JP2012214753A - Curable resin composition and cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition which can form a cured product having a low refractive index, high transparency, and furthermore, superior heat resistance as well.SOLUTION: The curable resin composition comprises an organic silicon compound (A); and a fluorine-containing polymer (B) having a structural unit represented by formula (L) (wherein Xand Xare H or F; Xis H, F, CH, or CF; Xand Xare H, F, or CF; and Rf is an organic group of which 1-3 hydrogen atoms are substituted with a monovalent organic group containing at least one 1-30C hydrolysable metal alkoxide site at the terminus, or a 2-10C monovalent organic group having an ethylenic carbon-carbon double bond at the terminus, and which is a 1-40C fluorine-containing hydrocarbon group which may optionally have an amide bond or urea bond, or a 2-100C fluorine-containing hydrocarbon group having an ether bond which may optionally have an amide bond, carbonate bond, urethane bond or urea bond).

Description

The present invention relates to a curable resin composition and a cured product obtained by curing the curable resin composition.

In recent years, various devices such as CCD elements, CMOS elements, liquid crystals, and MEMS have been widely used, but such devices are structurally susceptible to the external environment, and are used in an airtight package to avoid this. Yes.

For example, in an image sensor such as a CCD used in a camera module of a mobile phone, after the sensor is stored in a ceramic package, electrical connection is made by wire bonding, and then covered with a transparent lid such as glass and sealed. The way to stop was taken. However, the connection by wire bonding has a drawback that the overall size of the image sensor is significantly larger than that of the sensor element.

Therefore, as a method of reducing the size of the entire image sensor, holes and grooves that penetrate from the back surface to the front surface of the silicon wafer on which the CCD and CMOS elements are formed are provided, and the front side and the back side of the wafer are electrically connected to an external circuit. There has been proposed a method in which the connection is performed by ball bumps arranged on the back surface of the wafer. By using such a method, the entire image sensor can be reduced in size.
However, even when this method is used, as a sealing method, sealing is performed by covering the sensor element with a transparent lid such as glass. Therefore, the size of the image sensor is limited and the number of processes increases. Further, since a space exists between the sensor element and the lid, and the visibility is inferior due to reflection at the interface, a sealing method in place of the above method is required.

On the other hand, for example, it is conceivable to seal the surface of the sensor element with a transparent lid such as glass directly through a sealing member. In this method, since a device can be manufactured by dicing after laminating with glass through a sealing member at the wafer level, the number of steps can be greatly reduced. However, when a CCD element having such a structure is manufactured, a sealing member having a low refractive index and high transparency is required, but there has been no sealing member having sufficient characteristics. .

For example, Patent Document 1 describes a curable fluorine-containing polymer having a specific structure having a hydrolyzable metal alkoxide moiety. However, 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 a CCD element.

Patent Document 2 discloses a structural unit having a fluorine-containing alkyl group having an ethylenic carbon-carbon double bond at a 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), a fluorine-containing surface modifier (B), and hollow silica fine particles (C) is disclosed. However, the curable resin composition described in Patent Document 2 has no problem with transparency as long as it is a thin film of about 100 nm. However, when the thickness is about 1 to 10 μm, which is a necessary thickness for a sealing member, hollow silica is used. The haze was increased by the aggregation of the fine particles, which was not sufficient from the viewpoint of transparency.

International Publication 2006/027958 Pamphlet JP 2008-40262 A

The present invention provides a curable resin composition that can form a cured product having a low refractive index, high transparency, and excellent heat resistance.

As a result of intensive studies on the fluorine-containing resin composition for sealing that the present inventors can suitably use as a sealing agent for optical elements, a modified fluorine-containing allyl ether polymer having a specific structure and a specific organic silicon It has been found that by using a fluorine-containing resin composition comprising a compound, a cured product having a low refractive index, high transparency, and excellent heat resistance can be obtained.

That is, the present invention
An organosilicon compound (A), and
The following formula (L):

（式中、Ｘ^１およびＸ^２は同じか又は異なり、Ｈ又はＦ；Ｘ^３はＨ、Ｆ、ＣＨ_３又はＣＦ_３；Ｘ^４およびＸ^５は同じか又は異なり、Ｈ、Ｆ又はＣＦ_３；Ｒｆは、アミド結合若しくはウレア結合を有していてもよい炭素数１〜４０の含フッ素炭化水素基、又は、アミド結合、カーボネート結合、ウレタン結合若しくはウレア結合を有していてもよい炭素数２〜１００のエーテル結合を有する含フッ素炭化水素基であって、水素原子の１〜３個がＹ（Ｙは、末端に炭素数１〜３０の加水分解性金属アルコキシド部位を少なくとも１個含む１価の有機基、又は、末端にエチレン性炭素−炭素二重結合を有する炭素数２〜１０の１価の有機基である。）で置換されている有機基；ａは０〜３の整数；ｂおよびｃは同じか又は異なり、０又は１である。）で示される構造単位を有する含フッ素ポリマー（Ｂ）、からなることを特徴とする硬化性樹脂組成物である。

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 ; Rf is a fluorine-containing hydrocarbon group having 1 to 40 carbon atoms which may have an amide bond or a urea bond, or 2 carbon atoms which may have an amide bond, a carbonate bond, a urethane bond or a urea bond. A fluorine-containing hydrocarbon group having an ether bond of ˜100, wherein 1 to 3 of the hydrogen atoms are Y (Y is a monovalent containing at least one hydrolyzable metal alkoxide moiety having 1 to 30 carbon atoms at the terminal) Or a monovalent organic group having 2 to 10 carbon atoms having an ethylenic carbon-carbon double bond at the terminal.); A is an integer of 0 to 3; b And c are the same or different and are 0 or 1 A curable resin composition comprising a fluorine-containing polymer (B) having a structural unit represented by:

The organosilicon compound (A) has the following formula (1):
{Si (R ^a ) _s (R ^b ) _t (R ^c ) _u (R ^d ) _v (R ^e ) _w } _n (1)
(Wherein 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, an alkyl group having 1 to 10 carbon atoms, or 5 to 5 carbon atoms. An aryl group having 10 carbon atoms, an allyl group having 1 to 10 carbon atoms, or a glycidyl group, and R ^e is the same or different and is —O—, —NH—, —C≡C—, or a silane single bond. s, t, u and v are the same or different and are 0 or 1, w is an integer of 0 to 4, and n is 1 to 20. When 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 and is 0 to 4, w is the same or different and is 0 to 4, and when w is an integer of 1 or more, at least 2 This of Si through R ^e, linear, ladder, attached cyclic, or double cyclic It is preferably a compound represented by (A1) in).

The organosilicon compound (A) is preferably tetraalkoxysilane.

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

The cured product preferably has a refractive index of 1.35 or less.

The optical element is preferably a light receiving element.

The optical element is preferably a light emitting element.

The curable resin composition of the present invention can form a cured product having a low refractive index, high transparency, and excellent heat resistance.

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.

The curable resin composition of this invention consists of an organosilicon compound (A). The organosilicon compound (A) is a compound containing carbon and silicon. The organosilicon compound (A) is preferably liquid at normal temperature (for example, 25 ° C.).

Examples of the organosilicon compound (A) include Si-H compounds having Si-H bonds; Si-N compounds having Si-N bonds such as aminosilane compounds, silazanes, silylacetamides, 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 (A) is selected from the group consisting of Si—H compound, Si—N compound, halogenosilane, Si— (C) ₄ compound, Si—Si compound, vinyl silane, allyl silane, and ethynyl silane. 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 (A) is represented by the following formula (1):
{Si (R ^a ) _s (R ^b ) _t (R ^c ) _u (R ^d ) _v (R ^e ) _w } _n (1)
(Wherein 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, an alkyl group having 1 to 10 carbon atoms, or 5 to 5 carbon atoms. An aryl group having 10 carbon atoms, an allyl group having 1 to 10 carbon atoms, or a glycidyl group, and R ^e is the same or different and is —O—, —NH—, —C≡C—, or a silane single bond. s, t, u and v are the same or different and are 0 or 1, w is an integer of 0 to 4, and n is 1 to 20. When 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 and is 0 to 4, w is the same or different and is 0 to 4, and when w is an integer of 1 or more, at least 2 This of Si through R ^e, linear, ladder, attached cyclic, or double cyclic And more preferably a compound represented by (A1) in). 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.
The amino group includes —NH ₂ , —NHR, and —NRR ′ (R and R ′ are the same or different and are alkyl groups having 1 to 10 carbon atoms).

In formula (1), 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, otherwise It is preferable that they are a C1-C10 alkyl group, a C5-C10 aryl group, a C1-C10 allyl group, or a 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 (1), 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 5 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, Or it is preferable that it is an 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. Further, a 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, and a butyl group. For example, as R ^a , R ^b , R ^{c, and} R ^d , a methyl group, an ethyl group, a propyl group, or An isopropyl group is preferred. More preferably, they are a methyl group and an ethyl group.
The aryl group is preferably, for example, a pentyl group, a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, or a dimethylphenyl group.
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. Further, a 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 single bond.
The case R ^e is a silane bond is substantially not through the R ^h, it refers to the case where Si and Si are directly bonded. 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 (A1) 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 (A1) is preferably tetraalkoxysilane, and in the above formula (1), 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 (A1) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, and tetra-tert-butoxysilane. Tetraphenoxysilane and the like, and among these, at least one compound selected from the group consisting of tetramethoxysilane and tetraethoxysilane is preferable, and more preferably, it is easily available 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 (A1) is an allyl group having 1 to 5 carbon atoms, a glycidyl group having 1 to 5 carbon atoms, an acryl group (CH ₂ ═CHCOO—), or a methacryl group (CH _2). = CCH ₃ COO-) is also preferred. That is, in the compound (A1), 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 acrylic group, or a methacryl group. It is preferable.

The fluorine-containing polymer (B) has the following formula (L):

（式中、Ｘ^１およびＸ^２は同じか又は異なり、Ｈ又はＦ；Ｘ^３はＨ、Ｆ、ＣＨ_３又はＣＦ_３；Ｘ^４およびＸ^５は同じか又は異なり、Ｈ、Ｆ又はＣＦ_３；Ｒｆは、アミド結合若しくはウレア結合を有していてもよい炭素数１〜４０の含フッ素炭化水素基、又は、アミド結合、カーボネート結合、ウレタン結合若しくはウレア結合を有していてもよい炭素数２〜１００のエーテル結合を有する含フッ素炭化水素基であって、水素原子の１〜３個がＹ（Ｙは、末端に炭素数１〜３０の加水分解性金属アルコキシド部位を少なくとも１個含む有機基、又は、末端にエチレン性炭素−炭素二重結合を有する炭素数２〜１０の１価の有機基である。）で置換されている有機基；ａは０〜３の整数；ｂおよびｃは同じか又は異なり、０又は１である。）で示される構造単位（以下、「構造単位Ｌ」ともいう。）を有する。上記エーテル結合は、−Ｏ−で表される２価の基である。アミド結合は、−ＣＯＮＨ−で表される２価の基である。カーボネート結合は、−Ｏ−ＣＯＯ−で表される２価の基である。ウレタン結合は、−Ｏ−ＣＯＮＨ−で表される２価の基である。上記ウレア結合は、−ＮＨ−ＣＯＮＨ−で表される２価の基である。
なお、本明細書中で、後述する「炭化水素基」は、炭素及び水素からなる有機基であり、「含フッ素炭化水素基」は、炭化水素基が有する一部又は全部の水素原子がフッ素原子で置換されたものである。「炭化水素基」としては、例えば、アルキル基、アリル基、環状アルキル基、不飽和アルキル基等が挙げられる。「含フッ素炭化水素基」としては、含フッ素アルキル基、含フッ素アリル基、含フッ素環状アルキル基、含フッ素不飽和アルキル基等が挙げられる。
上記Ｙは、ケトン結合（−ＣＯ−）、エーテル結合又はエステル結合（−ＣＯＯ−）を有していてもよい。

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 ; Rf is a fluorine-containing hydrocarbon group having 1 to 40 carbon atoms which may have an amide bond or a urea bond, or 2 carbon atoms which may have an amide bond, a carbonate bond, a urethane bond or a urea bond. A fluorine-containing hydrocarbon group having an ether bond of ˜100, wherein 1 to 3 of hydrogen atoms are Y (Y is an organic group containing at least one hydrolyzable metal alkoxide moiety having 1 to 30 carbon atoms at the terminal) Or an organic group substituted with a monovalent organic group having 2 to 10 carbon atoms having an ethylenic carbon-carbon double bond at the terminal); a is an integer of 0 to 3; b and c are Same or different, 0 or 1. ) (Hereinafter also referred to as “structural unit L”). The ether bond is a divalent group represented by —O—. The amide bond is a divalent group represented by —CONH—. The carbonate bond is a divalent group represented by —O—COO—. The urethane bond is a divalent group represented by —O—CONH—. The urea bond is a divalent group represented by -NH-CONH-.
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.
Y may have a ketone bond (—CO—), an ether bond, or an ester bond (—COO—).

By having the above-mentioned configuration, the fluoropolymer (B) can be suitably crosslinked with SiOx formed from the compound (A), and the formed cured product has excellent flexibility. it can. Moreover, since the hardened | cured material formed consists of SiOx, it is excellent in heat resistance and transparency.

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 (B) containing the structural unit L1 has a particularly low refractive index, can increase the transparency of the thin film obtained from the curable resin composition of the present invention, and can be used for various substrates. It is preferable in that it can improve the adhesion durability. Moreover, it is preferable also in the point which can make high the curing reactivity by contact of a heat | fever, a radical, or a cation.

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 of the present invention, has good adhesion to various substrates, and improves durability. In addition to being excellent in that it can be produced, 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 -T (T _{is, -CH 2 O- (CO) -CF} = CH 2, or, -ry-Si (OR ²⁰ ) (OR ²¹ ) (OR ²² ) and (Ry are the same as those described below. R ²⁰ , R ²¹ and R ²² are the same or different and are alkyl groups having 1 to 5 carbon atoms. Where n is 0, 1 or 2).

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, as described above, a fluorine-containing hydrocarbon group having 1 to 40 carbon atoms that may have an amide bond or a urea bond, or an amide bond, a carbonate. A fluorine-containing hydrocarbon group having an ether bond having 2 to 100 carbon atoms, which may have a bond, a urethane bond or a urea bond, wherein 1 to 3 hydrogen atoms are Y (Y is a carbon atom at the terminal) An organic group containing at least one hydrolyzable metal alkoxide moiety having 1 to 30 or a monovalent organic group having 2 to 10 carbon atoms having an ethylenic carbon-carbon double bond at the terminal. It is an organic group.
Fluorine-containing hydrocarbon group having 1 to 40 carbon atoms which may have amide bond or urea bond, or 2 to 100 carbon atoms which may have amide bond, carbonate bond, urethane bond or urea bond In the fluorine-containing hydrocarbon group having an ether bond, the upper limit of the carbon number thereof is preferably 30, more preferably 20, and particularly preferably 10.

Rf may have Rf ¹ (a fluorine-containing hydrocarbon group having 1 to 40 carbon atoms which may have an amide bond or a urea bond, or an amide bond, a carbonate bond, a urethane bond or a urea bond. A fluorine-containing hydrocarbon group having an ether bond having 2 to 100 carbon atoms, wherein 1 to 3 hydrogen atoms are Y ¹ (Y ¹ is at least a hydrolyzable metal alkoxide moiety having 1 to 30 carbon atoms at the end. An organic group substituted with 1), or Rf ² (an fluorinated hydrocarbon group having 1 to 40 carbon atoms which may have an amide bond or a urea bond). Or a fluorine-containing hydrocarbon group having an ether bond having 2 to 100 carbon atoms, which may have an amide bond, a carbonate bond, a urethane bond or a urea bond, 1 to 3 are Y ² (Y ² is an organic group substituted with a C 2-10 monovalent organic group having an ethylenic carbon-carbon double bond at the end), Or Rf ³ (a fluorine-containing hydrocarbon group having 1 to 40 carbon atoms which may have an amide bond or a urea bond, or an amide bond, a carbonate bond, a urethane bond or a urea bond). A fluorine-containing hydrocarbon group having an ether bond having 2 to 100 carbon atoms, wherein 1 to 2 hydrogen atoms are substituted with Y ¹ , and ¹ to 2 hydrogen atoms are substituted with Y ² Organic group). From the viewpoint of ease of production, Rf is preferably Rf ¹ or Rf ² .

The Rf is preferably ^one of Rf ¹ . The structural unit in which Rf of the structural unit L is Rf ¹ is hereinafter referred to as the structural unit M. In the structural units L1, L2, and L3, structural units in which Rf is Rf ¹ are hereinafter referred to as structural units M1, M2, and M3, respectively. In Rf ¹ above, the hydrolyzable metal alkoxide having 1 to 30 carbon atoms plays a role of causing hydrolysis and polycondensation reaction, thereby cross-linking with SiOx formed from the compound (A), heat resistance and transparency. A cured product having excellent properties and flexibility can be formed.

Preferred Rf ¹ is the formula (Rf ¹ ):
-D-Ry ^(Rf 1)
[Wherein, -D- represents the formula (D):

(In the formula, n is an integer of 0 to 20, R is a C 1-5 divalent fluorine-containing alkylene group in which at least one hydrogen atom is substituted with a fluorine atom, and n is 2 or more. Ry may have an amide bond or a urea bond, and a part or all of the hydrogen atoms may be substituted with fluorine atoms. May have a hydrocarbon group having 1 to 39 carbon atoms, or an amide bond, a carbonate bond, a urethane bond or a urea bond, and a part or all of the hydrogen atoms are substituted with fluorine atoms. Or a hydrocarbon group having an ether bond having 1 to 99 carbon atoms, wherein 1 to 3 hydrogen atoms are substituted with Y ¹ (Y ¹ is the same as above))]] It is done.
The Ry may have an amide bond, a carbonate bond, a urethane bond, a urea bond, or an ether bond, and a part or all of the hydrogen atoms may be substituted with fluorine atoms, having 1 to 39 carbon atoms It is a hydrocarbon group, and preferably an organic group in which ^{1 to} 3 hydrogen atoms are substituted with Y ¹ (Y ¹ is the same as described above).

R is a divalent fluorine-containing alkylene group having 1 to 5 carbon atoms, and has at least one fluorine atom, thereby having a conventional fluorine-free alkoxyl group or alkylene ether unit. The viscosity of the compound can be further reduced as compared with those having it, and it can contribute to an improvement in heat resistance, a decrease in refractive index, an improvement in solubility in a general-purpose solvent, and the like.

As — (O—R) — or (R—O) — in —D—, specifically, — (OCF ₂ CF ₂ CF ₂ ) —, — (CF ₂ CF ₂ CF ₂ O) —, — (OCFQ ¹ CF ₂ )-,-(CFQ ¹ CH ₂ O)-,-(CFQ ¹ CF ₂ O)-,-(OCF ₂ CFQ ¹ )-,-(OCFQ ² )-,-(CFQ ² O) _{-, - (OCH 2 CF 2} CF 2) -, (OCF 2 CF 2 CH 2) -, - (OCH 2 CH 2 CF 2) -, - (OCF 2 CH 2 CH 2) -, - (CH 2 CF _{2 CF 2 O) -, -} (OCF 2 CF 2 CF 2 CF 2) -, - (CF 2 CF 2 CF 2 CF 2 O) -, - (OCFQ 2 CH 2) -, - (CH 2 CFQ 2 O _{) -, - (OCH (CH} 3) CF 2 CF 2) -, - (OCF 2 CF 2 CH (CH ₃ ))-,-(OCQ ³ ₂ )-and-(CQ ³ ₂ O)-(Q ¹ and Q ² are the same or different, H, F or CF ₃ ; Q ³ is CF ₃ ), etc. , -D- is preferably one or more of these repeating units.

Among them, -D- is-(OCFQ ¹ CF ₂ )-,-(OCF ₂ CF ₂ CF ₂ )-,-(OCH ₂ CF ₂ CF ₂ )-,-(OCFQ ² )-,-(OCQ ^{3 _{2) -, - (CFQ 1}} CF 2 O) -, - (CFQ 1 CH 2 O) -, - (CF 2 CF 2 CF 2 O) -, - (CH 2 CF 2 CF 2 O) -, - ( One or more repeating units selected from CFQ ² O)-and-(CQ ³ ₂ O)-are preferred, and in particular,-(OCFQ ¹ CF ₂ )-,-(OCF ₂ CF ₂ CF _{2) -, - (OCH 2} CF 2 CF 2) -, - (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) -} 1 , two or more repeating units selected from -(OCFQ ¹ CF ₂ )-,-(OCF ₂ CF ₂ CF ₂ )-,-(CFQ ¹ CF ₂ O)-,-(CFQ ¹ CH ₂ O)-and-(CF ₂ CF ₂ CF _{2 O)} - it is preferably one or more repeating units selected from. In the case where the structural unit L is the structural unit L2, as -D-, R is-(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) - is preferably at least one selected from the group consisting _{^{of, - (CFQ 1 CF 2 O}} ) -, - (CFQ 1 CH 2 O) - And at least one selected from the group consisting of-(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 .

However, in the units -D- and Rf ^{1 of the} fluorine-containing ether, -OO- (specifically, -R-O-O-R-, -O-O-R-, and -R- OO) etc.) not including structural units.

As Ry in the formula (Rf ¹ ), more specifically, the formula (Ry):
-Ry ¹ (Ry)
[Wherein Ry ¹ represents the formula (Ry ¹ ):
_{^{- (R 11) q - (}} A) p -R 12 - (Y 1a) m (Ry 1)
(In the formula, q is 0 or 1, p is 0 or 1, m is an integer of 1 to 3, and R ¹¹ may have a hydrogen atom partially or entirely substituted with a fluorine atom. A divalent hydrocarbon group having 1 to 5 carbon atoms, A is —O—, —CONH—, —O—COO—, —O—CONH— or —NH—CONH—, and R ¹² represents one hydrogen atom. 1 to 98 carbon atoms in which some or all of the hydrogen atoms may be partially or entirely substituted with fluorine atoms, or part or all of the hydrogen atoms may be substituted with fluorine atoms. Y ^1a is a divalent to tetravalent hydrocarbon group having an ether bond of the formula:
_{^{- [M 1 O (R 29}} ) a (R 30) b (R 31) c (R 32) d] n -M 2 (R 33) e (R 34) f (R 35) g (R 36) h (R ³⁷ ) _i (wherein M ¹ and M ² are the same or different and are a divalent to hexavalent metal atom; a, b, c and d are 0 or 1, and a + b + c + d + 2 is a metal atom M ^1. E, f, g, h and i are 0 or 1, and e + f + g + h + i + 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 have 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 fluorine atoms) An organic group represented by a good hydrocarbon group having 1 to 10 carbon atoms) Represented by n = 0 to 11 integer); and and ^{R 29, R 30, R 31} , R 32, R 33, R 34, R 35, at least one of ^{R 36} and ^{R 37} is a ^{OR 38} there It is preferably a group represented by an organic-inorganic composite group represented by (functional group). If the structural unit M is a structural unit M2, the Ry is preferably -ry ^1.

Specific examples of —R ¹² — in formula (Ry ¹ ) include the following.

As —R ¹² —, for example, at least one selected from the group consisting of — (CH ₂ ) ₃ — and — (CH ₂ ) ₂ — is preferable.

Metals M ¹ and M ^{2 in} Y ^1a include: Cu as group IB; Ca, Sr, Ba as group IIA; Zn as group IIB; B as group IIIA, B, 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.

In particular, Y ^1a is preferably a group IVA, of 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 hydrolyzed / heavy. After condensation, it is preferable from the viewpoint of good adhesion with a substrate having a hydroxyl group and adhesion durability, and-[SiO (OCH ₃ ) ₂ ] _n -Si (OCH ₃ ) ₃ ,-[SiO (OC ₂ H ₅ ) ₂ ] _n— Si (OC ₂ H ₅ ) ₃ (where n is an integer of 1 to 11) and the like, in addition to good adhesion with a substrate having a hydroxyl group after hydrolysis and polycondensation and its durability, surface It is preferable in terms of improvement in hardness.

Among these, as Y ^1a , 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 is used. Particularly preferred.

Specific examples of metals other than the group IVA include, for example, Y ^1a
Group IIA is Ca: —Ca (OR ³⁹ ), with preferred examples being —Ca (OCH ₃ );
Group IIB is Zn: —Zn (OR ³⁹ ), with preferred specific examples being —Zn (OC ₂ H ₅ );
Group IIIA is B: —B (OR ³⁹ ) ₂ , with preferred examples being —B (OCH ₃ ) ₂ ;
Group IIIB is Y: —Y (OR ³⁹ ) ₂ , with preferred examples being —Y (OC ₄ H ₉ ) ₂ ;
Group IVB is _{^{Pb: -Pb (OR 39) 3}} , a preferred embodiment is _{-Pb (OC 4 H 9) 3} ;
Group VB is Ta: -Ta (OR ³⁹ ) ₄ , with preferred examples being -Ta (OC ₃ H ₇ ) ₄ ;
Group VIB is W: —W (OR ³⁹ ) ₅ , with preferred specific examples being —W (OC ₂ H ₅ ) ₅ ;
The lanthanide is La: -La (OR ³⁹ ) ₂ , and a preferred specific example is -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.

As the structural unit M, the structural unit M1 is preferable, and as the structural unit M1, the structural unit M2 or the structural unit M3 is more preferable. Therefore, when -Rf ¹ is represented as -D-Ry, the structural unit M is represented by the formula (2-2):

(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 lowering viscosity and excellent heat resistance.

Specifically, the structural unit M1 of the formula (2-2) is

Among them, the structural unit of the formula (2-2) is preferably the formula (2-3):

(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 formula (2-3) is

Are preferred, and in particular,

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

The Rf, it is also one of the preferred embodiments is Rf ^2. The carbon-carbon double bond in Y ² has the ability to cause a polycondensation reaction and the like, and can give a cured (crosslinked) product. Specifically, for example, by contact with radicals or cations, a polymerization reaction or a condensation reaction is caused between the fluorine-containing polymer molecules or between the compound (A) and a curing (crosslinking) agent that is added as necessary. ) Things that can be given.

The above structural units L Rf is Rf 2 ^(an amide bond or a urea bond and has even been good C1-40 fluorinated hydrocarbon group, or an amide bond, carbonate bond, a urethane bond or urea bond A fluorine-containing hydrocarbon group having an ether bond having 2 to 100 carbon atoms, wherein 1 to 3 of the hydrogen atoms have Y ² (Y ² has an ethylenic carbon-carbon double bond at the terminal) The structural unit which is a monovalent organic group having 2 to 10 carbon atoms)) is also referred to as a structural unit N hereinafter. Further, the structural unit L1, L2, and L3, a structural unit Rf is Rf ^2, respectively, the structural unit N1, N2, and called N3.

Preferred Rf ² is the formula (Rf ² ):
^-D-Ry 2 ^(Rf 2)
[Wherein, -D- is the same as defined above. Ry ² may have an amide bond or a urea bond, a hydrocarbon group having 1 to 39 carbon atoms, in which part or all of the hydrogen atoms may be substituted with fluorine atoms, or an amide bond, A hydrocarbon group having an ether bond having 1 to 99 carbon atoms, which may have a carbonate bond, a urethane bond or a urea bond, and part or all of the hydrogen atoms may be substituted with fluorine atoms. And an organic group in which 1 to 3 hydrogen atoms are substituted with Y ² (Y ² is the same as above). As a preferable form of -D-Ry ^{2, in} the preferable form exemplified by the above-mentioned -D-Ry, Ry may be changed to Ry ² .
Ry ² may have an amide bond, a carbonate bond, a urethane bond, a urea bond, or an ether bond, and a part or all of the hydrogen atoms may be substituted with a fluorine atom. And an organic group in which 1 to 3 hydrogen atoms are substituted with Y ² (Y ² is the same as above).

As the preferred first Y ² ,

( ^Wherein Y ^2a is an alkenyl group having 2 to 5 carbon atoms or a fluorine-containing alkenyl group having an ethylenic carbon-carbon double bond at the terminal; d and e are the same or different and are 0 or 1).

As preferred Y ^2a ,
-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), and this group has high curing reactivity due to contact with radicals or cations, It is preferable.

Specific examples of preferable Y ^2a include

Etc.

As more preferred Y ² ,
^{-O (C = O) 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 more highly reactive to curing, particularly by contact with a radical. It is preferable at a point, and it is preferable at the point which can obtain hardened | cured material easily by photocuring etc.

As a more preferable example of the above Y ² ,

Etc.

As other preferable examples of Y ² ,

Etc.

Among Y ² , those having a structure of —O (C═O) CF═CH ₂ can increase the near-infrared transparency, and particularly have high curing (crosslinking) reactivity, so that a cured product can be obtained efficiently. It is preferable at the point which can do.

Incidentally, the carbon in the side chain of the above - the organic group Y ² having a carbon double bond may be introduced into the polymer main chain terminal.

In the fluorine-containing polymer used in the present invention, the —Rf ^2a — group (the group obtained by removing Y ² from the aforementioned —Rf ² ) contained in the structural units N, N1, N2, and N3 has an amide bond or a urea bond. A divalent fluorine-containing hydrocarbon group having 1 to 40 carbon atoms, or a divalent hydrocarbon having 2 to 100 carbon atoms which may have an amide bond, a carbonate bond, a urethane bond or a urea bond. These are fluorine-containing hydrocarbon groups. This -Rf ^2a -may have a fluorine atom bonded to a carbon atom contained, and generally has a divalent fluorine-containing hydrocarbon group in which a fluorine atom and a hydrogen atom or a chlorine atom are bonded to a carbon atom, or an ether bond. Although it is a divalent fluorine-containing hydrocarbon group, those containing more fluorine atoms (high fluorine content) are preferred, and more preferably a divalent perfluorohydrocarbon group having a perfluoroalkylene group or an ether bond It is. The fluorine content in the fluoropolymer is 25% by mass or more, preferably 40% by mass or more. These make it possible not only to increase the near-infrared transparency of the fluoropolymer (B) but also to reduce the refractive index, and in particular to increase the degree of cure (crosslink density) for the purpose of increasing the heat resistance and elastic modulus of the cured product. Even if it is made high, it is preferable because high near-infrared transparency or low refractive index can be maintained.

When the number of carbon atoms in the —Rf ^2a — group is too large, the divalent fluorine-containing hydrocarbon group may reduce the solubility in a solvent or the transparency, and may also be divalent. In the case of a fluorine-containing hydrocarbon group, the hardness and mechanical properties of the polymer itself and its cured product may be lowered, which is not preferable. Carbon number of a bivalent fluorine-containing hydrocarbon group becomes like this. Preferably it is 1-20, More preferably, it is 1-10. The carbon number of the divalent fluorine-containing hydrocarbon group having an ether bond is preferably 2 to 30, more preferably 2 to 20.

As preferred specific examples of —Rf ^2a —,

Etc.

The structural unit N constituting the fluoropolymer used in the present invention is preferably the structural unit N1, and the structural unit N1 is more preferably the structural unit N2 or the structural unit N3. Therefore, specific examples of the structural unit N2 and the structural unit N3 will be described below.

Specific preferred examples of the monomer constituting the structural unit N2 include

(N is an integer from 1 to 30; Y ² is the same as above).

More details

(Rf ⁷ and Rf ⁸ are perfluoroalkyl groups having 1 to 5 carbon atoms, n is an integer of 0 to 30; X is H, CH ₃ , F or CF ₃ )
Etc.

Specific preferred examples of the monomer constituting the structural unit N3 include

(Wherein Y ² is the same as above; n is an integer of 1 to 30).

For more details,

(Rf ⁹ and Rf ¹⁰ are perfluoroalkyl groups having 1 to 5 carbon atoms; m is an integer of 0 to 30; n is an integer of 1 to 3; X is H, CH ₃ , F or CF ₃ ) can give.

In addition to these structural units N2 and N3, preferred specific examples of the monomer constituting the structural unit N of the fluoropolymer include, for example,

(Y ² and Rf ² are the same as in the above example)
Etc.

More specifically,

(Above, ^{Y 2} is as defined above) and the like, such as.

The fluorine-containing polymer (B) may further comprise a structural unit A. 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, in addition.

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, a functional group selected from the group consisting of an epoxy group and a cyano group), among others,
^{_{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 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).

(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 in that Further, by selecting a monomer, the mechanical properties and glass transition temperature of the polymer can be adjusted, and in particular, it can be copolymerized with the structural unit L to increase the glass transition point, 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 are 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 its cured product 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 esters, and methacrylic esters, maleic anhydride, maleic acid, maleic 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 structural units M and N derived from an alicyclic monomer, the structural units M and N and the above-mentioned fluorine-containing ethylenic monomer or non-fluorine ethylenic monomer are more preferable. In addition to the structural units of the monomers (A3 and A4 described above), the alicyclic monomer structural unit A5 may be introduced as the third component, thereby increasing the glass transition temperature and increasing the hardness. .

As a specific example of the alicyclic monomer A5,

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

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

The fluorine-containing polymer (B) 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 be only the structural unit M, or may be only the structural unit N, and the fluorine-containing polymer (B) is composed of both the structural unit M and the structural unit N. It may be contained in the polymer (B). Moreover, the copolymer which consists of the structural unit M, the structural unit N, and the structural unit A may be sufficient.

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 structural units constituting the fluoropolymer (B), 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.

In applications that require the formation of a cured product that is particularly excellent in 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 (B).

The molecular weight of the fluoropolymer (B) can be selected, for example, from the range of 500 to 1,000,000 in the number average molecular weight, but 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 forming property and leveling property are liable to be deteriorated particularly during the formation of the thin film, and the storage stability of the fluoropolymer (B) is liable to be unstable. 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 by gel permeation chromatography (GPC) based on polystyrene.

The fluorine-containing polymer (B) is composed of, for example, the structural unit L, and if necessary, further composed of the structural unit A. It may be a fluorine-containing polymer having a number average molecular weight of 500 to 1,000,000 containing 0% to 99.9% by mole of the structural unit A. In this case, the structural unit L may be 0.1 to 100 mol% of the structural unit M, 0 to 99.9 mol% of the structural unit N, or 0.1 to 100 mol of the structural unit N. %, And the structural unit M may be 0 to 99.9 mol%.

The fluorine-containing polymer (B) 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 the structural units constituting the fluoropolymer (B). 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 (B) 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 structural units A1 and A2 are both 99.9 mol% or less. The total mol% of A1 + A2 is 10 to 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 be low, which is not preferable. More preferably, the total mol% of A1 + 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 fluoropolymer (B), a combination of the structural unit L [structural unit M (M1, M2, and M3) and structural unit N (N1, N2, and N3)] and the structural unit A (A1 and A2) As for the composition ratio, the combination of the structural unit M, the structural unit N, and the structural unit A is variously selected from the above examples depending on the intended application, physical properties (especially glass transition temperature, hardness, etc.), function (transparency), etc. That's fine.

The molecular weight of the fluoropolymer (B) is, for example, 500 to 1,000 in the 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 is deteriorated, the film forming property and leveling property are liable to be deteriorated particularly during the formation of the thin film, and the storage stability of the fluorine-containing polymer is liable to be unstable. Most preferably, the number average molecular weight is selected from the range of 5,000 to 100,000.

The fluoropolymer (B) is preferably soluble in a general-purpose solvent. For example, the fluorine-containing polymer (B) is soluble in at least one of a ketone solvent, an acetate ester solvent, an alcohol solvent, and an aromatic solvent, or at least one general-purpose solvent. It is preferably soluble in a mixed solvent containing seeds.

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 (B) is
(1) A method in which a monomer having Rf is synthesized beforehand and polymerized (2) Once a polymer having another functional group is synthesized, the functional group is converted into a functional group by a polymer reaction. Method of introducing group Rf (3) Any of the methods of introducing by using both methods (1) and (2) can be adopted.
Among these methods, the method (3) is a method of obtaining a curable fluoropolymer having a hydrolyzable metal alkoxide moiety of the present invention without causing a curing reaction of the carbon-carbon double bond at the end of the fluoropolymer side chain. To the method (3) is preferred.

The fluoropolymer (B) can be produced, for example, by the method described in International Publication No. 02/18457 pamphlet and Japanese Patent Application Laid-Open No. 2006-027958.

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

The fluorine-containing ethylenic monomer giving the structural unit L has 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 ; Rf is the same as above; a is an integer of 0 to 3; b and c are the same or different and are monomers represented by 0 or 1). 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.

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

Examples of the organic solvent include cellosolve solvents such as methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, and 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, Examples thereof include alcohol solvents such as butanol; 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 (B), 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,

Fluorinated alcohols such as
Examples thereof 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 and coating productivity.

It is preferable that the curable resin composition of the present invention further contains a curing initiator. In particular, when Y is Y ² which is a monovalent organic group having 2 to 10 carbon atoms having an ethylenic carbon-carbon double bond at the terminal, it is preferable that a curing initiator is included.

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 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 having a wavelength region of 350 nm or less, that is, ultraviolet rays, electron beams, X rays, γ rays, It functions as a catalyst for initiating curing (crosslinking reaction) of the crosslinking group (for example, carbon-carbon double bond) of the fluoropolymer (B), and usually generates radicals and cations (acids) with ultraviolet rays, particularly Use those that generate radicals.

When Y is a monovalent organic group having 2 to 10 carbon atoms having an ethylenic carbon-carbon double bond at the terminal, the curable resin composition of the present invention is easily cured by the active energy ray. Is preferable because

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 fluorine-containing polymer (B), and when the compound (A) has a crosslinking group, the crosslinking group. In addition, the curing initiator is appropriately selected depending on the type of curing initiator used, the type of active energy rays, and the amount of irradiation energy (strength and time, etc.). For example, the curing initiator may be compound (A) and fluoropolymer ( It is preferable that it is 0.01-30 mass parts with respect to a total of 100 mass parts of B). 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. In particular, when Y is a monovalent organic group having 2 to 10 carbon atoms having an ethylenic carbon-carbon double bond at the terminal, it is preferable to include a curing agent.

The curing agent is preferably one having at least one carbon-carbon unsaturated bond and capable of being polymerized with a radical or an acid, specifically, a radical polymerizable monomer such as an acrylic monomer, a vinyl ether monomer or the like. And cationically polymerizable monomers. 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 the like. The fluorine-containing polymer (B) in the composition can be cross-linked by copolymerization with a carbon-carbon double bond in the side chain.

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^ａ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 Rfa 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,

などがあげられる。
多官能アクリル系単量体としては、ジオール、トリオール、テトラオールなど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など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あげられる。
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, each of 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,

など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あげられる。
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 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 (B), 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 amount of the fluoropolymer (B) 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 (B). 0.5 to 10 mol%.

When using a curing agent, the total number of moles of the carbon-carbon double bond content (number of moles) contained in the fluoropolymer (B) 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 according to 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 Nos. 3716189 and 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 2004-203683 A, JP 2006-021938 A, and the like 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 (B). 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, discoloration inhibitors, antioxidants, inorganic fillers, leveling agents, viscosity modifiers, light stabilizers, moisture absorbers, pigments, dyes, and reinforcing agents. 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 in which fine particles or ultrafine particles of an inorganic compound are blended in the composition of the present invention can have a refractive index lower than the refractive index of a single film by utilizing this void.

When using inorganic compound fine particles, it should be used in the form of an organic sol dispersed in advance in an organic dispersion medium in order not to lower the dispersion stability in the composition and the adhesion in the low refractive index material. 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 the various coupling agents include organic 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 (B) 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 (A) and a fluoropolymer (B) is 10-100 mass% with respect to the total mass. More preferably, it is 20-50 mass%.

The curable resin composition of the present invention is necessary, for example, by adding a fluorine-containing polymer (B) and, if necessary, a curing initiator, a crosslinking agent, and other additives to the liquid compound (A). 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 baking, or irradiating with 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 1.35 or less. For example, a thin film having a film thickness of 1 to 10 μm, a refractive index of 1.35 or less, and a haze value of 5% or less can be produced from the curable resin composition of the present invention. 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, when it is necessary to control the film thickness, roll coating, gravure coating, micro gravure coating, flow coating, bar coating, spray coating, die coating, spin coating, dip coating, etc. are used. it can.

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

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, or a semiconductor element (optical semiconductor element) such as an EPROM 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 imparting low reflectivity on a substrate. Examples of the base material 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 covers for photo and photo stands; protective plates for CRTs, liquid crystal displays, plasma displays, rear projection displays; read-only optical disks such as magneto-optical disks, CDs, LDs, and DVDs Optical recording media represented by phase transition type optical discs such as PD, hologram recording, etc .; members related to photolithography in manufacturing semiconductors such as photoresists, photomasks, pellicles, reticles; halogen lamps, fluorescent lamps, incandescent lamps, etc. Light emission Sheet or film for pasting on the article; protective cover.

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 tape / substrate, lead frame, printed circuit board, wiring substrate such as module substrate, wiring sheet, surface layer of package substrate or interlayer insulating layer surface.

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.

As a more preferable configuration of the curable resin composition of the present invention, for example, the following can be exemplified, but the present invention is not limited to these.

(Example I)
Organosilicon compound (A) component: Hydrolyzable condensable silane compound fluoropolymer (B) component: Homopolymer composed of structural unit L2 having a silane coupling group in the side chain, or from structural unit L2 and structural unit N A copolymer (for example, a copolymer having a structure of (L2)-(N))
Solvent: A ketone solvent, an acetate ester solvent, an alcohol solvent, a fluorinated alcohol solvent, or an aromatic solvent composition ratio (A) 100 parts by mass (solid content) of the component (B) 50 parts by mass solvent: appropriate amount as needed

(Example II)
Organosilicon compound (A) component: Hydrolyzable condensable silane compound fluorine-containing polymer (B) component: L2 homopolymer having a radically polymerizable group in the side chain, or a copolymer consisting of structural unit L2 and structural unit N Compound (for example, a copolymer having a structure of (L2)-(N))
Curing agent (crosslinking agent): Compound having radical crosslinking group and hydrolyzable silane coupling group Curing initiator: Ultraviolet light radical generator Solvent: Ketone solvent, acetate solvent, alcohol solvent, fluorine-containing alcohol 1 to 50 parts by weight of component (B), 0.1 to 10 parts by weight of cross-linking agent, and 0 to 0 parts by weight of the solvent or aromatic solvent composition ratio (A) 100 parts by weight (solid content) .01-0.5 parts by mass, appropriate amount of solvent as required

Next, the present invention will be described based on synthesis examples, production examples, and examples, but the present 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.

で表されるパーフルオロ（１，１，９，９−テトラハイドロ−２，５−ビストリフルオロメチル−３，６−ジオキサノネノール）を２０ｇ、下記式：
［Ｈ−（ＣＦ_２ＣＦ_２）_３−ＣＯＯ−］_２
で表される化合物の８．０質量％パーフルオロヘキサン溶液を２１．２ｇ入れ、十分に窒素置換を行った後、窒素気流下２０℃で２４時間攪拌を行ったところ、高粘度の固体が生成した。得られた固体をジエチルエーテルに溶解させたものをパーフルオロヘキサンに注ぎ、分離、真空乾燥させ、重合体１７．６ｇを得た。この重合体を^１９Ｆ−ＮＭＲ、^１Ｈ−ＮＭＲ分析、ＩＲ分析により分析したところ、上記含フッ素アリルエーテルに由来する構造単位のみからなり、側鎖末端にヒドロキシル基を有する含フッ素重合体であった。また、テトラヒドロフラン（ＴＨＦ）を溶媒に用いるＧＰＣ分析により測定した数平均分子量は９０００、重量平均分子量は２２０００であった。 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 following formula:
[H- (CF ₂ CF ₂ ) ₃ —COO—] ₂
21.2 g of a 8.0% by mass perfluorohexane solution of the compound represented by formula (2) was added and thoroughly purged with nitrogen, and then stirred at 20 ° C. for 24 hours under a nitrogen stream, whereby a highly viscous solid was produced. did. 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 side chain terminal. It was. Further, the number average molecular weight measured by GPC analysis using tetrahydrofuran (THF) as a solvent was 9000, and the weight average molecular weight was 22,000.

Synthesis Example 2 (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 under 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. After the reaction, the ether solution 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 3 (Synthesis of fluorine-containing curable polymer having α-fluoroacryloyl group)
A homopolymer of —O—COCF═CH ₂ group-containing fluorine-containing allyl ether was obtained in the same manner as in Synthesis Example 2 except that 2.5 g of α-fluoroacrylic acid fluoride [CH ₂ ═CFCOF] was used.

Synthesis Example 4 (Synthesis of fluorine-containing curable polymer having triethoxysilane group)
In a 300 mL four-necked flask equipped with a thermometer, a stirrer, and a dropping funnel, MIBK 150 mL, 20.0 g of the hydroxyl group-containing fluorine-containing allyl ether homopolymer obtained in Synthesis Example 1, and isocyanatopropyltriethoxysilane 17 .4g was charged and ice-cooled to 5 ° C or lower. While stirring in a nitrogen stream, 18 mg of lauryl dibutyltin was further added, and then the temperature was raised to room temperature and stirring was continued for 4.0 hours. When the IR analysis was performed on a cast film applied to a NaCl plate at room temperature, it was confirmed that the hydroxyl group absorption disappeared and the reaction was completed. The reaction product was put into 1 L of n-hexane and the precipitate was collected. The target polymer represented by the following formula was obtained by drying under reduced pressure at room temperature.

Synthesis Example 5 (Synthesis of fluorine-containing curable polymer having triethoxysilane group and α-fluoroacryloyl group)
By reacting 20.0 g of the fluorine-containing allyl ether homopolymer having an α-fluoroacryloyl group obtained in Synthesis Example 3 with 8.7 g of isocyanatopropyltriethoxysilane in the same manner as in Synthesis Example 4, triethoxy was reacted. A polymer having a silane group and an α-fluoroacryloyl group of 50:50 could be obtained.

Example 1
To 20 g of the polymer-containing MIBK solution obtained in Synthesis Example 4, 36 g of tetraethoxysilane (TEOS) and 54 g of MIBK were added and stirred sufficiently to prepare a thermal hydrolysis type insulating film material solution. [TEOS / Synthesis Example 4 Obtained polymer] = 9/1, and a MIBK solution having a total of 40 wt% of TEOS and the polymer obtained in Synthesis Example 4 was obtained.

Example 2
10 g of the polymer-containing MIBK solution obtained in Synthesis Example 4, 18 g of TEOS, and 72 g of MIBK were prepared in the same manner as in Example 1. [TEOS / polymer obtained in Synthesis Example 4] = 9/1, which was synthesized with TEOS. A MIBK solution having a total of 20 wt% with the polymer obtained in Example 4 was obtained.

Example 3
40 g of the polymer-containing MIBK solution obtained in Synthesis Example 4 and 32 g of TEOS and 28 g of MIBK were prepared in the same manner as in Example 1. [TEOS / polymer obtained in Synthesis Example 4] = 4/1, and TEOS and Synthesis Example A MIBK solution having a total of 40 wt% with the polymer obtained in 4 was obtained.

Example 4
20 g of the polymer-containing MIBK solution obtained in Synthesis Example 4 and 16 g of TEOS and 64 g of MIBK were prepared in the same manner as in Example 1. [TEOS / polymer obtained in Synthesis Example 4] = 4/1, and TEOS and Synthesis Example A MIBK solution having a total of 20 wt% with the polymer obtained in 4 was obtained.

Example 5
13.3 g of TEOS, 0.5 g of tripropoxypropyl methacrylate, 0.1 g of a polymerization initiator Irgacure 907 (manufactured by Ciba Specialty) and 68.7 g of MIBK are added to 13.3 g of the polymer-containing MIBK solution obtained in Synthesis Example 2. Sufficiently stirring to prepare an ultraviolet heat hydrolyzable insulating film material solution, [TEOS / polymer obtained in Synthesis Example 2] = 9/1, and the total of TEOS and the polymer obtained in Synthesis Example 2 is A MIBK solution of 20 wt% was obtained.

Example 6
Example 5 26.7 g of the polymer-containing MIBK solution obtained in Synthesis Example 2; 15.5 g of TEOS; 0.5 g of tripropoxypropyl methacrylate; 0.1 g of the polymerization initiator Irgacure 907 (manufactured by Ciba Specialty); and 57.3 g of MIBK. The MIBK solution was prepared in the same manner as [TEOS / polymer obtained in Synthesis Example 2] = 4/1, and the total of TEOS and the polymer obtained in Synthesis Example 2 was 20 wt%.

Example 7
In 20.0 g of the polymer-containing MIBK solution obtained in Synthesis Example 5, 36.0 g of TEOS, 0.1 g of polymerization initiator Irgacure 907 (manufactured by Ciba Specialty), and 68.7 g of MIBK were prepared in the same manner as in Example 5. / Polymer obtained in Synthesis Example 5] = 9/1, and a MIBK solution having a total of 40 wt% of TEOS and the polymer obtained in Synthesis Example 5 was obtained.

Example 8
Example 5: 17.5 g of TEOS, 0.5 g of tripropoxypropyl methacrylate, 0.1 g of polymerization initiator Irgacure 907 (manufactured by Ciba Specialty) and 68.7 g of MIBK were added to 13.3 g of the polymer-containing MIBK solution obtained in Synthesis Example 5. Thus, a MIBK solution in which [TEOS / polymer obtained in Synthesis Example 5] = 9/1 and the total of TEOS and the polymer obtained in Synthesis Example 5 was 20 wt% was obtained.

Example 9
40.0 g of the polymer-containing MIBK solution obtained in Synthesis Example 5 and 18.0 g of TEOS, 0.1 g of polymerization initiator Irgacure 907 (manufactured by Ciba Specialty), and 28.0 g of MIBK were prepared in the same manner as in Example 5, and [TEOS / Polymer obtained in Synthesis Example 5] = 4/1, and a MIBK solution having a total of 40 wt% of TEOS and the polymer obtained in Synthesis Example 5 was obtained.

Example 10
26.7 g of the polymer-containing MIBK solution obtained in Synthesis Example 5 and 16.0 g of TEOS, 0.1 g of polymerization initiator Irgacure 907 (manufactured by Ciba Specialty), and 57.3 g of MIBK were prepared in the same manner as in Example 5. / Polymer obtained in Synthesis Example 5] = 4/1, and a MIBK solution having a total of 20 wt% of TEOS and the polymer obtained in Synthesis Example 5 was obtained.

Comparative Example 5.6 g of the fluorinated curable polymer having an α-fluoroacryloyl group obtained in Synthesis Example 2, 0.1 g of polymerization initiator Irgacure 907 (manufactured by Ciba Specialty), and 22.4 g of MIBK were used in the same manner as in Example 5. The MIBK solution was prepared and the polymer obtained in Synthesis Example 2 was 20 wt%.

Test Example 1 (Curing conditions and appearance evaluation of cured product)
Each of the compositions obtained in Examples 1 to 10 and Comparative Example 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 the film thickness.
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 was 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 5 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
With respect to 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 the comparative example, 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 was applied on a slide glass using a spin coater under the conditions of 500 rpm and 30 seconds. Using a hot stage, it was heat-cured under conditions of 120 ° C., 1 hour, 200 ° C. and 10 minutes, and the haze value and total light transmittance were measured. The results are shown in Table 1.

Test Example 5 (Durability evaluation)
Among the cured films obtained in Test Example 4, the absorption spectrum of the cured film produced using the composition obtained in Example 3, 6 or 9 was measured using a Hitachi spectrophotometer U-4100. (default 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 endurance 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 endurance test), presence or absence of coloring, change in refractive index, and change in transmittance at 450 nm and 550 nm (relative value when initial value is 100) Is shown in Table 2. Almost the initial value was maintained, and high durability could be confirmed.

The composition of the present invention is particularly suitable as a raw material for a sealing member used in a light receiving element such as a CCD module because it can form a thin film having a low refractive index, high transparency, and excellent heat resistance. is there.

DESCRIPTION OF SYMBOLS 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 the outside

Claims (11)

An organosilicon compound (A), and
The following formula (L):

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 ; Rf is a fluorine-containing hydrocarbon group having 1 to 40 carbon atoms which may have an amide bond or a urea bond, or 2 carbon atoms which may have an amide bond, a carbonate bond, a urethane bond or a urea bond. A fluorine-containing hydrocarbon group having an ether bond of ˜100, wherein 1 to 3 of the hydrogen atoms are Y (Y is a monovalent containing at least one hydrolyzable metal alkoxide moiety having 1 to 30 carbon atoms at the terminal) Or a monovalent organic group having 2 to 10 carbon atoms having an ethylenic carbon-carbon double bond at the terminal.); A is an integer of 0 to 3; b And c are the same or different and are 0 or 1 A fluorine-containing polymer (B) having a structural unit represented by:
A curable resin composition comprising: The organosilicon compound (A) has the following formula (1):
{Si (R ^a ) _s (R ^b ) _t (R ^c ) _u (R ^d ) _v (R ^e ) _w } _n (1)
(Wherein 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, an alkyl group having 1 to 10 carbon atoms, or 5 to 5 carbon atoms. An aryl group having 10 carbon atoms, an allyl group having 1 to 10 carbon atoms, or a glycidyl group, and R ^e is the same or different and is —O—, —NH—, —C≡C—, or a silane single bond. s, t, u and v are the same or different and are 0 or 1, w is an integer of 0 to 4, and n is 1 to 20. When 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 and is 0 to 4, w is the same or different and is 0 to 4, and when w is an integer of 1 or more, at least 2 This of Si through R ^e, linear, ladder, attached cyclic, or double cyclic ) A compound represented by (A1) a is claim 1 curable resin composition. The curable resin composition according to claim 1 or 2, wherein the organosilicon compound (A) is tetraalkoxysilane. The curable resin composition according to claim 1, 2, or 3, wherein the organosilicon compound (A) is 50% by mass or more based on the total mass of the organosilicon compound (A) and the fluoropolymer (B). The curable resin composition according to claim 1, comprising an organic solvent. The curable resin composition according to claim 1, 2, 3, or 4, which is used for sealing an optical element. A cured product obtained by curing the curable resin composition according to claim 1, 2, 3, 4, 5 or 6. The cured product according to claim 7, having a refractive index of 1.35 or less. The cured product according to claim 7, which is a sealing member for an optical element. The cured product according to claim 9, wherein the optical element is a light receiving element. The cured product according to claim 9, wherein the optical element is a light emitting element.

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