JP2013087162A - Fluorine-containing polymer, curable resin composition, and cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluorine-containing polymer having low refractive index, high transparency, excellent heat resistance, capable of forming a cured product having high heat resistance, transparency in a visible light region and excellent low dielectric constant and flexibility, and having physical and chemical stability, and to provide a curable resin composition and the cured material.SOLUTION: The fluorine-containing polymer has a structural unit expressed by formula (L) ( in the formula, Xand Xare the same or different from each other and represent H or F, Xrepresents H, F, CHor CF, Xand Xare the same or different from each other respectively and represent H, F or CF, Rf represents a 4-40C fluorine-containing hydrocarbon group or a 5-100C fluorine-containing hydrocarbon group having an ether bond, (a) represents integer of 0-3, and (b) and (c) are the same or different from each other and represent 0 or1).

Description

The present invention relates to a fluorine-containing polymer, a curable resin composition, and a cured product obtained by curing the curable resin composition.

In recent years, various devices such as a CCD element, a CMOS element, a light emitting diode (LED), a liquid crystal, and a MEMS have been widely used. However, such a device is structurally susceptible to an external environment and is airtight to avoid this. Used as a package.

For example, in an image sensor such as a CCD employed in a camera module of a mobile phone, it has been studied to seal the surface of the sensor element with a transparent lid such as glass directly through a sealing member. This method has an advantage that the number of steps can be greatly reduced because a device can be manufactured by dicing after laminating with glass via a sealing member at the wafer level.

As a material for such a sealing member, a fluorine-containing compound is often used because of its excellent light transmission and durability against light. When manufacturing a CCD element having the above-described structure, a sealing member that has a low refractive index and high transparency is required, but a fluorine-containing compound that has been conventionally studied for optical members. Then, the sealing member of sufficient characteristics was not obtained.

For example, in Patent Document 1, as a material that is useful as a laminate having practical low reflectivity that maintains anti-glare properties, does not have "white blur" due to surface scattering, and has excellent adhesion, A specific structural unit having a functional group containing at least one hydrolyzable metal alkoxide moiety having 1 to 50 carbon atoms at the terminal, and a monovalent having 2 to 10 carbon atoms having an ethylenic carbon-carbon double bond at the terminal A curable fluorine-containing polymer having a specific structural unit having 1 to 3 organic groups bonded thereto is described. Patent Document 2 discloses a structure having a fluorine-containing alkyl group having an ethylenic carbon-carbon double bond at the terminal as a curable composition for forming an antireflection film having a low refractive index and excellent antifouling property. A curable composition containing a curable fluorine-containing polymer (A) containing units, a fluorine-containing surface modifier (B), and hollow silica fine particles (C) is disclosed.

Further, for example, in Patent Document 3, as a curable fluorine-containing polymer for forming an antireflection film, a monovalent organic group having 2 to 10 carbon atoms having an ethylenic carbon-carbon double bond at the terminal is 1 to 1. A composition relating to a curable fluorinated polymer having a specific structure in which three are bonded is proposed. Patent Document 4 cures a fluorinated polymer having an ethylenic carbon-carbon double bond by a hydrosilylation reaction. It has also been proposed to do so.

Patent Document 5 discloses a polyfunctional fluorine-containing compound having two or more groups containing a sulfur atom and a hydrolyzable metal alkoxide. In the examples, a cured film obtained from a composition containing such a compound is disclosed. However, it describes that it is excellent in appearance, coatability, chemical resistance and the like.

In addition, thin film transistors (TFTs) currently used in large liquid crystal display devices and the like are mainly in the inverted coplanar type, but in such TFTs, the gap between the gate and the channel is the mainstream. The insulator layer is formed by depositing TEOS or silicon nitride (SiN) by CVD (Chemical Vapor Deposition) or sputtering.

However, due to the demand for larger screens and lower prices due to the larger screen of display devices and intensifying price competition, attempts have been made to manufacture insulator layers of thin film transistors by a coating type film forming method. .

Examples of the coating type insulating film forming composition include those using polysiloxane. For example, Patent Document 6 contains, as a polysiloxane composition for forming a highly flexible insulating film, a polysiloxane having a specific repeating unit and a compound that generates at least one of an acid and a radical by heating. A polysiloxane composition is described.

International Publication 2006/027958 Pamphlet JP 2008-40262 A International Publication No. 02/18457 Pamphlet International Publication No. 2008/153002 Pamphlet JP 2009-242350 A JP-A-9-188814

However, in sealing member applications, the curable resin composition described in Patent Document 1 has a high refractive index, and a low refractive index is required for use as a sealing member for CCD elements. In addition, the curable resin composition described in Patent Document 2 has no problem with transparency if it is a thin film of about 100 nm, but hollow silica when the thickness is about 1 to several tens μm, which is a necessary thickness as a sealing member. The haze was increased by the aggregation of the fine particles, which was not sufficient from the viewpoint of transparency. Furthermore, cured products obtained from the fluoropolymers described in Patent Document 3 and Patent Document 4 have optical properties such as light transmittance and refractive index, heat resistance at high temperatures, light resistance, and curing shrinkage. There was room for further improvement. As described above, the conventional technique can form a member having a low refractive index, high transparency, and excellent physical properties such as heat resistance, and also has physical and chemical stability. There was room for further study of excellent fluorine-containing compounds.

In application type insulating film applications, as disclosed in Patent Document 6, an insulating film formed from polysiloxane is still poor in flexibility and may be cracked due to bending, and is more flexible. There has been a demand for a material capable of forming an insulating film. Further, in order to form a gate insulating film of a thin film transistor, higher heat resistance, transparency in the visible light region, and a low dielectric constant have been demanded.

The present invention has been made in view of the above situation, and has a low refractive index, high transparency, and excellent heat resistance, and can form a cured product suitable for a sealing member for optical elements. Furthermore, it aims at providing the fluorine-containing polymer which is excellent also in physical and chemical stability, curable resin composition, and hardened | cured material. The present invention also has high heat resistance, transparency in the visible light range, low dielectric constant and flexibility, and can form a cured product suitable for an insulating film of a thin film transistor, etc. Another object is to provide a resin composition and a cured product.

The present inventors have intensively studied about a fluorine-containing polymer that can be suitably used as a sealing agent for optical elements and an insulating film of a thin film transistor. Has been found to be sufficiently low and excellent in physical and chemical stability. And the curable resin composition obtained using such a polymer has a low refractive index, high transparency, and further a cured product excellent in heat resistance, or high heat resistance, in the visible light region. It was found that a cured product excellent in transparency, low dielectric constant and flexibility was obtained. Furthermore, it has been found that these cured products can be suitably applied to sealants for optical elements and coating-type insulating films in thin film transistors, etc. is there.

（式中、Ｘ^１及びＸ^２は、同一又は異なり、Ｈ又はＦである。Ｘ^３は、Ｈ、Ｆ、ＣＨ_３又はＣＦ_３である。Ｘ^４及びＸ^５は、夫々同一又は異なり、Ｈ、Ｆ又はＣＦ_３である。Ｒｆは、炭素数４〜４０の含フッ素炭化水素基、又は、炭素数５〜１００のエーテル結合を有する含フッ素炭化水素基である。ａは０〜３の整数である。ｂ及びｃは同一又は異なり、０又は１である。）で表される構造単位を有する含フッ素ポリマーであって、上記式（Ｌ）中のＲｆは、下記式（Ｒｆ）：
−（Ｒ−Ｏ）_ｎ−Ｒ’_ｎ’−ＣＨ_２−ｘ｛（ＣＸ^ａＸ^ｂ）_ｍＣＲ^１ＨＣＲ^２Ｒ^３Ｙ｝_ｘＯＨ_１−ｙ｛（ＣＸ^ａＸ^ｂ）_ｍＣＲ^１ＨＣＲ^２Ｒ^３Ｙ｝_ｙ （Ｒｆ）
（式中、Ｒは、同一又は異なり、水素原子の少なくとも１個がフッ素原子で置換されている炭素数１〜５の含フッ素アルキレン基である。Ｒ’は、同一又は異なり、水素原子の一部又は全部がフッ素原子で置換されていてもよい炭素数１〜５の含フッ素アルキレン基である。Ｘ^ａ及びＸ^ｂは、夫々同一又は異なり、Ｈ、ハロゲン原子、又は、置換基を有してもよい炭素数１〜１０の炭化水素基である。Ｒ^１、Ｒ^２及びＲ^３は、夫々同一又は異なり、Ｈ、ハロゲン原子、又は、置換基を有してもよい炭素数１〜１０の炭化水素基である。Ｙは、同一又は異なり、炭素数１〜５０の加水分解性金属アルコキシド部位である。ｎは、０〜２０の整数であり、ｎ’は、０〜１０の整数である。ｍは、１〜１２の整数である。ｘは、０〜２の整数であり、ｙは、０又は１である。ただし、ｘが０のとき、ｙは１である。）で表される含フッ素炭化水素基であることを特徴とする含フッ素ポリマーである。 That is, the present invention
The following formula (L):

Wherein X ¹ and X ² are the same or different and are H or F. X ³ is H, F, CH ₃ or CF _3. X ⁴ and X ⁵ are the same or different, respectively F or CF _3. Rf is a fluorine-containing hydrocarbon group having 4 to 40 carbon atoms or a fluorine-containing hydrocarbon group having an ether bond having 5 to 100 carbon atoms, a is an integer of 0 to 3; B and c are the same or different and are 0 or 1.), wherein Rf in the above formula (L) is represented by the following formula (Rf):
_{- (R-O) n -R} 'n' -CH 2-x {(CX a X b) m CR 1 HCR 2 R 3 Y} x OH 1-y {(CX a X b) m CR 1 HCR 2 R ³ Y} _y (Rf)
(In the formula, R is the same or different and is a fluorine-containing alkylene group having 1 to 5 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom. R ′ is the same or different and represents one hydrogen atom. Part or all is a fluorine-containing alkylene group having 1 to 5 carbon atoms which may be substituted with a fluorine atom, X ^a and X ^b are the same or different and have H, a halogen atom or a substituent. R ¹ , R ² and R ³ may be the same or different and each may have H, a halogen atom, or a substituent, which may have a substituent. Y is the same or different and is a hydrolyzable metal alkoxide moiety having 1 to 50 carbon atoms, n is an integer of 0 to 20, and n ′ is an integer of 0 to 10. M is an integer of 1 to 12. x is an integer of 0 to 2. , Y is 0 or 1. However, when x is 0, y is a fluorine-containing polymer which is a fluorinated hydrocarbon group represented by a 1.).

The fluoropolymer of the present invention preferably further has other structural units other than the structural unit represented by the above formula (L).

The present invention is also a curable resin composition comprising (A) the above-mentioned fluoropolymer and (B) an organosilicon compound.

In the curable resin composition of the present invention, the organosilicon compound (B) is preferably 50% by mass or more based on the total mass of the fluoropolymer (A) and the organosilicon compound (B).

The curable resin composition of the present invention preferably contains an organic solvent.

The curable resin composition of the present invention is preferably for optical element sealing.

The curable resin composition of the present invention is preferably for LED sealing.

The curable resin composition of the present invention is also preferably used for a gate insulating film of a thin film transistor.

The present invention is also a cured product obtained by curing the curable resin composition.

The cured product preferably has a refractive index of 1.40 or less.

The cured product is preferably a sealing member for an optical element.

The optical element is preferably a light receiving element.

The optical element is preferably a light emitting element.

The optical element is preferably an LED.

The cured product is preferably a gate insulating film of a thin film transistor.

The fluoropolymer of the present invention provides a curable resin composition having a low refractive index, high transparency, excellent heat resistance, and capable of forming a cured product suitable for a sealing member for optical elements. be able to. The fluorine-containing polymer of the present invention also has high heat resistance, transparency in the visible light region, low dielectric constant and flexibility, and can be used to form a cured product suitable for an insulating film of a thin film transistor. A resin composition can be provided.

FIG. 1 is a schematic cross-sectional view showing an example of the structure of a CCD module. 2A to 2F are flowcharts schematically showing the manufacturing flow of the CCD module. FIG. 3 is a schematic cross-sectional view illustrating an example of an inverted coplanar thin film transistor.

（式中、Ｘ^１及びＸ^２は、同一又は異なり、Ｈ又はＦである。Ｘ^３は、Ｈ、Ｆ、ＣＨ_３又はＣＦ_３である。Ｘ^４及びＸ^５は、夫々同一又は異なり、Ｈ、Ｆ又はＣＦ_３である。Ｒｆは、炭素数４〜４０の含フッ素炭化水素基、又は、炭素数５〜１００のエーテル結合を有する含フッ素炭化水素基である。ａは０〜３の整数である。ｂ及びｃは同一又は異なり、０又は１である。）で表される構造単位を有する。 The fluoropolymer of the present invention (hereinafter also referred to as fluoropolymer (A)) is represented by the following formula (L):

Wherein X ¹ and X ² are the same or different and are H or F. X ³ is H, F, CH ₃ or CF _3. X ⁴ and X ⁵ are the same or different, respectively F or CF _3. Rf is a fluorine-containing hydrocarbon group having 4 to 40 carbon atoms or a fluorine-containing hydrocarbon group having an ether bond having 5 to 100 carbon atoms, a is an integer of 0 to 3; And b and c are the same or different and are 0 or 1.

Rf in the above formula (L) is the following formula (Rf):
_{- (R-O) n -R} 'n' -CH 2-x {(CX a X b) m CR 1 HCR 2 R 3 Y} x OH 1-y {(CX a X b) m CR 1 HCR 2 R ³ Y} _y (Rf)
(In the formula, R is the same or different and is a fluorine-containing alkylene group having 1 to 5 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom. R ′ is the same or different and represents one hydrogen atom. Part or all is a fluorine-containing alkylene group having 1 to 5 carbon atoms which may be substituted with a fluorine atom, X ^a and X ^b are the same or different and have H, a halogen atom or a substituent. R ¹ , R ² and R ³ may be the same or different and each may have H, a halogen atom, or a substituent, which may have a substituent. Y is the same or different and is a hydrolyzable metal alkoxide moiety having 1 to 50 carbon atoms, n is an integer of 0 to 20, and n ′ is an integer of 0 to 10. M is an integer of 1 to 12. x is an integer of 0 to 2. , Y is 0 or 1. However, when x is 0, y is a fluorine-containing hydrocarbon group represented by a 1.).

In this specification, the structural unit represented by the above formula (L) and Rf represented by the above formula (Rf) is also referred to as “structural unit L”.
The ether bond is a divalent group represented by —O—.
In the present specification, the “hydrocarbon group” described later is an organic group composed of carbon and hydrogen, and the “fluorinated hydrocarbon group” means that some or all of the hydrogen atoms of the hydrocarbon group are fluorine. It is substituted with an atom. Examples of the “hydrocarbon group” include an alkyl group, an allyl group, a cyclic alkyl group, and an unsaturated alkyl group. Examples of the “fluorinated hydrocarbon group” include a fluorine-containing alkyl group, a fluorine-containing allyl group, a fluorine-containing cyclic alkyl group, and a fluorine-containing unsaturated alkyl group.

As the structural unit L, among them, the formula (L1):

A structural unit L1 represented by the formula (wherein X ¹ , X ² , X ³ , X ⁴ , X ⁵ , Rf, a and c are the same as described above) is preferable.

The fluorine-containing polymer (A) containing the structural unit L1 has a particularly low refractive index, and can increase the transparency of a thin film obtained from the curable resin composition containing the fluorine-containing polymer (A). It is preferable in that it has good adhesion to various substrates and can improve adhesion durability. Moreover, it is also preferable in that the curing reactivity due to contact with heat, radicals and cations can be increased.

Furthermore, one of the more preferable specific examples of the structural unit L1 is the formula (L2):

(Wherein Rf is the same as described above), which is a structural unit L2 derived from a fluorine-containing ethylenic monomer.

This structural unit L2 has a low refractive index, can increase the transparency of a thin film obtained from the curable resin composition containing the fluoropolymer (A), has good adhesion to various substrates, and is durable. In addition to being excellent in that it can improve the properties, it is preferable because it has good copolymerizability with other fluorine-containing ethylene monomers. Moreover, it is preferable not only because the near-infrared transparency can be increased but also the refractive index can be lowered.

In the structural unit L2, Rf is, for example, — (CF (CF ₃ ) CF ₂ —O) _n —Ry (Ry is the same as described later. N is 0, 1 or 2). It is also a preferred form.

Another preferred specific example of the structural unit L1 is the formula (L3):

(Wherein Rf is the same as described above), which is a structural unit L3 derived from a fluorine-containing ethylenic monomer.

This structural unit L3 has a low refractive index, is excellent in that it has good adhesion to various base materials and can improve adhesion durability, and other structural units L3. It is also preferable in terms of good copolymerizability. Moreover, it is preferable not only because the near-infrared transparency can be increased but also the refractive index can be lowered.

Rf contained in the structural units L, L1, L2, and L3 is a fluorine-containing hydrocarbon group represented by the formula (Rf) as described above.
In Rf, the hydrolyzable metal alkoxide moiety Y having 1 to 50 carbon atoms plays a role in causing a hydrolysis / polycondensation reaction. Thus, when the curable resin composition comprising the fluoropolymer (A) of the present invention and the organosilicon compound (B) described later is cured, the fluoropolymer (A) and the compound (B) are formed. SiO _x to be crosslinked can form a cured product having excellent heat resistance, transparency, and flexibility.

R in — (R—O) _n — in the above formula (Rf) is a divalent fluorine-containing alkylene group having 1 to 5 carbon atoms and has at least one fluorine atom, thereby Compared to conventional fluorine-free alkoxyl groups and alkylene ether units, the viscosity of the compound can be further reduced, heat resistance is improved, refractive index is lowered, and solubility in general-purpose solvents is improved. And so on.
The fluorine-containing alkylene group represented by R further has another halogen atom or any organic group as long as it has 1 to 5 carbon atoms and has at least one fluorine atom. May be.

- as, in _{particular, - - (R-O)} (CF 2 CF 2 CF 2 O) -, - (CFQ 1 CF 2 O) -, - (CFQ 1 CH 2 O) -, - (CFQ 2 O)-,-(CF ₂ CF ₂ CF ₂ CF ₂ O)-,-(CH ₂ CFQ ² O)-,-(CQ ³ ₂ O)-(Q ¹ , Q ² are the same or different; F or CF ₃ ; Q ³ is CF ₃ ) and the like, and — (R—O) _n — is preferably a structural site constituted by one or more of these.

Among _{them, - (R-O) n} - is ^{_{- (CFQ 1 CF 2 O)}} -, - (CFQ 1 CH 2 O) -, - (CF 2 CF 2 CF 2 O) -, - (CH 2 CF 2 It is preferably a structural moiety constituted by one or two or more kinds selected from CF ₂ O)-,-(CFQ ² O)-and-(CQ ³ ₂ O)-, particularly-(CFQ ¹ CF ₂ O)-,-(CFQ ¹ CH ₂ O)-,-(CF ₂ CF ₂ CF ₂ O)-and-(CH ₂ CF ₂ CF ₂ O)- A structural part constituted by repetition, and further, one or more selected from-(CFQ ¹ CF ₂ O)-,-(CFQ ¹ CH ₂ O)-and-(CF ₂ CF ₂ CF ₂ O)- It is preferable that it is a structure part comprised by repeating. In addition, when the structural unit L is the structural unit L2,-(RO) _n -may be represented by-(RO)-being-(CFQ ¹ CF ₂ O)-,-(CFQ ¹ CH ₂ O _{) -, - (CF 2 CF} 2 CF 2 O) - and _{- (CH 2 CF 2 CF 2} O) - it is preferably at least one selected from the group consisting _{^{of, - (CFQ 1 CF 2 O}} ) More preferably, it is at least one selected from the group consisting of-,-(CFQ ¹ CH ₂ O)-and-(CF ₂ CF ₂ CF ₂ O)-. In the above formula, Q ¹ is H, F or CF ₃ . Q ¹ is preferably CF ₃ .

_{N in} — (R—O) _n — represents the number of repeating structural units represented by — (R—O) — and is an integer of 0 to 20. As n, 0-10 are preferable, 1-5 are more preferable, and 1-3 are still more preferable.

In —R ′ _{n ′} — in the above formula (Rf), R ′ is a divalent fluorine-containing alkylene group having 1 to 5 carbon atoms, and has at least one fluorine atom. As long as the fluorine-containing alkylene group represented by R ′ has 1 to 5 carbon atoms and has at least one fluorine atom, the fluorine-containing alkylene group further has another halogen atom or any organic group. Also good.
Preferably, it is a C1-C5 fluorine-containing alkylene group by which all the hydrogen atoms were substituted by the fluorine atom.

Specifically, R ′ is CFQ ¹ , CFQ ¹ CF ₂ , CFQ ¹ CH ₂ , CH ₂ CFQ ¹ , CF ₂ CFQ ² , CF ₂ CF ₂ CF ₂ , CH ₂ CF ₂ CF ₂ , C (CF ₃ ) _{2 and the} like, and —R ′ _{n ′} — is preferably a structural moiety constituted by one or two or more of these. In the above formula, Q ¹ is H, F or CF ₃ . Q ¹ is preferably CF ₃ . In the above formula, Q ² is H or CF ₃ . Q ² is preferably CF ₃ .
R ′ is preferably CF (CF ₃ ), CF (CF ₃ ) CF ₂ , CF ₂ CF ₂ CF ₂ , or C (CF ₃ ) ₂ among the above.

_{N ′} in —R ′ _{n ′} — is the number of repeating structural units represented by R ′, and is an integer of 0 to 10. n ′ is preferably 0 to 5, and more preferably 1 to 3.

Preferable specific examples of the moiety represented by — (R—O) _n —R ′ _{n ′} — include the following.

X ^a and X ^b in the above formula (Rf) are each H, a halogen atom, or an optionally substituted hydrocarbon group having 1 to 10 carbon atoms. X ^a and X ^b may be the same or different from each other.
As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. Among these, a fluorine atom and a chlorine atom are preferable, and a fluorine atom is particularly preferable.

Although it does not specifically limit as a C1-C10 hydrocarbon group which may have the said substituent, An aryl group, such as an aliphatic hydrocarbon group and a phenyl group, a benzyl group, etc. are mentioned. Specifically, for _{example, -CH 3, -C 2 H 5} , -C 3 H 7 having 1 to 10 carbon atoms such as an alkyl _{group; -CX '3, -C 2 X} ' 5, -CH 2 X ' _{, -CH 2 CX '3, -CH} 2 C 2 X' 5 such as a halogen atom-containing alkyl group having 1 to 10 carbon atoms (X 'is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom); a phenyl group; _benzyl; -C ₆ F _5, such as -CH ₂ C 6 _{F 5,} phenyl or benzyl 1-5 hydrogen atoms with fluorine atoms is _{substituted; -C 6 H 5-n (} CF 3) _n , —CH ₂ C ₆ H _5-n (CF ₃ ) _n (n is an integer of 1 to 5), etc., a phenyl group or a benzyl group in which 1 to 5 hydrogen atoms are substituted with —CF ₃ Can be mentioned. Among these, —CH ₃ and —CF ₃ are preferable.

As ^Xa and ^Xb , H is particularly preferable among the above-mentioned.

M in the above formula (Rf) is the number of repeating structural units represented by-(CX ^a X ^b )-, and is an integer of 1 to 12. As m, 1-5 are more preferable, and 1-3 are still more preferable. Most preferably, m = 1.

R ¹ , R ² and R ³ in the above formula (Rf) are H, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent. R ¹ , R ² and R ³ may be the same or different from each other.
The halogen atom and a hydrocarbon group having carbon atoms of 1 to 10 optionally having the substituent group include the same as those exemplified for X ^a and X ^b.

Further, ^{R 1} and, if ^{R 2} or ^{R 3} is a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and ^{R 1,} and ^{R 2} or ^{R 3,} their A ring structure (cycloalkane structure) may be formed together with two carbon atoms to which the group is bonded. Such a ring structure includes 2 to 10 carbon atoms of R ¹ and R ² or R ³ , the above two carbon atoms (that is, the carbon atom to which R ¹ is bonded, and R ² or a carbon atom to which R ³ is bonded). More preferably, it is a ring structure composed of 2 to 4 carbon atoms of R ¹ and R ² or R ³ and the two carbon atoms.

R ¹ is preferably H, F, or —CH ₃ , and more preferably —CH ₃ among those described above.
Among R ² and R ³ , H and F are preferable and H is more preferable among those described above.

Y in the above formula (Rf) is a hydrolyzable metal alkoxide moiety having 1 to 50 carbon atoms. Specifically, Y represents the following formula (Y):
_{^{- [M 1 O (R 29}} ) d (R 30) e (R 31) f (R 32) g] p -M 2 (R 33) h (R 34) i (R 35) j (R 36) k (R ³⁷ ) _l (Y)
(Wherein M ¹ and M ² are the same or different and are 2 to 6 valent metal atoms; d, e, f and g are 0 or 1, and d + e + f + g + 2 is equal to the valence of the metal atom M ¹ H, i, j, k and l are 0 or 1, and h + i + j + k + 1 + 1 is equal to the valence of the metal atom M ² ; R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ^35; , R ³⁶ and R ³⁷ are the same or different and are represented by the formula OR ³⁸ or R ³⁸ (wherein R ³⁸ is a hydrogen atom, or a part or all of the hydrogen atoms may be substituted with a fluorine atom. 10 hydrocarbon groups), and at least one of R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ and R ³⁷ is OR ³⁸ . ; An integer represented by p = 0 to 11) It is preferably a degradable metal alkoxide sites.

Metals M ¹ and M ^{2 in} Y include Cu as Group IB; Ca, Sr, Ba as Group IIA; Zn as Group IIB; B as Group IIIA, Al, Ga; Y as Group IIIB; Si as Group IVA, Ge; Pb as the IVB group; P as the VA group; Sb; V as the VB group; Ta; W as the VIB group; La and Nd as the lanthanides.

Particularly, as Y, Si is preferable, among which Si is preferable, and in particular, -Si (OCH ₃ ) ₃ , -Si (OC ₂ H ₅ ) ₃ , -SiCH ₃ (OC ₂ H ₅ ) _{2 and the} like are subjected to hydrolysis and polycondensation. , Preferable in terms of good adhesion and adhesion durability to a substrate having a hydroxyl group, and-[SiO (OCH ₃ ) ₂ ] _{p 1} -Si (OCH ₃ ) ₃ ,-[SiO (OC ₂ H ₅ ) ₂ ] _p1- Si (OC ₂ H ₅ ) ₃ (p1 is an integer of 1 to 11) etc. are hydrolyzed / polycondensed and have good adhesion to the substrate having a hydroxyl group and its durability, as well as surface hardness. It is preferable in terms of improvement.

Among these, Y is particularly at least one selected from the group consisting of —Si (OCH ₃ ) ₃ , —Si (OC ₂ H ₅ ) ₃ , and —SiCH ₃ (OC ₂ H ₅ ) _2. preferable.

As an example of Y using a metal other than the group IVA,
Group IIA, Ca: —Ca (OR ³⁹ ), with preferred examples being —Ca (OCH ₃ );
Group IIB, Zn: —Zn (OR ³⁹ ), with preferred specific examples being —Zn (OC ₂ H ₅ );
Group IIIA, B: —B (OR ³⁹ ) ₂ , preferred specific examples are —B (OCH ₃ ) ₂ ;
Group IIIB, Y (yttrium): —Y (OR ³⁹ ) ₂ , preferred examples include —Y (OC ₄ H ₉ ) ₂ ;
Group IVB, Pb: -Pb (OR ³⁹ ) ₃ , preferred specific examples are -Pb (OC ₄ H ₉ ) ₃ ;
Group VB, Ta: —Ta (OR ³⁹ ) ₄ , with preferred examples being —Ta (OC ₃ H ₇ ) ₄ ;
Group VIB, W: —W (OR ³⁹ ) ₅ , preferred specific examples are —W (OC ₂ H ₅ ) ₅ ;
Lanthanide, La: —La (OR ³⁹ ) ₂ , and preferred examples include —La (OC ₃ H ₇ ) ₂
(Wherein R ³⁹ is a hydrocarbon group having 1 to 10 carbon atoms in which part or all of the hydrogen atoms may be substituted with fluorine atoms).

These various metals are not limited to the same metal, but may be a combination of different metals.

X in the formula (Rf) is an integer of 0 to 2, and y is 0 or 1. However, when x is 0, y is 1. The sum of x and y corresponds to the number of groups represented by — (CX ^a X ^b ) _m CR ¹ HCR ² R ³ Y in Rf. That is, Rf has x + y groups, specifically, 1 to 3 groups represented by-(CX ^a X ^b ) _m CR ¹ HCR ² R ³ Y.

Depending on the combination of x and y, Rf has a structure of any of the following formulas (a) to (e).

In the above formulas (a) to (e), Rf ^a represents a moiety represented by — (R—O) _n —R ′ _{n ′} — in Rf. Y ′ represents a group represented by — (CX ^a X ^b ) _m CR ¹ HCR ² R ³ Y.
The above formula (a) is (x, y) = (0, 1), (b) is (x, y) = (1, 0), and (c) is (x, y) = (1, 1). ), (D) corresponds to (x, y) = (2, 0), and (e) corresponds to (x, y) = (2, 1), respectively.
What is necessary is just to set suitably the combination of x and y according to the use of the fluorine-containing polymer (A) of this invention, and the calculated | required characteristic.

As described above, the structural unit L is preferably the structural unit L1, and the structural unit L1 is more preferably the structural unit L2 or the structural unit L3. Therefore, “— (R—O) _n —” in the above formula (Rf) is replaced by “—D—”, “—R ′ _{n ′} —CH _2−x {(CX ^a X ^b ) _m CR ¹ HCR ² R”. ³ Y} _x OH _1-y {(CX ^a X ^b ) _m CR ¹ HCR ² R ³ Y} _y ”is represented by“ —Ry ”, the structural unit L is represented by the formula (1):

(Wherein, X ¹ , X ² , X ³ , X ⁴ , X ⁵ , D, Ry, a, b and c are the same as described above), and the adhesion durability to the substrate Furthermore, it is preferable in terms of lower viscosity and excellent heat resistance.

Specifically, the structural unit L in the above formula (1) is

Among them, the structural unit of the above formula (1) is preferably the formula (1-1):

(Wherein, X ¹ , X ² , X ³ , X ⁴ , X ⁵ , D, Ry, a, and c are the same as above) are excellent in heat resistance and chemical resistance Is preferable.

More specifically, the structural unit of the above formula (1-1) is

Etc. are preferred, and in particular,

These structural units are more preferable in terms of heat resistance and chemical resistance.

The fluorine-containing polymer (A) of the present invention has, for example, the following formula (L ′):

(In the formula, X ¹ , X ² , X ³ , X ⁴ , X ⁵ , a, b and c are the same as those in the above formula (L). Rf ′ is the following formula (Rf ′):
_{- (R-O) n -R} 'n' -CH 2-x {(CX a X b) m CR 1 = CR 2 R 3} x OH 1-y {(CX a X b) m CR 1 = CR ² R ³ } _y (Rf ′)
(Wherein R, R ′, X ^a , X ^b , R ¹ , R ² , R ³ , n, n ′, m, x and y are the same as those in the above formula (Rf)). It is a fluorine-containing hydrocarbon group represented. ) An alkenyl group (group represented by —CR ¹ = CR ² R ³ ) at the end of the side chain of the fluoropolymer having the structural unit L ′ represented by (hereinafter also referred to as fluoropolymer (A ′)). A metal hydride (a compound having a bond represented by HM (M represents a metal atom)) is added to the metal atom by a hydrometallation reaction in the presence of a suitable catalyst, and then an alkoxyl group is formed on the metal atom. Can be obtained.

As the structural unit L ′, among them, the formula (L1 ′):

(Wherein X ¹ , X ² , X ³ , X ⁴ , X ⁵ , Rf ′, a, and c are the same as those described above) are preferable, and the structural unit L1 ′ is further represented by the formula ( L2 ′):

(Wherein Rf ′ is the same as defined above), or the structural unit L2 ′ or the formula (L3 ′):

The structural unit L3 ′ represented by the formula (wherein Rf ′ is the same as described above) is preferable.

The preferred structure of the site excluding Rf ′ from the structural unit L ′ is the same as that described for the structural unit L.

The preferred structure of the moiety represented by — (RO) _n —R ′ _{n ′} — in the above formula (Rf ′) is the same as that described for the above formula (Rf).

In the above formula (Rf ′), as the terminal alkenyl group represented by —CR ¹ ═CR ² R ³ , the following formula:
-CX ⁶ = CX ⁷ X ⁸
(Wherein X ⁶ is H, F, CH ₃ or CF ₃ ; X ⁷ and X ⁸ are the same or different, H or F), and this group is highly reactive in hydrometallation reaction and is hydrolyzed This is preferable because the conductive metal alkoxide moiety (the moiety represented by Y in the above formula (Rf)) can be easily formed.

Preferred specific examples of the terminal alkenyl group include

Etc.

As the terminal alkenyl group represented by —CR ¹ = CR ² R ³ , R ¹ and R ² or R ³ are optionally substituted hydrocarbon groups having 1 to 10 carbon atoms. In addition, R ¹ and R ² or R ³ may form a ring structure (cycloalkene structure) together with two carbon atoms to which these groups are bonded. Such a ring structure includes 2 to 10 carbon atoms of R ¹ and R ² or R ³ , the above two carbon atoms (that is, the carbon atom to which R ¹ is bonded, and R ² or a carbon atom to which R ³ is bonded). More preferably, it is a ring structure composed of 2 to 4 carbon atoms of R ¹ and R ² or R ³ and the two carbon atoms.

^Further, - a group represented by _{^{(CX a X b) m CR}} 1 = CR 2 R 3,
_{^{-CH 2 CX 6 = CX 7 X}} 8
(Wherein X ⁶ is H, F, CH ₃ or CF ₃ ; X ⁷ and X ⁸ are the same or different and H or F). This group is particularly preferable in terms of higher reactivity in the hydrometalation reaction.

As preferred specific examples of the group represented by — (CX ^a X ^b ) _m CR ¹ ═CR ² R ³ ,

Etc.

As preferred specific examples of the monomer constituting the structural unit L2 ',

(N is an integer from 0 to 20; Ry ′ is the above-described —CH _2−x {(CX ^a X ^b ) _m CR ¹ = CR ² R ³ } _x OH _1−y {(CX ^a X ^b ) _m CR ¹ = CR ² R ³ } represents a group represented by _y .) and the like.

More details

(Where n is an integer from 0 to 20; X is H, CH ₃ , F or CF ₃ )
Etc.

Specific preferred examples of the monomer constituting the structural unit L3 ′ include

(Wherein Ry 'is the same as above; n is an integer of 0 to 20).

For more details,

(In the above, n is an integer of 0 to 20; n ′ is an integer of 1 to 3; X is H, CH ₃ , F or CF ₃ ).

In addition to these structural units L2 ′ and L3 ′, preferred specific examples of the monomer constituting the structural unit L ′ of the fluoropolymer include, for example,

(Rf ^' is the same as the above example)
Etc.

More specifically,

(Wherein Ry 'is the same as above).

The fluoropolymer (A) may further contain a structural unit A other than the structural unit L described above. The structural unit A may be a structural unit derived from a monomer copolymerizable with the fluorine-containing ethylenic monomer that gives the structural unit L represented by the formula (L). The structural unit A is an optional component and is not particularly limited as long as it is a monomer that can be copolymerized with the fluorinated ethylenic monomer that gives the structural unit L, and the intended use of the fluorinated polymer and its cured product, What is necessary is just to select suitably according to a required characteristic.

Examples of the structural unit A include the following structural units.

(A1) Structural unit derived from a fluorine-containing ethylenic monomer having a functional group. This structural unit A1 is an adhesive property of a fluorine-containing polymer and its cured product to a substrate, and solubility in a solvent, particularly a general-purpose solvent. It is preferable at the point which can provide, and it is preferable at the point which can provide functions, such as crosslinkability besides that.

The structural unit A1 of a preferred fluorine-containing ethylenic monomer having a functional group has the formula (A1):

Wherein X ¹¹ , X ¹² and X ¹³ are the same or different H or F; X ¹⁴ is H, F, CF ₃ ; h is an integer from 0 to 2; i is 0 or 1; Rf ⁴ is carbon number A divalent fluorine-containing alkylene group having 1 to 40 carbon atoms or a divalent fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms; Z ¹ is —OH, —CH ₂ OH, —COOH, a carboxylic acid derivative, —SO ₃ H, a sulfonic acid derivative, an epoxy group, a cyano group, and —CH ₂ OSiR ¹¹ ₃ (R ¹¹ is the same or different and is a hydrocarbon group having 1 to 10 carbon atoms, an allyl group, or 1 to 1 carbon atoms. 10 represents an alkoxy group.) Is a structural unit represented by a functional group selected from the group consisting of:
^{_{CH 2 = CFCF 2 ORf 4 -Z}} 1
(Wherein Rf ⁴ and Z ¹ are the same as above) Formula (A1-1):

A structural unit represented by the formula (wherein Rf ⁴ and Z ¹ are the same as those in the formula (A1)) is preferable.

More specifically,

A structural unit derived from a fluorine-containing ethylenic monomer such as (Z ¹ is the same as above) is preferred.

Also,
CF ₂ = CFORf ⁴ -Z ¹
(Wherein Rf ⁴ and Z ¹ are the same as above) Formula (A1-2):

A structural unit represented by the formula (wherein Rf ⁴ and Z ¹ are the same as those in the formula (A1)) can also be preferably exemplified.

More specifically,

(Wherein Z ¹ is the same as above), and structural units derived from such monomers.

In addition, as the functional group-containing fluorine-containing ethylenic monomer,
^{_{CF 2 = CFCF 2 -O-Rf}} 4 -Z 1, CF 2 = CF-Rf 4 -Z 1,
_{^{CH 2 = CH-Rf 4 -Z}} 1, CH 2 = CHO-Rf 4 -Z 1
(Above, -Rf ⁴ - is the -Rf ⁴ of - the same; is ^{Z 1} wherein the same) and the like, and more specifically,

(Z ¹ is the same as above) and the like.

(A2) A structural unit derived from a fluorine-containing ethylenic monomer that does not contain a functional group. This structural unit A2 has a lower refractive index in that the refractive index of the fluorine-containing polymer or its cured product can be kept low. It is preferable at the point which can do. Further, by selecting the monomer, the mechanical properties of the polymer, the glass transition temperature, and the like can be adjusted, and in particular, the glass transition point can be increased by copolymerizing with the structural unit L, which is preferable.

As the structural unit (A2) of the fluorine-containing ethylenic monomer, the formula (A2):

Wherein X ¹⁵ , X ¹⁶ and X ¹⁸ are the same or different H or F; X ¹⁷ is H, F or CF ₃ ; h1, i1 and j are the same or different 0 or 1; Z ² is H, F, Cl or a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms; Rf ⁵ is a divalent fluorine-containing alkylene group having 1 to 20 carbon atoms or 2 containing an ether bond having 2 to 100 carbon atoms. (A valent fluorine-containing alkylene group) is preferable.

As a specific example,

Preferred examples include structural units derived from monomers such as

In particular, these are at least one unit selected from the group consisting of tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, and hexafluoropropylene because the refractive index of the curable fluorine-containing polymer or a cured product thereof can be kept low. A structural unit derived from a monomer is preferable.

(A3) Aliphatic cyclic structural unit having fluorine When this structural unit A3 is introduced, transparency can be increased, a fluorine-containing polymer having a high glass transition temperature can be obtained, and further hardness can be expected in the cured product. This is preferable.

The fluorine-containing aliphatic cyclic structural unit A3 is represented by the formula (A3):

Wherein X ¹⁹ , X ²⁰ , X ²³ , X ²⁴ , X ²⁵ and X ²⁶ are the same or different H or F; X ²¹ and X ²² are the same or different 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 and 0 or An integer of 1 is preferable.

For example,

(Wherein, Rf ⁶ , X ²¹ and X ²² are the same as above).

In particular,

(Wherein, X ¹⁹ , X ²⁰ , X ²³ and X ²⁴ are the same as described above).

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

Etc.

(A4) By introducing structural unit structural unit A4 derived from an ethylenic monomer that does not contain fluorine, solubility in general-purpose solvents is improved, and additives such as photocatalysts and additives are added as necessary. Compatibility with the curing agent can be improved.

Specific examples of non-fluorinated ethylenic monomers include
α-olefins:
Vinyl ether monomers or vinyl ester monomers such as ethylene, propylene, butene, vinyl chloride, vinylidene chloride:
Allyl monomers such as CH ₂ = CHOR, CH ₂ = CHOCOR ¹⁰ (R ¹⁰ : hydrocarbon group having 1 to 20 carbon atoms):
Allyl ether monomers such as CH ₂ = CHCH ₂ Cl, CH ₂ = CHCH ₂ OH, CH ₂ = CHCH ₂ COOH, CH ₂ = CHCH ₂ Br, etc .:
^{_{CH 2 = CHCH 2 OR 10 (}} R 10: a hydrocarbon group having 1 to 20 carbon atoms),
CH ₂ = CHCH ₂ OCH ₂ CH ₂ COOH,

Acrylic or methacrylic monomers:
In addition to acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters, maleic anhydride, maleic acid, maleic acid esters, and the like can be given.

Those in which the hydrogen atoms of these non-fluorinated ethylenic monomers are partially or completely substituted with deuterium atoms are more preferable in terms of transparency.

(A5) As a copolymerization component of the structural unit L derived from the alicyclic monomer, more preferably the structural unit L and the above-mentioned fluorine-containing ethylenic monomer or non-fluorine ethylenic monomer (described above In addition to the structural units of A3 and A4), an alicyclic monomer structural unit A5 may be introduced as the third component, thereby achieving a high glass transition temperature and a high hardness.

As a specific example of the alicyclic monomer A5,

(Where 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, a C 1-5 perfluoroalkyl group, or the like) Derivatives,

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

The fluorine-containing polymer (A) may be a polymer composed only of the structural unit L, or may be a copolymer composed of the structural unit L and the structural unit A. Further, the structural unit L may include only the structural unit L2, may include only the structural unit L3, or may include both the structural unit L2 and the structural unit L3. Further, the fluoropolymer (A) may be a copolymer comprising the structural unit L2, the structural unit L3, and the structural unit A.

When the fluorine-containing polymer is composed only of the structural unit L, it is advantageous in that it can provide a function of imparting adhesion durability to the substrate and further increase the hardness of the coating.

When the fluoropolymer is a copolymer, the structural unit L may be 0.1 mol% or more with respect to all the structural units constituting the fluoropolymer (A), but the hardness is increased by curing (crosslinking). In order to obtain a cured product having excellent wear resistance and scratch resistance, and excellent chemical resistance and solvent resistance, it is at least 2 mol%, preferably at least 5 mol%, more preferably at least 10 mol%. It is preferable.

Especially in applications that require the formation of cured products with excellent heat resistance, transparency and low water absorption, it is contained in an amount of 10 mol% or more, preferably 20 mol% or more, more preferably 30 mol% or more, particularly 40 mol% or more. It is preferable to do. Moreover, it is preferable that the structural unit L is less than 100 mol% with respect to all the structural units which comprise a fluorine-containing polymer (A).

The molecular weight of the fluorine-containing polymer (A) can be selected, for example, from the range of 500 to 1,000,000 in the number average molecular weight, preferably from 1,000 to 500,000, particularly from the range of 2,000 to 200,000. What is chosen is preferred.

If the molecular weight is too low, the mechanical properties tend to be insufficient even after curing, and the cured product is particularly brittle and tends to have insufficient strength. If the molecular weight is too high, the solvent solubility is deteriorated, the film formability and leveling property are liable to be deteriorated particularly during the formation of a thin film, and the storage stability of the fluoropolymer (A) is also liable to be lowered. Most preferably, the number average molecular weight is selected from the range of 5,000 to 100,000.
The number average molecular weight is a value measured according to polystyrene.

The fluorine-containing polymer (A) is composed of, for example, the structural unit L, and if necessary, further composed of the structural unit A, and the structural unit L is 0.1 to 100 with respect to all the structural units constituting the fluoropolymer. It may be a fluorine-containing polymer having a number average molecular weight of 500 to 1,000,000 including 0% to 99.9% by mole of the structural unit A.

The fluorine-containing polymer (A) is also composed of the structural unit L and, if necessary, further composed of the structural unit A1 and the structural unit A2, with respect to all structural units constituting the fluoropolymer (A). The unit L is 0.1 to 90 mol%, the structural unit A1 is 0 to 99.9 mol%, the structural unit A2 is 0 to 99.9 mol%, and the sum of the structural unit A1 and the structural unit A2 is It is one of the preferable forms that it is 10-99.9 mol% and a number average molecular weight is 500-1,000,000.

The content of the structural unit L in the fluoropolymer (A) may be 0.1 mol% or more with respect to all the structural units constituting the fluoropolymer, but it has high hardness and wear resistance by curing (crosslinking). In order to obtain a cured product excellent in scratch resistance, chemical resistance and solvent resistance, it is preferably 2 mol% or more, preferably 5 mol% or more, more preferably 10 mol% or more. In particular, in applications that require the formation of a cured film excellent in heat resistance, transparency, and low water absorption, it is preferably contained in an amount of 10 mol% or more, preferably 20 mol% or more, and more preferably 50 mol% or more. The upper limit is less than 100 mol%.

The contents of the structural units A1 and A2 are both 99.9 mol% or less. Moreover, the total mol% of A1 and A2 shall be 10-99.9 mol%. If it is less than 10 mol%, the refractive index cannot be kept low, and the film hardness after curing tends to decrease, which is not preferable. The more preferable total mol% of A1 and A2 is 20 mol% or more, further 30 mol% or more, 60 mol% or less, and further 50 mol% or less. Moreover, 90 mol% or less may be sufficient, 80 mol% or less may be sufficient, and 50 mol% or less may be sufficient.

In the fluorine-containing polymer (A), the combination and composition ratio of the structural unit L [structural units L1, L2 and L3) and the structural unit A (A1 and A2) can be determined from the above-mentioned examples. Various selections may be made according to functions (transparency), glass transition temperature, hardness, etc.).

The molecular weight of the fluoropolymer (A) is, for example, 500 to 1,000 in terms of number average molecular weight.
It can be selected from the range of 0,000, preferably 1,000 to 500,000, especially 2,
What is selected from the range of 000-200,000 is preferable.

If the molecular weight is too low, mechanical properties are likely to be insufficient even after curing, and in particular, the cured product and the cured film tend to be brittle and insufficient in strength. If the molecular weight is too high, the solvent solubility tends to be poor, the film formability and leveling properties tend to be poor, particularly during the formation of a thin film, and the storage stability of the fluoropolymer tends to be unstable and low. Most preferably, the number average molecular weight is selected from the range of 5,000 to 100,000.

The fluoropolymer (A) is preferably soluble in a general-purpose solvent, for example, soluble in at least one of a ketone solvent, an acetate solvent, an alcohol solvent, an aromatic solvent, or It is preferably soluble in a mixed solvent containing at least one general-purpose solvent.

It is preferable to be soluble in a general-purpose solvent, especially when it is necessary to form a thin film of 3 μm or less, for example, about 0.1 μm in the process of forming a film, because it is excellent in film formability and homogeneity. But it is advantageous.

The fluoropolymer (A) is
(1) A method in which a monomer having a functional group Rf is synthesized beforehand and polymerized (2) A polymer having another functional group is once synthesized, and the polymer is converted into a functional group by a polymer reaction. Any method of introducing the functional group Rf can be adopted.

When the fluorine-containing polymer (A) is synthesized by the method (1), the following formula:

(Wherein X ¹ and X ² are the same or different and H or F; X ³ is H, F, CH ₃ or CF ₃ ; X ⁴ and X ⁵ are the same or different and H, F or CF _{3, respectively.} Rf is the same as above; a is an integer of 0 to 3; b and c are the same or different, and the monomer represented by 0 or 1) is polymerized to form the fluorine-containing polymer (A). Can be obtained. In monomers of the ^above, the preferred embodiment of ^{X 1, X 2, X 3} , X 4, X 5, a, b, c, and Rf are the same as those described above.

Examples of the polymerization method include a radical polymerization method, an anionic polymerization method, a cationic polymerization method, etc., and the monomers exemplified for obtaining a polymer having a hydrolyzable metal alkoxide moiety can control the quality such as composition and molecular weight. The radical polymerization method is particularly preferred from the viewpoint of easy production and industrialization.

The method (2) is a preferable method in that the functional group Rf can be introduced into the side chain of the polymer without impairing the polymerizability of the monomer.

When the fluoropolymer (A) of the present invention is synthesized by the method (2), for example, the following formula:

(Wherein, X ¹ , X ² , X ³ , X ⁴ , X ⁵ , R, R ′, a, b, c, n and n ′ are the same as those in the above formula (L). X ^C Represents Cl or F.) The functional group Rf is introduced by modifying the acid halide site at the end of the side chain of the polymer obtained by polymerizing the monomer having an acid halide site. It is preferable. More specifically, the acid halide site is modified to obtain a fluorine-containing polymer (A ′) by introducing 1 to 3 alkenyl groups at the terminal, and then the alkenyl group is hydrometalated. It is preferable to obtain a fluoropolymer (A).
As a method for polymerizing the monomer having an acid halide moiety, a method similar to the polymerization method described in the method (1) can be employed.

The method for hydrometalating the alkenyl group after obtaining a polymer having a structural unit represented by the above formula (L ′) by modifying the acid halide moiety and introducing an alkenyl group will be described in detail below. Describe.

Assuming that the structural unit derived from the monomer having an acid halide moiety is (C-0), as shown in the following reaction formula, a reaction between the structural unit (C-0) and alcohol R ⁴ OH results in an esterification product. (C-1) is obtained.

However, in said formula, L' ^a is following formula (L' ^a ):

(Wherein X ¹ , X ² , X ³ , X ⁴ , X ⁵ , R, R ′, a, b, c, n and n ′ are the same as those in the above formula (L)). Is a structural unit represented, and X ^C is a halogen atom. R ⁴ is a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent. As the halogen atom, Cl or F is preferable.

From the esterified product (C-1), a fluorine-containing polymer (A ′) corresponding to each combination of x and y in Rf ′ in the structural unit L ′ can be synthesized.

Fluoropolymer (A ′) with (x, y) = (0, 1)
As shown in the following reaction formula, after the alcohol (C-2) is obtained by the reduction reaction of the esterified product (C-1), the substitution for the organic halide Y ″ -X ^d (Y ″, ^Xd is described later) is performed. By the reaction, a fluorine-containing polymer (A ′) (polymer (a ′)) corresponding to (x, y) = (0, 1) in which one alkenyl group is introduced at the terminal is obtained.

However, in the formula, L ′ ^a and R ⁴ are the same as those described above. Y ″ is represented by (CX ^a X ^b ) _m CR ¹ = CR ² R ³ (X ^a , X ^b , R ¹ , R ² , R ³ and m are the same as those described above). And X ^d is a halogen atom.

Examples of the reducing agent used for the reduction reaction of the esterified product (C-1) include lithium aluminum hydride, diisobutylaluminum hydride, lithium borohydride, and sodium bis (2-methoxyethoxy) aluminum hydride. The reaction may be performed under the reaction conditions usually employed when these reducing agents are used.

The above substitution reaction, under alkaline conditions, as the alcohol (C-2) is reacted with an organic halide Y "-X ^d. Above halogen atom, Cl or Br are preferred.

As another method for synthesizing the fluoropolymer (A ′) (polymer (a ′)) corresponding to (x, y) = (0, 1), for example, the following method may be mentioned. That is, the following general formula:

(Wherein X ¹ , X ² , X ³ , X ⁴ , X ⁵ , R, R ′, a, b, c, n and n ′ are the same as those in the above formula (L)). After the obtained monomer having a hydroxyl group is polymerized to obtain a fluorine-containing polymer having a hydroxyl group corresponding to the alcohol (C-2), the fluorine-containing polymer having the hydroxyl group is converted to the organic halide. a method of reacting with Y "-X ^d and the like.

(X, y) = (1, 0), (1, 1) fluoropolymer (A ′)
As shown in the following reaction formula, after the aldehyde (C-3) was obtained by the reduction reaction of the esterified product (C-1), the Grignard reaction using Y ″ -MgX ^e (X ^e will be described later) A fluorine-containing polymer (A ′) (polymer (b ′)) corresponding to (x, y) = (1, 0) in which one group is introduced is obtained.
Further, by reacting the polymer (b ′) with an organic halide Y ″ -X ^f (X ^f is described later), two Y ″ groups were introduced, and (x, y) = (1, 1). The corresponding fluoropolymer (A ′) (polymer (c ′)) is obtained.

However, in the formula, L ′ ^a , R ⁴ and Y ″ are the same as those described above, and X ^e and X ^f are each a halogen atom.

Examples of the reducing agent used in the reduction reaction for obtaining the aldehyde (C-3) from the esterified product (C-1) include diisobutylaluminum hydride and the like, and the reaction can be performed under reaction conditions usually employed. In addition, although the pathway for obtaining the aldehyde (C-3) directly from the esterified product (C-1) was shown in the above reaction formula, for example, after the esterified product (C-1) was once reduced to alcohol, chlorochromic acid The aldehyde (C-3) may be obtained by an oxidation reaction using pyridinium or the like.
The above Grignard reaction may be performed under the reaction conditions usually employed. The ^{X e} in Grignard reagent Y "-MgX ^e, I, preferably Br and Cl, I and Br are more preferable.
The above substitution reaction can be carried out in the same manner as in the reaction of the alcohol (C-2) with an organic halide Y "-X ^d.

(X, y) = (2, 0), (2, 1) fluoropolymer (A ′)
As shown in the following reaction formula, two Y ″ groups were introduced by Grignard reaction using 2 equivalents of Y ″ -MgX ^g (X ^g will be described later) per 1 equivalent of the esterified product (C-1). In addition, a fluoropolymer (A ′) (polymer (d ′)) corresponding to (x, y) = (2, 0) is obtained.
Further, by reacting the polymer (d ′) with an organic halide Y ″ -X ^h (X ^h is described later), three Y ″ groups were introduced, and (x, y) = (2, 1). The corresponding fluoropolymer (A ′) (polymer (e ′)) is obtained.

In the formula, L ′ ^a , R ⁴ and Y ″ are the same as those described above, and X ^g and X ^h are each a halogen atom.

Both the Grignard reaction and the substitution reaction can be performed in the same manner as described above.

The fluorine-containing polymer (A ′) obtained as described above is further subjected to a hydrometallation reaction in the presence of a catalyst as shown in the following reaction formula, whereby a hydrolyzable metal alkoxide is present at the end of the side chain. Sites can be introduced.

However, in the formula, L ′ ^b is the following formula (L ′ ^b ):

(Wherein X ¹ , X ² , X ³ , X ⁴ , X ⁵ , R, R ′, a, b, c, n and n ′ are the same as those in the above formula (L)). It is a structural unit represented, and X ^a , X ^b , R ¹ , R ² , R ³ , and m are the same as those described above. M is a metal atom. L ¹ is the same or different and represents a ligand. R ⁵ is an organic group having 1 to 50 carbon atoms, which may have a substituent. x1 is (valence of the metal atom M) -1 and x2 is an integer of 1 or more and x1 or less.

Examples of the catalyst include H ₂ PtCl ₆ (Speier catalyst), a Karstedt catalyst prepared from H ₂ PtCl ₆ and vinylsiloxane, and PtCl ₂ (COD).
H-ML ¹ _x1 in the above reaction formula is a metal hydride. As M, silicon is particularly preferable. As H-ML ¹ _x1 , for example, trichlorosilane, trimethoxysilane, triethoxysilane, dimethoxypropoxysilane and the like are preferably used.
As the alcohol R ⁵ OH, methanol, ethanol, propanol, isopropanol and the like are preferable.
In addition, when one or more of the ligands L ¹ are alkoxyl groups, the subsequent reaction with the alcohol R ⁵ OH can be omitted.

Details of the hydrometallation reaction are disclosed in, for example, International Publication No. 2006/107082 and International Publication No. 2006/107083.

The fluorine-containing polymer (A) may constitute a curable resin composition together with the organosilicon compound (B). Since the fluoropolymer (A) has the above-described configuration, it can be suitably cross-linked with SiOx formed from the compound (B), and the formed cured product has excellent flexibility. be able to. Moreover, since the hardened | cured material formed consists of SiOx, it is excellent in heat resistance and transparency.
The organosilicon compound (B) is a compound containing carbon and silicon. The organosilicon compound (B) is preferably liquid at normal temperature (for example, 25 ° C.).

Examples of the organosilicon compound (B) include Si—H compounds having Si—H bonds; Si—N compounds having Si—N bonds such as aminosilane compounds, silazanes, silylacetamides, and silylimidazoles; monoalkoxysilanes, dialkoxys. Si-O compounds having Si-O bonds such as silane, trialkoxysilane, tetraalkoxysilane, siloxane, silyl ester, silanol; Si-- having Si-Cl bonds such as monochlorosilane, dichlorosilane, trichlorosilane, tetrachlorosilane Examples include halogenosilanes such as Cl compounds, Si— (C) ₄ compounds, Si—Si compounds having a Si—Si bond, vinyl silane, allyl silane, and ethynyl silane. That is, the organosilicon compound (B) is selected from the group consisting of Si—H compound, Si—N compound, halogenosilane, Si— (C) ₄ compound, Si—Si compound, vinylsilane, allylsilane, and ethynylsilane. Preferably it is at least one compound. As the organosilicon compound, a compound in which at least one atom selected from the group consisting of hydrogen, oxygen and halogen is bonded to Si is more preferable.
Specific examples of the above compounds are shown below.

[Si-H compound]

[Si-N compound]

[Si-O compound]

[Halogenosilane]
Si-Cl compound:

ＳｉＣｌ_４

SiCl ₄

Halogenosilanes other than Si-Cl compounds:

[Si- (C) ₄ compound]

[Si-Si compound]

[Vinyl silane, allyl silane, and ethynyl silane]

The organosilicon compound (B) has the following formula (2):
{Si (R ^a ) _s (R ^b ) _t (R ^c ) _u (R ^d ) _v (R ^e ) _w } _n (2)
(In the formula, R ^a , R ^b , R ^c and R ^d are the same or different and are hydrogen, halogen, an alkoxyl group having 1 to 10 carbon atoms, an amino group having 1 to 10 carbon atoms, or an alkyl having 1 to 10 carbon atoms. Group, an aryl group having 6 to 10 carbon atoms, an allyl group having 3 to 10 carbon atoms, or a glycidyl group having 3 to 10 carbon atoms, R ^e is the same or different and represents —O—, —NH—, —C. ≡C— or a silane bond, s, t, u and v are the same or different and are 0 or 1, w is an integer of 0 to 4, n is 1 to 20. n is 1 S + t + u + v is 4 and w is 0. When n is 2 to 20, s + t + u + v is the same or different 0-4, w is the same or different 0-4, w If is an integer of 1 or more, at least two Si through R ^e, linear, ladder-type, Jo, or more preferably multiple annularly attached.) And a compound represented by (B1). R ^a , R ^b , R ^c , and R ^d are monovalent groups bonded to Si. R ^e is a divalent group bonded to two Si atoms.

In formula (2), R ^a , R ^b , R ^c and R ^d are the same or different, and at least one is hydrogen, halogen, an alkoxy group having 1 to 10 carbon atoms, or an amino group having 1 to 10 carbon atoms. Other than that, it is preferable that it is a C1-C10 alkyl group, a C6-C10 aryl group, a C3-C10 allyl group, or a C3-C10 glycidyl group. When n is 2 to 20, s + t + u + v is the same or different and is 1 to 3, and w is preferably 1 to 3.

In the formula (2), R ^a , R ^b , R ^c and R ^d are the same or different and are an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, Or it is preferable that it is a C1-C6 amino group, More preferably, it is a C1-C4 alkoxy group.

In the above R ^a , R ^b , R ^c and R ^d , the alkyl group preferably has 1 to 5 carbon atoms. The alkyl group may be linear, cyclic or branched. Moreover, the hydrogen atom may be substituted with a fluorine atom or the like. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Examples of the R ^a , R ^b , R ^{c, and} R ^d include a methyl group, an ethyl group, and a propyl group, respectively. It is preferably a group or an isopropyl group. More preferably, they are a methyl group and an ethyl group.
As the aryl group, for example, a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, or a dimethylphenyl group is preferable.
As the halogen, fluorine, chlorine, bromine or iodine is preferable, and chlorine is particularly preferable.

In the above R ^a , R ^b , R ^c and R ^d , the alkoxy group preferably has 1 to 5 carbon atoms. The alkoxy group may be chained, cyclic or branched. Moreover, the hydrogen atom may be substituted with a fluorine atom or the like. As an alkoxy group, a methoxy group, an ethoxy group, a propyloxy group, or a butoxy group is preferable, More preferably, it is a methoxy group or an ethoxy group.

R ^e is the same or different and is —O—, —NH—, —C≡C—, or a silane bond. As R ^e , —O—, —NH—, or —C≡C— is preferable. R ^e is a divalent group which is bonded to two Si, that two or more silicon atoms by R ^e via the R ^e, binds a linear, ladder-type, cyclic, or double cyclic Can do. When n is an integer of 2 or more, silicon atoms may be bonded to each other. Specific examples of the compound (B1) include one Si such as the Si-H compound, Si-N compound, halogenosilane, Si- (C) ₄ compound, Si-Si compound, vinylsilane, allylsilane, and ethynylsilane. Or the compound containing 2 or more is mentioned.

The compound (B1) is preferably tetraalkoxysilane, and in the above formula (2), n is 1, and R ^a , R ^b , R ^c and R ^d are the same or different and have the same number of carbon atoms. More preferably, it is a 1-10 alkoxy group. The alkoxy group may be chained, cyclic or branched. Further, a hydrogen atom may be substituted with a fluorine atom. The alkoxy group preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms.

Examples of the compound (B1) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, and tetra-tert-butoxysilane. Tetraphenoxysilane and the like. Among these, at least one compound selected from the group consisting of tetramethoxysilane and tetraethoxysilane is preferable, and more preferably, it is easy to obtain and inexpensive, and is used for glass. It is tetraethoxysilane (TEOS) in terms of a close refractive index.

From the viewpoint of improving the crosslinkability, the compound (B1) preferably has an allyl group having 1 to 5 carbon atoms, a glycidyl group having 1 to 5 carbon atoms, an acryl group, or a methacryl group. That is, in the compound (B1), at least one of R ^a , R ^b , R ^c and R ^d is an allyl group having 1 to 5 carbon atoms, a glycidyl group having 1 to 5 carbon atoms, an acryl group, or a methacryl group. It is preferable.

In the curable resin composition of the present invention, the compound (B) is preferably 50% by mass or more based on the total mass of the compound (B) and the fluoropolymer (A). More preferably, a compound (B) is 60 mass% or more, More preferably, it is 80 mass% or more. When there are too few compounds (B), there exists a possibility that it may be inferior to heat resistance or transparency. Moreover, it is preferable that a fluorine-containing polymer (A) is 0.1 mass% or more with respect to the total mass of a compound (B) and a fluorine-containing polymer (A), and it is 0.5 mass% or more. Is more preferable. When there is too little fluoropolymer (A), there exists a possibility that a dielectric constant may become high and it may be inferior to flexibility.

The curable resin composition preferably contains an organic solvent in addition to the compound (B) and the fluoropolymer (A). The organic solvent is preferably one that can dissolve the fluorine-containing polymer (A).

Examples of organic solvents include cellosolve solvents such as methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate; diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate, ethyl acetoacetate, butyl acetate, amyl acetate Ester solvents such as ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate; propylene glycol monomethyl ether , Propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Propylene glycol solvents such as propylene glycol monobutyl ether acetate and dipropylene glycol dimethyl ether; ketone solvents such as 2-hexanone, cyclohexanone, methylaminoketone, 2-heptanone and methylisobutylketone; methanol, ethanol, propanol, isopropanol, butanol, etc. Alcohol solvents such as: aromatic hydrocarbons such as toluene and xylene, or a mixed solvent of two or more of these.

Furthermore, in order to improve the solubility of the fluoropolymer (A), a fluorine-based solvent may be used as necessary.

Examples of the fluorine-based solvent include CH ₃ CCl ₂ F (HCFC-141b), CF ₃ CF ₂ CHCl ₂ / CClF ₂ CF ₂ CHClF mixture (HCFC-225), perfluorohexane, perfluoro (2-butyltetrahydrofuran). , Methoxy-nonafluorobutane, 1,3-bistrifluoromethylbenzene, etc.

Fluorine alcohols such as
Examples include benzotrifluoride, perfluorobenzene, perfluoro (tributylamine), ClCF ₂ CFClCF ₂ CFCl _{2 and the} like.

These fluorinated solvents may be used singly or as a mixed solvent of fluorinated solvents or one or more of non-fluorinated and fluorinated solvents.

Among these, at least one solvent selected from the group consisting of ketone solvents, acetate solvents, alcohol solvents, and aromatic solvents is preferable. More specifically, methyl isobutyl ketone, propylene glycol At least one solvent selected from the group consisting of methyl ether acetate (PGMEA), 2-heptanone (MAK) and ethyl lactate is preferable in terms of paintability, coating productivity, and the like.

It is preferable that the curable resin composition of the present invention further contains a curing initiator.

Examples of the curing initiator in the curable resin composition of the present invention include a photo radical generator and a heat radical generator. For example, in addition to the active energy ray curing initiator, heat curing or room temperature two-component curing agent can be used. An active energy ray curing initiator is preferable from the viewpoint that a curing reaction can be performed at a relatively low temperature. It is appropriately selected depending on the type of Y (radical reactivity or cation (acid) reactivity), the type of active energy ray to be used (wavelength range, etc.) and the irradiation intensity.

The active energy ray curing initiator, for example, generates radicals and cations (acids) for the first time by irradiating an active energy ray such as an electromagnetic wave in a wavelength region of 350 nm or less, that is, an ultraviolet ray, an electron beam, an X ray, a γ ray, It functions as a catalyst for initiating curing (crosslinking reaction) of the crosslinking group of the fluorine-containing polymer (A). Usually, those that generate radicals and cations (acids) with ultraviolet rays, particularly those that generate radicals are used.

In the case of curing using an active energy ray in the ultraviolet region, examples of the curing initiator include the following.

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 photoinitiator adjuvants, such as amines, sulfones, and sulfines, as needed.

Moreover, the following can be illustrated as a cation (acid) reactive initiator (photoacid generator).

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.

In the curable resin composition of the present invention, the addition amount of the curing initiator is the content of the crosslinking group in the fluoropolymer (A), and when the compound (B) has a crosslinking group, the crosslinking group. In addition, the curing initiator, the type of active energy ray used, and the amount of irradiation energy (strength and time, etc.) are appropriately selected. It is preferable that it is 0.01-30 mass parts with respect to a total of 100 mass parts of A). More preferably, it is 0.05-20 mass parts, More preferably, it is 0.1-10 mass parts.

The curable resin composition of the present invention preferably contains a curing agent.

As the curing agent, one having at least one carbon-carbon unsaturated bond and capable of being polymerized with a radical or an acid is preferable. Specifically, a radical polymerizable monomer such as an acrylic monomer, a vinyl ether monomer, etc. Cationic polymerizable monomers can be mentioned. These monomers may be monofunctional having one carbon-carbon double bond or polyfunctional monomers having two or more carbon-carbon double bonds.

These so-called curing agents having a carbon-carbon unsaturated bond react with radicals and cations generated by the reaction of the active energy ray curing initiator in the composition of the present invention with active energy rays such as light, and crosslink. It is something that can be done.

Monofunctional acrylic monomers include acrylic acid, acrylic esters, methacrylic acid, methacrylic esters, α-fluoroacrylic acid, α-fluoroacrylic esters, maleic acid, maleic anhydride, maleic acid In addition to esters, (meth) acrylic acid esters having an epoxy group, a hydroxyl group, a carboxyl group, and the like are exemplified.
Among these, in order to keep the refractive index of the cured product low, an acrylate monomer having a fluoroalkyl group is preferable.

（ＸはＨ、ＣＨ_３又はＦ、Ｒｆ^ｂは炭素数２〜４０の含フッ素アルキル基又は炭素数２〜１００のエーテル結合を有する含フッ素アルキル基）で表わされる化合物が好ましい。
具体的には、

A compound represented by (X is H, CH ₃ or F, and Rf ^b is a fluorine-containing alkyl group having 2 to 40 carbon atoms or a fluorine-containing alkyl group having an ether bond having 2 to 100 carbon atoms) is preferable.
In particular,

等が挙げられる。
多官能アクリル系単量体としては、ジオール、トリオール、テトラオール等の多価アルコール類のヒドロキシル基をアクリレート基、メタアクリレート基、α−フルオロアクリレート基に置き換えた化合物が一般的に知られている。
具体的には、１，３−ブタンジオール、１，４−ブタンジオール、１，６−ヘキサンジオール、ジエチレングリコール、トリプロピレングリコール、ネオペンチルグリコール、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール等のそれぞれの多価アルコール類の２個以上のヒドロキシル基がアクリレート基、メタクリレート基、α−フルオロアクリレート基のいずれかに置き換えられた化合物が挙げられる。
また、含フッ素アルキル基、エーテル結合を含む含フッ素アルキル基、含フッ素アルキレン基又はエーテル結合を含む含フッ素アルキレン基を有する多価アルコールの２個以上のヒドロキシル基をアクリレート基、メタアクリレート基、α−フルオロアクリレート基に置き換えた多官能アクリル系単量体も利用でき、特に硬化物の屈折率を低く維持できる点で好ましい。
具体例としては、

Etc.
As polyfunctional acrylic monomers, compounds in which the hydroxyl groups of polyhydric alcohols such as diols, triols, and tetraols are replaced with acrylate groups, methacrylate groups, or α-fluoroacrylate groups are generally known. .
Specifically, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, tripropylene glycol, neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, etc. Examples thereof include compounds in which two or more hydroxyl groups of polyhydric alcohols are replaced with any one of an acrylate group, a methacrylate group, and an α-fluoroacrylate group.
In addition, two or more hydroxyl groups of a polyhydric alcohol having a fluorine-containing alkyl group, a fluorine-containing alkyl group containing an ether bond, a fluorine-containing alkylene group or a fluorine-containing alkylene group containing an ether bond are converted into an acrylate group, a methacrylate group, α A polyfunctional acrylic monomer substituted with a fluoroacrylate group can also be used, and is particularly preferable in that the refractive index of the cured product can be kept low.
As a specific example,

等の一般式で示される含フッ素多価アルコール類の２個以上のヒドロキシル基をアクリレート基、メタアクリレート基又はα−フルオロアクリレート基に置き換えた構造のものが好ましく挙げられる。
また、これら例示の単官能、多官能アクリル系単量体を硬化剤として本発明の組成物に用いる場合、なかでも特にα−フルオロアクリレート化合物が硬化反応性が良好な点で好ましい。

Preferred are those having a structure in which two or more hydroxyl groups of fluorine-containing polyhydric alcohols represented by the general formulas such as the above are replaced with acrylate groups, methacrylate groups or α-fluoroacrylate groups.
In addition, when these exemplified monofunctional and polyfunctional acrylic monomers are used in the composition of the present invention as a curing agent, an α-fluoroacrylate compound is particularly preferable in terms of good curing reactivity.

In the composition of the present invention, the amount of the active energy ray curing initiator added depends on the content of the carbon-carbon double bond in the fluoropolymer (A), whether or not the curing agent is used, and the amount of the curing agent used. Furthermore, the curing initiator used, the type of active energy rays, and the amount of irradiation energy (strength and time, etc.) are appropriately selected. When no curing agent is used, the fluoropolymer (A) is 100 parts by weight. 0.01 to 30 parts by weight, further 0.05 to 20 parts by weight, and most preferably 0.1 to 10 parts by weight.
Specifically, it is 0.05 to 50 mol%, preferably 0.1 to 20 mol%, most preferably based on the content (number of moles) of the carbon-carbon double bond contained in the fluoropolymer (A). 0.5 to 10 mol%.

When a curing agent is used, the total number of moles of the carbon-carbon double bond content (number of moles) contained in the fluoropolymer (A) and the number of moles of carbon-carbon unsaturated bonds of the curing agent. 0.05 to 50 mol%, preferably 0.1 to 20 mol%, most preferably 0.5 to 10 mol%.

When a curing agent is used, the amount of curing agent used is appropriately selected depending on the target hardness and refractive index, the type of curing agent, the content of the curable group of the curable fluorinated polymer used, and preferably curable. It is 1 to 80% by weight, preferably 5 to 70% by weight, more preferably 10 to 50% by weight based on the fluorine-containing polymer. If the addition amount of the curing agent is too large, the refractive index tends to increase, which is not preferable.

The curable resin composition of the present invention may further contain hollow fine particles. When the curable resin composition of the present invention contains hollow fine particles having a low refractive index, the refractive index can be lowered.

The hollow fine particles are components to be blended in order to lower the refractive index. The upper limit of the refractive index of the hollow fine particles is, for example, 1.48. The hollow fine particles preferably have a refractive index of 1.45 or less, and more preferably 1.40 or less. If the refractive index is too high, it may be difficult to use depending on the application, such as a sealing agent for a CCD module. By being the said range, the refractive index of the thin film obtained from the curable resin composition of this invention can be made low. The lower limit of the refractive index is, for example, 1.15. The refractive index of the hollow fine particles can be measured by the methods described in Japanese Patent No. 3716189 and Japanese Patent No. 4046921.

The hollow fine particles preferably have a porosity of 1 to 60%, more preferably 2 to 40%. The porosity of the hollow fine particles is converted into air using the refractive index obtained by the above method, for example, in the case of silica hollow fine particles, from the difference from the refractive index of pure SiO ₂ (1.45). Thus, the voids included can be calculated and obtained.

The hollow fine particles are preferably 1 to 150 nm, more preferably 10 to 80 nm from the viewpoint of particularly good optical properties of the sealing member (protective layer) and the antireflection film obtained from the curable resin composition of the present invention. .

The hollow fine particles are preferably hollow silica fine particles. The hollow silica fine particle is a known material used in JP 2002-277604 A, JP 2002-265866 A, and the like.

Specifically, hollow silica fine particles described in JP-A Nos. 2004-203683 and 2006-021938 can be used. Preferable examples include through rears manufactured by JGC Catalysts & Chemicals.

The hollow silica fine particles are preferably 1 to 1000 parts by mass, more preferably 3 to 250 parts by mass, and particularly preferably 5 to 150 parts by mass with respect to 100 parts by mass of the fluoropolymer (A). When blended in this range, the refractive index of the thin film obtained from the curable resin composition of the present invention can be lowered, which is suitable for a sealant for a CCD module. In addition, characteristics such as heat resistance and chemical resistance are particularly excellent.

The curable resin composition of the present invention may contain various additives as necessary in addition to those described above.

Examples of additives include silane coupling agents, plasticizers, anti-discoloring agents, antioxidants, inorganic fillers, leveling agents, viscosity modifiers, light stabilizers, moisture absorbers, pigments, dyes, reinforcing agents, and the like. It is done.

The curable resin composition of the present invention may contain fine particles or ultrafine particles of an inorganic compound for the purpose of increasing the hardness of the cured product and controlling the refractive index.

The inorganic compound fine particles are not particularly limited, but compounds having a refractive index of 1.5 or less are preferable. Specifically, magnesium fluoride (refractive index 1.38), silicon oxide (refractive index 1.46), aluminum fluoride (refractive index 1.33-1.39), calcium fluoride (refractive index 1.44) Fine particles such as lithium fluoride (refractive index 1.36 to 1.37), sodium fluoride (refractive index 1.32 to 1.34), thorium fluoride (refractive index 1.45 to 1.50) are desirable. . The particle diameter of the fine particles is desirably sufficiently smaller than the wavelength of visible light in order to ensure the transparency of the low refractive index material. Specifically, it is preferably 300 nm or less, particularly 100 nm or less.

Voids can be formed by fine particles or ultrafine particles of an inorganic compound. That is, a film obtained by blending inorganic fine particles or ultrafine particles with the composition of the present invention can have a refractive index lower than the refractive index of the single film by utilizing this void.

When using inorganic compound fine particles, it should be used in the form of an organic sol previously dispersed in an organic dispersion medium in order not to lower the dispersion stability in the composition, the adhesion in the low refractive index material, etc. Is desirable. Furthermore, in order to improve the dispersion stability of the inorganic compound fine particles and the adhesion in the low refractive index material in the composition, the surface of the inorganic fine particle compound may be modified in advance using various coupling agents. it can. Examples of various coupling agents include organically substituted silicon compounds; metal alkoxides such as aluminum, titanium, zirconium, antimony or mixtures thereof; salts of organic acids; coordination compounds bonded to coordination compounds, and the like. .

The curable resin composition of the present invention may be a dispersion-like or solution-containing fluoropolymer (A) or additive with respect to the organic solvent, but from the viewpoint of forming a uniform thin film, A uniform solution is preferable in that the film can be formed at a relatively low temperature.

The curable resin composition of the present invention preferably has an appropriate viscosity, that is, about 1 to 10 cp, so that the formed film has a thickness of 0.1 to 5 μm. Therefore, it is preferable that the sum total of the mass of a compound (B) and a fluoropolymer (A) is 10-100 mass% with respect to the total mass. More preferably, it is 20-50 mass%.
Moreover, when using the curable resin composition of this invention for optical element sealing, it is preferable that it is an appropriate viscosity, for example, 100-10000 mPa * s at room temperature, for using it for casting shaping | molding or potting shaping | molding. For that purpose, it is preferable that the sum total of the mass of a compound (B) and a fluoropolymer (A) is 10-100 mass% with respect to the total mass of the curable resin composition of this invention. More preferably, it is 20-50 mass%.
The viscosity is measured at 25 ° C. under the condition of 100 rpm using a CP-100 cone in a cone plate viscometer CV-1E manufactured by Tokai Yagami Co., Ltd., and a stable value is adopted for 60 seconds.

The curable resin composition of the present invention is necessary, for example, by adding a fluorine-containing polymer (A) and, if necessary, a curing initiator, a crosslinking agent, and other additives to the liquid compound (B). It can manufacture by stirring and mixing according to.

The curable resin composition of the present invention can form a cured product by crosslinking, for example, thermal crosslinking or photocrosslinking. The cured product may be crosslinked by applying the curable resin composition of the present invention to a substrate, drying and then firing, or irradiating active energy rays such as ultraviolet rays, electron beams or radiation. It may be formed by photocuring. The present invention is also a cured product obtained by curing the curable resin composition.

The cured product preferably has a refractive index of 1.40 or less. For example, from the curable resin composition of the present invention, a thin film having a film thickness of 1 to 10 μm, a refractive index of 1.40 or less, and a haze value of 5% or less can be produced. Moreover, such a low refractive index and haze value are obtained after a heat resistance test at 125 ° C. for 1000 hours, a heat resistance test at 85 ° C. and a humidity of 85% for 500 hours, and a heat resistance test at 265 ° C. for 10 minutes. But it does not fluctuate. Furthermore, it does not fluctuate even after the light resistance test exposed to 1000 lux for 1 hour.

The curable resin composition of this invention can utilize the hardened | cured material obtained for various uses with a various form.

For example, a cured film can be formed and used for various purposes. As a method of forming the film, a known method suitable for the application can be employed. For example, the method of apply | coating the said composition to a base material, drying, and baking after that as needed is mentioned. Specifically, for example, a roll coating method, a gravure coating method, a micro gravure coating method, a flow coating method, a bar coating method, a spray coating method, a die coating method, a spin coating method, a dip coating method, a slit coating method, etc. And can be selected in consideration of the type, shape, productivity, and controllability of the film thickness. In the case of forming a gate insulating film of a thin film transistor, the above composition is preferably applied by a slit coating method.

The curable resin composition of the present invention is particularly useful as a molding material for various molded products, for example. As the molding method, extrusion molding, injection molding, compression molding, blow molding, transfer molding, stereolithography, nanoimprinting, vacuum molding and the like can be employed.

The curable resin composition of the present invention is preferably for optical element sealing. That is, the curable resin composition of the present invention can be suitably used as a sealant used for optical elements.

The curable resin composition of the present invention is preferably a sealant. For example, a sealant used for a light receiving element such as a phototransistor, a photodiode, or a CCD, a light emitting element such as an LED or an organic EL, a semiconductor element (optical semiconductor element) such as an EPROM, or the like is preferable. The sealing agent can be cured to obtain a sealing member (cured product). The cured product of the present invention is preferably a sealing member for an optical element, and particularly preferably a sealing member for a light receiving element or a light emitting element.

FIG. 1 is a schematic cross-sectional view showing an example of the structure of a CCD module. In the CCD module having the structure shown in FIG. 1, since the light reaching the CCD element portion 12 passes through the sealing agent layer 13, the sealing agent layer 13 has a low refractive index and transparency. High is required. Since the curable resin composition of the present invention can form a thin film having a low refractive index and high transparency, it is suitable as a sealing material for forming a sealing agent applied to the CCD module.

2A to 2F are flowcharts schematically showing the manufacturing flow of the CCD module. Below, the manufacturing method of a CCD module is demonstrated using Fig.2 (a)-(f). First, as shown in FIG. 2A, a silicon wafer 21 is prepared, and a CCD element portion 22 is formed thereon (FIG. 2B). Next, the curable resin composition of the present invention is applied on the CCD element portion 22 by using a coating method such as spin coating to form the sealant layer 23 (FIG. 2C). Thereafter, a glass 24 is laminated on the sealant layer 23 (FIG. 2 (d)), and then, as shown in FIG. 2 (e), dicing is performed to manufacture a CCD element.

Thereafter, holes are formed in the silicon wafer 21 by anisotropic etching using RIE or the like, and the through electrodes 25 are formed on the back surface of the silicon wafer 21. The semiconductor chip thus manufactured can be bonded to the electrode 26 connected to the outside, and the CCD module shown in FIG. 2F can be manufactured.

As a sealing member for a light emitting element such as an LED or an organic EL, it may be one that is directly sealed. In addition, for example, after sealing an element using a conventionally used epoxy-based or silicone-based sealing member, the curable resin composition of the present invention is laminated on the outermost surface, so that the light emitting device is changed to the air layer. A structure in which the refractive index decreases gradually may be employed. For example, when sealing with an epoxy sealing resin having a refractive index of 1.57, the loss based on Fresnel reflection at the air interface is calculated to be 4.92%. If a layer having a refractive index of 1.32 is formed on the outermost surface of this epoxy sealing resin using the curable resin composition of the present invention, the number of interfaces increases, but the total Fresnel reflection is 2.65%. As a result, the reflection loss can be greatly reduced, and as a result, the light extraction efficiency from the light emitting element can be improved.

The curable resin composition of the present invention is also suitably used for a coated article having a thin film that imparts low reflectivity on a substrate. Examples of the substrate include inorganic materials such as glass, stone, concrete, and tile; metals such as iron, aluminum, and copper; wood, paper, printed matter, photographic paper, and painting.

Examples of the base material include cellulose resins such as vinyl chloride resin, polyethylene terephthalate and triacetyl cellulose, polycarbonate resins, polyolefin resins, acrylic resins, phenol resins, xylene resins, urea resins, melamine resins, diallyl phthalate resins, furans. Examples thereof include synthetic resin base materials such as resins, amino resins, alkyd resins, urethane resins, vinyl ester resins, polyimide resins and polyamide resins.

Among the substrates, an antiglare substrate for liquid crystal display (LCD) display is preferably used because its surface is coated with fine inorganic fine particles, and can effectively exhibit antiglare and low reflection effects.

The curable resin composition of the present invention is also effective when applied to articles having the following forms.
Prism, lens sheet, polarizing plate, optical filter, lenticular lens, Fresnel lens, rear projection display screen, reduction projection exposure lens, optical components such as optical fiber and optical coupler; show window glass, showcase glass, advertisement Transparent protective plates typified by cover, photo stand cover, etc .; protective plates for CRT, liquid crystal display, plasma display, rear projection display, etc .; read-only optical disk such as magneto-optical disk, CD / LD / DVD Optical recording media represented by phase transition type optical discs such as PD, hologram recording, etc .; photolithographic-related members in manufacturing semiconductors such as photoresists, photomasks, pellicles, reticles; halogen lamps, fluorescent lamps, incandescent lamps, etc. Protective cover for illuminant; Sheet or film for pasting into the serial goods.

The curable resin composition of the present invention is also suitable as an adhesive when applied to an article having the following form.
Semiconductor device carrier tapes / substrates, lead frames, printed circuit boards, module substrates, and other wiring boards and wiring sheets, as well as surface layers or interlayer insulating layer surfaces of package substrates.

Further, by using the curable resin composition of the present invention, a thin film is formed on a portion other than a specific portion of the article, and the shape of the specific portion is raised by reflected light, thereby improving the decorativeness of the article. Is possible.

In addition to the above, the curable resin composition of the present invention is particularly suitable as a material for forming an insulating film for use in forming a large-area insulating film and in applications that require flexibility. For example, the use of the insulating film obtained by the composition of the present invention includes a multilayer printed wiring board interlayer insulating film, a light emitting diode element insulating film, a multilayer chip interlayer insulating film, and the like. Further, it is suitable as an insulating film for a semiconductor element, and examples thereof include an interlayer insulating film, a passivation film, and a gate insulating film of a thin film transistor. Further, since it has a low dielectric constant and high transparency in the visible light region, it is particularly suitable as a material for forming a gate insulating film of a thin film transistor.

The insulating film may be cross-linked by applying the curable resin composition of the present invention to a substrate, drying, and then baking, or irradiating active energy rays such as ultraviolet rays, electron beams or radiation. It may be formed by photocuring.

The insulating film of the present invention is formed from the curable resin composition. Since it is formed from the said curable resin composition, this insulating film is excellent in flexibility. Furthermore, it is excellent in heat resistance, low dielectric constant and transparency.

Although the curable resin composition of the present invention can form an insulating film, it is also excellent as a composition for forming an insulating film for forming a semiconductor element because it is excellent in low dielectric constant and transparency.

The curable resin composition of the present invention is preferably used for forming a gate insulating film of a thin film transistor. The curable resin composition of the present invention has high heat resistance, transparency in the visible light region, excellent low dielectric constant and flexibility, and is soluble in general-purpose solvents, so when a gate insulating film of a thin film transistor is formed. Since it is a coating type, the cost can be reduced, and a large-area film can be easily formed.

The thin film transistor having a gate insulating film obtained from the curable resin composition of the present invention preferably has a semiconductor layer, the gate insulating film, and a gate electrode layer laminated in this order. Such a thin film transistor in which the semiconductor layer, the gate insulating film, and the gate electrode layer are stacked in this order is also one aspect of the present invention. Since the thin film transistor uses the gate insulating film, it is excellent in flexibility, heat resistance, and transparency.

The thin film transistor is suitable as a thin film transistor for a display device such as a liquid crystal display device or an organic electroluminescence display device.
Moreover, since it is excellent in flexibility, it is also useful as a thin film transistor used for a display device using a flexible substrate, for example.

FIG. 3 shows an example of an inverted coplanar thin film transistor. In the thin film transistor 1 shown in FIG. 3, a gate insulating film 31 and a semiconductor layer 33 are formed in this order on a gate electrode layer 30, and a source / drain electrode 34 is formed with an oxide film 35 interposed therebetween. A passivation film 32 is formed on the source / drain electrode 34.
The thin film transistor of the present invention is not limited to such a back gate type thin film transistor, and may be a top gate type thin film transistor.

The semiconductor layer is a layer that becomes an active layer of the thin film transistor and is made of a semiconductor. The semiconductor may be a group IV semiconductor such as silicon or germanium, a group III-V compound semiconductor such as gallium arsenide or gallium nitride, or a group II-VI compound such as zinc oxide. It may be a semiconductor or the like. Organic semiconductors such as pentacene and thiophene may also be used. From a practical viewpoint, silicon is preferable. As the semiconductor layer, various semiconductors such as single crystal, polycrystal, and amorphous can be used.

A material for forming the gate electrode layer is not particularly limited, and a material for forming a normal gate electrode layer can be used. For example, metals such as copper, aluminum, and gold can be used.

Moreover, since the insulating film of the present invention has high transparency, it is also useful as an insulating film in LED elements.

As a more preferable structure of the curable resin composition of this invention, the following can be illustrated, for example, but this invention is not limited to this.

(Example I)
Fluoropolymer (A) component: Homopolymer organosilicon compound (B) composed of structural unit L2 having a silane coupling group in the side chain Component: Hydrolytic condensable silane compound Solvent: Ketone solvent, acetate solvent, alcohol 1 to 50 parts by mass of component (A) for 100 parts by mass (solid content) of component (B) component (B) component based on solvent, fluorine-containing alcohol solvent or aromatic solvent composition solvent: an appropriate amount as required

Next, although this invention is demonstrated based on a synthesis example, a manufacture example, an Example, etc., this invention is not limited to these examples. In addition, the apparatus and measurement conditions used for physical property evaluation are as follows.

(1) NMR: manufactured by BRUKER
¹ H-NMR measurement conditions: 300 MHz (tetramethylsilane = 0 ppm)
¹⁹ F-NMR measurement conditions: 282 MHz (trichlorofluoromethane = 0 ppm)

(2) IR analysis: FT-IR SPECTROMETER 1760X manufactured by PERKIN ELMER

(3) Weight average molecular weight Mw and number average molecular weight Mn:
By gel permeation chromatography (GPC). Using Shodex GPC-104 manufactured by Showa Denko KK, using a column manufactured by Shodex (1 GPC KF-604, 1 GPC KF-603, 2 GPC KF-602 connected in series) Calculated from data measured by flowing tetrahydrofuran (THF) as a solvent at a flow rate of 0.5 ml / min.

Synthesis Example 1 (Synthesis of fluorinated allyl ether homopolymer having OH group)
In a 100 mL glass four-necked flask equipped with a stirrer and a thermometer, the following formula:

20 g of perfluoro (1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxanonenol) represented by the formula: [H- (CF ₂ CF ₂ ) ₃ —COO -] ₂ 8.0% by weight perfluorohexane solution was placed 21.2g of, after thorough nitrogen substitution was performed for 24 hours with stirring under 20 ° C. nitrogen stream, a solid having a high viscosity was produced. A solution obtained by dissolving the obtained solid in diethyl ether was poured into perfluorohexane, separated and vacuum dried to obtain 17.6 g of a polymer. When this polymer was analyzed by ¹⁹ F-NMR, ¹ H-NMR analysis, and IR analysis, it was a fluorine-containing polymer consisting only of structural units derived from the fluorine-containing allyl ether and having a hydroxyl group at the end of the side chain. . Moreover, the number average molecular weight measured by GPC analysis using tetrahydrofuran (THF) as a solvent was 62000, and the weight average molecular weight was 151000.

Synthesis Example 2 (Synthesis 1 of fluorine-containing curable polymer having an allyl group)
In a 200 mL four-necked flask equipped with a reflux condenser, a thermometer, a stirring device, and a dropping funnel, 80 mL of dimethylformamide (DMF), 10.0 g of a hydroxyl group-containing fluorine-containing allyl ether homopolymer obtained in Synthesis Example 1 Then, 1.0 g of NaOH was charged and stirred at 60 ° C. for 3 hours. While stirring in a nitrogen stream, 4.0 g of allyl bromide was further added dropwise over about 5 minutes. After completion of dropping, stirring was continued at 60 ° C. for 4.0 hours. When the DMF solution after the reaction was added to 100 ml of 0.1N hydrochloric acid water, a solid was precipitated. This solid is dissolved in 50 ml of diisopropyl ether, 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 the ether solution separated by filtration. did. When this ether solution was examined by ¹ H-NMR analysis, the proton of the hydroxyl group disappeared. Moreover, when it applied to the NaCl board and made the cast film | membrane at room temperature by IR analysis, the absorption (3200cm < ^-1 >) of the hydroxyl group lose | disappeared.

Synthesis Example 3 (Synthesis 2 of fluorine-containing curable polymer having an allyl group)
The reaction was carried out in the same manner except that pyridine was used in place of the base NaOH in Synthesis Example 2 to obtain the desired product.

Synthesis Example 4 (Synthesis of fluorine-containing curable polymer having trimethoxysilyl group)
In a 300 mL four-necked flask equipped with a thermometer, a stirrer, and a dropping funnel, 100 mL of diisopropyl ether, 10.0 g of the allyl group-containing fluorinated allyl ether homopolymer obtained in Synthesis Examples 2 and 3, and 10.0 g of chlorosilane was added and stirred at 60 ° C. for 4 hours. While stirring under a nitrogen stream, 5 mg of chloroplatinic acid was added and stirring was continued for another 0.5 hours. To this mixture, 15.0 g of trimethyl orthoformate and 1.0 g of methanol were added and reacted at 60 ° C. for 14 hours. When applied to a NaCl plate and made into a cast film at room temperature, IR and ¹ H-NMR analysis revealed that absorption of double bonds disappeared and the reaction was completed. The reaction product was filtered through activated carbon and celite, and diisopropyl ether was distilled off to obtain a fluorine-containing curable polymer having a trimethoxysilyl group as an amorphous solid.

Synthesis Example 5 (Synthesis of fluorine-containing curable polymer having triethoxysilyl group)
The reaction is carried out in the same manner as in Synthesis Example 4 except that triethoxysilane is used instead of trichlorosilane, and the dehydrochlorination reaction with alcohol is not performed, and it contains a triethoxysilyl group which is an amorphous solid. A fluorine curable polymer was obtained.

Synthesis Example 6 (Synthesis of fluorine-containing curable polymer having α-fluoroacryloyl group)
In a 200 mL four-necked flask equipped with a reflux condenser, thermometer, stirrer, and dropping funnel, 80 mL of diethyl ether, 5.0 g of the hydroxyl group-containing fluorine-containing allyl ether homopolymer obtained in Synthesis Example 1, and pyridine 1.0 g was charged and ice-cooled to 5 ° C. or lower. While stirring in a nitrogen stream, a solution of 1.2 g of α-fluoroacrylic acid fluoride [CH ₂ ═CFCOF] in 20 mL of diethyl ether 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. The ether solution after the reaction was 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 was separated by filtration. When this ether solution was examined by ¹⁹ F-NMR analysis, a copolymer of [—O—COCF═CH ₂ group-containing fluorine-containing allyl ether] / [OH group-containing fluorine-containing allyl ether] = 50/50 mol% was obtained. Included. Further, by coating the 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 . The obtained fluorine-containing curable polymer (ether solution) having an α-fluoroacryloyl group was put into 100 ml of n-hexane, and the precipitate was collected. The target polymer was obtained by drying under reduced pressure at room temperature.

Synthesis example 7
In a 500 ml glass four-necked flask equipped with a stirrer and a thermometer, 80 g of methyl methacrylate (MMA), 20 g of hydroxyethyl methacrylate (HEMA), 1.5 g of azobisisobutyronitrile (AIBN), solvent As a starting material, 300 g of butyl acetate was added, and the mixture was stirred well at room temperature and polymerized under a nitrogen stream at a temperature of 70 ° C. for 16 hours. The obtained polymer was reprecipitated in n-hexane to obtain 91 g of polymer. Its number average molecular weight was 33,000. When this polymer was analyzed by ¹⁹ F-NMR, ¹ H-NMR analysis, and IR analysis, it was confirmed to be a copolymer of MMA and HEMA. The composition ratio was determined by NMR as MMA: HEMA = 83: 17 (molar ratio).
10 g of the obtained polymer was weighed and dissolved in 40 g of methyl isobutyl ketone (MIBK) previously dehydrated with molecular sieves 4A, and charged into a 100 ml glass four-necked flask equipped with a stirrer and a thermometer. From the dropping funnel, 0.74 g of allyl isocyanate was added dropwise at room temperature, and the mixture was sufficiently stirred to homogenize. Thereafter, it was placed in an oil bath, and the internal temperature was kept at 80 ± 5 ° C. and stirred for 5 hours. By measuring the IR of the reaction solution, it was confirmed that the raw material allyl isocyanate was not present in the system. Thereafter, the reaction solution was concentrated with a rotary evaporator, the solvent was removed by a casting method, and the precipitated solid was dissolved again in a small amount of acetone. The polymer was purified by reprecipitation of this solution in a sufficiently large amount of n-hexane. This purification operation was repeated a total of 3 times, and the obtained polymer was analyzed by ¹⁹ F-NMR, ¹ H-NMR analysis, and IR analysis.

(Wherein, m: n: o = 10: 6: 84).

Example 1 (Tetraethoxysilane (TEOS) / Synthesis Example 3 Preparation of 40 wt% MIBK Solution of Polymer = 9/1)
4 g of the polymer of Synthesis Example 4 and 36 g of TEOS were dissolved in 60 g of MIBK and sufficiently stirred to prepare a heat hydrolysis type heat-resistant transparent film material solution.

Example 2 (Tetraethoxysilane (TEOS) / Synthesis Example 3 Preparation of 20 wt% MIBK Solution of Polymer = 9/1)
2 g of the polymer of Synthesis Example 4 and 18 g of TEOS were dissolved in 80 g of MIBK and sufficiently stirred to prepare a thermal hydrolysis type heat-resistant transparent film material solution.

Example 3 (Tetraethoxysilane (TEOS) / Synthesis Example 3 Preparation of 40 wt% MIBK Solution of Polymer = 4/1)
8 g of the polymer of Synthesis Example 4 and 32 g of TEOS were dissolved in 60 g of MIBK and sufficiently stirred to prepare a heat hydrolysis type heat-resistant transparent film material solution.

Example 4 (Tetraethoxysilane (TEOS) / Synthesis Example 3 Preparation of 20 wt% MIBK Solution of Polymer = 4/1)
4 g of the polymer of Synthesis Example 4 and 16 g of TEOS were dissolved in 80 g of MIBK and sufficiently stirred to prepare a thermal hydrolysis type high heat resistant transparent film material solution.

Example 5 (Tetraethoxysilane (TEOS) / Synthesis Example 5 Preparation of 40 wt% MIBK Solution of Polymer = 9/1)
4 g of the polymer of Synthesis Example 5 and 36 g of TEOS were dissolved in 60 g of MIBK and sufficiently stirred to prepare a heat hydrolysis type heat-resistant transparent film material solution.

Example 6 (Tetraethoxysilane (TEOS) / Synthesis Example 5 Preparation of 20 wt% MIBK Solution of Polymer = 9/1)
2 g of the polymer of Synthesis Example 5 and 18 g of TEOS were dissolved in 80 g of MIBK and sufficiently stirred to prepare a heat hydrolysis type heat-resistant transparent film material solution.

Example 7 (Tetraethoxysilane (TEOS) / Synthesis Example 5 Preparation of 40 wt% MIBK Solution of Polymer = 4/1)
8 g of the polymer of Synthesis Example 5 and 32 g of TEOS were dissolved in 60 g of MIBK and sufficiently stirred to prepare a thermal hydrolysis type heat-resistant transparent film material solution.

Example 8 (Tetraethoxysilane (TEOS) / Synthesis Example 5 Preparation of 20 wt% MIBK Solution of Polymer = 4/1)
4 g of the polymer of Synthesis Example 5 and 16 g of TEOS were dissolved in 80 g of MIBK and sufficiently stirred to prepare a thermal hydrolysis type heat-resistant transparent film material solution.

Example 9 (Synthesis Example 4 Preparation of 20 wt% PGMEA solution of polymer)
20 g of the polymer of Synthesis Example 5 was dissolved in 80 g of MIBK and sufficiently stirred to prepare a heat hydrolysis type high heat-resistant transparent film material solution.

Example 10 (Synthesis Example 5 Preparation of 20 wt% PGMEA solution of polymer)
20 g of the polymer of Synthesis Example 5 was dissolved in 80 g of MIBK and sufficiently stirred to prepare a heat hydrolysis type high heat-resistant transparent film material solution.

Comparative Example 1
5.6 g of the fluorinated curable polymer having an α-fluoroacryloyl group obtained in Synthesis Example 6 and 0.1 g of a polymerization initiator Irgacure 907 (manufactured by Ciba Specialty) were dissolved in 22.4 g of MIBK and stirred sufficiently. A MIBK solution in which the polymer obtained in Synthesis Example 6 was 20 wt% was obtained.

Example 11 (Oxetane-modified silsesquioxane / Synthesis Example 3 polymer = 9/1 composition)
To 1.0 g of the polymer of Synthesis Example 5, 9.0 g of OX-SQ-H (manufactured by Toagosei Co., Ltd.), 0.2 g of triethoxysilylpropyl methacrylate, 0.03 g of polymerization initiator Irgacure 907 (manufactured by Ciba Specialty) In addition, the composition for sealing was prepared by sufficiently stirring.

Example 12 (Oxetane-modified silsesquioxane / Synthesis Example 4 polymer = 4/1 composition)
To 2.0 g of the polymer of Synthesis Example 4, 8.0 g of OX-SQ-H (manufactured by Toagosei Co., Ltd.), 0.2 g of triethoxysilylpropyl methacrylate, and 0.03 g of a polymerization initiator Irgacure 907 (manufactured by Ciba Specialty) In addition, the composition for sealing was prepared by sufficiently stirring.

Comparative Example 2 (Oxetane-modified silsesquioxane / Synthesis Example 7 polymer = 9/1 composition)
A sealing composition was prepared by adding 1.0 g of the polymer of Synthesis Example 7, 9.0 g of OX-SQ-H (manufactured by Toagosei Co., Ltd.) and 0.03 g of a polymerization initiator Irgacure 907 (manufactured by Ciba Specialty) and stirring sufficiently. A product was prepared.

Test Example 1 (Curing conditions and appearance evaluation of cured product)
Each of the compositions obtained in Examples 1 to 10 and Comparative Example 1 was applied using a spin coater while first rotating the wafer at 300 rpm for 3 seconds and then at 4000 rpm for 20 seconds, and after drying, 1 to 2 μm. A film was formed while adjusting to a film thickness of.
When the film obtained by the above method was thermally cured using a hot stage at 120 ° C. for 1 hour, absorption of Si—OH could be confirmed by IR. As a result, the absorption of Si—OH disappeared and a transparent cured film was obtained.
In addition, when the compositions obtained in Examples 1 to 10 and Comparative Example 1 were used, a high-pressure mercury lamp was used for the heat-cured coating, and UV curing was performed at room temperature with an intensity of 1 J / cm ² for photocuring. It was. The appearance was confirmed visually. The results are shown in Table 1.
The criteria for visual confirmation are shown below.
○: Transparent △: Partly cloudy ×: Whole cloudy

Test example 2
For each cured film obtained in Test Example 1, the glass transition temperature (Tg) and the thermal decomposition temperature (Td) were measured. The results are shown in Table 1.
Glass transition temperature (Tg):
Using a differential scanning calorimeter (manufactured by SEIKO, RTG220), the temperature range from 30 ° C. to 600 ° C. was raised / lowered / heated under the condition of 10 ° C./minute (the second temperature increase is called a second run). ) Is the intermediate point of the endothermic curve in the second run obtained as Tg (° C.).
Thermal decomposition temperature (Td):
Using a TGA-50 type thermobalance manufactured by Shimadzu Corporation, the temperature at which a 1% mass decrease starts is measured at a heating rate of 10 ° C./min.

Test example 3
Using the compositions (MIBK solution) obtained in Examples 1 to 10 and Comparative Example 1, the transmittance and refractive index of the cured film were measured by the following method. The results are shown in Table 1.
Sample preparation:
Each of the compositions obtained in Examples 1 to 10 was applied to an 8-inch silicon wafer substrate using a spin coater while rotating the wafer at 300 rpm for 3 seconds and then at 4000 rpm for 20 seconds, and after drying. The film was formed while adjusting to a film thickness of 1 to 2 μm.
Refractive index measurement:
The refractive index and film thickness of each wavelength light are measured using a spectroscopic ellipsometer (VASE ellipsometer manufactured by JA Woollam).

Test Example 4 (Measurement of haze value and total light transmittance)
The composition obtained in Examples 1 to 10 or Comparative Example 1 was applied on a slide glass using a spin coater under conditions of 500 rpm and 30 seconds. Using a hot stage, it was cured by heating at 120 ° C. for 1 hour, 200 ° C. for 10 minutes, and the haze value and total light transmittance were measured. The results are shown in Table 1.
Measurement of haze value:
Measurement was performed according to ASTM D1003 using a haze meter (Hazeguard II manufactured by Toyo Seiki Co., Ltd.).
Measurement of total light transmittance:
It measured using the self-recording spectrophotometer (U-3310 (brand name) by Hitachi, Ltd.).

Test Example 5 (Durability evaluation)
Among the cured films obtained in Test Example 4, a cured film produced using the compositions obtained in Examples 4, 7 and 9 was measured using a spectrophotometer U-4100 (manufactured by Hitachi, Ltd.). The absorption spectrum was measured using (initial value). The coating film obtained by heat-curing showed very high transparency in the visible band (400 to 650 nm).
Next, the durability of the coating film was evaluated under the following three conditions.
[1] High temperature heat resistance test at 265 ° C. for 10 minutes [2] High temperature and high humidity durability test at 85 ° C. and 85% (measured absorption spectrum after 600 hours)
[3] Dry heat durability test at 125 ° C. (Measurement of absorption spectrum after 1050 hours)
265 ° C. after 10 minutes (high temperature heat resistance test), 85 ° C., 85%, after 600 hours (high temperature and high humidity durability test), and 125 ° C. after 1050 hours (dry heat durability test) Table 2 shows presence / absence, change in refractive index, and change in transmittance at 450 nm and 550 nm (relative values when the initial value is 100). Almost the initial value was maintained, and high durability could be confirmed.

Test Example 6
For the sealing compositions obtained in Examples 11 and 12, and Comparative Example 2, the appearance of the liquid composition before curing at 25 ° C. was visually observed, and a self-recording spectrophotometer U-3310 (Hitachi Co., Ltd.) By measuring the light transmittance at 550 nm using a manufacturing method), the following criteria were used for evaluation, and the viscosity at 25 ° C. of the liquid composition before curing was measured by the following method. The results are shown in Table 3.
Appearance evaluation criteria:
○: 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.
Measurement of viscosity (mPa · s):
CP-100 cone is used in a cone plate viscometer CV-1E manufactured by Tokai Yagami Co., Ltd., and the viscosity at 25 ° C. is measured under the condition of 100 rpm, and a stable value is adopted for 60 seconds.

Test Example 7
NF-0100 (thickness: 100 μm) manufactured by Daikin Industries, Ltd., which is a fluororesin film for mold release, is placed on a glass plate, and the sealing composition obtained in Examples 11, 12 and Comparative Example 2 is used. Are coated with an applicator so that the film thickness becomes about 100 μm, and further, NF-0100 (thickness 100 μm) manufactured by Daikin Industries, Ltd., which is a fluororesin film for mold release, is further covered from the top. After placing a slide glass having a thickness of 1 mm, it was cured at 100 ° C. for 2 hours and subsequently at 150 ° C. for 1 hour. After curing, the release fluororesin film was peeled off to obtain a cured film.
The fluorine content, refractive index (n), thermal decomposition temperature (Td), and visible light transmittance (550 nm) (T) of the sample film (after curing) were measured. The results are shown in Table 3.
Method for measuring fluorine content (% by mass):
By burning 10 mg of sample by the oxygen flask combustion method, absorbing the decomposition gas in 20 ml of deionized water, and measuring the fluorine ion concentration in the absorption liquid by the fluorine selective electrode method (fluorine ion meter, model 901 manufactured by Orion) Ask.
In addition, the measuring method of refractive index (n), thermal decomposition temperature (Td), and visible light transmittance (550 nm) (T) is as having mentioned above.

Moreover, the external appearance of the said cured film was evaluated visually. The results are shown in Table 3. The evaluation criteria are as follows.
○: Transparent and uniform.
Δ: Some cloudiness is observed.
X: Opaque and cloudy.

Moreover, the solvent resistance of the cured film was evaluated. The results are shown in Table 3. The test methods and evaluation criteria are as follows.
Test method:
A 10 mm × 10 mm × 0.1 mm sample is immersed in 20 mL of butyl acetate, and the appearance after 8 hours at room temperature is visually observed.
Evaluation criteria:
○: No swelling is visually observed.
Δ: Swelling is visually observed.
X: Dissolve.

Furthermore, the heat resistance of the cured film was evaluated. The results are shown in Table 3. The test methods and evaluation criteria are as follows.
Test method:
Each sample is held at a temperature of 180 ° C. for 1 hour, and the change in appearance is visually observed.
Evaluation criteria:
○: No change is visually observed.
Δ: Slight discoloration and turbidity are observed visually.
X: Discoloration, white turbidity, deformation, etc. that are clearly visible are observed.

The fluorine-containing polymer of the present invention provides a curable resin composition that can form a thin film having a low refractive index, high transparency, and excellent heat resistance, and also provides physical and chemical properties. Since it is excellent in stability, it is particularly suitable as a raw material for a sealing member used in a light receiving element such as a CCD module. The cured product obtained from the curable resin composition containing the fluoropolymer of the present invention has excellent heat resistance, high light transmittance, and excellent light resistance. It can be particularly suitably used as a material for forming the member. The fluorine-containing polymer of the present invention can also constitute a composition capable of forming a coating type insulating film, and can be applied to various applications. In particular, it can be suitably used as a material for forming an insulating film used for an application for forming a large area insulating film or an application requiring flexibility. Further, it is suitable as an insulating film for a semiconductor element, and particularly suitable as a material for forming a gate insulating film of a thin film transistor.

1: Thin film transistor 11, 21: Silicon wafer 12, 22: CCD element part 13, 23: Sealant layer 14, 24: Glass 15, 25: Through electrode 16, 26: Electrode connected to outside 30: Gate electrode layer 31 : Gate insulating film 32: Passivation film 33: Semiconductor layer 34: Source / drain electrode 35: Oxide film

Claims (15)

The following formula (L):

Wherein X ¹ and X ² are the same or different and are H or F. X ³ is H, F, CH ₃ or CF _3. X ⁴ and X ⁵ are the same or different, respectively F or CF _3. Rf is a fluorine-containing hydrocarbon group having 4 to 40 carbon atoms or a fluorine-containing hydrocarbon group having an ether bond having 5 to 100 carbon atoms, a is an integer of 0 to 3; B and c are the same or different and are 0 or 1.) and a fluorine-containing polymer having a structural unit represented by
Rf in the formula (L) represents the following formula (Rf):
_{- (R-O) n -R} 'n' -CH 2-x {(CX a X b) m CR 1 HCR 2 R 3 Y} x OH 1-y {(CX a X b) m CR 1 HCR 2 R ³ Y} _y (Rf)
(In the formula, R is the same or different and is a fluorine-containing alkylene group having 1 to 5 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom. R ′ is the same or different and contains at least a hydrogen atom. 1 is a fluorine-containing alkylene group having 1 to 5 carbon atoms, which is substituted with a fluorine atom, X ^a and X ^b are the same or different and each may have H, a halogen atom or a substituent. A hydrocarbon group having 1 to 10 carbon atoms, R ¹ , R ² and R ³ are the same or different and each having 1 to 10 carbon atoms which may have H, a halogen atom or a substituent; Y is the same or different and is a hydrolyzable metal alkoxide moiety having 1 to 50 carbon atoms, n is an integer of 0 to 20, and n ′ is an integer of 0 to 10. m Is an integer from 1 to 12. x is an integer from 0 to 2, Is 0 or 1. However, when x is 0, the fluorine-containing polymer characterized by y is a fluorine-containing hydrocarbon group represented by a 1.). The fluorine-containing polymer according to claim 1, further comprising another structural unit other than the structural unit represented by the formula (L). A curable resin composition comprising the fluoropolymer (A) according to claim 1 or 2 and an organosilicon compound (B). The curable resin composition according to claim 3, wherein the organosilicon compound (B) is 50% by mass or more based on the total mass of the fluoropolymer (A) and the organosilicon compound (B). The curable resin composition of Claim 3 or 4 containing an organic solvent. The curable resin composition according to claim 3, 4 or 5, which is used for sealing an optical element. The curable resin composition according to claim 6, which is for LED sealing. 6. The curable resin composition according to claim 3, 4 or 5, which is used for a gate insulating film of a thin film transistor. Hardened | cured material formed from the curable resin composition of Claim 3, 4, 5, 6, 7 or 8. The cured product according to claim 9, having a refractive index of 1.40 or less. The cured product according to claim 9, which is a sealing member for an optical element. The cured product according to claim 11, wherein the optical element is a light receiving element. The cured product according to claim 11, wherein the optical element is a light emitting element. The cured product according to claim 13, wherein the optical element is an LED. The cured product according to claim 9 which is a gate insulating film of a thin film transistor.

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