, it is possible to produce an organic optical waveguide with low optical signal loss. However, in order to realize an organic optical waveguide with further low loss, a material with further improved transparency. Is desired.

  Known fluorine-based organic materials for optical waveguides include fluorine-containing polyimide-based materials (Patent Document 1) and fluorine-containing acrylic polymers (Patent Document 2).

  By the way, in order to process into an optical waveguide, a prepolymer and / or a polymer is dissolved in an organic solvent, and a thin film (core layer, cladding layer) is formed by a method such as spin coating, dipping, or casting, and is appropriately cured. The processing method is generally taken.

  However, in such molding using an organic solvent, when the core layer is formed, the surface of the previously formed cladding layer is dissolved by the organic solvent and mixed with each other. There is a problem that the interface becomes non-uniform and the loss of the optical signal increases remarkably. In addition, after forming each layer, it is necessary to volatilize the organic solvent in the film that forms the layer by drying, etc., but the light in the near infrared region is still absorbed by a small amount of the organic solvent remaining in the film. In other words, the transparency in the near-infrared region is lowered due to being scattered or scattered. Further, microvoids resulting from the volatilization of the organic solvent remaining in the film cause light scattering, resulting in a problem that transparency in the near infrared region is lowered. In particular, residual organic solvents and microvoids significantly reduce the transparency in the near infrared region, so that the loss of the optical waveguide is greatly increased.

  In order to solve this problem, it has been proposed to use a curable composition comprising an acrylic monomer and a fluorine-containing acrylic polymer (Patent Document 3).

  Patent Document 3 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 curable monomer containing a fluorinated alkyl group. A curable composition comprising a monomer and a polyfunctional monomer containing two or more (meth) acryloyl groups in the molecule is disclosed, and a (meth) acrylate-based monomer is used as a fluorine-based curable monomer. A monomer containing a linear fluoroalkyl group having a high fluorine content in the ester part is used for the purpose of further improving the fluorine content.

  However, such a fluorine-based monomer has low solubility of the fluoropolymer, and the liquid composition itself may become cloudy. Even if a uniform liquid composition can be formed, even if a cured product to be obtained becomes cloudy or even a transparent cured product is obtained, the fluorine-containing polymer and the linear fluorine-containing product can be obtained by heating. There is a problem in that phase separation from a linear fluoroalkyl group having a high rate occurs, resulting in white turbidity or the like, resulting in a decrease in transparency. Furthermore, even in the cured product, crystallization of linear fluoroalkyl groups proceeds, resulting in white turbidity due to recrystallization at high temperature, and transparency of the cured product in the near infrared region. There is a problem that decreases.

JP-A-2-281037 JP 2000-81520 A Japanese Patent Laid-Open No. 5-9043

  Therefore, the present invention can form a liquid composition without using an organic solvent to obtain a cured product, and improves the transparency and heat resistance of the cured product even when the cured product has a high fluorine content. It aims at providing a curable fluorine-containing resin composition.

  Furthermore, it aims at providing the optical waveguide using this composition.

1st invention of this invention is the uniform liquid composition which consists of following (A) and (B), Comprising: (A) 5-99 mass% and (B) 1-95 mass% hardening Relates to a fluorinated resin composition.
(A) Formula (1):

Wherein X ¹ is at least one selected from the group consisting of H, CH ₃ , F, Cl and CF ₃ ; R is R ¹ and / or R ² ;
R ¹ represents the formula (1-1):

(Wherein Z is F or CF ₃ ; m1, m2, m3, m4 are 0 or an integer of 1 to 10, where m1 + m2 + m3 + m4 is an integer of 1 to 10),
R ² represents the formula (1-2):

(In the formula, Rf ¹ and Rf ² are the same or different and each is a perfluoroalkyl group having 1 to 5 carbon atoms; R ³ is a carbon number 1 to which some or all of the hydrogen atoms may be substituted with fluorine atoms. Fluorine-containing alkyl group containing a moiety represented by 5 hydrocarbon group)
One or more fluorine-containing monomers represented by:
(B) A fluorinated acrylic polymer having a fluorine content of 25% by mass or more, essentially a polymer obtained by polymerizing only an acrylic monomer.

  In the first invention of the present invention, the “homogeneous liquid composition” means that the fluorine-containing acrylic polymer (B) is completely dissolved or dispersed in the solvent component comprising the fluorine-containing monomer (A). In other words, the composition is transparent, for example, the light (550 nm) transmittance is 80% or more.

A second invention of the present invention is a uniform liquid composition comprising the following (A-1), (C) and (D), wherein (A-1) is 5 to 98% by mass, (C) The present invention relates to a curable fluorine-containing resin composition containing 1 to 94% by mass and 1 to 94% by mass of (D).
(A-1) Formula (1a):

(In the formula, X ¹ is at least one selected from the group consisting of H, CH ₃ , F, Cl and CF ₃ ; R ¹ is a formula (1-1):

(Wherein Z is F or CF ₃ ; m1, m2, m3 and m4 are 0 or an integer of 1 to 10, where m1 + m2 + m3 + m4 is an integer of 1 to 10). A fluorine-containing monomer represented,
(C) Formula (2):

Wherein X ² and X ³ are the same or different and are at least one selected from the group consisting of H, CH ₃ , F, Cl and CF ₃ ; n is an integer from 1 to 6, for example from 1 to 3; ⁴ is an (n + 1) -valent organic group in which some or all of hydrogen atoms having 1 to 50 carbon atoms, for example 3 to 50 carbon atoms, may be substituted with fluorine atoms, and R ⁴ has a hetero atom in the R ^4. A polyfunctionality represented by an organic group containing at least one site selected from a portion of an aromatic hydrocarbon structure which may have an aromatic hydrocarbon structure which may have a hetero atom Fluorine-containing monomer,
(D) An amorphous fluorine-containing polymer having a fluorine content of 25% by mass or more.

  In the second invention of the present invention, the “uniform liquid composition” means that the amorphous fluorine-containing polymer (D) is a fluorine-containing monomer (A-1) and a polyfunctional fluorine-containing monomer ( The composition is completely dissolved or dispersed in the solvent component consisting of C) and the composition is transparent. For example, the composition has a light (550 nm) transmittance of 80% or more.

  3rd invention of this invention is related with the hardened | cured material which hardens the curable fluorine-containing resin composition of the said 1st or 2nd invention, and a glass transition temperature is 85 degreeC or more.

  A fourth invention of the present invention is an optical material comprising the cured product of the third invention and an optical waveguide comprising a core portion and a clad portion, wherein at least one of the core portion and the clad portion is that of the third invention. The present invention relates to an optical waveguide characterized by comprising a cured product.

  According to the present invention, it is possible to provide a curable fluorinated resin composition capable of providing an optical material having high heat resistance and high transparency without using a solvent, for example, an optical waveguide. Various effects are produced.

The present invention relates to a uniform liquid composition comprising the following (A) and (B), and relates to a curable fluorinated resin composition containing 5 to 99% by mass of (A) and 1 to 95% by mass of (B).
(A) is a fluorine-containing acrylic monomer and has the formula (1):

Wherein X ¹ is at least one selected from the group consisting of H, CH ₃ , F, Cl and CF ₃ ; R is R ¹ and / or R ² ;
R ¹ represents the formula (1-1):

(Wherein Z is F or CF ₃ ; m1, m2, m3, m4 are 0 or an integer of 1 to 10, where m1 + m2 + m3 + m4 is an integer of 1 to 10),
R ² represents the formula (1-2):

(In the formula, Rf ¹ and Rf ² are the same or different and each is a perfluoroalkyl group having 1 to 5 carbon atoms; R ³ is a carbon number 1 to which some or all of the hydrogen atoms may be substituted with fluorine atoms. Fluorine-containing alkyl group containing a moiety represented by 5 hydrocarbon group)
One or more fluorine-containing monomers represented by:
(B) A fluorinated acrylic polymer having a fluorine content of 25% by mass or more, essentially a polymer obtained by polymerizing only an acrylic monomer.

  That is, in a composition comprising a fluorine-containing acrylic monomer and a fluorine-containing acrylic polymer, a specific fluorine-containing acrylic monomer (fluorine-containing acrylic monomer represented by the formula (1)) is selected and cured. By using a fluororesin composition, it is possible to obtain a homogeneous liquid composition having good solubility with various fluorine-containing acrylic polymers (B) in the composition before curing, and further in the cured product after curing. The present inventors have found that it is excellent in compatibility with the fluorine-containing acrylic polymer (B) and can eliminate the decrease in transparency due to white turbidity caused by lack of compatibility. In addition, partial crystallization in the cured product was suppressed, and the resulting decrease in transparency such as white turbidity could also be solved.

In the curable fluorine-containing resin composition according to the first aspect of the present invention, the fluorine-containing acrylic monomer (A) is characterized by the fluorine-containing acrylic monomer having a specific ester moiety represented by the formula (1). It is in point to use. That is, by using the ester moiety containing the fluorine-containing alkylene ether structure R ¹ of the formula (1-1) and / or the fluorine-containing tertiary alkyl structure R ² of the formula (1-2) as the ester moiety, the above-described curing is performed. It is possible to ensure the solubility, uniformity, compatibility and transparency after curing in the previous composition.

A first preferred example of the fluorine-containing acrylic monomer (A) represented by the formula (1) includes a fluorine-containing alkylene ether structure R ¹ in the ester portion. In addition to the above-mentioned characteristics and effects, these monomers are liquid at room temperature, dissolve the fluorinated acrylic polymer (B) more effectively, and are more uniform to more various fluorinated acrylic polymers. This is preferable in that a liquid composition is easily obtained. In addition, these monomers have a lower viscosity than a monomer having a linear fluoroalkyl group in the ester portion, and the composition can be reduced in viscosity, so that the processability is also excellent. In addition, since these monomers have low volatility, there is no problem that the composition of the liquid composition changes due to the volatilization of the monomer components during the molding process, and the physical properties such as the refractive index of the cured product change. . Moreover, since the compatibility with the fluorine-containing acrylic polymer (B) is high even after curing, there is no problem of causing cloudiness or phase separation due to heating. The obtained cured product has a characteristic that it exhibits amorphousness despite the high fluorine content.

Non-limiting examples of R ¹ constituting the ester moiety of formula (1) are shown below.
(1-3):

(1-4):

(1-5):

(1-6):

(1-7):

(1-8):

  Among these, high fluorine content, solubility of the fluorinated acrylic polymer (B), compatibility with the fluorinated acrylic polymer (B) after curing, transparency in the near infrared region of the cured product is good From the viewpoint of being present, a particularly preferred structure is represented by formula (1-3):

(Wherein m5 is an integer of 1 to 5).

  Among these, m5 is most preferably 1 to 3, and m5 is most preferably 1 from the viewpoints of heat resistance (high glass transition temperature) and mechanical strength of the cured product.

X ¹ in the formula (1) is fluorine from the viewpoint of good polymerization reactivity of the fluorinated monomer (A), transparency in the near infrared region of the cured product, and heat resistance (high glass transition temperature). Atoms are most preferred.

Examples of the non-limiting fluorine-containing acrylic monomer (A) containing R ¹ include the following.
(1a):

(1b):

(1c):

(1d):

(1e):

(1f):

Of these, the fluorine-containing monomer R ^1, in particular m5 of the formula (1-3) has a R ¹ a 1 (1a-1):

Are most preferable from the viewpoints of solubility of the fluorinated acrylic polymer (B), compatibility with the fluorinated acrylic polymer (B) after curing, and transparency in the near-infrared region of the cured product.

A second preferable example of the fluorine-containing acrylic monomer (A) represented by the formula (1) includes a fluorine-containing tertiary alkyl structure R ² in the ester portion.

The characteristic of the monomer containing R ² in the ester site is a branched structure, and in addition to the above-mentioned effects, it particularly imparts heat resistance (high glass transition temperature) and appropriate mechanical strength and hardness to the cured product.

R ² constituting the ester moiety of the formula (1) is
Formula (1-2):

(In the formula, Rf ¹ and Rf ² are the same or different and each is a perfluoroalkyl group having 1 to 5 carbon atoms; R ³ is a carbon number 1 to which some or all of the hydrogen atoms may be substituted with fluorine atoms. 5 is a fluorine-containing tertiary alkyl structure.

Rf ¹ and Rf ² are the same or different perfluoroalkyl groups having 1 to 5 carbon atoms, specifically CF ₃ , CF ₂ CF ₃ , CF ₂ CF ₂ CF ₃ , CF ₂ CF ₂ CF ₂ CF _3. a _{CF 2 CF 2 CF 2 CF 2} CF 3, are CF _3, especially in view of the heat resistance of the compatibility and the cured product (glass transition temperature) is good preferred.

R ³ is a hydrocarbon group having 1 to 5 carbon atoms which may be substituted with a fluorine atom. Specifically, CH ₃ , CH ₂ CH ₃ , CH ₂ CH ₂ CH ₃ , CH ₂ CH ₂ CH ₂ CH ₃ , CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ CF ₂ CF ₃ , especially good compatibility and heat resistance (glass transition temperature) of the cured product From the viewpoint of being, CH ₃ is preferable. If the number of carbon atoms in each of Rf ¹ , Rf ² and R ³ is 6 or more, the branched chain is likely to be crystallized and the transparency of the cured product is lowered, which is not preferable.

Specific monomers having a fluorine-containing tertiary alkyl structure R ² include, for example, hexafluoroneopentyl methacrylate (6FNPM: X ¹ = CH ₃ , Rf ¹ = Rf ² = CF ₃ , R ³ = CH ₃ ), Hexafluoroneopentyl α-fluoroacrylate (6FNPF: X ¹ = F, Rf ¹ = Rf ² = CF ₃ , R ³ = CH ₃ ), 2,2-bistrifluoromethylbutyl methacrylate (X ¹ = CH ₃ , Rf ¹ = Rf ² = CF ₃ , R ³ = CH ₂ CH ₃ ), 2,2-bistrifluoromethylbutyl α-fluoroacrylate (X ¹ = F, Rf ¹ = Rf ² = CF ₃ , R ³ = CH ₂ CH ₃ ),

Etc. can be exemplified. Among these, hexafluoroneopentyl methacrylate (6FNPM), which is excellent in heat resistance of the cured product and easy to synthesize,

Hexafluoroneopentyl α-fluoroacrylate (6FNPF)

It is preferable, 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 at a high temperature for FA applications, etc. 6FNPF having high heat resistance (high glass transition temperature) and high transparency in the near infrared region is preferable.

  The fluorine-containing acrylic polymer as component (B) is a polymer consisting essentially of an acrylic monomer having a fluorine content of 25% by mass or more.

  By using this polymer (B), the fluorinated acrylic monomer (A) and a curable fluorinated resin composition that is a uniform liquid composition are formed. In combination with the monomer (A), the polymer (B) has a function of adjusting the viscosity of the curable fluorine-containing resin composition, a function of reducing polymerization shrinkage during curing, and a function of increasing the fluorine content of the cured product. Together. Moreover, when shape | molding with a metal mold | die etc. at the time of shaping | molding and making it harden | cure, it also has a function which improves the peelability of hardened | cured material from a metal mold | die.

  The fluorine-containing acrylic polymer (B) may be a homopolymer or copolymer of a fluorine-containing acrylic monomer. Moreover, as long as a fluorine content rate will be 25 mass% or more, it is good also as a copolymer of a fluorine-containing acrylic monomer and a non-fluorine acrylic monomer. Further, two or more kinds of fluorine-containing acrylic polymers (B) may be blended and used.

  As a specific example of the fluorine-containing acrylic monomer forming the fluorine-containing acrylic polymer (B), the formula (3-1):

(Wherein X ⁶ is H, F, Cl, CH ₃ or CF ₃ ; R ⁵ is a saturated hydrocarbon group in which some or all of the hydrogen atoms having 1 to 30 carbon atoms may be fluorine-substituted. ^At least one of ⁶ and R ⁵ contains a fluorine atom). X ⁶ is preferably a fluorine atom from the viewpoint that the fluorine-containing acrylic polymer (B) has good fluorine content, heat resistance (high glass transition temperature), and transparency in the near infrared region.

Preferred R ⁵ is
(1) a saturated hydrocarbon group in which some or all of the hydrogen atoms containing an alkylene ether bond may be fluorine-substituted,
(2) a saturated hydrocarbon group in which some or all of the hydrogen atoms including a branched structure may be fluorine-substituted,
(3) an aromatic hydrocarbon group in which some or all of the hydrogen atoms optionally having heteroatoms may be fluorine-substituted,
(4) an aliphatic monocyclic structure in which some or all of the hydrogen atoms optionally having heteroatoms may be fluorine-substituted,
(5) An aliphatic polycyclic structure in which some or all of the hydrogen atoms optionally having heteroatoms may be fluorine-substituted. When the monomer component containing these structures (1) to (5) in the ester portion is present in the polymer, the above-described effects are remarkably exhibited.

Particularly preferably, R ⁵ contains a fluorine atom, and a structure containing a larger number of fluorine atoms (high fluorine content) is preferred.

  From this point of view, part or all of the hydrogen atoms are replaced by fluorine atoms, the fluorine-containing hydrocarbon groups of the above (1) to (5), particularly perfluoroalkylene ether groups, perfluoroaromatic hydrocarbon groups, perfluoroaliphatics. Preferred are those containing an aromatic monocyclic structure and a perfluoroaliphatic bicyclic structure. Specific examples will be described later.

  As a thing containing a fluorine-containing alkyl group, especially a perfluoroalkyl group, the thing containing a C1-C10 perfluoroalkyl group is preferable, and the thing containing a C1-C5 perfluoroalkyl group is especially preferable. A perfluoroalkyl group having an excessively large number of carbon atoms is not preferable because the obtained cured product is likely to be crystallized, and transparency is likely to decrease due to white turbidity.

Examples of the non-fluorinated acrylic monomer include monomers in which X ⁶ and R ⁵ in Formula (3-1) do not contain a fluorine atom. Details will be described later.

Next, specific examples of R ⁵ will be described individually.

(1) A saturated hydrocarbon group in which part or all of the alkylene ether bond is optionally substituted with fluorine:
This alkylene ether group can increase the fluorine content of the fluorine-containing acrylic polymer (B), and can increase the solubility in the fluorine-containing acrylic monomer (A). It is preferable at the point which becomes easy to obtain.

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

A preferred specific example is the fluorine-containing alkylene ether group R ^{1 represented} by the formula (1-1). This is preferable in that it is easy to obtain a uniform liquid composition because of its high fluorine content and good solubility in the fluorine-containing acrylic monomer (A). Further, as more specific examples of R ⁵ and examples of monomers, the specific examples (1-3) to (1-8) and (1a) to (1f) described above with reference to the formula (1-1) ) Can also be illustrated here.

Furthermore, preferable examples of R ⁵ include those represented by the above formula (1-3), and m5 is also from the viewpoint of good heat resistance (high glass transition temperature) and mechanical strength of the cured product. 1 to 3 is most preferable.

(2) A saturated hydrocarbon group in which part or all of the branched structure may be fluorine-substituted:
By including a branched structure, solubility in the fluorine-containing monomer (A) is improved, a uniform liquid composition can be easily obtained, and the heat resistance (high glass transition temperature) of the cured product can be increased.

Specific examples of R ⁵ include the following.
(B-2-1)

(In the formula, Rf ⁴ and Rf ⁵ are the same or different and each is a perfluoroalkyl group having 1 to 5 carbon atoms; R ⁶ is a carbon number 1 to which some or all of the hydrogen atoms may be substituted with fluorine atoms. 5 is a hydrocarbon group, H or F; n is an integer of 1 to 6; m is an integer of 1 to 6)
More specifically,

It is.
(B-2-2)

  More specifically,

It is.
(B-2-3)

  More specifically,

It is.

Specific examples of the fluorine-containing monomer include the following.
(B-2a):

  In particular,

It is.
(B-2b):

In particular,
6FNPF:

Or 6FNPM:

It is.
(B-2c):

(In the formula, X ⁶ , Rf ⁴ , Rf ⁵ and R ⁶ are the same as those in formula (B-2a)).
In particular,
Hexafluoroisopropyl α-fluoroacrylate (HFIPF)

Or hexafluoroisopropyl methacrylate (HFIPM)

It is.

  Among these, 6FNPM, 6FNPF, hexafluoroisopropyl methacrylate (HFIPM), and hexafluoroisopropyl α-fluoroacrylate (HFIPF) have good heat resistance (high glass transition temperature) of the cured product and good transparency in the near infrared region. From the viewpoint of Among them, 6FNPF and HFIPF have a good solubility in the fluorine-containing acrylic monomer (A), so that it is easy to obtain a uniform liquid composition, heat resistance of the cured product (high glass transition temperature), near infrared region Most preferable from the viewpoint of good transparency.

(3) Aromatic hydrocarbon group which may be partially or entirely substituted with fluorine which may have a hetero atom:
This aromatic hydrocarbon group is preferable in terms of good heat resistance (high glass transition temperature). In particular, 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.

Specific examples of R ⁵ include the following.
(B-3-1)

(In the formula, R ⁷ is the same or different and is an alkyl group having 1 to 14 carbon atoms which may be substituted with F, Cl or a halogen atom; R ⁸ may have a bond or a branched chain. An alkylene group having 1 to 6 carbon atoms; a is an integer of 1 to 5; provided that any one of R ⁷ and R ⁸ has a fluorine atom)

  More specifically,

It is.

  The following can be preferably exemplified as specific fluorine-containing monomers.

Perfluorophenyl α-fluoroacrylate

Perfluorophenyl methacrylate

Are preferred.

  Among these, perfluorophenyl methacrylate and perfluorophenyl α-fluoroacrylate are preferable in terms of improving heat resistance (high glass transition temperature) and transparency in the near infrared region.

(4) Aliphatic monocyclic structure in which part or all of optionally having a hetero atom may be substituted with fluorine:
This aliphatic monocyclic structure is preferable in terms of good heat resistance (high glass transition temperature). In particular, 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.

As specific examples of R ^5, the following can be exemplified without limitation.
(B-4-1)

(In the formula, R ⁹ is the same or different and may be substituted with F, Cl or a halogen atom. The alkyl group having 1 to 14 carbon atoms may be substituted; R ¹⁰ may have a bond or a branched chain. An alkylene group having 1 to 6 carbon atoms; b is an integer of 1 to 5; provided that any one of R ⁹ and R ¹⁰ has a fluorine atom)
More specifically,

Is given.

(B-4-2) Those containing an aliphatic cyclic hydrocarbon structure having one or two monocyclic structures are also preferred.

  The following can be preferably exemplified as specific fluorine-containing monomers.

(5) An aliphatic polycyclic structure in which part or all of the hetero atoms may have fluorine substitution:
This aliphatic polycyclic structure is preferable in terms of good heat resistance (high glass transition temperature). In particular, 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.

Specific examples of R ⁵ include the following.
(B-5-1) adamantane and its derivatives,
(B-5-2) norbornane and its derivatives,
(B-5-3) perhydroanthracene and its derivatives,
(B-5-4) perhydronaphthalene and its derivatives,
(B-5-5) tricyclo [5.2.1.0 ^2,6 ] decane and its derivatives, and the like.

Etc.

  Among these examples, in the present invention, 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.

  Further, among these organic groups containing a hydrocarbon moiety of a polycyclic structure, those containing adamantane and derivatives thereof, norbornane and derivatives thereof are preferable, and these are particularly heat resistant (high glass transition temperature) and transparent in the near infrared region. Property can be effectively imparted to the cured product.

The following can be preferably exemplified as specific fluorine-containing monomers.
(B-5-1a) Monomer having adamantane represented by the following formula and its derivative in the side chain:

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

  More specifically,

Etc.

(B-5-2a) Monomer having norbornane represented by the following formula and derivatives thereof in the side chain:

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

  More specifically,

Etc.

  The non-fluorine acrylic monomer that may be copolymerized with the fluorine-containing acrylic monomer is not particularly limited as long as the fluorine content of the fluorine-containing acrylic polymer (B) is 25% by mass or more. .

  Non-limiting specific examples of non-fluorinated acrylic monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n- Aliphatic ester (meth) acrylates such as butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, etc .; phenyl (meth) acrylate, adamantyl ( (Meth) acrylate, dimethyladamantyl (meth) acrylate, and the like.

  The fluorine content of the fluorinated acrylic polymer (B) may be 25% by mass or more, but the larger one is preferable in terms of excellent transparency in the near infrared region of the cured product, and preferably 30% by mass. As mentioned above, More preferably, it is 40 mass% or more, Most preferably, it is 50 mass% or more. The upper limit is the fluorine content when all of the hydrogen atoms in each polymer are replaced with fluorine atoms.

  The fluorine-containing acrylic polymer (B) preferably has a glass transition temperature (Tg) of 85 ° C. or higher, preferably 90 ° C. or higher, particularly 95 ° C. or higher, from the viewpoint of improving the heat resistance of the resulting cured product.

  The upper limit of the number average molecular weight of the fluorine-containing acrylic polymer (B) is 500,000, preferably 100,000, particularly preferably 50,000 from the viewpoints of solubility in other components and compatibility. The lower limit is not particularly limited, but is preferably an oligomer that is a quantifier from the same viewpoint, specifically 300, preferably 500.

  The preparation method and additives in the composition of the first invention will be described later.

  The content ratio of the fluorine-containing acrylic monomer (A) and the fluorine-containing acrylic polymer (B) can be appropriately selected depending on the required viscosity of the uniform liquid composition, the heat resistance (glass transition temperature) of the cured product, and the like. (A) is 5% by mass or more, preferably 10% by mass or more, more preferably 25% by mass or more and 99% by mass or less, preferably 80% by mass or less, more preferably 75% by mass or less. B) is 1% by mass or more, preferably 20% by mass or more, more preferably 25% by mass or more and 95% by mass or less, preferably 90% by mass or less, more preferably 75% by mass or less. If the amount of the fluorine-containing monomer (A) is too small, it becomes difficult to obtain a uniform liquid composition. If the amount of the fluorine-containing acrylic polymer (B) is too small, the viscosity of the uniform liquid composition is lowered, the operability at the time of molding is deteriorated, or the shape of the designed optical waveguide is changed due to increased polymerization curing shrinkage. There is not preferable.

  The preferable viscosity range of the uniform liquid composition is in the range of 10 mPa · s to 20000 mPa · s, but from the viewpoint of workability, the range of 20 to 10,000 mPa · s is more preferable, and the range of 50 to 8000 mPa · s is more preferable.

  Further, it is preferable that the organic solvent is not substantially contained, but a solvent or the like may be added within a range that does not adversely affect the physical properties of the cured product for the purpose of adjusting the viscosity.

Next, the second invention of the present invention will be described. The second invention is a uniform liquid composition comprising the following (A-1), (C) and (D), wherein (A-1) is 5 to 98% by mass, and (C) is 1 to The present invention relates to a curable fluorinated resin composition containing 94% by mass and 1 to 94% by mass of (D).
(A-1) Formula (1a):

(In the formula, X ¹ is at least one selected from the group consisting of H, CH ₃ , F, Cl and CF ₃ ; R ¹ is a formula (1-1):

(Wherein Z is F or CF ₃ ; m1, m2, m3, m4 are 0 or an integer of 1 to 10, where m1 + m2 + m3 + m4 is an integer of 1 to 10). A fluorine-containing monomer represented,
(C) Formula (2):

Wherein X ² and X ³ are the same or different and are at least one selected from the group consisting of H, CH ₃ , F, Cl and CF ₃ ; n is an integer from 1 to 6, for example from 1 to 3; ⁴ is an (n + 1) -valent organic group in which some or all of hydrogen atoms having 1 to 50 carbon atoms, for example 3 to 50 carbon atoms, may be substituted with fluorine atoms, and R ⁴ has a hetero atom in the R ^4. A polyfunctionality represented by an organic group containing at least one site selected from a portion of an aromatic hydrocarbon structure which may have an aromatic hydrocarbon structure which may have a hetero atom Fluorine-containing monomer,
(D) An amorphous fluorine-containing polymer having a fluorine content of 25% by mass or more.

In the second invention, in a composition comprising a fluorine-containing acrylic monomer, a polyfunctional fluorine-containing monomer, and an amorphous fluorine-containing polymer, a specific fluorine-containing acrylic monomer (A-1 ) (A fluorine-containing acrylic monomer in which R is fluorine-containing alkylene ether structure R ¹ in formula (1)) and a specific polyfunctional fluorine-containing monomer (polyfunctional fluorine-containing monomer of formula (2) The curable fluorine-containing resin composition is selected, and the same characteristics and effects as those described above (the first invention) are obtained. Further, in the cured product after curing, the heat resistance of the cured product (high glass) (Transition temperature), mechanical strength and hardness are improved, and the polyfunctional fluorine-containing monomer (C) has a cross-linked structure, so that phase separation is suppressed. As a result, the amorphous fluorine-containing polymer (D) Cloudiness caused by lack of compatibility due to improved compatibility with A reduction in the transparency in the near-infrared region by etc. can be eliminated.

  Moreover, partial crystallization in the cured product is also suppressed by the cured product having a cross-linked structure, and a decrease in transparency in the near infrared region such as white turbidity due to crystallization can be solved.

In the curable fluorine-containing resin composition of the second invention, the fluorine-containing acrylic monomer (A-1) is characterized by a specific ester moiety in which R is a fluorine-containing alkylene ether structure R ¹ in the general formula (1) It is what has. That is, it is selected from ester sites containing the fluorine-containing alkylene ether structure of formula (1-1), and by using these ester sites, excellent solubility and uniformity of the composition before curing described above are obtained. And good compatibility and transparency after curing.

In the curable fluorine-containing resin composition of the second invention, the polyfunctional fluorine-containing monomer (C) is characterized by having a specific ester site R ⁴ represented by the formula (2). That is, an organic group containing at least one site selected from a portion of an aromatic hydrocarbon structure that may have a heteroatom or a portion of an aliphatic cyclic hydrocarbon structure that may have a heteroatom. By using these ester sites, the transparency, heat resistance (high glass transition temperature), mechanical strength, and hardness in the near-infrared region of the cured product as described above can be ensured.

  Next, individual components will be described.

The fluorine-containing acrylic monomer (A-1) is a fluorine-containing acrylic monomer in which R is a fluorine-containing alkylene ether structure R ¹ in the formula (1). In the three-component system (A, D, C), it is important that the fluorine-containing acrylic monomer (A-1) dissolves other components well to form a uniform liquid composition. A fluorine-containing alkylene ether structure such as 1-1), preferably a structure such as formula (1-3) is preferable in that it exhibits the same characteristics and effects as described above.

R ¹ is the same as described above including specific examples. Preferable R ^{1 is} also represented by the formula (1-3) and is the same as that described above including the specific example.

  The polyfunctional fluorine-containing monomer (C) has the formula (2):

Wherein X ² and X ³ are the same or different and are at least one selected from the group consisting of H, CH ₃ , F, Cl and CF _3. N is an integer of 1-6, for example 1-3; ⁴ is an (n + 1) -valent organic group in which part or all of hydrogen atoms having 1 to 50 carbon atoms, for example 3 to 50 carbon atoms, may be substituted with fluorine atoms, and R ⁴ has a heteroatom. An organic group containing at least one portion selected from a portion of an aromatic hydrocarbon structure which may be substituted or a portion of an aliphatic cyclic hydrocarbon structure which may have a hetero atom, provided that X ² , X ³ and R ^At least one of ⁴ includes a fluorine atom).

In the formula (2), it is preferable that X ² and X ³ are fluorine atoms from the viewpoint that the reactivity of the polyfunctional fluorine-containing monomer is good and the heat resistance of the resulting cured product is improved ( High glass transition temperature). Further, it is preferable in that the fluorine content is high and the transparency of the cured product in the near infrared region is also high.

In the formula (2), R ⁴ is an (n + 1) -valent organic group in which part or all of hydrogen atoms having 1 to 50 carbon atoms, for example 3 to 50 carbon atoms, may be substituted with fluorine atoms. By replacing some or all of the hydrogen atoms with fluorine atoms, the transparency of the obtained cured product in the near infrared region is improved.

Furthermore, this organic group R ⁴ has (C-1) a portion of an aromatic hydrocarbon structure which may have a heteroatom in the structure, and (C-2) an aliphatic which may have a heteroatom. It is an organic group containing at least one kind of part selected from a part of a group monocyclic structure or (C-3) a part of an aliphatic polycyclic structure optionally having a hetero atom. By including these cyclic structures, the heat resistance of the resulting cured product is improved (high glass transition temperature).

  This polyfunctional fluorine-containing monomer (C) 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 improvement in the heat resistance of the cured product due to the cyclic structure in the polyfunctional site is a small amount of cyclic structure compared to the case of the fluorinated acrylic monomer having a cyclic structure in the monofunctional monomer site. Introducing heat resistance (high glass transition temperature) can be achieved. Moreover, although a reason is unknown, hardening shrinkage can also be reduced by having a cyclic structure in a polyfunctional site.

Next, each part will be described. For convenience of explanation, specific examples of R ⁴ in -O-R ⁴ -O- shape, but it is not limited thereto.

(C-1) Aromatic hydrocarbon structure moiety optionally having a hetero atom:
(C-1-1) Formula:

(Wherein R ¹¹ and R ¹² 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 ¹ and Z ² are the same or different, and the alkyl group, A fluorine alkyl group, a functional group or a halogen atom; p and q are the same or different and are an integer of 1 to 4), or (C-1-2) formula:

(Wherein R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are the same or different and are an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms; Z ³ is an alkyl group or a fluorinated alkyl group; Group represented by a group, a functional group, or a halogen atom; p is an integer of 1 to 4.

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

In the formula, Bz is an alkyl group, a fluorine-containing alkyl group, a divalent benzene ring or a heteroaromatic ring which may be substituted with a functional group or a halogen atom, n and m each have a carbon number of R ⁴ of 50, further 30 It is an integer of 0 or 1 or more so as not to exceed.

(C-2) A portion of an aliphatic monocyclic structure which may have a hetero atom:
(C-2-1) Monocyclic hydrocarbon structure:
For example,
(C-2-1-1) Formula:

(Wherein R ¹¹ and R ¹² 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 ¹ and Z ² are the same or different, and the alkyl group, A fluorine alkyl group, a functional group, or a halogen atom; p and q are the same or different and are an integer of 1 to 4, or a formula (C-2-1-2):

(Wherein R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are the same or different and are an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms; Z ³ is an alkyl group or a fluorinated alkyl group; Group represented by a group, a functional group, or a halogen atom; p is an integer of 1 to 4.

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

In the formula, cHx is an alkyl group, a fluorine-containing alkyl group, a divalent cyclohexane ring or heteroalicyclic monocyclic compound which may be substituted with a functional group or a halogen atom, and n and m each have a carbon number of R ⁴ of 50. In addition, it is 0 or an integer of 1 or more so as not to exceed 30.

(C-3) Aliphatic polycyclic structure optionally having a hetero atom:
For example,
(C-3-1) Formula:

(Wherein R ¹¹ and R ¹² 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 ¹ and Z ² are the same or different, and the alkyl group, A fluorine alkyl group, a functional group or a halogen atom; p and q are the same or different and are an integer of 1 to 4), or a formula (C-3-2):

(Wherein R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are the same or different and are an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms; Z ³ is an alkyl group or a fluorinated alkyl group; Group represented by a group, a functional group, or a halogen atom; p is an integer of 1 to 4.

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

In the formula, NB represents an alkyl group, a fluorine-containing alkyl group, a divalent norbornene ring or heteroalicyclic bicyclic compound which may be substituted with a functional group or a halogen atom, and n and m each have a carbon number of R ⁴ of 50. In addition, it is 0 or an integer of 1 or more so as not to exceed 30.

  The above is an example of n = 1. Specific examples when n = 2 or 3 include the following.

  Specific examples of the polyfunctional fluorine-containing monomer (C) represented by the formula (2) include the following, but are not limited thereto.

  In addition to the above examples, polyfunctional fluorine-containing monomers containing a heterocycle can be exemplified.

The R ⁴ in the polyfunctional fluorine-containing monomer (C) represented by the formula (2) is summarized as follows from a slightly different viewpoint. In the following description of R ⁴ , there is a description that overlaps with the description so far, but from the viewpoint of organization, the description will be made without any duplication.

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

First, preferred embodiments of R ⁴ will be described with specific examples.

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

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

  Formula (R2-1-1):

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

  More specifically,

Etc. are preferable.

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

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

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

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

  In particular,

Etc.

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

Etc.

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

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

  In particular,

Etc. are preferable.

A divalent or higher-valent organic group composed of these exemplified linear or branched alkylene groups as R ⁴ is preferable in that it can impart flexibility and elasticity to the polymer. Further, when introducing a fluorine atom, it can be introduced at a high content, which is advantageous in terms of transparency and a low refractive index.

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

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

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

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

Formula (R2-7):

Formula (R2-8):

Formula (R2-9)

Formula (R2-10):

Formula (R2-11):

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

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

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

  As a specific example of (R2-6),

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

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

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

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

Etc. are preferable.

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

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

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

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

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

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

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

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

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

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

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

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

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

Formula (R2-14):

Formula (R2-15):

Formula (R2-16):

Formula (R2-17):

Formula (R2-18):

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

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

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

  As a specific example of (R2-13),

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

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

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

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

Etc. are preferable.

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

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

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

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

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

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

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

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

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

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

And organic groups such as

Although R ⁴ has been mainly described above, specific examples of the polyfunctional acrylate represented by the formula (2) include the following.

Preferred are polyfunctional acrylate compounds such as

  Component (D) is an amorphous fluorine-containing polymer having a fluorine content of 25% by mass or more.

  Here, the term “amorphous” means that an endothermic peak based on melting is not substantially observed in the DSC analysis described above under the condition of a temperature increase rate of 10 ° C./min in 2nd run, or the heat of fusion is 1 J / The property which is below g is shown.

  When the fluorine content is 25% by mass or more, it is possible to impart the property of improving the transparency in the near infrared region of the obtained cured product. Moreover, by being amorphous, the solubility with respect to a fluorine-containing monomer (A-1) is high, and a uniform liquid composition is easy to be obtained. Moreover, since there is no scattering by a crystal component, the property of improving the transparency in the near infrared region of the cured product 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 that transparency in the near infrared region is good.

  The upper limit of the number average molecular weight of the fluoropolymer (D) is 500,000, preferably 100,000, particularly preferably 50,000, from the viewpoint of solubility in other components and compatibility. The lower limit is not particularly limited, but is preferably an oligomer that is a quantifier from the same viewpoint, specifically 300, preferably 500.

  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.

(D-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 (D-2) a fluorine-containing allyl ether type A polymer obtained by polymerizing monomers, wherein the fluorine content is 25% by mass or more of the amorphous fluorine-containing allyl ether polymer (D-3) having a fluorine content having a cyclic structure in the main chain Amorphous fluorine-containing cyclic polymer (D-4) of 25% by mass or more A copolymer comprising a fluorine-containing olefin and a hydrocarbon vinyl ether, and an amorphous fluorine-containing copolymer having a fluorine content of 25% by mass or more (D -5) 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 (D-6) vinylidene fluoride copolymer Coalesced Te, vinylidene fluorine content of amorphous above 25% by weight fluoride based copolymers.

  Of these, (D-1) and (D-2) are preferable structures from the viewpoint of solubility in the fluorine-containing monomer (A-1) and compatibility of the cured product, and the most preferable structure is (D -1). The amorphous fluorine-containing polymer (D) may be a blend of two or more of these polymers.

Next, (D-1) to (D-3) and (D-6) which are structures of (D) will be described.
(D-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:
The polymer (D-1) may be a homopolymer of an acrylic monomer or a copolymer with an acrylic monomer having a different structure. It is the same as (B) described above and can be used as it is, including specific examples.

  The glass transition temperature of the polymer (D-1) is more preferably 85 ° C. or higher from the viewpoint of improving the heat resistance of the cured product. More preferably, it is 90 ° C or higher. More preferably, it is 95 ° C. or higher. Since polymers having these structures have an acrylic polymer skeleton, they are essentially well dissolved in the fluorinated monomer component (A-1), become a uniform liquid composition, and the cured product has high compatibility. Transparency in the near infrared region is also high without white turbidity.

(D-2) A polymer obtained by polymerizing a fluorine allyl ether monomer, and an amorphous fluorine-containing allyl ether polymer having a fluorine content of 25% by mass or more:
The polymer (D-2) is disclosed in WO95 / 33782, WO02 / 18457, WO02 / 73255, etc.

  Despite the high fluorine content, the polymer (D-2) is amorphous and has very high solubility in the fluorine-containing monomer (A). Further, it is possible to easily give a curing site capable of reacting with the fluorine-containing acrylic monomer (A-1) such as a carbon-carbon double bond to the end of the side chain. If there is a cured site capable of reacting with the acrylic monomer (A-1), the cured product forms a mutual network as a whole, so that the cured product is further excellent in solvent resistance, low linear expansion coefficient, heat resistance, etc. Express performance.

(D-3) Amorphous fluorine-containing cyclic polymer having a fluorine content of 25% by mass or more having a cyclic structure in the main chain:
The polymer (D-3) is preferable in that the glass transition temperature is very high and the heat resistance of the cured product is increased. As such a polymer (D-3), a polymer having an aliphatic cyclic structural unit preferably having fluorine and a polymer having a non-fluorinated alicyclic monomer structural unit can be exemplified.

(D-3-1) Aliphatic cyclic structural unit having fluorine:
When this structural unit is introduced, the transparency in the near infrared region can be increased, and an amorphous fluorine-containing cyclic polymer (D-3) having a high glass transition temperature can be obtained, and the hardness of the cured product can be further increased. Is preferable in that it can be expected.

  As the fluorine-containing aliphatic cyclic structural unit (D-3-1), the formula (5):

Wherein X ⁷ , X ⁸ , X ¹¹ , X ¹² , X ¹³ and X ¹⁴ are the same or different, H or F; X ⁹ and X ¹⁰ are the same or different and H, F, Cl or CF ₃ Rf ⁶ is a fluorine-containing alkylene group having 1 to 10 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 10 carbon atoms; n2 is an integer of 0 to 3; n1, n3, n4 and n5 are the same or different; , 0 or an integer of 1) is preferable.

  For example,

(Wherein Rf ⁶ , X ⁹ and X ¹⁰ are the same as above).

  In particular,

(Wherein, X ⁷ , X ⁸ , X ¹¹ and X ¹² are the same as above).

  As other fluorine-containing aliphatic cyclic structural units, for example,

Etc.

(D-3-2) Non-fluorinated alicyclic monomer structural unit:
Moreover, the amorphous fluoropolymer containing the non-fluorine-based alicyclic monomer structural unit (D-3-2) can achieve a higher glass transition temperature and higher hardness of the cured product.

  As a specific example of the non-fluorinated alicyclic monomer structural unit (D-3-2),

(Wherein m is an integer of 0 to 3; A, B, C and D are the same or different, and H, F, Cl, COOH, CH ₂ OH or a C 1-5 perfluoroalkyl group, etc.) Derivatives,

And alicyclic monomers such as these, and derivatives obtained by introducing substituents into these.

(D-6) A vinylidene fluoride copolymer, an amorphous vinylidene fluoride copolymer having a fluorine content of 25% by mass or more:
The amorphous vinylidene fluoride copolymer is preferably a copolymer of vinylidene fluoride and one or more of other monomers copolymerizable therewith.

  Typical examples of other monomers include tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, vinyl fluoride, hexafluoropropylene, pentafluoropropylene, hexafluoroisobutene, perfluorocyclobutene, perfluoro (methylcyclopropylene). ), Perfluoroallene, perfluoroalkyl vinyl ethers (eg, perfluoromethyl vinyl ether, perfluoropropyl vinyl ether, etc.), perfluorovinyl acetic acid or its ester, perfluorovinyl ether sulfonic acid, perfluorodienes, ethylene, propylene, vinyl acetic acid Or the ester etc. are mention | raise | lifted. The content of other monomers is not particularly limited, but it is preferable to carry out copolymerization so that the fluorine content is in the range of 25% by mass or more, usually 10 to 60% by mass.

  Amorphous vinylidene fluoride-based copolymers include vinylidene fluoride / hexafluoropropylene (85-60 / 15-40 mol% ratio) copolymer, vinylidene fluoride / hexafluoropropylene / tetrafluoroethylene (84-20 / 15 to 40/1 to 40 mol% ratio) is preferred from the viewpoint of excellent solubility in the fluorinated monomer (A-1) and compatibility of the cured product.

  The polymer (D-6) is particularly preferable in that it is excellent in transparency in the visible region and gives impact resistance to the cured product. When rubber elasticity is required for the cured product, the glass transition temperature of the polymer (D-6) is usually lower than room temperature, so that the glass transition temperature of the entire cured product is also made room temperature or lower by using the polymer (D-6). Can be preferred.

  The amorphous fluorine-containing polymer (D) having a fluorine content of 25% by mass or more may have a cured site. For example, if there is a curing site capable of reacting with the fluorine-containing acrylic monomer (A-1), such as the above-mentioned carbon-carbon double bond, or a crosslinkable cyclic ether structure such as epoxy or oxetane, the cured product However, since they form a mutual network as a whole, they exhibit further excellent cured product performance such as solvent resistance, low linear expansion coefficient, heat resistance and the like.

  In the second invention, the content ratio of the fluorine-containing monomer (A-1), the polyfunctional fluorine-containing monomer (C) and the amorphous fluorine-containing polymer (D) is required for a uniform liquid composition. The viscosity may be appropriately selected depending on the heat resistance of the cured product, etc., but (A-1) is 5% by mass or more, preferably 10% by mass or more, more preferably 25% by mass or more and 98% by mass or less, preferably 80 mass% or less, more preferably 70 mass% or less, and (C) is 1 mass% or more, preferably 10 mass% or more, more preferably 15 mass% or more and 94 mass% or less, preferably 89 mass% or less. More preferably, it is 74 mass% or less, and (D) is 1 mass% or more, preferably 10 mass% or more, more preferably 15 mass% or more and 94 mass% or less, preferably 89 mass% or less, more preferably. 74 It is equal to or less than the amount%. When there is too little quantity of a fluorine-containing monomer (A-1), it will become difficult to obtain a uniform liquid composition. When there are few polyfunctional fluorine-containing monomers (C), the heat resistance of hardened | cured material will fall, and when too large, hardened | cured material will become fragile. When there is too little amorphous fluorine-containing polymer (D), the viscosity of a uniform liquid composition will become low and superposition | polymerization hardening shrinkage will become large.

  The preferable viscosity range of the uniform liquid composition of the present invention is in the range of 10 mPa · s to 20000 mPa · s, but from the viewpoint of workability, the range of 20 to 10000 mPa · s is more preferable in the range of 50 to 8000 mPa · s. Is more preferable.

  Further, it is preferable that the organic solvent is not substantially contained, but a solvent or the like may be added within a range that does not adversely affect the physical properties of the cured product for the purpose of adjusting the viscosity.

  Moreover, you may add another compound separately as a mere viscosity modifier. However, the addition amount is in a range not impairing the effect intended by the present invention.

  For example, when an optical material is formed by coating, it is desirable that the viscosity of the coating composition is 50 to 8000 mPa · s in order to make workability and film thickness thin and uniform. When increasing the viscosity, the ratio of the fluorine-containing acrylic polymer (B), the amorphous fluorine-containing polymer (D), and the polyfunctional fluorine-containing monomer (C) may be increased.

In addition, the refractive index of the cured product obtained from the composition of the present invention is determined based on the fluorine-containing monomer (A), the fluorine-containing acrylic polymer (B), (D) and / or the polyfunctional fluorine-containing monomer (C ) 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 thereof include benzyl-n-butyl phthalate (refractive index: 1.575), 1-methoxyphenyl-1-phenylethane (refractive index: 1.571), benzyl benzoate (refractive index: 1.75). 568), bromobenzene (refractive index: 1.557), o-dichlorobenzene (refractive index: 1.551), m-dichlorobenzene (refractive index: 1.543), 1,2'-dibromoethane (refractive index). : 1.538), 3-phenyl-1-propanol (refractive index: 1.532), diphenyl phthalate _{(C 6 H 4 (COOC 6} H 5) 2), triphenylphosphine ((C ₆ H _{5) 3} P), dibenzyl phosphate ((C ₆ H ₅ CH ₂ O) ₂ PHO ₂ ), 4,4′-dibromobenzyl, 4,4′-dibromobiphenyl, 2,4′-dibromoacetophenone, 3 ′, 4'-dichloroa Examples thereof include compounds such as cetophenone, 3,4-dichloroaniline, 2,4-dibromoaniline, 2,6-dibromoaniline 1,4-dibromobenzene.

  In the composition of the present invention, known additives may be appropriately used according to the application and required characteristics. Typical examples of other additives include leveling agents and antioxidants.

  The first and second curable fluorine-containing resin compositions of the present invention are publicly known such as a method of irradiating active energy rays, a method of starting a radical polymerization (such as a radical polymerization initiator), and a method of heating, for example. It can be made to harden by the method of.

  First, the composition of the type that irradiates active energy rays will be described.

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

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

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

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

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

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

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

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

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

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

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

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

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

Other sulfonimide compounds, diazomethane compounds, etc.

  The amount of the active energy ray curing initiator is usually 0.1% by mass, preferably 0.2% by mass, more preferably 0.3% by mass, particularly preferably 0.5%, based on the total amount of monomers. The upper limit is 15% by mass, preferably 10% by mass, more preferably 8% by mass, and particularly preferably 7% by mass.

  Next, a composition of a type that initiates radical polymerization by heating, for example, will be described.

  As a method of initiating radical polymerization, for example, a method of generating radicals using a known radical polymerization initiator is preferable.

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

  The third invention of the present invention relates to a cured product obtained by curing the first or second curable fluorine-containing resin composition.

  For curing, after adding a polymerization initiator and various additives as necessary to the first or second curable fluorine-containing resin composition, for example, it is applied to molding or a substrate and irradiated with active energy rays, or It can be manufactured by heating and curing.

  What is necessary is just to select the irradiation dose of an active energy ray suitably according to the kind of active energy ray hardening | curing agent to be used, the film thickness of a cured film, etc. The heating temperature may be appropriately selected depending on the type of radical polymerization initiator used.

  The cured product of the present invention is excellent in heat resistance, transparency, and low refractive index. Furthermore, the cured product obtained by using a curable fluororesin composition prepared without using a solvent is not affected by the residual solvent, can greatly reduce the occurrence of macrovoids, and is used as an optical material. , Light loss can be reduced.

  Hereinafter, the physical properties and characteristics of the cured product of the present invention will be described.

  When the polyfunctional fluorine-containing monomer (C) is used, the molecular weight is the fluorine-containing acrylic polymer (B), (D), the fluorine-containing monomer (A), and the polyfunctional fluorine-containing monomer ( Since C) is complexly reacted (crosslinking, grafting, IPN structure), it cannot be specified.

  The glass transition temperature Tg can be selected within a wide range depending on the composition. The Tg is preferably 85 ° C. or higher. Furthermore, by selecting each monomer or polymer, it is possible to make Tg 90 ° C. or higher, further 95 ° C. or higher, further 100 ° C. or higher, particularly 120 ° C. or higher. In order to increase Tg, the polyfunctional fluorine-containing monomer (C) component may be increased, or a ring structure may be introduced into the fluorine-containing polymer (B) or (D) component.

  The thermal decomposition temperature Td is 180 ° C. or higher and has excellent heat resistance. Furthermore, Td can be set to 200 ° C. or higher, further 230 ° C. or higher by selecting each monomer or polymer.

  The cured product of the present invention uses a fluorine-containing monomer (A) containing an ether bond, and the fluorine-containing polymers (B) and (D) are amorphous, depending on the ratio and selection of each component. In this case, the whole may be amorphous, and particularly when the polyfunctional fluorine-containing monomer (C) is blended, the whole becomes amorphous. When the cured product is amorphous, it is advantageous in that it has excellent transparency and can reduce transmission loss in optical transmission media such as optical waveguides and optical fibers.

  The cured product of the present invention can have a refractive index of 1.44 or less. Further reduction of the refractive index, for example, 1.42 or less can be realized by increasing the total fluorine content. Such a low refractive index is advantageous as an optical waveguide, a clad material for optical fibers, and an antireflection material.

  The cured product of the present invention is highly transparent with respect to light in the visible region, and particularly highly transparent with respect to light having a wavelength of 650 nm (more preferably 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 650 nm (or 850 nm) wavelength light of 90% or more, further 92% or more, particularly 94% or more.

  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 viewpoint, when the cured product of the present invention is used as an optical material, it is possible to provide a light transmittance of 1310 nm (or 1550 nm) wavelength light of 90% or more, further 92% or more, particularly 94% or more.

  4th of this invention is related with the optical material which consists of hardened | cured material of a curable fluorine-containing resin composition. An optical waveguide comprising a core part and a clad part, wherein at least one of the core part and the clad part is made of a cured product of the first or second curable fluorine-containing resin composition. Also related.

  First, the optical material will be described.

  The cured product of the present invention is transparent, has high heat resistance, and has a high fluorine content. Therefore, the optical material has a low refractive index. For example, it is useful as an optical transmission medium. In particular, the clad material of plastic clad optical fiber whose core material is quartz or optical glass, clad material of all plastic optical fiber whose core material is plastic, antireflection coating material, lens material, optical waveguide material, prism material, optical window Optical materials such as materials, optical storage disk materials, nonlinear optical elements, hologram materials, photolithographic materials, sealing member materials, and optical devices including cured products obtained by curing these materials, etc. Can be used.

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

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

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

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

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

  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 type element is an optical functional element connected by an optical waveguide, and the optical waveguide part is composed of a core part and a clad part. 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, and has various forms, but is a waveguide like optical multiplexing / demultiplexing or optical amplification. There are functional elements of the type. 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. In addition, various functional compounds such as nonlinear optical materials, fluorescent organic functional organic dyes, photorefractive materials, and the like may be included in the optical material of the present invention and used as the core material of a waveguide type functional element. Is possible. Furthermore, it is more preferable that both the core part and the clad part are obtained by curing the curable fluorine-containing resin composition.

  According to the present invention, an optical waveguide element containing a cured product of a curable fluorine-containing resin composition can also be provided.

  When the optical waveguide element has a core part and a clad part, the refractive index of the core part must be higher than that of the clad part, but the difference in refractive index between the core part and the clad part is 0.003 or more. It is preferable that it is 0.01 or more. Since the refractive index of the material of the present invention can be widely controlled, the selection range of the material is wide.

  In the optical waveguide element, the width of the core part is preferably 1 to 200 μm, more preferably 5 to 50 μm. Further, the height of the core part is preferably 5 to 50 μm. The accuracy of the width and height of the core part is preferably 5% or less of the average value, and more preferably 1% or less.

  FIG. 1 illustrates a schematic cross-sectional view of a structure of a typical optical waveguide device. Reference numeral 1 denotes a substrate, 2 denotes a core portion, and 4 and 5 denote cladding portions. Such an optical waveguide type element is used for connecting between optical functional elements, and 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 and the cladding. It propagates to the other optical functional element terminal while repeating total reflection at the interface with the parts 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.

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

  An example of the manufacturing process of the optical waveguide device using the material of the present invention is shown in FIG. The optical waveguide device is manufactured by using a photolithography technique. First, as shown in FIG. 2A, a clad portion 4 is formed on a substrate 1 in advance, and a film 3 of the optical material of the present invention for forming a core portion is formed. In forming the optical waveguide material film 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 method using a mold There is. The uniform liquid composition is preferably prepared by filtering with a filter having a pore size of about 0.2 μm, for example.

  The preferred viscosity of each liquid composition is generally 10 to 20,000 mPa · s, particularly preferably 20 to 10,000 mPa · s, and further preferably 50 to 8,000 mPa · s. Here, the viscosity is adjusted with the polymer components (B) and (D) as described above.

  Next, as shown in FIG. 2B, the curable fluorine-containing resin composition is 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 fluorine-containing resin composition polymerizes between molecules. As a result, the resin hardness is increased, the mechanical strength is improved, and the heat resistance is improved. When a polyfunctional fluorine-containing monomer is used, it becomes insoluble in many other types of solvents as well as insoluble in the solvent dissolved before curing. That is, it functions as a photoresist material. Next, the uncured curable fluorine-containing resin composition is dissolved and distilled with a suitable solvent, thereby forming the core portion 2 having a predetermined pattern shape as shown in FIG. The optical waveguide element can be used as it is in the form having only the core part 2 formed as described above. However, after the core part 2 is formed, as shown in FIG. 5 is preferably formed. The clad 5 is preferably formed by applying the material solution by spin coating, cast coating, roll coating, or the like, and spin coating is particularly preferable. The uniform liquid composition of the clad part 5 is also preferably prepared by filtering with a filter having a pore diameter of about 0.2 μm, for example.

  A known method may be appropriately employed as the curing method. In addition, the photocuring as described above is advantageous because the process becomes simple. As a method for forming the waveguide, besides the above method, a new molding method using a curable resin composition has recently been proposed. For example, a stamper molding method for creating an optical waveguide using a fine mold, embossing, and a nanoimprint method via a silicone rubber mold. The resin composition of the present invention can be applied to any of these moldings.

  The cured product of the present invention is particularly suitable for optical applications. In addition, by utilizing the properties of organic polymers obtained by curing, applications other than optical applications such as adhesives, paints, various molding materials, and dental materials are used. It is also useful as a material for manufacturing such as.

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

In addition, various physical properties and characteristics in this specification are measured by the following methods.
(1) Polymer composition ( ¹ H-NMR, ¹⁹ F-NMR, IR)
NMR measuring device: manufactured by BRUKER
¹ H-NMR measurement conditions: 300 MHz (tetramethylsilane = 0 ppm)
¹⁹ F-NMR measurement conditions: 282 MHz (trichlorofluoromethane = 0 ppm)
^{From the 1} H-NMR data, the CH ₂ ═CF—C (═O)-(αF acryloyl) conversion rate (5.2 to 5.8 ppm (2H)) was determined from the ¹⁹ F-NMR data to be the αF acryloyl group. The ratio of (−116 to −118 ppm (1F)) and chain (−83 ppm (10F) and −129 ppm (1F)) can be calculated by a conventional method.
IR measurement device: Fourier transform infrared spectrophotometer 1760X manufactured by PERKIN ELMER
Measurement conditions: measured at room temperature

(2) Fluorine content (F)
Burn 10 mg of sample by the oxygen flask combustion method, absorb the decomposition gas in 20 ml of deionized water, and measure the fluorine ion concentration in the absorption liquid by the fluorine selective electrode method (fluorine ion meter, model 901 manufactured by Orion). The value obtained by the above is adopted (mass%).

(3) Glass transition temperature (Tg)
Using a DSC (Differential Scanning Calorimeter), the first run was increased to 200 ° C. at a temperature increase rate of 10 ° C./min, maintained at 200 ° C. for 1 minute, cooled to 25 ° C. at a temperature decrease rate of 10 ° C./min, and then increased. The midpoint of the 2nd run endothermic curve obtained at a temperature rate of 10 ° C./min is employed.

(4) Thermal decomposition temperature (Td)
A thermobalance (TGA) is used and heated from room temperature at a heating rate of 10 ° C./min at room temperature, and the temperature when the weight is reduced by 0.1 mass% is adopted.

(5) Amorphous Amorphous is DSC analysis used to measure Tg, and when a temperature rise rate of 10 ° C./min is measured in 2nd run, is an endothermic peak based on melting virtually not observed? Or the heat of fusion is 1 J / g or less.

(6) Number average molecular weight By gel permeation chromatography (GPC), Tosoh Co., Ltd. GPC HLC-8020 was used, Shodex column (one GPC KF-801, one GPC KF-802, It is calculated from data measured by using tetrahydrofuran (THF) as a solvent at a flow rate of 1 ml / min using two GPC KF-806Ms connected in series.

  The molecular weight of the cured product of the curable fluorine-containing resin composition of the present invention is the case where the polyfunctional fluorine-containing monomer (C) of the formula (2) is contained or an amorphous fluorine-containing polymer having a curable site. When it has (D), it cannot be specified because it has a crosslinked structure.

(7) Viscosity The viscosity value of the composition at 25 ° C. is employed with a B-type viscometer manufactured by Tokyo Keiki Co., Ltd.

(8) Refractive index (n)
A value measured with an Abbe refractometer at 25 ° C. using sodium D-line as a light source is adopted.

(9) Light transmittance (visible light region)
A value obtained by measuring a spectral transmittance curve of a sample (cured film) having a thickness of about 100 μm at a wavelength of 300 to 800 nm using a self-recording spectrophotometer (U-3310 (trade name) manufactured by Hitachi, Ltd.) is adopted.

(10) 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.

(11) Curing shrinkage (S)
The curable fluorine-containing resin composition is poured into a mold having a length of 50.0 mm and a width of 10.0 mm to prepare a sample of 1.0 mm (thickness) × 50 mm × 10 mm. A high pressure mercury lamp is used for this sample, UV curing is performed at room temperature with an intensity of 1500 mJ / cm ² , photocuring is performed, the dimension after curing is measured, the volume is calculated, and the curing shrinkage is obtained.
Curing shrinkage (S) (%) = {(volume before curing−volume after curing) / volume before curing} × 100

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

Synthetic Reference Example (Synthesis of fluorinated allyl ether copolymer having OH group)
In a 100 ml glass four-necked flask equipped with a stirrer and a thermometer, perfluoro- (1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxanonenol) was added.

To 15.3 g

4.8 g of (fluorinated allyl ether AEHF) is added,
further

After adding 21.2 g of the 8.0 mass% perfluorohexane solution and thoroughly purging with nitrogen, the mixture was stirred at 20 ° C. for 24 hours under a nitrogen stream to produce a highly viscous solid.

  A solution obtained by dissolving the obtained solid in diethyl ether was poured into perfluorohexane, separated and vacuum dried to obtain 13.1 g of a colorless and transparent polymer.

When this polymer was analyzed by ¹⁹ F-NMR, ¹ H-NMR analysis, and IR analysis, it was a fluorine-containing polymer comprising the above two types of fluorine-containing allyl ether structural units and having a hydroxyl group at the end of the side chain. . Moreover, the weight average molecular weight (Mw) measured by GPC analysis which uses tetrahydrofuran (THF) for a solvent was 21000, and ratio (Mw / Mn) with the number average molecular weight (Mn) was 1.3.

Synthesis Example 1 (Synthesis of fluoropolymer (I) having α-fluoroacryloyl group)
In a 200 ml four-necked flask equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel, 30 ml of methyl ethyl ketone (MEK), 7.0 g of a hydroxyl group-containing fluorine-containing allyl ether copolymer obtained in Synthesis Reference Example, 2.6 g of pyridine was charged and cooled to 5 ° C. or lower with ice.

While stirring in a nitrogen stream, 2.6 g of α-fluoroacrylic acid fluoride (CH ₂ ═CFCOF) dissolved in 10 ml of MEK was added dropwise over about 30 minutes.

  After completion of the dropwise addition, the temperature was raised to room temperature and stirring was continued for 4.0 hours.

  After the reaction, the ether solution is put into a separatory funnel, washed with water, washed with 2% hydrochloric acid, washed with 5% NaCl, and further washed with water, dried over anhydrous magnesium sulfate, and then the ether solution is separated by filtration and cured. Fluorine-containing prepolymer was obtained.

When this curable fluorine-containing prepolymer was examined by ¹⁹ F-NMR analysis,

It was a copolymer.

Was applied to NaCl plate, it was IR analysis what was cast film at room temperature, carbon - absorption of a carbon-carbon double bonds in 1661Cm ^-1, absorption of C = O group was observed at 1770 cm ^-1. It was an amorphous polymer having a fluorine content of 57%. The resulting polymer is referred to as Polymer 1.

Synthesis example 2 (bulk polymerization)
2-perfluoropropoxy-2,3,3,3-tetrafluoropropyl α-fluoroacrylate (6FOn1-F) in a three-necked flask:

20 g of AIBN and 20 mg of AIBN as an initiator were substituted with nitrogen. The reaction temperature was 60 ° C., and bulk polymerization was performed with stirring for 10 hours. The obtained transparent liquid was dissolved in 50 ml of acetone, dropped into hexane, and reprecipitated. The resulting precipitate was transferred onto a petri dish and vacuum dried at 60 ° C. for 10 hours. The obtained polymer was 18 g, and the glass transition temperature Tg was 80 ° C. The number average molecular weight measured by GPC analysis using tetrahydrofuran (THF) as a solvent was 120,000, and the weight average molecular weight was 270,000. This polymer is referred to as P6FOn1-F.

  Similarly, hexafluoroneopentyl α-fluoroacrylate (6FNPF):

And hexafluoroisopropyl α-fluoroacrylate (HFIP-F):

Were respectively polymerized to obtain a total of three fluorine-containing acrylic polymers in the present invention. Table 1 shows the glass transition temperature Tg, fluorine content, and molecular weight of each polymer. Both polymers were amorphous. The homopolymers of 6FNPF and HFIP-F are referred to as P6FNPF and PHFIP-F, respectively.

Comparative Synthesis Example 1
A comparative polymer was obtained in the same manner as in Synthesis Example 2 except that methyl methacrylate (MMA) was used as the monomer. Table 1 shows the glass transition temperature and fluorine content of this polymer. This polymer is called PMMA.

Synthesis example 3 (copolymerization)
In a three-necked flask, 20 g of 6FOn1-F, benzyl α-fluoroacrylate (Bz-F):

20 g of AIBN and 20 mg of AIBN as an initiator were substituted with nitrogen. The reaction temperature was 60 ° C., and bulk polymerization was performed with stirring for 10 hours. The obtained transparent liquid was dissolved in 100 ml of acetone, dropped into hexane, and reprecipitated. The resulting precipitate was transferred onto a petri dish and vacuum dried at 60 ° C. for 10 hours. The obtained copolymer was 36 g. Table 1 shows the glass transition temperature, fluorine content, and molecular weight of this copolymer. This copolymer is referred to as Copolymer 1:

That's it.

Synthesis example 4
In a three-necked flask, 20 g of HFIP-F, 40 mg of AIBN as an initiator, 60 g of benzene as a solvent were added, and the reaction temperature was set to 60 ° C. in a nitrogen stream, and solution polymerization was performed with stirring for 10 hours. The obtained transparent liquid was dropped into hexane to reprecipitate. The resulting precipitate was transferred onto a petri dish and vacuum dried at 60 ° C. for 10 hours. The obtained polymer was 15 g. Table 1 shows the glass transition temperature, fluorine content, and number average molecular weight of this polymer. This polymer is referred to as PHFIP-F-LMW.

Example 1
50 parts by weight of 6FOn1-F as a fluorine-containing acrylic monomer, 50 parts by weight of P6FNPF as a fluorine-containing acrylic polymer, and 0. 2-hydroxy-2-methylpropiophenone as an active energy ray curing initiator. The liquid curable fluorine-containing resin composition of the present invention was prepared by adding 1% by weight.

The viscosity at 25 ° C. of the composition before curing 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.

Next, it was applied on an aluminum foil using an applicator so that the film thickness was about 100 μm, and a high-pressure mercury lamp was used to irradiate the coating with ultraviolet light at an intensity of 1500 mJ / cm ² U. A film was obtained.

Sample film (after curing) refractive index (n), glass transition temperature (Tg), thermal decomposition temperature (Td), fluorine content (F), light transmittance visible (633 nm) (T (633)), light transmission The near-infrared (1310 nm) (T (1310)) was examined.
Moreover, the external appearance was evaluated visually.
○: Transparent and uniform.
Δ: Some cloudiness is observed.
X: Opaque and cloudy.

  Furthermore, measurement (S) of curing shrinkage was performed. The results are shown in Table 2.

Example 2
Active energy ray-curable fluorine-containing resin as in Example 1 except that 50 parts by weight of 6FNPF was used as the fluorine-containing acrylic monomer and 50 parts by weight of copolymer 1 synthesized in Synthesis Example 3 was used as the fluorine-containing acrylic polymer. A composition was obtained, and various physical properties were measured in the same manner as in Example 1. The results are shown in Table 2.

Example 3
40 parts by weight of 6FOn1-F as a fluorine-containing acrylic monomer, 50 parts by weight of polymer 1 as an amorphous fluorine-containing polymer, 1,4-bis (hexafluoroisopropyl α- Fluoroacryl) benzene (FB-DFA):

The active energy ray-curable fluorine-containing resin composition was obtained in the same manner as in Example 1 except that 10 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.

Example 4
Except for using 40 parts by weight of 6FOn1-F as a fluorine-containing acrylic monomer, 50 parts by weight of PHFIP-F as an amorphous fluorine-containing polymer, and 10 parts by weight of FB-DFA as a polyfunctional fluorine-containing monomer Obtained an active energy ray-curable fluorine-containing resin composition in the same manner as in Example 1, and various physical properties were measured in the same manner as in Example 1. The results are shown in Table 2.

Example 5
40 parts by weight of 6FOn1-F as a fluorine-containing acrylic monomer, 50 parts by weight of P6FNPF as an amorphous fluorine-containing polymer, and bisphenol AF-ethylene glycol methacrylate (BisAFEOOMA) as a polyfunctional fluorine-containing monomer:

The active energy ray-curable fluorine-containing resin composition was obtained in the same manner as in Example 1 except that 10 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.

Comparative Example 1
1H, 1H, 5H-octafluoropentyl α-fluoroacrylate (8FF) as a fluorinated monomer as a curable fluorinated resin composition:

Was obtained in the same manner as in Example 1 except that 50 parts by weight of polymethyl methacrylate (PMMA) was used as an acrylic polymer, and various physical properties were the same as in Example 1. And measured. The results are shown in Table 2.

Comparative Example 2
2- (Perfluorooctyl) ethyl methacrylate (17FMA) as fluorine-containing acrylic monomer:

Was obtained in the same manner as in Example 1 except that 50 parts by weight of P6FOn1-F was used as the fluorine-containing acrylic polymer, and various physical properties were measured in the same manner as in Example 1. did. The results are shown in Table 2.

Comparative Example 3
1H, 1H, 5H-octafluoropentyl methacrylate (8FM) as a fluorine-containing acrylic monomer:

In the same manner as in Example 1 except that 40 parts by weight of PMMA was used as an amorphous polymer, 50 parts by weight of PMMA as a non-crystalline polymer, and 10 parts by weight of trimethylolpropane trimethacrylate as a polyfunctional monomer. A resin composition was obtained, and various physical properties were measured in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 4
40 parts by weight of 17FMA as a fluorine-containing acrylic monomer, 50 parts by weight of P6FOn1-F as an amorphous fluorine-containing polymer, and triethylene glycol dimethacrylate (3G) as a polyfunctional monomer:

The active energy ray-curable resin composition was obtained in the same manner as in Example 1 except that 10 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.

Example 6
45 parts by weight of 6FOn1-F as a fluorine-containing acrylic monomer, and 50 parts by weight of vinylidene fluoride / hexafluoropropylene copolymer (Daiel Industries, Ltd., Daiel G-801) as an amorphous fluorine-containing polymer. The active energy ray-curable resin composition was obtained in the same manner as in Example 1 except that 5 parts by weight of BisAFEOOMA used in Example 5 was used as the polyfunctional fluorine-containing monomer. The measurement was performed in the same manner. The results are shown in Table 2.

  Moreover, when Izod impact strength with a notch was measured according to ASTM D256 using a U-F impact tester manufactured by Ueshima Seisakusho Co., Ltd., it showed no impact fracture and had high impact resistance.

Example 7
From the results of the above examples, the curable fluorine-containing resin composition of Example 3 (refractive index after curing: 1.367) is used as the cladding, and the curable fluorine-containing resin composition of Example 4 (refraction after curing). It was found that a core / cladding type optical waveguide can be formed by using a ratio of 1.377) for the core.

Therefore, the curable fluorine-containing resin composition obtained in Example 3 was filtered through a 0.5 μm filter, and spin-coated on a silicon wafer at 200 rpm for 10 seconds and then at 500 rpm for 30 seconds. A high pressure mercury lamp was used to irradiate ultraviolet rays with an intensity of 1500 mJ / cm ² U to obtain a clad layer having a thickness of about 15 μm on the silicon substrate. Next, the curable fluorinated resin composition of Example 4 was filtered through a 0.5 μm filter, and then spin-coated on the previous cladding layer at 500 rpm for 10 seconds and then at 1000 rpm for 30 seconds.

  Next, light irradiation was performed 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 μm, and a height of 8 μm as the core portion. After processing, the clad part was applied onto the core part in the process described with reference to FIG. 2 to produce an optical waveguide.

  Next, when the transmission loss of the obtained optical waveguide was measured by a cutback method, it was 0.80 dB / cm or less at a wavelength of 633 nm, 0.75 dB / cm at a wavelength of 850 nm, and 0.9 dB / cm at a wavelength of 1310 nm. It was able to transmit light in the communication wavelength band from visible light to near infrared light well.

  In addition, Table 3 shows changes in transmission loss (dB / cm) after an endurance test of holding in a constant temperature bath at 85 ° C. and 85% humidity for 168 hours.

Comparative Example 5
An optical waveguide was obtained in the same manner as in Example 7 except that the curable fluorine-containing resin composition of Comparative Example 4 (refractive index after curing: 1.382) was used as the core material. Table 3 shows changes in the transmission loss (dB / cm) of the obtained optical waveguide and the transmission loss (dB / cm) after the durability test.

Example 8
Except for using 80 parts by weight of 6FOn1-F as a fluorine-containing acrylic monomer, 8 parts by weight of P6FOn1-F as an amorphous fluorine-containing polymer, and 12 parts by weight of FB-DFA as a polyfunctional fluorine-containing monomer Obtained an active energy ray-curable fluorine-containing resin composition in the same manner as in Example 1, and various physical properties were measured in the same manner as in Example 1. The results are shown in Table 4.

Example 9
Except for using 80 parts by weight of 6FOn1-F as a fluorine-containing acrylic monomer, 8 parts by weight of PHFIP-F as an amorphous fluorine-containing polymer, and 12 parts by weight of FB-DFA as a polyfunctional fluorine-containing monomer Obtained an active energy ray-curable fluorine-containing resin composition in the same manner as in Example 1, and various physical properties were measured in the same manner as in Example 1. The results are shown in Table 4.

Example 10
As a fluorine-containing acrylic monomer, 75 parts by weight of 6FOn1-F and perfluorophenyl α-fluoroacrylate (PFP-F):

In the same manner as in Example 1 except that 5 parts by weight of PHFIP-F-LMW was used as an amorphous fluorine-containing polymer and 8 parts by weight of FB-DFA was used as a polyfunctional fluorine-containing monomer. An energy ray-curable fluorine-containing resin composition was obtained, and various physical properties were measured in the same manner as in Example 1. The results are shown in Table 4.

It is a schematic sectional drawing of the structure of an optical waveguide type element. It is a block diagram of the manufacturing process of an optical waveguide type device.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Substrate 2 Core part 3 Film 4 Clad part 5 Clad part 6 Mask 7 Active energy ray

Claims (18)

A curable fluorinated resin composition comprising the following uniform liquid composition (A) and (B), comprising 5 to 99% by mass of (A) and 1 to 95% by mass of (B).
(A) Formula (1):

Wherein X ¹ is at least one selected from the group consisting of H, CH ₃ , F, Cl and CF ₃ ; R is R ¹ and / or R ² ;
R ¹ represents the formula (1-1):

(Wherein Z is F or CF ₃ ; m1, m2, m3, m4 are 0 or an integer of 1 to 10, where m1 + m2 + m3 + m4 is an integer of 1 to 10),
R ² represents the formula (1-2):

(In the formula, Rf ¹ and Rf ² are the same or different and each is a perfluoroalkyl group having 1 to 5 carbon atoms; R ³ is a carbon number 1 to which some or all of the hydrogen atoms may be substituted with fluorine atoms. Fluorine-containing alkyl group containing a moiety represented by 5 hydrocarbon group)
One or more fluorine-containing monomers represented by:
(B) A fluorinated acrylic polymer having a fluorine content of 25% by mass or more, essentially a polymer obtained by polymerizing only an acrylic monomer. The curable fluorine-containing resin composition according to claim 1, wherein the fluorine-containing monomer (A) is a fluorine-containing monomer (A-1) in which R is R ¹ in the formula (1). In the fluorine-containing monomer of the formula (1), R ¹ is a formula (1-3):

The curable fluorine-containing resin composition according to claim 1 or 2, wherein m5 is an integer of 1 to 5. The curable fluorine-containing resin composition according to any one of claims 1 to 3, wherein the fluorine-containing acrylic polymer (B) has a fluorine content of 50% by mass or more. The curable fluorinated resin composition according to any one of claims 1 to 4, wherein the fluorinated acrylic polymer (B) has a glass transition point of 85 ° C or higher. A uniform liquid composition comprising the following (A-1), (C) and (D), wherein (A-1) is 5 to 98% by mass, (C) is 1 to 94% by mass and (D ) Curable fluorine-containing resin composition containing 1 to 94% by mass.
(A-1) Formula (1a):

(In the formula, X ¹ is at least one selected from the group consisting of H, CH ₃ , F, Cl and CF ₃ ; R ¹ is a formula (1-1):

(Wherein Z is F or CF ₃ ; m1, m2, m3 and m4 are 0 or an integer of 1 to 10, where m1 + m2 + m3 + m4 is an integer of 1 to 10). A fluorine-containing monomer represented,
(C) Formula (2):

(Wherein X ² and X ³ are the same or different and are at least one selected from the group consisting of H, CH ₃ , F, Cl and CF ₃ ; n is an integer of 1 to 6; R ⁴ is carbon number 1 An aromatic hydrocarbon structure which is a (n + 1) valent organic group in which part or all of ˜50 hydrogen atoms may be substituted with fluorine atoms and may have a hetero atom in the R ⁴ Or an organic group containing at least one kind of part selected from the part of the aliphatic cyclic hydrocarbon structure which may have a hetero atom, or a polyfunctional fluorine-containing monomer represented by
(D) An amorphous fluorine-containing polymer having a fluorine content of 25% by mass or more. The curable fluorinated resin composition according to claim 6, wherein in the formula (2), n is an integer of 1 to 3 and R ⁴ is an (n + 1) -valent organic group having 3 to 50 carbon atoms. In the fluorine-containing monomer of the formula (1a), R ¹ is a formula (1-3):

The curable fluorinated resin composition according to claim 7, wherein m5 is an integer of 1 to 5. The curable fluorine-containing resin composition according to any one of claims 6 to 8, wherein the fluorine content of the amorphous fluorine-containing polymer (D) is 50% by mass or more. The curing according to any one of claims 6 to 9, wherein the amorphous fluorine-containing polymer (D) is a fluorine-containing acrylic polymer (D-1) obtained by essentially polymerizing only an acrylic monomer. Fluorinated resin composition. The curable fluorine-containing resin composition according to claim 10, wherein the amorphous fluorine-containing polymer (D-1) is a fluorine-containing acrylic polymer having a glass transition point of 85 ° C or higher. In the polyfunctional fluorine-containing monomer represented by the formula (2), a part or all of hydrogen atoms may be substituted with fluorine atoms in the aromatic hydrocarbon structure site in R ⁴ ( The curable fluorinated resin composition according to any one of claims 6 to 11, which has an (n + 1) -valent benzene ring structure. In the polyfunctional fluorine-containing monomer represented by the formula (2), a part or all of the hydrogen atoms may be substituted with fluorine atoms at the portion of the aliphatic cyclic hydrocarbon structure in R ^4. The curable fluorinated resin composition according to any one of claims 6 to 11, which has a (n + 1) -valent cyclohexane ring structure. In the polyfunctional fluorine-containing monomer represented by the formula (2), a part or all of the hydrogen atoms may be substituted with fluorine atoms at the portion of the aliphatic cyclic hydrocarbon structure in R ^4. The curable fluorinated resin composition according to any one of claims 6 to 11, which has a (n + 1) -valent norbornane ring structure and / or an adamantane ring structure. A cured product obtained by curing the curable fluorinated resin composition according to claim 1, wherein the cured product has a glass transition temperature of 85 ° C. or higher after curing. The hardened | cured material of Claim 15 whose glass transition temperature after hardening is 100 degreeC or more. An optical material comprising the cured product according to claim 15 or 16. 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 claim 15 or 16.

Images