WO2004088422A1 - Fluoro compound and fluoropolymer - Google Patents

Abstract

Novel polymer being useful as, for example, a material of protective coating agent, photoresist film, masking agent at etching, separator for fuel cell, coating for fuel cell catalyst immobilization or pellicle; compound being useful as a raw material of the polymer; and novel intermediate being useful in the production of the compound. Further, there are provided a pellicle film and adhesive for pellicle film in which a novel material is employed. In particular, a pellicle constituted of a polymer comprising units of the formula (A), for example, units of the formula (A1), and a novel compound of the formula (a1). In the formulae, each of X1 and X2 independently represents a fluorine, chlorine or hydrogen atom. n is an integer of 1 or 2. Rf1 represents a fluorine atom or trifluoromethyl. Rf2 represents a fluorine atom or a C1-C5 perfluoroalkyl.

Description

 Specification

 Fluorinated compounds and fluorinated polymers

<Technical field>

 The present invention relates to a novel fluorinated compound and a novel fluorinated polymer obtained by polymerizing the fluorinated compound. The present invention also relates to a novel fluorinated polymer adhesive having a high transparency in the ultraviolet region, for pellicle and pellicle films. Further, the present invention relates to an exposure processing method using the pellicle.

<Background technology>

 Fluorinated dioxole compounds having a fluorine-substituted carbon-carbon double bond are known (US Pat. No. 3,865,845) and US Pat. No. 4,429,144. No. statement). Further, as a fluorine-containing dioxole compound having a spiro ring structure, a compound represented by the following formula (T) is known (Japanese Patent No. 3057588).

 A polymer obtained by polymerizing the compound represented by the formula (c) is soluble in a specific solvent and has a high glass transition temperature (hereinafter, referred to as Tg). However, since the thermal decomposition onset temperature of the polymer was low and the Tg was close to the thermal decomposition onset temperature, it was necessary to strictly control the temperature range during melt molding. Further, the transmittance and durability of the polymer were insufficient.

 It is also known that a fluoropolymer having a saturated ring structure in the main chain can be a transparent fluoropolymer having an amorphous property. Such a fluorine-containing polymer is useful as a transparent coating material or an optical material.

3-39963 and Japanese Unexamined Patent Publication (Kokai) No. Hei 3-67272. Also the Lord A substantially linear fluorine-containing polymer containing a hydrogen atom in the chain (Japanese Patent Application Laid-Open No. 2001-330943); a polymer containing a perfluoro-1,3-dioxole structure (International Publication No. / 37044 pamphlet) is known to have high transparency in the ultraviolet region. It is also known to use these materials for pellicles.

A pellicle is a process in the manufacture of semiconductor devices or liquid crystal display panels. In photolithography, foreign matter is placed on a photomask reticle (hereafter referred to as a mask). A protective film that is mounted on a mask pattern to prevent it from occurring. The pellicle usually has a structure in which a transparent thin film is attached to a frame via an adhesive. Pellicles are installed at a certain distance from the mask surface. In the field of manufacturing semiconductor devices and liquid crystal display panels that use pellicles, wiring and wiring intervals are becoming finer. The wavelength is rapidly shortening. In recent years, a KrF excimer laser has been introduced for wiring processing with a minimum pattern size of 0.3 m or less, but its oscillation wavelength is 248 nm. At this wavelength, the durability of conventional nitrocellulose-based film materials is insufficient, so that an amorphous perfluoropolymer described in Japanese Patent Application Laid-Open No. 3-39963 has been proposed as a film material. I have. On the other hand, in recent lithography, wiring processing with a minimum pattern size of 0.2 m or less is required.For these processing, a laser with a wavelength of 200 nm or less is used as an argon fluoride excimer with a wavelength of 193 nm. laser (hereinafter, referred to as a r F excimer one tHE one.) wavelength 1 57 nm of fluorine Gasuekishi Mareza (hereinafter, referred to as F ₂ excimer lasers.) use of the like have been studied.

However, since the laser light from these lasers has very high energy, the polymer described in the above-mentioned US Pat. No. 3,865,845 has insufficient durability. Further, the polymer described in the US Patent Specification (trade name: CYTOP, manufactured by Asahi Glass Co., Ltd.) has a property that light transmittance for light of 170 nm or less, durability is rapidly reduced, and wavelength 1 57 nm F ₂ excimer laser There is a drawback that the light transmittance is extremely low. Further, the polymer is excellent in transparency to light of 170 nm or more, but has a problem that the film strength is insufficient and handling is difficult.

Further, F as ₂ excimer one The one pellicle film can respond to light, Japanese Patent the third 0 7 5 5 8 8 No. describes fluorinated polymer chain structure, Japanese Patent 3 3 9 9 No. 63 discloses a copolymer containing vinylidene fluoride or the like as a main component. However, these polymers had transparency at 157 nm, but had insufficient durability.

 Further, the adhesive for bonding the pellicle film and the frame has the same deterioration problem due to the stray light or reflected light of the laser light, and therefore, the development of an adhesive having high durability has been desired.

<Disclosure of Invention>

 An object of the present invention is to provide a novel polymer useful as a protective coating agent, a photoresist film, a masking agent at the time of etching, a separator for a fuel cell, a catalyst fixing film for a fuel cell, a velcro material, and the like. . Another object of the present invention is to provide a compound useful as a raw material of the polymer and a novel intermediate useful for producing the compound. Another object of the present invention is to provide a pellicle film and a pellicle film adhesive using a novel material.

 The present inventors have concluded that a polymer containing a specific unit has a laser beam of 200 nm or less, preferably a laser beam of 180 nm or less (hereinafter, these laser beams are collectively referred to as short-wavelength laser beams). It has been found to have high transparency and durability to light. Furthermore, they have found that they have excellent transparency and durability in the short wavelength light range. It has been found that the use of the polymer as a pellicle film and / or a pellicle film adhesive provides an optimal pellicle as a pellicle for exposure processing with short wavelength light.

 That is, the present invention provides the following inventions.

'A pellicle for exposure processing with light having a wavelength of 200 nm or less, wherein the film is adhered to a frame via an adhesive, and the pellicle film and the Z Or a pellicle, wherein the adhesive comprises a polymer containing a unit represented by the following formula (A).

 However, Q represents a group in which one or more of the hydrogen atoms present in the following group (B) are substituted with a fluorine atom.

Group (B):-(CH ₂ ) _a — (where a is an integer of 1 to 3), wherein two hydrogen atoms present in the group include two or more etheric oxygen atoms An alkylene group, or a group in which at least one hydrogen atom in the alkylene group is substituted by an alkyl group optionally containing an etheric oxygen atom,

X ¹ and X ² independently represent a fluorine atom, a chlorine atom or a hydrogen atom.

 <2> The pellicle according to <1>, wherein Q is a group in which all of the hydrogen atoms present in the group (B) are substituted with fluorine atoms.

 The pellicle according to <1>, wherein the unit represented by the formula (A) is a unit represented by the following formula (A1).

X ¹ and X ² are each independently a fluorine atom, a chlorine atom or a hydrogen atom, n is an integer of 1 or 2, R ^fl is a fluorine atom or a trifluoromethyl group, and R ^{f 2} is a fluorine atom Or a perfluoroalkyl group having 1 to 5 carbon atoms.

(A1)

<4> The pellicle according to any one of <1> to <3>, wherein the pellicle film requires a unit represented by the formula (A) and comprises a polymer having no functional group.

 <5> The pellicle according to any one of <1> to <4>, wherein the adhesive essentially includes a unit represented by the formula (A) and comprises a polymer having a functional group.

<6> The pellicle according to any one of <1> to <5>, wherein the polymer containing a unit represented by the formula (A) is a polymer having no —CH ₂ CH ₂ — structure.

 <7> An exposure treatment method using a pellicle according to any one of <1> to <6>, in an exposure treatment method using light having a wavelength of 200 nm or less in photolithography.

<8> A compound represented by the following formula (al). However, X ¹ and X ² are each independently a fluorine atom, a chlorine atom or a hydrogen atom, n is an integer of 1 or 2, R ^fl is a fluorine atom or a trifluoromethyl group, and R ^{f 2} is It is a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms.

<9> The compound according to <8>, wherein X ¹ and X ² are each a fluorine atom, n is 1, and R ^{f 1} and R ^{f 2} are each a fluorine atom.

 <10> Polymer containing a monomer unit of the compound described in <8> or <9>

<11> A compound represented by the following formula (b2) or a compound represented by the following formula (b3).

However, Y and Z each independently represent a fluorine atom, a chlorine atom or a hydrogen atom, n is an integer of 1 or 2, R ^fl represents a fluorine atom or a trifluoromethyl group, and R ^{f 2} represents fluorine. It represents an atom or a perfluoroalkyl group having 1 to 5 carbon atoms.

 (b2) Best mode for carrying out the invention>

 In the present specification, a group in which one or more of the hydrogen atoms of a group having a hydrogen atom is substituted by a fluorine atom is referred to as a polyfluoro group, and a group in which all of the hydrogen atoms are substituted by a fluorine atom is referred to as a perfluoro group. Write. In this specification, the expression (

The polymer represented by A) is represented by polymer (A), the compound represented by formula (al) is represented by compound (al), and the same applies to the compounds and units represented by other formulas. Write. Further, in the following description, the description regarding the formula (A) also applies to the formula (a l) unless otherwise specified.

 The present invention provides a novel pellicle. That is, a pellicle film is adhered to a frame via an adhesive, and is a particle for exposure processing with light having a wavelength of 200 nm or less, wherein the pellicle film and / or the adhesive are represented by the following formula: A pellicle comprising a polymer containing a unit represented by (A) is provided. Hereinafter, a polymer containing a unit represented by the formula (A) is referred to as a polymer (A).

(A)

 Q in the formula (A) represents a group in which one or more of the hydrogen atoms present in the following group (B) has been replaced by a fluorine atom.

Group (B): — (CH ₂ ) _a — (where a represents an integer of 1 to 3) An alkylene group containing two or more etheric oxygen atoms, or one or more hydrogen atoms in the alkylene group containing two or more etheric oxygen atoms is an ether. A group substituted with an alkyl group which may contain a neutral oxygen atom;

The group connecting two hydrogen atoms in the group (B) is preferably a group containing two etheric oxygen atoms, and one (CH ₂ ) _b O (CH ₂ ) _d O (CH ₂ ) _e — (however, , B, d, and e each independently represent an integer of 1 to 2, and (b + d + e) is preferably 3 or 4. The group represented by the following formula is particularly preferable.

 Q is a group in which one or more of the hydrogen atoms present in the group (B) have been replaced by fluorine atoms, and a group in which all of the hydrogen atoms present in the group (B) have been replaced by fluorine atoms Is preferred.

When a substituent is present in the group (B), the group is an alkyl group and / or an alkyl group containing an etheric oxygen atom, and preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms. Is preferable, and 1 or 2 is particularly preferable. In the group (B), two hydrogen atoms present in the group represented by one (CH ₂ ) _a — include two hydrogen atoms bonded to the same carbon atom, or-. It is preferably two hydrogen atoms bonded to each other, and particularly preferably two hydrogen atoms bonded to the same carbon atom. Further, it is preferable that the two hydrogen atoms be connected by the above-mentioned group to form a 5- to 7-membered ring structure.

 Specific examples of Q can be exemplified in the specific examples of unit (A) described below.

X ¹ and X ² each independently represent a fluorine atom, a chlorine atom or a hydrogen atom. When X ¹ and X ² are each a fluorine atom or a chlorine atom, it is preferable because the heat resistance, weather resistance and light resistance of the polymer (A) are improved, and X ¹ and X ^{2 are} more preferable. Is preferably a fluorine atom because the optical properties of the polymer (A) are also improved.

The unit (A) is particularly preferably the following unit (Α '). However, in the formula, X ¹ and X ² and Q have the same meanings as described above, and Q ^F represents a perfluoroalkylene group containing two or more etheric oxygen atoms.

The following units can be exemplified as the unit (で き る). However, X ¹ and X ² have the same meaning as described above, and the preferred embodiments are also the same.

The unit (A) is preferably a monomer unit obtained by polymerizing the following compound (a), and the unit (Α ′) is preferably a monomer unit obtained by polymerizing the following compound (a ′). Similarly, the unit exemplified as the unit (A) is preferably a monomer unit obtained by polymerizing a polymerizable monomer having a structure corresponding to the unit.

 (a ')

Further, the unit (A) is preferably the following monomer unit (A1) obtained by polymerizing the following compound (al). The polymer containing the compound (al) and the monomer unit (A1) is a novel compound.

 (a1) (A1)

Here, n is 1 or 2. Among these, n is preferably 1 in terms of easy formation of a ring structure, stable ring structure, and easy availability of raw materials. R ^fl is a fluorine atom or a trifluoromethyl group, and a fluorine atom is preferable in terms of availability of raw materials and the like. R ^f2 is a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and the perfluoroalkyl group may be linear or branched. As R ⁱ² , a fluorine atom, a trifluoromethyl group or a pentafluoroethyl group is preferable, and a fluorine atom is particularly preferable. Specific examples of the compound (al) include the following compounds, and the following compound (a2) is preferable.

Compound (a) is a compound that can be produced by applying a known reaction to a known compound. For example, compound (al) can be manufactured according to the following manufacturing route. However, n and R ^f \ R ^f2 in the following formula have the same meanings as described above, and Y and Z each independently represent a fluorine atom, a chlorine atom, or a hydrogen atom.

 That is, by adding ethylenoxide to the following compound (b1) which can be obtained by the method described below, or by adding 2-chloroethanol and then dehydrochlorinating in the presence of a base. The compound (b 2) is obtained by the method of ring closure.

 The reaction for adding ethylene oxide to the compound (bl) can be carried out by a known method (for example, a method described in US Pat. No. 3,324,144). For example, there is a method in which the compound (bl) and ethylene oxide are reacted in the presence of a catalyst (for example, a catalyst comprising potassium iodide and water). The reaction temperature of the reaction is preferably from 100 to 150 ° C, more preferably from 130 to 130 ° C.

 For the reaction of adding ethylene chlorohydrin to the compound (bl) and then closing the ring, for example, the method described in Example 3 of US Pat. No. 2,925,424 can be employed.

Next, the compound (b 2) is photochlorinated to obtain a compound (b 3). This photochlorination can be carried out, for example, according to the method described in US Pat. No. 2,925,424 and Example 9 therein. Specifically, there is a method in which the reaction is performed while blowing a chlorine gas under ultraviolet irradiation. The reaction is preferably carried out in the absence of a solvent, and the reaction temperature is preferably 0 ° C to 100 ° C. 30 ° C to 80 ° C is preferred.

 In the photochlorination of the compound (b2), the compound (b3) having a different degree of chlorination can be obtained by controlling the supply amount of chlorine gas. The supply of chlorine gas is continued until at least one of each of the hydrogen atoms present in the two methylene groups of compound (b 2) is chlorinated.

 The reaction for obtaining the compound (al) from the compound (b3) is classified according to the following chlorination reaction and selective fluorination reaction conditions and the progress of the reaction.

For example, when chlorine gas is supplied until the photochlorination of the compound (b 3) has completely proceeded, the following compound (b 3—Cl) wherein Y and Z in the formula (b 3) are chlorine atoms ) Is obtained. Next, the compound (b3_Cl) is subjected to selective fluorination to fluorinate chlorine atoms Y and Z to obtain the following compound (b3-F). Further, by subjecting the compound (b3-F) to a dechlorination reaction, a compound (1-F) in which X ¹ and X ² in the formula (al) are a fluorine atom can be obtained.

Depending on the conditions for the selective fluorination of compound (b 3-C 1), only the following compound (b 3) wherein only one of Y and Z is fluorinated, one of Y and Z is a fluorine atom and the other is a chlorine atom One or both of —FC l) can be formed. Also in this compound, the same dechlorination reaction as in the compound (b 3-F) is carried out, whereby ^one of X ¹ and X ² in the formula (al) is a fluorine atom and the other is a chlorine atom. The compound (al—FC 1) is obtained.

The selective fluorination of compound (b 3-C 1) is preferably carried out according to the method described in US Pat. No. 3,865,845. Specifically with S b F ₃ and S b C 1 _5, the solvent (e.g., Perufuruoro (2-Petit Le tetrahydrofuran)) in, or a method of reacting in the absence of a solvent can be mentioned up. The reaction temperature of the reaction is preferably from 50 to 200, particularly preferably from 100 ° C to 150.

In addition, in the case of the compound (b 3 —Cl), the compound (a 1 —C 1) in which both X ¹ and X ² in the formula (al) are chlorine atoms can be obtained by directly dechlorinating the compound. Can be

In addition, when the supply of chlorine gas is stopped when the photochlorination partially proceeds in the photochlorination of the compound (b3), the following formula in which Y and Z in the formula (b3) are hydrogen atoms Compound (b3-H) is obtained. In the compound (b 3-H), Compound X ¹ and X · ² is water atom (al-H) is obtained by performing as dechlorination. PT / JP2003 / 014743

 13

(b3-H) ( ^a1 ' ^H )

 The dechlorination reaction is preferably performed using a dehalogenating agent in a polar solvent. A dehalogenating agent is a reactant that acts on a halogen atom in a raw material to extract the halogen atom. Among them, a dehalogenating agent that acts as a dechlorinating agent is used in each method for producing the compound (al) of the present invention. As the dehalogenating agent, zinc, sodium, magnesium, tin, copper, iron or other metals are preferred. Among these, zinc is preferable as the dehalogenating agent because a relatively low reaction temperature can be employed. The dehalogenating agent may be activated before acting before the reaction. Activation is preferably performed using an activator. As the activator, dibromoethane, hydrochloric acid, iodine, mercuric chloride and the like are preferable. The amount of the dehalogenating agent relative to the substrate for dechlorination is preferably 2- to 10-fold molar, and particularly preferably 5- to 8-fold molar. The reaction temperature of the dechlorination reaction is preferably from 40 to 100 ° C, particularly preferably from 40 to 80 ° C. The polar solvent is preferably an organic polar solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, 1,4-dioxane, diglyme, methanol, or water.

 The dechlorination reaction is preferably performed by a method in which a dechlorination substrate is dropped into a dehalogenating agent and a polar solvent. Further, it is preferable that the compound (al) produced by the reaction is promptly extracted from the reaction system by reaction distillation.

In the chlorination reaction and the fluorination reaction, the product may be two or more compounds having different degrees of chlorination or fluorination. In this case, the desired compound is appropriately separated from the product, and the necessary reaction is appropriately performed. 03014743

 14 or the reaction in the next step may be carried out as a mixture, followed by separation.

Compound (b2) and compound (b3), which are intermediates for producing compound (al), are novel compounds. In the compound (b 2) and the compound (b 3), R ^{f 1} and R ^{f 2} are preferably a fluorine atom, and n is preferably 1. In the compound (b3), Y and Z are preferably each independently a fluorine atom or a chlorine atom, and both are preferably fluorine atoms. Further, the following compound (b20) is preferable as the compound (b2), and the following compound (b30) is preferable as the compound (b3).

 (b20) (b30)

 The compound (b2) is useful as an intermediate for the production of the polymer (Al) described later, or as an electrolyte for batteries such as capacitors, batteries, etc., or as an additive to the electrolyte.

Compound (b1), which is a starting material for the production of compound (al), can be synthesized using the method described in WO200 / 18314 pamphlet. For example, compound R ^{f 1} and R ^{f 2} is a fluorine atom and n is 1 in formula (b 1) (b 10) can be produced by the following production route.

 (b12)

 (b10) (b15)

 (blO)

That is, a glycerol-formal mixture which is an adduct of dalyserin and formaldehyde (the mixture is usually a mixture in which the compound (b11) and the compound (b12) are present in an equilibrium state) and the formula R ^F COF (R ^F is. showing a good pel full O b alkyl group optionally having ether oxygen atoms) performs esterification reaction between the table are the compounds of then fluorinated in a liquid phase As a result, a mixture of the compound (b13) and the compound (b14) is obtained. Next, the mixture is thermally decomposed to obtain a mixture of the compound (b10) and the compound (b15).

In the present invention, it is preferable to separate compound (b10) from compound (b10) and compound (b15). The separation may be performed on a mixture of the compound (b10) and the compound (b15), or each compound may be converted into a compound which can be easily separated and then separated, and the latter method is preferred. preferable. As the latter method, a method of adding water to a mixture of the compound (bl0) and the compound (bl5), followed by dehydration can be mentioned. In the compound (blO), the keto group is converted to a C (OH) ₂ structure by adding water, and then converted to the compound (b10) by dehydration. On the other hand, in compound (b15), one COF moiety is converted to one COOH group by the addition of water, and does not change in the next dehydration reaction. By distilling the mixture after the dehydration reaction, the compound (blO) is separated and obtained. Can be

The compound (b 10) compound having R ^{f 2} groups other than (b 1) is an adduct of glycerin and formaldehyde in the how, adduct of glycerin and § Seto aldehyde, or, propanal or the like Can be obtained by changing to an adduct with alkanal. For example, a compound (bl) in which R ^{f 2} in the formula (bl) is a trifluoromethyl group can be obtained by using an adduct of glycerin and acetylaldehyde.

Further, by using various triols, various compounds having different R ^fl in the formula (bl) can be obtained. For example, by using 1,2,3-butanetriol as a triol, a compound represented by the formula (bl) in which R ^f1 is a trifluoromethyl group can be obtained. Further, by using 1,2,4-butanol, a compound represented by the formula (bl) in which n is 2 can be obtained.

 Since the compound (a) such as the compound (a1) obtained by the above method has a polymerizable unsaturated bond, it can be polymerized to obtain a polymer (A). The polymer (A) is a polymer having a saturated ring structure in the main chain of the polymer. Due to the presence of the saturated ring structure, the polymer (A) in the present invention exhibits an amorphous property and can be a highly transparent polymer. In addition, the ring structure has an effect of cutting off long electronic conjugation to the polymer chain. Therefore, the polymer (A) of the present invention can be a transparent polymer even in a short wavelength light region.

 Further, the polymer (A) of the present invention is soluble in a specific solvent. At the same time, it has high T g and thermal decomposition temperature, and the difference between T g and thermal decomposition temperature is large, so that melt molding is possible.

 When the polymer (A) of the present invention is a polymer (A1) having a monomer unit of the compound (al), two oxygen atoms are contained in a saturated ring structure existing in the main chain of the polymer (A1). It is thought that the presence of the polymer makes the polymer flexible and easily eliminates the strain when exposed to high temperatures, thus raising the pyrolysis temperature.

The molecular weight of the polymer (A) of the present invention is such that the intrinsic viscosity (unit: dlZg) measured at 30 ° C. in perfluoro (2-butyltetrahydrofuran) is 0. Preferably the molecular weight is between 1 and 5.0. When the intrinsic viscosity is 0.1 or more, the film obtained from the polymer (A) has sufficient mechanical strength. In addition, when the intrinsic viscosity is 5.0 or less, the solubility in a specific solvent is good and preferable. A more preferable range of the intrinsic viscosity is 0.2 to 3.0. As the polymer (A) containing the monomer unit of the compound (a), a homopolymer obtained by polymerizing one kind of the compound (a), a copolymer obtained by polymerizing two or more kinds of the compound (a), or a compound A copolymer of (a) and another monomer having copolymerizability with the compound (a) (hereinafter, referred to as another monomer) is preferable. The other monomer is a monomer having radical polymerizability, and is not particularly limited as long as it is a monomer having copolymerizability with compound (a). Further, the other monomer may be a fluorine-containing monomer other than compound (a) or a monomer having no fluorine atom.

 Examples of the monomer having no fluorine atom include a hydrocarbon-based monomer. Examples of the hydrocarbon-based monomer include olefins such as ethylene, propylene, butylene and isobutylene, styrene, vinyl ethers and pinyl esters. In particular, olefins and vinyl ethers have good alternating copolymerizability with compound (a) such as compound (al), and the resulting fluoropolymer greatly improves the transmittance of light with a wavelength of 200 nm or less. It is preferable because it can be performed.

 When the other monomer is a fluorine-containing monomer other than the compound (a), it is selected from monomers having a polymerizable unsaturated bond and having a fluorine atom.

For example, monomers represented by the formula CFR ³ = CR ⁴ R ⁵ (hereinafter, referred to the monomer and monomer (k).) Can be mentioned.

 As the monomer (k), the following monomers (k-1) to (k-3) are preferred.

Monomer (k_l): A monomer in which R ³ , R ⁴ , and R ⁵ are each independently a hydrogen atom, a fluorine atom, or a monovalent fluorine-containing organic group.

Monomer (k_2): a monomer in which R ³ and R ⁴ together form a divalent fluorinated organic group, and R ⁵ is a fluorine atom or a monovalent fluorinated organic group. 03014743

18 Monomer (k_3): A monomer in which R ⁴ and R ⁵ together form a divalent fluorinated organic group, and R ³ is a fluorine atom or a monovalent fluorinated organic group.

 Examples of the monomer (k-1) include fluorofluorenes having a hydrogen atom such as vinyl fluoride, 1,2-difluoroethylene, vinylidene fluoride, and trifluoroethylene; tetrafluoroethylene, and chlorofluoroethylene. Perfluoro (methyl vinyl ether) and perfluoro (alkyl vinyl ether) such as perfluoro (methyl vinyl ether) and perfluoro (methyl vinyl ether) which do not have a hydrogen atom, such as propylene and hexafluoro propylene; and the like.

 The monomer (k-2) and the monomer (k_3) are monomers having both an unsaturated bond and a ring structure. The monomer (k-1) and the monomer (k-1) include the following monomer (k-1), the following monomer (k-1), and the following monomer (k-30).

However, R ¹¹ to R ¹⁷ each independently represent a fluorine atom or a monovalent fluorine-containing organic group. When R ¹¹ to R ¹⁶ are a monovalent fluorine-containing organic group, a perfluoroalkyl group is preferable, and a perfluoroalkyl group having 1 or 2 carbon atoms is particularly preferable. Further, when R ¹⁷ is a monovalent fluorine-containing organic group, a perfluoroalkyl group or a perfluoroalkoxy group is preferable, and the group having 1 or 2 carbon atoms is particularly preferable.

Another example of the case where the other monomer is a fluorine-containing monomer other than the compound (a) is a fluorine-containing monomer having two or more types of polymerizable unsaturated bonds having different reactivities in a molecule (for example, a fluorine-containing monomer) And the following monomers (k-1 4) or (k-1 5) are preferred. Monomers (k-1 4): Formula CH _? = CR ⁷ — Q ¹⁰ — CR ⁸ = Expressed by CF Monomer (However, R ⁷ and R ⁸ each independently represent a hydrogen atom, a fluorine atom, or a monovalent fluorinated organic group, and Q ^1Q represents a divalent fluorinated organic group.) Monomer (k-1 5): A monomer represented by the formula CF ₂ = CR ⁹ — Q — CR ^ -CFs (where R ⁹ and R ^1D each independently represent a hydrogen atom, a fluorine atom, or a monovalent fluorine-containing organic group, and Q ¹¹ Represents a divalent fluorine-containing organic group

) o

As Q ^1Q and Q ¹¹ , a perfluoroalkylene group which may have an etheric oxygen atom having 1 to 10 carbon atoms is preferable. When the compound has an etheric oxygen atom, the number of oxygen atoms may be one, two or more, and it may be present at one terminal of the perfluoroalkylene group or at both terminals. Or between carbon atoms.

(^^ ぉ. ¹ ^ When each is a perfluoroalkylene group, the number of carbon atoms is preferably 2 to 6, and has an etheric oxygen atom at one end of the perfluoroalkylene group or between carbon atoms. When it is a group, it preferably has 1 to 4 carbon atoms, and when it is a group having ether oxygen atoms at both ends of a perfluoroalkylene group, it preferably has 1 to 3 carbon atoms. Most preferably, the chain length (the chain length is the total number of carbon atoms and oxygen atoms excluding the branch portion ^{) of} 3 < ¹¹ () is 3 to 4.

Q ^{1 G} and Q ¹¹ are a perfluoroalkylene group having 1 to 4 carbon atoms having an etheric oxygen atom at a terminal bonded to a 2,2-difluorovinyl group, and a carbon atom having an etheric oxygen atom between carbon atoms. A perfluoroalkylene group having 2 to 4 or less and a perfluoroalkylene group having 1 to 4 carbon atoms and having no etheric oxygen atom are preferable. More preferred Q ^{1 Q} and Q ¹¹ are each a perfluoroalkylene group having 1 to 4 carbon atoms and having an etheric oxygen atom at the terminal bonded to the 2,2 difluorovinyl group.

 Specific examples of the monomer (k-14) include the following compounds.

CH ₂ = CHCF ₂ CF ₂ 〇CF = CF ₂ ,

CH ₂ = CHCF ₂ CF ₂ CF ₂ OCF = CF ₂ ,

CH ₂ = CHCF ₂ OCF = CF CH ₂ = CHC F (CF ₃ ) CF ₂ OCF = CF ₂ ,

CH ₂ = CHCF ₂ OCF ₂ CF = CF ₂ ,

CH ₂ = CHCF ₂ CC 1 ₂ 〇CF = CF ₂ ,

CH ₂ = CFCF ₂ CF ₂ OCF = CF ₂ ,

CH ₂ = CFCF (CF ₃ ) CF ₂ OCF = CF

 Specific examples of the monomer (k-15) include the following compounds.

CF ₂ = CFCF ₂ CF (CF ₃ ) OCF = CF ₂ ,

CF ₂ = CFOCF ₂ OCF = CF ₂ ,

CF ₂ = CFOC (CF ₃ ) ₂ OCF = CF ₂ ,

CF ₂ = CFCF ₂ C (CF ₃ ) ₂ OCF = CF ₂ ,

CF ₂ = CFCF ₂ CF ₂ OCF = CF ₂ ,

CF ₂ = CHCF ₂ CF ₂ OCF = CF ₂ ,

CF ₂ = CHC F (CF ₃ ) CF ₂ 〇CF = CF ₂ ,

CF ₂ = CFCF ₂ CF ₂ CF ₂ 〇CF = CF ₂ ,

CF ₂ = CFCF ₂ OCF = CF ₂ ,

CF ₂ = CFCF (CF ₃ ) CF ₂ OCF = CF ₂ ,

CF ₂ = CFCF ₂ CF (CF ₃ ) OCF-CF ₂

CF ₂ = CFOCF ₂ OCF = CF ₂ ,

CF ₂ = C FOC (CF ₃ ) ₂ OCF = CF ₂ ,

CF ₂ = CFCF ₂ C (CF ₃ ) ₂ OCF = CF ₂₀

 The polymer (A) in the present invention can be made into a polymer having a different glass transition temperature while maintaining transparency by changing the copolymer composition. Further, by copolymerizing the polymer with another monomer having a functional group, the adhesion of the polymer to the base material can be improved or a crosslinked site can be provided. Examples of the functional group include groups such as a hydroxyl group, a carboxyl group, and a sulfonic acid group, and groups that can be converted into the group. The other monomers may be used alone or in combination of two or more.

In order that the polymer (A) of the present invention is a non-crystalline polymerizable polymer having solubility in a solvent, the unit (A) in all units of the polymer (A) may be used. The lower limit of the ratio is preferably 10 mol%, particularly preferably 20 mol%, and the upper limit of the ratio of the unit (A) is preferably 100 mol%. Further, the unit (A) is When it is a monomer unit of the compound (a) such as the compound (al), the content of the monomer unit (A) relative to all monomer units is preferably at least 10 mol%, particularly preferably at least 20 mol%. The upper limit of the monomer unit is preferably 100 mol%.

 Further, the polymer (A) of the present invention has high durability against light in a short wavelength light region. The reason for this property is not necessarily clear, but it is considered that the main chain is hardly cleaved even if light is absorbed due to the small distortion of the main chain saturated ring structure.

 The polymer (A) of the present invention is used as a pellicle film and a glue or an adhesive. The present invention provides a pellicle for exposure treatment with light having a wavelength of 200 nm or less, wherein the pellicle film is adhered to a frame via an adhesive. A pellicle for use in an agent is provided. Further, according to the present invention, an exposure processing method using light having a wavelength of 200 nm or less in photolithography can be performed using the pellicle of the present invention.

 The polymer (A) as the pellicle material is preferably a polymer (A) that requires the unit (A) or a polymer (A 1) that requires the unit (A 1).

The pellicle of the present invention is intended to prevent a reduction in yield due to dust adhering to a mask and a reticle used in exposure processing using light having a wavelength of 200 nm or less, particularly excimer laser light. The pellicle of the present invention can be applied to any kind of exposure treatment, but is preferably used in the exposure treatment of photolithography, which is one step in manufacturing a semiconductor device or a liquid crystal display panel. The light used for the exposure process is highly durable against KrF excimer laser light (wavelength 248 nm) and ArF excimer laser light (wavelength 193 nm). In particular, light having a wavelength of 180 nm or less (for example, F ₂ excimer laser light (wavelength: 157 nm)) can be preferably used.

The pellicle of the present invention includes a pellicle film and a frame, and the pellicle film is bonded to the frame via an adhesive. The material for forming the frame is not limited as long as it can support the pellicle film, and is preferably a metal material in terms of strength, and particularly a metal material having resistance to short-wavelength light used in exposure processing. Can be adopted without restriction. Aluminum, 18- 8 Examples include stainless steel, nickel, synthetic quartz, calcium fluoride, and palladium fluoride. Among these, aluminum or synthetic quartz is preferable as the material from the viewpoints of environmental resistance, strength, and specific gravity.

 In the present invention, the polymer (A) is used as a pellicle film and / or an adhesive in the pellicle.

 Among them, the pellicle film is preferably manufactured by forming a film using a solution of the polymer (A). The solvent is not particularly limited as long as it dissolves the polymer (A) of the present invention having a fluorine atom, and it is preferable to select a solvent having high polymer solubility, particularly a fluorine-containing organic solvent.

 Specific examples of the fluorinated organic solvent include the following.

 Polyfluoroaromatic compounds such as perfluorobenzene, pentafluorobenzene, and 1,3-bis (trifluoromethyl) benzene. Polyfluorotrialkylamine compounds such as perfluorotributylamine and perfluorotripropylamine. Polyfluorocycloalkane compounds such as perfluorodephosphorus and perfluorocyclohexane. Polyfluoro cyclic ether compounds such as perfluoro (2-butyltetrahydrofuran). Perfluorooctane, Perfluorodecane, 1,3—Dichloro-1,1,2,2,3—Penfufluoropropane, 2 H, 3 H—Perfluoropentane, 1 H—Perfluo Polyfluoroalkanes such as xane. Polyfluoroethers such as methyl perfluoroisopropyl ether, methyl perfluoro mouth butyl ether, methyl (perfluoro mouth hexyl methyl) ether, methyl perfluorooctyl ether, and ethyl perfluorobutyl ether.

As a method for producing a pellicle film from a solution of the polymer (A), a known method for forming a polymer thin film on a substrate can be adopted, and a roll coating method, a casting method, a dip method, a spin coating method, The water casting method, the die coating method, the Langmuir project method and the like can be mentioned. Of these, the pellicle film is required to form a strict film thickness, and therefore, it is particularly preferable to employ the spin coating method. The substrate is preferably a silicon wafer, quartz glass or the like having a flat surface. Usually, the thickness of the pellicle film is preferably in the range of 0.01 to 50. As the polymer (A) used for the pellicle membrane, the polymer (A1) is preferable. Further, the polymer (A1) is preferably a polymer which requires the unit (A) and has no functional group. Further, the polymer (A) is preferably a polymer having no CH ₂ CH ₂ structure. The polymer (A) may be a polymer composed of one or more units (a) (preferably, units (al)), and a unit other than the units (a) and (a). (Hereinafter, referred to as other units), and the latter is preferable. When the polymer (A1) as a pellicle membrane has other units, the ratio of the other units to the total units in the polymer is 0.1 to 60 mol in terms of the mechanical strength and transmittance of the membrane. %, Particularly preferably 1.0 to 50 mol%. As another unit, a monomer unit obtained by polymerizing monomers (k-1) to (k-5) is preferable.

 Further, as the adhesive for adhering the pellicle film to the frame, a polymer containing the unit (A) is preferably used, and a polymer containing the unit (A) and having a functional group is particularly preferable.

 Further, a copolymer having a unit represented by the formula (A) and a monomer unit (k-1) as essential and having a functional group, a unit represented by the formula (A) and a monomer (k-1) And a copolymer having an essential and functional group of a monomer unit of Z or a monomer (k-1), or a unit represented by the formula (A) and a monomer (k-1 4) and / or a monomer (k-1 5) ) Is a copolymer having essential functional units and having a functional group. Since high transparency is not always required for the adhesive polymer (A), the proportion of the unit (A) in the adhesive polymer (A) may be small. For example, the ratio of the monomer unit (A) to one monomer unit in the polymer may be less than 1 mol%, preferably from 0.0001 mol% to less than 1 mol%. When the polymer (A) of the present invention is used as an adhesive between a pellicle frame and a pellicle membrane, an adhesive polymer (A) into which a functional group effective for improving adhesiveness is introduced is used. Is preferred. On the other hand, the polymer (A) in the present invention for a pellicle film is preferably a polymer having no functional group from the viewpoint of light transmission.

When the adhesive polymer (A) has a functional group, the functional group may be a frame or a base. It is selected from functional groups that exhibit adhesiveness to the icle film, and includes carboxylic acid groups, sulfonic acid groups, alkoxycarbonyl groups, acyloxy groups, alkenyl groups, hydrolyzable silyl groups, hydroxyl groups, maleimide groups, amino groups, and cyano groups. And at least one group selected from a group and an isocyanate group. Further, as a functional group, it exhibits good adhesiveness to metals such as aluminum as a frame material, can exert its effect at a relatively low temperature, and has a high storage stability. Lupoxyl groups are particularly preferred.

 When the adhesive polymer (Α) contains a functional group, the number of functional groups is preferably from 0.01 to 1 mmol per gram of the polymer. When the number of the functional groups is within 1 mmol, the possibility that the short-wavelength light absorptivity of the functional groups impairs the durability of the adhesive is reduced.

 The adhesive polymer (A) into which a functional group is introduced can be synthesized by a known method (for example, Japanese Patent Application Laid-Open No. 4-189890, Japanese Patent Application Laid-Open No. 4-226261). No. 7 Japanese Patent Application Laid-Open No. Hei 6-222022).

 As a method for introducing a functional group, (Method 1) After polymerizing the monomer (a) or polymerizing the monomer (a) with another monomer, a polymer terminal group derived from a polymerization initiator, a chain transfer agent, etc. (Method 2) Monomer-(a), a method of copolymerizing another monomer having no functional group, and another monomer having a functional group, or (Method 3) Monomer ( a) a method of copolymerizing another monomer having no functional group and another monomer having a group that can be converted into a functional group, and then converting a group that can be converted into a functional group into a functional group, etc. Is mentioned. Of these, method 1 is preferred because the introduction operation is easy.

 As a specific example of the method for introducing a carbonyl group, a method of copolymerizing a monomer having an alkoxycarbonyl group, and then converting the alkoxy group in the copolymer into a carbonyl group by a hydrolysis reaction ( Example of Method 3), and a method of obtaining a polymer having an alkoxylcarbonyl group at a terminal group and hydrolyzing the polymer (an example of Method 1).

As a method other than the above, a method in which a polymer is subjected to high temperature treatment to oxidatively decompose a side chain or a terminal of the polymer to introduce a hydroxyl group into the polymer is also employed. it can.

 Further, a polymer other than the polymer (A) may be used as the adhesive. The polymer is not particularly limited, and examples thereof include compounds described in Japanese Patent Application Laid-Open No. 2001-330943 and International Publication No. 2001/37044. Specific examples include polymers having no saturated aliphatic ring structure in the main chain, such as propylenenovinylidene fluoride tetrafluoroethylene copolymer, vinylidene fluoride hexafluoropropylene copolymer, and the like. For example, a copolymer mainly composed of It is preferable to introduce a functional group into these polymers by a method such as the method 1.

 Further, in the present invention, in addition to the adhesive polymer (A), a coupling agent such as a silane-based, epoxy-based, titanium-based, or aluminum-based coupling agent is used for the purpose of improving the adhesiveness of the adhesive polymer (A). Etc. may be used. When an adhesive polymer (A) containing a functional group is used, the polymer (A) is coated thinly on a frame, and the polymer (A) of the present invention having no functional group on its surface is used. The pellicle film can be firmly adhered even if) is applied and adhered.

 The polymer (A1) having the monomer unit (A1) among the polymers (A) in the present invention is a novel polymer.

 (A1)

In formula (A1), X ¹ , X ² , n, R ^fl , and R ⁱ² have the same meaning as described above, and the preferred embodiments are also the same. When X ¹ and X ² are independently a fluorine atom or a chlorine atom, the polymer has good heat resistance, weatherability and light resistance. In particular, when X ¹ and X ² are both fluorine atoms, Quality is further improved. As the polymer (A 1), a polymer containing a monomer unit in which X ¹ , X ² , R ^fl and R ^{f 2} in the formula (A 1) are all fluorine atoms and n is 1 is particularly preferable.

 Even when the polymer (A 1) is used for purposes other than pellicles, the polymer (A 1) may be used as it is, or may be used after being converted into another compound. When used as it is, it is preferable to use it after dissolving it in a solvent. As the solvent, a fluorinated solvent is preferable. In addition to the above-mentioned fluorinated solvent, a perfluorotetrahydrofuran derivative such as perfluoro (2-butyltetrahydrofuran); a perfluoroalkylamine such as perfluorotriptylamin; And perfluorocycloalkanes (including condensed rings) such as perfluorocyclohexane; hydrofluoroethers; and fluorene-containing fluorocarbons. The polymer (A) of the present invention is soluble in these fluorinated solvents.

 The polymer (A) of the present invention can be obtained by ordinary radical polymerization. As a polymerization method, a technique of a radical polymerization reaction can be applied. For example, polymerization by an organic or inorganic radical initiator, light, ionizing radiation or heat, etc. may be mentioned. As the polymerization method, bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization can be used. Examples of the initiator used for the main polymerization include the following compounds.

Diisopropylperoxydipotionate, di (2-ethylhexyl) ぺ -roxydicarbonate, diarylperoxydicarbonate, isobutylyl ruperoxide, t-butylperoxypivalate, bisperfluo Peroxide or azo compound such as lovtyrilperoxide, perfluorobenzoylperoxide, bisperfluoride or the like, or azo compound; etc. The molecular weight of the polymer (A) of the present invention It can be adjusted by using a known chain transfer agent. Examples of the chain transfer agent include black-mouthed carbon such as black-mouthed form, alcohols such as methanol and isopropyl alcohol, hidden-mouthed fluorocarbons such as difluorochloromethane, and sulfides. . 43

27 Compound (a) such as compound (al) in the present invention has a relatively high boiling point and an appropriate polymerization rate, and is a polymerization method for directly obtaining parts and the like from monomers, such as potting polymerization or cast polymerization. Bulk polymerization method (hereinafter also referred to as direct polymerization method). For example, in the case of cast polymerization, it is possible to manufacture a lens-like product, manufacture a rod for an optical fiber, and directly manufacture a core or a clad of an optical waveguide. Usually, a monomer and a polymerization initiator are mixed, and if necessary, other additives are added, and the mixture is injected into a molding die. Thereafter, a heat polymerization method of curing by heating, or a photopolymerization method of curing by actinic rays such as light curing can be adopted.

 After polymerizing the compound (a) such as the compound (al), it is difficult to remove impurities mixed during the polymerization step, but at the monomer stage, it is easy to remove impurities by high-precision filtration or the like. Therefore, if parts and components can be manufactured by the direct polymerization method, the chance of impurity contamination can be reduced. Therefore, by employing the direct polymerization method, optical members and components such as optical lenses, optical cells, optical fiber preforms, optical waveguides, etc., having extremely few impurities can be produced with extremely high purity and high quality. Therefore, it is possible to produce members and parts having good transparency without scattering.

 The type of the initiator used in the direct polymerization method is not particularly limited, and the same initiator as described above can be used. Generally, the amount of the initiator added is preferably 0.05 to 5%, more preferably 0.1 to 3%, based on the total amount of the monomers.

 When the thermal polymerization method is used as the direct polymerization method, the temperature is preferably set to 0 to 50 at the initial stage, and the temperature is preferably gradually increased as the polymerization proceeds, and finally to 60 to 150. Heating is preferred. After removal from the mold, boss cure can be performed if necessary.

 When the photopolymerization method is used as the direct polymerization method, a photosensitizer, such as benzoin, benzoin methyl ether, benzoethyl ether, benzophenone, acetate phenone, etc., is added to the total amount of the monomers. It is polymerized and cured by irradiating ultraviolet rays with addition of 0.01 to 5%. In the photopolymerization method, the polymerization initiator may be used in combination.

The polymer (A) of the present invention can be used not only in a direct polymerization method but also in a polymer obtained by a usual polymerization method, such as extrusion molding, injection molding, etc., melt coating such as solution coating, casting, and dipping. It is possible to adopt the processing means of You. Thereby, the polymer (A) of the present invention can be applied to various uses.

 For example, the novel polymer (A 1) of the present invention has a property that its elastic modulus is maintained even at high temperatures, so that its strength at high temperatures is higher than that of other general-purpose fluoropolymers such as PTFE and PFA. Have. Moreover, the chemical stability is equivalent to PTF E and PFA. Therefore, it can be applied to products in which structural parts such as piping, valves, sight glass, silicon wafer cases, and various chemical tanks come into direct contact with chemicals in various chemical and semiconductor factories.

 Further, since the polymer (A 1) of the present invention has excellent thermal stability, additives such as a plasticizer and a heat stabilizer are not required when the above-mentioned molded product is melt-molded. In addition, high decomposition temperature makes it difficult to generate decomposition products. These characteristics have an advantage that when the polymer (A 1) of the present invention is applied to the food industry and bioindustry, contamination of impurities into products can be avoided.

 In addition, the polymer (A 1) of the present invention has a transmittance of ultraviolet light of 200 nm to 400 nm of 90% or more and is hardly deteriorated by ultraviolet rays. Therefore, it can be used as an optical transmission member such as a lens, an optical fiber, or an optical waveguide in various optical devices and optical components using ultraviolet light. For example, a component for DVD using a blue laser having a wavelength of 400 nm or less, a surface protective film of a disk for DVD, or a surface protective film of a solar cell are exemplified.

— Higher transparency in the near-infrared region of the wavelength range of 700 to 170 nm. Therefore, it is particularly suitable for optical components such as optical fibers for optical communications, optical waveguides and the like, lasers for optical communications, protective films or lenses for photodiodes, adhesives for optical components, waveguide substrates for mixed optical and electronic components, etc. is there. Further, since the polymer (A 1) of the present invention has a high glass transition temperature, it can be used under severe conditions (for example, long-term high-temperature conditions such as solder reflow conditions or around an engine, or heat generation conditions such as inside a computer). Under long-term use, etc.) It has the advantage that the characteristics are hardly deteriorated. Furthermore, it has high transparency and low dispersion even in visible light. Therefore, it can be used as a lens for correcting chromatic aberration. Further, since the polymer (A 1) of the present invention has excellent resistance to various chemicals, it can be used as a protective coating agent, a photoresist film, and a masking agent for etching. It is useful as a separator for fuel cells, a catalyst fixing film for fuel cells, and the like. In particular, when used as a photoresist film or as a masking agent at the time of etching, the photopolymerization method of the direct polymerization method can be used to simplify the process as compared with the conventional method.

That is, when a mixture of a monomer and a photopolymerization initiator is applied to a substrate and irradiated with light of a desired pattern by a photoresist method, only the irradiated portion is polymerized. Thereafter, a desired pattern can be formed by removing the monomer in a portion which is not irradiated with light and is not polymerized. In addition, because of the high transmittance of ultraviolet light, resist film materials for low wavelengths, for example, for an F ₂ excimer laser that oscillates at 157 nm, or for an Ar F excimer laser that oscillates at 193 nm, for lithography It is also useful. In this case, the polymer (A1) of the present invention has a low refractive index, and may be used in combination with various photoacid generators, leveling agents, surfactants, and the like, instead of the monomer alone. It is also useful as a low reflection processing agent. Coating of the polymer (A1) of the present invention on the surface of spectacle lenses, optical lenses, various optical members, pellicles, show windows, show cases or various displays (PDP, LCD, FED, organic EL, projection TV) By forming, an antireflection effect can be obtained. In addition, since the homopolymer of the compound (a1) of the present invention has a refractive index of about 1.33, which is almost the same as that of water, the protective film for bioindustry, lenses, and protection for analytical instruments It is also useful as a film or molded article.

Furthermore, since the polymer (A1) of the present invention has a low dielectric constant, when it is used as a protective film of a semiconductor device, it has the effect of increasing the calculation speed. In addition, since the water absorption is low, the dielectric constant is hardly affected by humidity, and the effect of shielding the semiconductor element from moisture is high. Taking advantage of these characteristics, interlayer insulating films (for example, for semiconductor devices, liquid crystal displays, and multilayer wiring boards), buffer coating films, passivation films, wire shielding films, element sealing materials, and various semiconductors It can be used as an adhesive (for LOC, for dipoles, etc.), an interlayer insulating film for high-density mounting boards, a moisture-proof film and a protective film for high-frequency devices (for example, RF circuit devices, GaAs devices, and InP devices). Further, the polymer (A1) of the present invention is laminated with a single film or a resin such as polyimide. They can be used as layered films, and these are useful as films for circuit boards and film capacitors.

 Further, it is possible to impart water / oil repellency to various substrate surfaces by utilizing the low surface free energy of the polymer (A1) of the present invention. By combining these and other characteristics, anti-fouling or lubricating films for magnetic disk substrates, optical disks, and sunset panels, photosensitive and fixing drum coating materials for electrophotography, various films for glass windows, electric wire coating materials, It can be used for inks (eg, for coating, printing equipment such as ink jet ejection surfaces), anti-reflective coatings for resists, etc.

 In the solution composition obtained by dissolving the polymer of the present invention in a solvent, the solvent may be perfluoro (2-butyltetrahydrofuran), perfluorotriptylamin, perfluorocycloalkane (including a condensed ring), or a hydride. Solvents that do not attack the base material itself, such as mouth fluoroesters and hide mouth fluorocarbons, can be used. Therefore, there is an advantage that the solution composition can be coated on various substrates and the formed film is tough.

(Example)

 Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

 [Example 1] Synthesis example of mixture of compound (18) and compound (19)

To, 0. / CF (CF ₃ ) OCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₃

,

 (18)

CF (CF ₃ ) OCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₃

 (19)

A 2 L autoclave made of Hastelloy C was charged with F (CF ₂ ) ₃ 〇CF (CF ₃ ) CF ₂ 〇CF (CF ₃ ) COF (2515 g) and NaF powder (240 g). Cool the reactor with sufficient agitation and keep the internal temperature below 30 at normal pressure. Glycerol-formal (401 g) was introduced slowly so as to be dripping. The HF generated by the reaction was removed by adsorption with NaF. After charging the whole amount of glycerol * formal, the mixture was further stirred for 24 hours, and then the NaF powder was removed by pressure filtration to obtain a product. The product was analyzed by NMR and GC, and as a result, it was a mixture of the compound (18) and the compound (19), and the selectivity as a mixture was 99.4%. Unreacted glycerol-formal was not detected. This product was used for the next reaction without purification.

Compound (18) of ¹ H- NMR (300. 4MHz, solvent: CDC 1 _3, standards: TMS) δ (p pm) : 3. 93~ 4. 1 0 (4H), 4. 82 (1 H) , 4.95 (2H).

¹⁹ F- NMR of the compound (18) (282. 7MHz, solvent CDC 1 _{3, criteria: CFC 1 3) δ (p} pm): - 79. 0~- 80. 7 (4 F), - 8 1. 9--83.1 (8 F), 1 84.6-1 85.6 (1 F),-1 30.1 (2 F),-1 32.0 (IF),-145.7 (1 F).

Compound (19) of ¹ H- NMR (300. 4MHz, solvent: CDC 1 _3, standards: TMS) δ (p pm) : 3. 74 (1H), 3. 93~ 4. 1 0 (1 H) 4.27 to 4.54 (3H), 4.90 (1H), 5.04 (1H). ¹⁹ F- NMR of the compound (19) (282. 7MH z, solvent CDC 1 _{3, criteria: CFC 1 3) δ (p} pm): - 79. 0~- 80. 7 (4 F), - 8 1 9--83.1 (8 F),-84.6--85.6 (IF),-1 30.1 (2 F),-1 32.0 (IF),-145.7 (1 F).

 [Example 2] Example of fluorination reaction

CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) COF (4 kg) was added to the stainless steel autoclave ( ₃ ) equipped with a condenser, a pump, and a circulation line connected to the pump. Circulation (flow rate 300 L / h). A heat exchanger was installed on a part of the circulation line extending from the pump discharge side to the autoclave top plate to maintain the temperature of the circulating liquid at 25 ° C. A stainless steel ejector is installed in the middle of the circulation line so that gas can be sucked into the circulating liquid, and a raw material supply pipe between the ejector and the pump, and a reaction crude liquid reacted in the autoclave. Take out the extraction tube for extraction Attached. After nitrogen gas was blown through the ejector for 2.0 hours, fluorine gas diluted to 50% with nitrogen gas (hereinafter referred to as 50% diluted gas) was blown at a flow rate of 113.2 NL / h for 1.5 hours. .

Next, while blowing the 50% diluted fluorine gas at the same flow rate, the product obtained in Example 1 was circulated from the raw material supply pipe without dilution, and the CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) COF was fed continuously at an average supply of about 50 gZh, for a total of 4800 g of raw material. On the other hand, about 270 g of the reaction crude liquid was withdrawn from the circulation line about 12 times in total every about 8 hours from the start of raw material supply. Even after the supply of the raw materials is completed, 50% dilution of fluorine gas is supplied for 1 hour.Fluorine gas is supplied, and nitrogen gas is further blown in for 3.5 hours. The reaction crude liquid was recovered.

The product was analyzed by ¹⁹ F-NMR. As a result, the yield of compound (b 13-1) from compound (18) was 57.5%, and that of compound (b 14-1) from compound (19). The yield was 81%, and it was confirmed that the main component was CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) CF OCF (CF ₃ ) COF used for circulation except for the compound. The obtained crude liquid was used for the next reaction as it was.

 F2

 -CL 0 8 "(€ ^? * 3) 0 u2 ^" (¾ ^ ¾ ¾ ^ u2 ^ "2 ^" 3

 CF

 2 0

 (bl3-l)

_{CF (CF 3) OCF 2 CF} (CF 3) OCF 2 CF. CF ₃

 (bl4 "l)

. Compound (b 13 - 1) of the ¹⁹ F- NMR (282. 7 MH z solvent CDC 1 _{3, reference: CFC 1 3) δ (ppm} ): -52 8 (2 F), 78. 5 80. 5 ( 4 F) — 81 9 (8 F) -83. 0 89. 1 (5 F) 130. 1 (2 F) 132.0 (IF) 139.8 (IF),-145.5 (1 F).

¹⁹ F-NMR (282.7 MHz, solvent CD CI) of compound (bl 4-1) Standard: CFC 1 δ (p pm) 54.5 to 15.8 (2 F)

78.5-1 80.5 (4F), 1 81.9 (8F), -83.0-89

1 (5 F),-127.9 (IF), 1 1 30.1 (2 F),-1 32.

0 (IF), one 145.5 (IF).

 [Example 3] Synthesis example of compound (b10) by liquid phase pyrolysis reaction

 Combine the crude liquid (355.6 g) obtained in Example 2 with KF powder (15.7 g)

The mixture was charged into an L round bottom flask and heated in an oil bath at 90 for 5 hours with vigorous stirring. A condenser cooled to 20 from the top of the flask and a round bottom flask cooled to 178 ° C were connected in series. The product was collected in a cooled round bottom flask. The thermal decomposition was terminated after heating and stirring at 10 Ot: for about 1 hour from the point when gas generation was not observed due to the progress of the reaction. Liquid products (463

2 g) was recovered. As a result of analysis by ¹⁹ F-NMR, it was confirmed that the liquid product was a mixture of the compound (b10) and the compound (b15).

 15)

Next, ion-exchanged water (95.5 g) was slowly added dropwise while cooling so that the internal temperature of the collected round bottom flask did not exceed 1 ° C. After dropping the whole amount, the temperature was returned to room temperature and stirring was continued for 16 hours. As a result of analysis by ¹⁹ F-NMR, it was found that the compound (22) in which the compound (b10) was hydrated, and the compound (23) in which the sulfonic acid fluoride group of the compound (b15) was converted to a carboxylic acid group were obtained. It was confirmed that it was a mixture.

(22) (23) ^The yield (internal standard: C ₆ F ₆ ) obtained from the ¹⁹ F—NMR measurement was 91% based on compound (b 10) for compound (22) and compound (b 15) based on compound (23). At 75%.

¹⁹ F-NMR of the compound (b 10) (282. 7 MH z, solvent CDC 1 _{3, reference: CFC 1 3) δ (ppm} ):.. -51 9 (2 F), -80 6 (4F

) o

Compound (b 15) of the ^{19 F-NMR (282. 7 MH} z, solvent CDC 1 _{3, reference: CFC 1 3) δ (ppm} ): 25. 5 (IF), - 53. 6 (IF), -58 4 (IF), -77.5 (IF), -88. 5 (IF), — 1 19.2 (1 F).

¹⁹ F-NMR of the compound (22) (282. 7 MHz, solvent CDC 1 _{3, criteria: CFC 1 3) 6 (ppm} ): -. 52. 2 (2 F), -87 9 (4 F) Compound ( 23) of the ¹⁹ F- NMR (282. 7MHz, solvent CDC 1 _{3, criteria: CFC 1 3) δ (m} ):.. -54 0 (IF), - 59. 2 (IF), -79 1 ( IF), 19.2 (IF), —119.5 (IF;). Concentrated sulfuric acid (203.2 g) was charged into a 50 OmL round bottom flask and heated to 130 ° C in an oil bath with vigorous stirring. Thereto, a mixture (304.4 g) of the compound (22) and the compound (23) was slowly added dropwise. From the top of the flask, a condenser cooled to 2 Ot: and a round bottom flask cooled to 78 were connected in series. The product was recovered in a cooled round-bottomed flask, heated and stirred at 145 for about 1 hour after the entire amount was dropped, and the process was terminated. As a result of ¹⁹ F-NMR, it was confirmed that almost all of the recovered product was compound (b10).

 [Example 4] Synthesis example of compound (b 20)

The round bottom flask in which the compound (blO) was recovered in Example 3 was cooled to -78 ° C, and ethylene chlorohydrin (40.5 g) was slowly added dropwise. After dropping the whole amount, the temperature was raised to room temperature with stirring, and then stirring was continued for 16 hours. A colorless transparent liquid (106.8 g) was recovered by simple distillation. — As a result of NMR and ¹⁹ F_ NMR analysis, the recovered colorless and transparent liquid is ethylene chlorohydroxide. The compound (24) to which phosphorus was added was confirmed. The yield determined by NMR (internal standard: C ₆ F ₆ ) was 83%.

¹ H- NMR of the compound (24) (300. 4MHz, solvent _{CDC 1 3,: TMS) δ} (ppm): 3. 68 (2H), 4. 17 (2H).

¹⁹ F- NMR of the compound (24) (282. 7 MH z , solvent CDC 1 _{level: CFC 1 3) δ (pm} ) 48. 4 (IF) 54. 5 (IF)

18.0 (1 F), — 86.3 (1 F).

 {

 b

 Subsequently, the 50 OmL four-neck glass flask equipped with a reflux condenser, stirrer, and dropping funnel was sufficiently purged with nitrogen, and then methanol (160.0 g) and sodium hydroxide (17.6 g) were charged. The solution was completely dissolved while cooling the system in a water bath.

Thereafter, compound (24) (99.8 g) was charged into the dropping funnel, and the mixture was dropped while keeping the inside of the flask at 10 or less. After stirring for 12 hours as it was to complete the reaction, the solution in the flask was added to ion-exchanged water (40 OmL), and the solution was extracted with dichloropentafluoropropane (40 g). The extract was concentrated by a rotary evaporator, and pentafluoropropane having a diclo opening was distilled off under reduced pressure to obtain 82.0 g of a colorless transparent liquid. As a result of analysis using —NMR and ¹⁹ F—NMR, it was confirmed that the colorless and transparent liquid was Compound (b20), and the yield was determined by gas chromatography to be 84.5%.

(24) ¹ H- NMR of the compound (b 20) (300. 4MHz, solvent CDC 1 _3, 3 quasi: TMS) δ (ppm): 4. 32 (4H).

Compound (b 20) of the ¹⁹ F- NMR (282. 7MHz, solvent CDC 1 _{3, reference: CFC 1 3) δ (ppm} ):.. -52 7 (2 F), -86 6 (4 F ) o

 [Example 5] Example of synthesis of compound (b31) by photochlorination

 After thoroughly replacing the inside of a 2 L flask equipped with a dry ice reflux condenser, a chlorine gas inlet, and a thermocouple thermometer with a high-pressure mercury lamp in the side tube and a side tube, the compound synthesized in Example 4 (b20) ( 76 g) and R—113 (540 g) were charged. After the internal temperature was raised to 10 ° C, the mercury lamp was turned on, and at an internal temperature of 30, the introduction of chlorine gas was started slowly. Thereafter, the temperature of the system was raised and kept constant within the range of 45 to 50 ° C. The unreacted chlorine gas was reacted while circulating in the system by a dry ice reflux condenser. A total of 90.5 g of chlorine was charged, and the reaction was terminated when the chlorine was consumed.

Then, after removing residual chlorine with nitrogen, the content was recovered, and R-113 was distilled off with a rotary evaporator to obtain a colorless transparent liquid (120 g). As a result of analysis by ¹⁹ F-NMR, it was confirmed that the liquid was Compound (b31). Thereafter, using a simple distillation apparatus, a fraction (116 g) at an operating pressure (15 × 133.322) Pa of 40 ° C. to 41 ° C. was recovered as the target substance. The yield was 99%.

¹⁹ F- NMR of the compound (b 31) (282. 7MHz, solvent CDC 1 _{3, reference: CFC 1 3) δ (p} pm): -. 52. 3 (2 F), -85 9 (4 F

) o

[Example 6] Example of synthesis of compound (b30) by partial fluorination

A well-dried four-necked flask was equipped with a reflux condenser, stirrer, dropper port, and thermocouple thermometer, charged with antimony trifluoride (61.6 g), and used a vacuum pump at room temperature. And dried under reduced pressure for about 12 hours. Thereafter, the compound (b31) (100.0 g) synthesized in Example 6 and antimony pentachloride (18.0 g) were dropped into the system from a dropping funnel, and the mixture was heated to reflux while stirring. Thereafter, the reflux condenser was replaced with a simple distillation apparatus, and the product was distilled off from the system under reduced pressure to obtain a colorless transparent liquid (87.6 g). ^{As a} result of analysis by ¹⁹ F-NMR, it was confirmed that the liquid was Compound (b30). The yield determined by NMR (internal standard: C ₆ F ₆ ) was 97%.

Compound (b 30) of the ¹⁹ F- NMR (282. 7MHz, solvent CDC 1 _{3, reference: CFC 1 3) δ (ppm} ):. -53 2 (4 F), one 84.2 / - 8 5.0 (4F).

 [Example 7] Example of synthesis of compound (a 2) by dechlorination reaction

Zinc powder (42.1) and dimethylformamide (120 g) were placed in a 50-mL four-neck glass flask equipped with a mechanical mechanical mixer, a dropping funnel, a thermocouple thermometer, and a distillation column. Heated to 40 ° C. Thereafter, 1,2-dibromoethane (16.1 g) was added dropwise to the system. After the end of the vigorous exotherm, the system was adjusted to 55 and the compound (b30) (77.0 g) was slowly dropped. As the reaction proceeded, the product distilled off from the top of the distillation column. The compound (b30) was charged into the system in its entirety while maintaining the balance between the distillation and the dropwise addition, and the product (32.1 g) was recovered. The obtained product was a colorless and transparent liquid. As a result of analysis using —NMR and ¹⁹ F—NMR, it was confirmed that the liquid was Compound (a2), and the yield was determined by gas chromatography. As determined, it was 52%. The mass spectrum (CI method) of the obtained product was Upon measurement, a molecular ion peak was observed at mZ z = 288.

¹⁹ F- NMR of the compound (a 2) (282. 7MHz, solvent CDC 1 _{3, criteria: CFC 1 3) δ (p} pm): -. 53. 1 (2 F), -87 7 (4 F) ,-1 56. 1 (2 F;).

 [Example 8] Synthesis example of polymer (A 2) and polymer (A3)

The compound (a 2) (6.0 g) obtained in Example 7 and CF ₃ CF ₂ CF ₂ CF ₂ CF 2 CF 2 H (150 g) were added to a pressure-resistant glass autocrepe having an internal volume of 20 OmL. I put it.

As a polymerization initiator, a 3% solution of (C ₃ F ₇ COO) ₂ in dichloropentafluoropropane (0.74 g) was added, the system was replaced with nitrogen again, and polymerization was carried out at 110 ° C for 80 hours. Was. As a result, an amorphous polymer (hereinafter, referred to as polymer A2) (2.2 g) was obtained. When ¹⁹ F-NMR of polymer A 2 was measured, the peak of the fluorine atom bonded to the carbon atom constituting the unsaturated bond of the raw material monomer (compound (a 2)) was completely eliminated. It was confirmed that the ring structure of (a 2) was maintained as it was.

 The intrinsic viscosity [? 7] of the polymer A2 was 2.42 at 30 ° C in perfluoro (2-butylethyltetrahydrofuran). The polymer A2 was a tough and transparent glassy polymer at room temperature.

From the measurement by thermogravimetric analysis in nitrogen, the onset temperature of weight loss of the polymer A2 was about 400 ° C, and the 10% weight loss temperature was 480 ° C. After dissolving in perfluoro (2-butyltetrahydrofuran) to prepare a solution, the refractive index of the film obtained by casting on a glass substrate was measured using an Abbe refractometer to be 1.33. . In addition, DSC measurement showed a glass transition temperature of 305 ° C. Then, the polymer A 2 was charged into a nickel autoclave, nitrogen gas was charged with F ₂ gas diluted to 2 0%, the 12 hours fluorinated with 240 ° C. When the IR spectrum of the obtained polymer was measured, no terminal absorption was observed at 1600 cm- ¹ to 1900 cm " ^1. The terminal of the polymer A2 was fluorinated. The obtained polymer is hereinafter referred to as polymer A3.

 [Example 9] Synthesis example of polymer A4

Compound (a 2) (6.0 g), CH ₂ = CHCF (CF ₃ ) CF ₂ 〇CF = CF ₂ (1.3 g), and 1 H—perfluorohexane (130 g) in a volume of 20 g O'mL was placed in a pressure-resistant glass autoclave.

 A 3% solution of bis (heptyfluorobutyryl) peroxide in chloroform (0.8 g) was added as a polymerization initiator, and the system was replaced with nitrogen again. . As a result, an amorphous polymer (hereinafter, referred to as polymer A4) (6.5 g) was obtained. As in Example 8, it was confirmed that the ring structure of compound (a2) was maintained.

 The intrinsic viscosity [??] of polymer A4 was 0.31 at 30 in perfluoro (2-butyltetrahydrofuran). The polymer A4 was a tough and transparent glassy polymer at room temperature.

 The weight loss onset temperature of this polymer was about 400 and the 10% weight loss temperature was 480, as determined by thermogravimetric analysis in nitrogen. After dissolving in perfluoro (2-butyltetrahydrofuran) to prepare a solution, the film was cast on a glass substrate and the refractive index of the film obtained was measured using an Abbe refractometer to be 1/33. Was. Further, the glass transition temperature was observed at 14 ° C. from the DSC measurement.

 [Example 10] Synthesis example of fluoropolymer molded article (cast polymerization)

Compound (a2) (1.0 g) and (CH ₃ CH (CH ₃ ) OCOO) 2 (0.01 g) as a polymerization initiator were put into a flat-bottom Pyrex (registered trademark) glass tube having a diameter of 10 mm, and nitrogen was introduced. It was left in a gas atmosphere. After 5 days, it was taken out and vacuum-dried at 100 days and nights to obtain a cylindrical polymer having a diameter of 10 mm and a thickness of 5 mm. The light transmittance of this cylindrical polymer was at least 90% from the ultraviolet (250 nm) to the near infrared region (1700 nm). [Example 11] Production example of polymer A5

Compound (a 2) (4.9 g) and CF ₂ = CHCF (CF ₃ ) CF ₂ OCF = CF ₂ (hereinafter abbreviated as 5M monomer) (3.3 g), 1H—Perfluorinated Oxane (120 g) and 0.8 g of a 3% solution of bis (heptafluorobutyryl) peroxide as a polymerization initiator in dichloropentafluoropropane were previously cooled to 110 ° C. The system was placed in a crepe, and the system was replaced with nitrogen gas. Thereafter, polymerization was carried out at 30 ° C. for 80 hours. As a result, a polymer (hereinafter, referred to as polymer A5) (3.9 g) was obtained. As a result of ¹ H-NMR measurement of the polymer A5, the ratio of the monomer unit of the compound (5M monomer) to the total polymer units in the polymer A5 was 10 mol%, and the monomer of the compound (a2) was The unit ratio was 90 mol%. In addition, in the ¹⁹ F-NMR spectrum of polymer A5, the peak of the fluorine atom bonded to the carbon atom constituting the unsaturated bond has completely disappeared, and the spiacyclic ring structure has been retained. It was confirmed.

_Mw of the polymer A5 measured by the GPC method was 56,000. The polymer A5 was a tough and transparent glassy polymer at room temperature.

 [Example 12] Production example of polymer A 6

Compound (a 2) (4.9 g) ゝ 1 H—perfluorohexane (105 g) and bis (heppufurofolbutyryl) peroxide as a polymerization initiator in 3% dichloromouth pentafluoropropane solution (0 95 g) was charged with a pressure-resistant glass autoclave having a capacity of 20 OmL, which had been replaced with nitrogen in advance and cooled at −5. Then, vinylidene fluoride (0.6 g) was charged into the autoclave. Thereafter, polymerization was carried out at 25 at 20 hours and at 100 ° C for 37 hours. As a result, a polymer (hereinafter, referred to as polymer A6) (6.7 g) was obtained. As a result of measuring the ¹ H—NMR of polymer A6, the ratio of the monomer units of vinylidene fluoride to the total polymer units in polymer A6 was 27 mol%, and the monomer units of compound (a 2) Was 73 mol%. Also, in the ¹⁹ F-NMR spectrum of polymer A6, the peak of the fluorine atom bonded to the carbon atom constituting the unsaturated bond has completely disappeared, and the spiro ring structure has been retained. It was confirmed. _{Mw of} polymer A6 measured by the GPC method was 215,000. The polymer A6 was a tough and transparent glassy polymer at room temperature. Further, as a result of measurement by the DSC method, T _g was 120.

 [Example 13] Synthetic example of adhesive A7 composed of polymer A7

CH ₂ = CHCF ₂ CF ₂ OCF = CF ₂ (20 g) and 1H-perfluorohexane (40 g) were placed in a pressure-resistant glass autoclave having an internal volume of 200 ml. Bis (hepnofluorbutyryl) peroxide 2 Omg was added as a polymerization initiator, and the atmosphere in the system was replaced with nitrogen, and then polymerization was performed at 0 ° C for 24 hours. As a result, a fluoropolymer having an aliphatic ring structure in the main chain (hereinafter referred to as polymer A7) (10 g) was obtained.

 The intrinsic viscosity [7?] Of polymer A7 was 0.90 at 30 ° C in 1,3-bis (trifluoromethyl) benzene. Polymer A7 had a glass transition point of 90, was a tough and transparent glassy polymer at room temperature, and had a low refractive index of 1.36.

 The polymer A7 was heat-treated in air at 320 ° C. for 3 hours, and then denatured by immersion in water. An IR spectrum measurement of the modified polymer A7 confirmed a carboxyl group peak, and the amount was 0.005 mmol /. This modified polymer A7 is hereinafter referred to as an adhesive A7.

 [Example 14 (Comparative example)] Production example of polymer B and adhesive B

1,1,2,4,4,5,5-Heptane fluor-3-oxa 1,6-butadiene (20 g) and 1H-perfluorinated hexane (40 g) Content pressure 20 Oml Placed in glass autoclave. After adding bis (fluorobutyryl) peroxide (2 Omg) as a polymerization initiator and replacing the system with nitrogen, polymerization was carried out at 40 for 10 hours. As a result, a fluorinated polymer having an aliphatic ring structure in the main chain (hereinafter referred to as polymer B) (15 g) was obtained. The intrinsic viscosity [??] of polymer B is 1,3_bis (trifluene). It was 0.96 dl / g at 30 in Benzene. Polymer B had a glass transition point of 90, was a tough, transparent glassy polymer at room temperature, and had a low refractive index of 1.36. On the other hand, polymer B obtained in the same manner as above After heat treatment for an hour, it was immersed in water for denaturation. The peak of the lipoxyl group was confirmed by IR spectrum measurement of the modified polymer B, and its amount was 0.004 mmol / g. This modified polymer B is hereinafter referred to as adhesive B.

 [Example 15] Preparation and evaluation of pellicle

 (Example 15-1) Example of membrane synthesis using polymer A3

 Polymer A3 (1.5 g) synthesized in Example 8 and perfluoro (methyldecalin) (98.5 g) were put in a glass flask and heated and stirred at 70 ° C for 48 hours. As a result, a colorless, transparent, turbid, homogeneous solution was obtained. This solution was spin-coated on a polished quartz substrate. The spin coating was performed at a spin speed of 500 rpm for 10 seconds, and then at 700 rpm for 20 seconds. Furthermore, it was dried by heating at 80 at 1 hour and further at 200 at 2 hours to form a uniform and transparent polymer A3 film on a quartz substrate. Using a similar method, uniform and transparent films of the polymer A5 synthesized in Example 11 and the polymer A6 synthesized in Example 12 were formed on a quartz substrate.

 (Example 15-2) Example of pellicle production using adhesive A7 as an adhesive and polymer A3 as a pellicle film

Adhesive A7 (2 g) obtained in Example 13 and 1,3-bis (trifluoromethyl) benzene (38 g) were treated in the same manner as in Example 15-1, to obtain a uniform solution. Was used as an adhesive solution E. The adhesive solution E was applied to the surface of the aluminum frame to which the pellicle film was adhered, and dried at room temperature for 2 hours. Then, the aluminum frame was placed on a 120 hot plate with the adhesive side up and heated for 10 minutes. The aluminum frame was placed on the film surface of the polymer A3 on the quartz substrate obtained in Example 15-1. The bodies were overlapped and crimped such that the adhesive surfaces of the frames were in contact. It was kept at 12 O ^ C for 10 minutes to complete the adhesion. Next, a thin film of the polymer A3 was peeled off from the quartz substrate together with the aluminum frame. As a result, a pellicle was obtained in which a uniform free-standing film having a thickness of about 1 / m made of polymer A3 was adhered to an aluminum frame with an adhesive A7. Using a similar method, a pellicle was obtained in which a uniform free-standing film having a thickness of about 1 m comprising polymers A5 and A6 was adhered with adhesive A7. The transmittance of 157 nm light of the film composed of the polymers A3, A5, and A6 was 75% or more, 80% or more, and 90% or more, respectively. (Example 15-3 (Comparative Example)) Example of manufacturing pellicle using polymer B as pellicle film and adhesive

 The adhesive B (7 g) obtained in Example 14 and 1,3-bis (trifluoromethyl) benzene (93 g) were treated in the same manner as in Example 15-1, to obtain a homogeneous solution. This is used as an adhesive. Example 15-2 The adhesive B is applied to an aluminum frame in the same manner as described above.

 On the other hand, using the polymer B obtained in Example 14, a uniform and transparent film of the polymer B is formed on a quartz substrate in the same manner as in Example 15-1.

 Next, in the same manner as in Example 15-2, an aluminum frame is pressure-bonded, adhered, and separated from the film surface of the polymer B formed on the quartz substrate surface. As a result, a pellicle is obtained in which a uniform free-standing film having a film thickness of about 1 ^ m made of polymer B is adhered to the aluminum frame by the adhesive B. The transmittance of 157 nm light of the film made of the polymer B is 90% or more.

 (Example 15-4 (Example, Comparative Example)) 例 Example of durability evaluation of vehicle

Example 1 5-2 obtained in polymer A 3, A 5, pellicle with A 6, and in the pellicle employing the polymer B obtained in Example 1 5 _ 3, F ₂ which oscillates 1 5 7 nm The irradiation test was performed at a cycle of ²⁰⁰ Hz using an excimer laser beam at an intensity of 0.05 mJZ cm ² / pulse. As a result, the pellicle using polymers A3, A5, and A6 showed extremely good resistance, with a decrease in transmittance of the membrane within 30% of the initial value after 400,000 pulses or more. . In addition, the pellicle film is firmly adhered to the frame with an adhesive, and good durability is recognized. On the other hand, in the case of the pellicle using the polymer B, the transmittance of the film decreased at about 40,000 pulses, and thus a decrease in durability was observed. In addition, peeling of the pellicle film from the frame was observed, and the durability was poor. Industrial applicability>

 The present invention provides a polymer (A) having high transparency and durability to short wavelength light. The polymer (A) is useful as a pellicle material.

Further, the present invention provides a novel polymer (A 1) as the polymer (A). Also provided is a novel monomer that can be used for producing the polymer (A 1). The present invention This monomer is easily homopolymerized or copolymerized with another radically polymerizable monomer. The novel polymer (A1) has a low refractive index, is a solvent-soluble polymer and has good transparency. Further, the polymer (A1) has a high Tg and a high thermal decomposition temperature, and the difference between the Tg and the thermal decomposition temperature is large, so that melt molding is easy. Further, the polymer (A1) of the present invention also has the properties of other fluorinated polymers.

 Therefore, since the polymer (A1) of the present invention can be used to obtain an ultrathin film free of defects such as pinholes, it can be applied to coating materials, separation membrane materials, and the like. In addition, it can be applied to an optical material such as an antireflection agent, an optical fiber, a core of an optical waveguide or a cladding agent by utilizing the low refractive index. In addition, since it has a low dielectric constant and low water absorption, it can be used as an electronic material.

Claims

The scope of the claims

1. A pellicle for exposure processing using light having a wavelength of 200 nm or less, wherein a pellicle film is adhered to a frame via an adhesive, wherein the pellicle film and / or the adhesive is represented by the following formula (A) A pellicle comprising a polymer containing a unit represented by the formula:

 However, Q represents a group in which one or more of the hydrogen atoms present in the following group (B) are substituted with a fluorine atom.

Group (B):-(CH ₂ ) _a — (where a represents an integer of 1 to 3), wherein two hydrogen atoms present in the group include two or more etheric oxygen atoms An alkylene group, or a group in which at least one hydrogen atom in the alkylene group is substituted by an alkyl group optionally containing an etheric oxygen atom,

X ¹ and X ² independently represent a fluorine atom, a chlorine atom or a hydrogen atom.

2. The pellicle according to claim 1, wherein Q is a group in which all of the hydrogen atoms present in the group (B) are substituted with fluorine atoms.

3. The pellicle according to claim 1, wherein the unit represented by the formula (A) is a unit represented by the following formula (A1).

However, X ¹ and X ² are each independently a fluorine atom, a chlorine atom or a hydrogen atom, n is an integer of 1 or 2, R ^fl is a fluorine atom or a trifluoromethyl group, and R ⁱ² is a fluorine atom or It is a perfluoroalkyl group having 1 to 5 carbon atoms.

4. The pellicle according to any one of claims 1 to 3, wherein the pellicle film essentially comprises a polymer having a unit represented by the formula (A) and having no functional group.

5. The pellicle according to any one of claims 1 to 4, wherein the adhesive essentially comprises a polymer having a unit represented by the formula (A) and having a functional group.

6. The pellicle according to any one of claims 1 to 5, wherein the polymer containing the unit represented by the formula (A) is a polymer having no CH ₂ CH ₂ — structure.

7. An exposure processing method using light having a wavelength of 200 nm or less in photolithography, wherein the pellicle according to any one of claims 1 to 6 is used.

8. A compound represented by the following formula (a1). However, X ¹ and X ² are independently a fluorine atom, a chlorine atom or a hydrogen atom, n is an integer of 1 or 2, R ^{f 1} is a fluorine atom or a trifluoromethyl group, and R ^{f 2} is a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms.

 (a1)

9. The compound according to claim 8, wherein X ¹ and X ² are a fluorine atom, n is 1, and R ^fl and R ^{f 2} are a fluorine atom. ■

10. A polymer comprising a monomer unit of the compound according to claim 8 or 9.

1 1. A compound represented by the following formula (b 2) or a compound represented by the following formula (b 3) wherein Y and Z each independently represent a fluorine atom, a chlorine atom or a hydrogen atom, and n Is an integer of 1 or 2, R ^fl represents a fluorine atom or a trifluoromethyl group, and R ^{f 2} represents a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms.

 (b2) (b3)