JP2018024612A - Dendrimer, composition and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel compound that serves as a crosslinker and further can provide a molding having excellent heat resistance and plasma resistance.SOLUTION: The present invention provides a dendrimer of a cage silsesquioxane having a specific terminal group.SELECTED DRAWING: None

Description

The present invention relates to dendrimers, compositions and molded articles.

Fluorine-containing elastomers, especially perfluoroelastomers containing tetrafluoroethylene (TFE) units, exhibit excellent chemical resistance, solvent resistance, and heat resistance, and are therefore used in aerospace, semiconductor manufacturing equipment, chemical plant fields, etc. Widely used as a sealing material in harsh environments.

In the case of producing a molded product such as a sealing material, a crosslinking agent is used for the composition for forming the molded product. For example, Patent Document 1 discloses a semiconductor manufacturing device seal made of a composition composed of 1 to 10 parts by weight of an organic peroxide as a crosslinking agent with respect to 100 parts by weight of a fluorine-based elastomer.

Japanese Patent Laid-Open No. 06-302527

An object of the present invention is to provide a novel compound that can provide a molded article having excellent heat resistance and plasma resistance while acting as a crosslinking agent. The object of the present invention is also to provide a composition that can give a molded article excellent in heat resistance and plasma resistance without using a general crosslinking agent, and while being produced without using a general crosslinking agent, The object is to provide a molded article excellent in heat resistance and plasma resistance.

As a result of intensive studies by the present inventors, a silsesquioxane dendrimer having a specific structure acts as a crosslinking agent, and a molded product obtained using the specific dendrimer has excellent heat resistance and resistance. It was found to have plasma properties.

（一般式（１）中、Ｒ^１〜Ｒ^８は、下記式（２）：

で表される末端基を含む有機基である。式中、Ｒ^９は、同じかまたは異なり、−ＮＨ_２、−ＮＨＲ^１０、−ＯＨまたは−ＳＨであり、Ｒ^１０は、フッ素原子または１価の有機基である。） That is, the present invention is a cage silsesquioxane dendrimer represented by the general formula (1).
General formula (1):

(In the general formula (1), R ^{1 to} R ⁸ are represented by the following formula (2):

It is an organic group containing the terminal group represented by these. In the formula, R ⁹ is the same or different and is —NH ₂ , —NHR ¹⁰ , —OH or —SH, and R ¹⁰ is a fluorine atom or a monovalent organic group. )

The dendrimer of the present invention preferably has a particle size of 0.5 to 15 nm.

The dendrimer of the present invention preferably has 1 to 8 generations.

The present invention is also a composition comprising the fluorine-containing polymer and the dendrimer.

The fluoropolymer preferably has a cyano group.

The fluorine-containing polymer is preferably a fluorine-containing elastomer.

It is preferable that the composition of this invention contains the dendrimer represented by 0.5-100 mass parts general formula (1) with respect to 100 mass parts of said fluoropolymers.

The composition of the present invention is preferably a molding material.

The present invention is also a molded article obtained from the above composition.

Since the dendrimer of the present invention has the above-described configuration, it is possible to obtain a molded product that is further excellent in heat resistance and plasma resistance while acting as a crosslinking agent.
The composition of the present invention can be cross-linked without using a general cross-linking agent, and can further give a molded product having excellent heat resistance and plasma resistance.
The molded article of the present invention is excellent in heat resistance and plasma resistance, although a general crosslinking agent is not used.

Hereinafter, the present invention will be specifically described.

（一般式（１）中、Ｒ^１〜Ｒ^８は、下記式（２）：

で表される末端基を含む有機基である。式中、Ｒ^９は、同じかまたは異なり、−ＮＨ_２、−ＮＨＲ^１０、−ＯＨまたは−ＳＨであり、Ｒ^１０は、フッ素原子または１価の有機基である。） The dendrimer of the present invention is a cage silsesquioxane dendrimer represented by the general formula (1). The dendrimer of the present invention can act as a crosslinking agent and can give a molded product having excellent heat resistance. In addition, a molded product obtained by using the dendrimer of the present invention as a crosslinking agent is also excellent in plasma resistance. Therefore, a molded product obtained by using the dendrimer of the present invention as a crosslinking agent is particularly suitable as a sealing material for a semiconductor manufacturing apparatus.
General formula (1):

(In the general formula (1), R ^{1 to} R ⁸ are represented by the following formula (2):

It is an organic group containing the terminal group represented by these. In the formula, R ⁹ is the same or different and is —NH ₂ , —NHR ¹⁰ , —OH or —SH, and R ¹⁰ is a fluorine atom or a monovalent organic group. )

As an organic group containing the terminal group represented by the said Formula (2), it is preferable that they are an alkyl group, an alkoxy group, or a phenyl group containing the terminal group represented by the said Formula (2).
The alkyl group and alkoxy group preferably have 1 to 1000 carbon atoms, more preferably 1 to 600, and still more preferably 1 to 400. When the number of carbon atoms is 2 or more, two carbon atoms may be bonded by an amide bond, an imide bond, an ester bond, a urethane bond, a carbonate bond, or the like.
The phenyl group may be substituted with one or more substituents.
Said R < ¹ > -R < ⁸ > may contain cyclic structures, such as aromatic rings other than the benzene ring contained in the said terminal group. R ^{1 to} R ⁸ may include an amino group, a nitro group, a carboxyl group, a sulfo group, a hydroxyl group, a vinyl group, an epoxy group, a silyl group, an isocyanate group, and the like.
The phenyl group may be substituted with one or more substituents.
R ^{1 to} R ⁸ preferably include a cyclic structure such as an aromatic ring other than the benzene ring contained in the terminal group. Since R ^{1 to} R ⁸ include a cyclic structure such as an aromatic ring, a rigid structure is radially arranged at the apex of the cage-type silsesquioxane lattice, and all terminal functional groups face outward, so that heat resistance Excellent plasma resistance.
R ^{1 to} R ⁸ are more preferably those containing a terminal group represented by the formula (2), an alkylene group or an oxyalkylene group, and a divalent to hexavalent benzene ring. More preferably, the benzene ring is trivalent. Carbon number of the said alkylene group and oxyalkylene group may be 1-10, respectively, and it is preferable that it is 1-5.
In the present specification, the “n-valent benzene ring” means that n hydrogen atoms of the benzene ring are substituted with other organic groups.

The cage-type silsesquioxane dendrimer preferably has a particle size of 0.5 to 15 nm, more preferably 1 nm or more, still more preferably 5 nm or more, and more preferably 10 nm or less. preferable. It is possible to adjust the particle size by the type of R ¹ to R ^8.

The cage silsesquioxane dendrimer has a cage silsesquioxane skeleton as a core and R ^{1 to} R ⁸ as dendrons. When the cage-type silsesquioxane dendrimer is added to the fluoropolymer composition, a molded product that acts as a crosslinking agent and is excellent in heat resistance and plasma resistance can be obtained. Another advantage is that the size of the molecule can be controlled by the number of generations.

As the dendrimer of the cage silsesquioxane, R ^{1 to} R ⁸ in the general formula (1) are each independently a terminal group represented by the following general formula (2) (hereinafter referred to as “terminal group T”). Also called).

式中、Ｒ^９は、同じかまたは異なり、−ＮＨ_２、−ＮＨＲ^１０、−ＯＨまたは−ＳＨであり、Ｒ^１０は、フッ素原子または１価の有機基である。
上記Ｒ^１０における１価の有機基としては、例えば、脂肪族炭化水素基、フェニル基またはベンジル基があげられる。具体的には、たとえば、Ｒ^１０の少なくとも１つが−ＣＨ_３、−Ｃ_２Ｈ_５、−Ｃ_３Ｈ_７などの炭素数１〜１０、特に１〜６の低級アルキル基；−ＣＦ_３、−Ｃ_２Ｆ_５、−ＣＨ_２Ｆ、−ＣＨ_２ＣＦ_３、−ＣＨ_２Ｃ_２Ｆ_５などの炭素数１〜１０、特に１〜６のフッ素原子含有低級アルキル基；フェニル基；ベンジル基；−Ｃ_６Ｆ_５、−ＣＨ_２Ｃ_６Ｆ_５などのフッ素原子で１〜５個の水素原子が置換されたフェニル基またはベンジル基；−Ｃ_６Ｈ_５−ｎ（ＣＦ_３）_ｎ、−ＣＨ_２Ｃ_６Ｈ_５−ｎ（ＣＦ_３）_ｎ（ｎは１〜５の整数）などの−ＣＦ_３で１〜５個の水素原子が置換されたフェニル基またはベンジル基が好ましい。
架橋反応性が良好であるため、上記Ｒ^９は−ＮＨ_２又は−ＯＨであることが好ましく、−ＮＨ_２であることが好ましい。

In the formula, R ⁹ is the same or different and is —NH ₂ , —NHR ¹⁰ , —OH or —SH, and R ¹⁰ is a fluorine atom or a monovalent organic group.
Examples of the monovalent organic group for R ¹⁰ include an aliphatic hydrocarbon group, a phenyl group, and a benzyl group. Specifically, for example, at least one of R ¹⁰ is a lower alkyl group having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms such as —CH ₃ , —C ₂ H ₅ , —C ₃ H ₇ ; —CF ₃ , — A fluorine-containing lower alkyl group having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, such as C ₂ F ₅ , —CH ₂ F, —CH ₂ CF ₃ , —CH ₂ C ₂ F ₅ ; phenyl group; benzyl group; _{C 6 F 5, -CH 2 C} 6 F 5 phenyl or benzyl 1-5 hydrogen atoms with fluorine atoms is substituted, such _{as; -C 6 H 5-n (} CF 3) n, -CH 2 A phenyl group or a benzyl group in which 1 to 5 hydrogen atoms are substituted with —CF ₃ such as C ₆ H _5-n (CF ₃ ) _n (n is an integer of 1 to 5) is preferable.
In view of good crosslinking reactivity, R ⁹ is preferably —NH ₂ or —OH, and preferably —NH ₂ .

The dendrimer of the present invention can act as a cross-linking agent by including the specific end group T, and has excellent heat resistance and plasma resistance of a molded product obtained from the composition containing the dendrimer of the present invention. Can be

Examples of the dendrimer of the cage silsesquioxane include those in which R ^{1 to} R ⁸ include a trivalent group B represented by the following formula in the general formula (1).

In the formula, L ¹ and L ² are each independently a divalent group represented by —NH—CO—, —O—CO—, —O—, —CO— or —OCH ₂ —. L ¹ and L ² are preferably a divalent group represented by —NH—CO—.

The trivalent group B is preferably represented by the formula (3).

Formula (3):

As the cage-type silsesquioxane dendrimer, in the general formula (1), it is preferable that R ^{1 to} R ⁸ each include a terminal group T and a trivalent group B, and a trivalent group. B is bonded to a silicon atom of a cage silsesquioxane through a divalent group A represented by — (CH ₂ ) ₁ —NH—CO— (l is an integer of 1 to 5). More preferably, the trivalent group B is bonded to the silicon atom of the cage silsesquioxane through the above divalent group A, and the terminal group T is divalent through the trivalent group B. Those bonded to the group A are more preferred. A plurality of trivalent groups B may be bonded to form a regular repeating structure.

As the dendrimer of the cage silsesquioxane, those having 1 to 8 generations are preferable, and those having 1 to 6 are more preferable.

Examples of R ^{1 to} R ⁸ include those having the following structures. In the formula, A is a divalent group represented by — (CH ₂ ) ₁ —NH—CO— (l is an integer of 1 to 5).

Each of the above structures corresponds to the first to fifth generation dendrimers.

As an example, the structure of R ^{1 to} R ⁸ possessed by the second generation dendrimer is specifically shown in the following formula.

式中、Ａ、Ｌ^１、Ｌ^２及びＲ^９は、前記同様である。
第２世代のデンドリマーが有するＲ^１〜Ｒ^８の構造を以下に例示する。

In the formula, A, L ¹ , L ² and R ⁹ are the same as described above.
The structures of R ^{1 to} R ⁸ possessed by the second generation dendrimer are exemplified below.

式中、Ａ及びＲ^９は、前記同様である。

In the formula, A and R ⁹ are the same as described above.

で示される反応で得られる化合物（ＡＢ_２−Ｃｌ（オルト））を反応させた後、ヒドラジンと反応させることで得ることができる。Ｒ^９が−ＮＨ_２以外の末端基である場合も、適宜、対応する化合物を使用して同様に反応させればよい。反応条件は適宜設定すればよい。 The dendrimer of this invention can be manufactured by a well-known method except the following point.
The dendrimer of the present invention has a terminal group of formula (2) at the terminal. For example, when R ⁹ in the formula (2) is —NH ₂ , the dendrimer of the present invention can be converted to a dendrimer of a cage silsesquioxane having an NH ₂ group at the end by the following formula:

After the compound obtained by the reaction of (AB 2 _-Cl (ortho)) by the reaction shown in, it can be obtained by reacting with hydrazine. Even when R ⁹ is a terminal group other than —NH ₂ , the corresponding compound may be used in the same manner as appropriate. What is necessary is just to set reaction conditions suitably.

The composition of the present invention comprises a dendrimer of the above-mentioned cage-type silsesquioxane having a specific structure and a fluorine-containing polymer.

The fluorine-containing polymer is preferably a fluorine-containing elastomer because of its excellent sealing properties, chemical resistance and heat resistance.
The fluorine-containing elastomer may be a partially fluorinated elastomer or a perfluoroelastomer, but it is preferable to use a perfluoroelastomer from the viewpoint of further excellent chemical resistance and heat resistance.

As partially fluorinated elastomers, vinylidene fluoride (VdF) fluorine rubber, tetrafluoroethylene (TFE) / propylene (Pr) fluorine rubber, tetrafluoroethylene (TFE) / propylene / vinylidene fluoride (VdF) fluorine rubber , Ethylene / hexafluoropropylene (HFP) fluorine rubber, ethylene / hexafluoropropylene (HFP) / vinylidene fluoride (VdF) fluorine rubber, ethylene / hexafluoropropylene (HFP) / tetrafluoroethylene (TFE) fluorine rubber Etc. Especially, it is preferable that it is at least 1 sort (s) selected from the group which consists of vinylidene fluoride type | system | group fluorine rubber and tetrafluoroethylene / propylene type fluorine rubber.

The vinylidene fluoride-based fluororubber is preferably a copolymer composed of 45 to 85 mol% of vinylidene fluoride and 55 to 15 mol% of at least one other monomer copolymerizable with vinylidene fluoride. . Preferably, the copolymer is composed of 50 to 80 mol% of vinylidene fluoride and 50 to 20 mol% of at least one other monomer copolymerizable with vinylidene fluoride.

In the present specification, the content of each monomer constituting the fluoropolymer can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis depending on the type of monomer.

Examples of at least one other monomer copolymerizable with the vinylidene fluoride include tetrafluoroethylene [TFE], hexafluoropropylene [HFP], fluoroalkyl vinyl ether, chlorotrifluoroethylene [CTFE], trifluoroethylene, Trifluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, hexafluoroisobutene, vinyl fluoride, general formula (6): CH ₂ = CFRf ⁶¹ (wherein Rf ⁶¹ is a straight chain having 1 to 12 carbon atoms) Or a branched fluoroalkyl group), a general formula (7): CH ₂ ═CH— (CF ₂ ) _n —X ² (wherein X ² is H or F, and n is 3 to 3). Is an integer of 10.) and gives a crosslinking site. Monomers monomers, ethylene, propylene, and a non-fluorinated monomer such as an alkyl vinyl ether. These can be used alone or in any combination. Among these, it is preferable to use at least one selected from the group consisting of TFE, HFP, fluoroalkyl vinyl ether and CTFE.
As fluoroalkyl vinyl ether,
Formula _{(8): CF 2 = CF} -ORf 81
(Wherein Rf ⁸¹ represents a perfluoroalkyl group having 1 to 8 carbon atoms),
Formula (10): CF ₂ = CFOCF ₂ ORf ¹⁰¹
(In the formula, Rf ¹⁰¹ is a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, a cyclic perfluoroalkyl group having 5 to 6 carbon atoms, or 2 to 6 carbon atoms containing 1 to 3 oxygen atoms. A linear or branched perfluorooxyalkyl group), and
Formula ^{_{(11): CF 2 = CFO}} (CF 2 CF (Y 11) O) m (CF 2) n F
(Wherein Y ¹¹ represents a fluorine atom or a trifluoromethyl group, m is an integer of 1 to 4, and n is an integer of 1 to 4). Preferably at least one of
The fluoromonomer represented by the general formula (8) is more preferable.

Specific examples of vinylidene fluoride-based fluororubber are represented by VdF / HFP rubber, VdF / HFP / TFE rubber, VdF / CTFE rubber, VdF / CTFE / TFE rubber, VDF / general formula (6). Fluoromonomer rubber, VDF / fluoromonomer / TFE rubber represented by general formula (6), VDF / perfluoro (methyl vinyl ether) [PMVE] rubber, VDF / PMVE / TFE rubber, VDF / PMVE / Examples include TFE / HFP rubber. VDF / CH ₂ = CFCF ₃ rubber is preferred as the fluoromonomer rubber represented by VDF / general formula (6), and as the fluoromonomer / TFE rubber represented by VDF / general formula (6), VDF / TFE / CH ₂ = CFCF ₃ rubber is preferred.

The VDF / CH ₂ = CFCF ₃ rubber is preferably a copolymer composed of VDF 40 to 99.5 mol% and CH ₂ = CFCF ₃ 0.5 to 60 mol%, and VDF 50 to 85 mol%. , and _is more preferably a copolymer consisting of CH ₂ = CFCF 3 20~50 mol%.

The tetrafluoroethylene / propylene-based fluororubber is preferably a copolymer composed of 45 to 70 mol% tetrafluoroethylene, 55 to 30 mol% propylene, and 0 to 5 mol% of a fluoromonomer providing a crosslinking site. .

The fluorine-containing elastomer may be a perfluoroelastomer. Examples of the perfluoroelastomer include perfluoroelastomers containing TFE, for example, a fluoromonomer copolymer represented by TFE / general formula (8), (10) or (11), and TFE / general formula (8), (10 ) Or (11) is preferably at least one selected from the group consisting of a fluoromonomer / monomer copolymer that provides a crosslinking site.
In the case of a TFE / PMVE copolymer, the composition is preferably 45 to 90/10 to 55 (mol%), more preferably 55 to 80/20 to 45, still more preferably 55 to 70 / 30-45.
In the case of the monomer copolymer which gives TFE / PMVE / crosslinking site, it is preferably 45 to 89.9 / 10 to 54.9 / 0.01 to 4 (mol%), more preferably 55 to 77. It is 9 / 20-49.9 / 0.1-3.5, More preferably, it is 55-69.8 / 30-44.8 / 0.2-3.
In the case of the fluoromonomer copolymer represented by the general formula (8), (10) or (11) having 4 to 12 TFE / carbon, it is preferably 50 to 90/10 to 50 (mol%). More preferably, it is 60-88 / 12-40, More preferably, it is 65-85 / 15-35.
In the case of TFE / monomer copolymer which gives a fluoromonomer / crosslinking site represented by the general formula (8), (10) or (11) having 4 to 12 carbon atoms, preferably 50 to 89.9 / 10 It is -49.9 / 0.01-4 (mol%), More preferably, it is 60-87.9 / 12-39.9 / 0.1-3.5, More preferably, it is 65-84. .8 / 15-34.8 / 0.2-3.
When the composition is out of the range, the properties as a rubber elastic body are lost, and the properties tend to be similar to those of a resin.
In the perfluoroelastomer containing TFE, the monomer that gives a cross-linked site may not be a perfluoromonomer.

Examples of the perfluoroelastomer include TFE / fluoromonomer represented by the general formula (11) / fluoromonomer copolymer that gives a crosslinking site, TFE / perfluorovinyl ether copolymer represented by the general formula (11), and TFE. / At least one selected from the group consisting of a fluoromonomer copolymer represented by the general formula (8) and a fluoromonomer represented by TFE / the general formula (8) / a monomer copolymer giving a crosslinking site It is preferable that

Examples of the perfluoroelastomer include perfluoroelastomers described in International Publication No. 97/24381, Japanese Examined Patent Publication No. 61-57324, Japanese Examined Patent Publication No. 4-81608, Japanese Patent Publication No. 5-13961, and the like. Can do.

The monomer that gives a crosslinking site is a monomer (curing site monomer) having a crosslinkable group that gives the fluoropolymer a crosslinking site for forming a crosslink with a crosslinking agent.

As a monomer that gives a crosslinking site,
General formula (12): CX ³ ₂ = CX ³ -R _f ¹²¹ CHR ¹²¹ X ⁴
(In the formula, X ³ is a hydrogen atom, a fluorine atom or CH ₃ , and R _f ¹²¹ is a fluoroalkylene group, a perfluoroalkylene group, a fluoro (poly) oxyalkylene group or a perfluoro (poly) oxyalkylene group, R ¹²¹ Is a hydrogen atom or CH ₃ , and X ⁴ is an iodine atom or a bromine atom),
General formula (13): CX ³ ₂ = CX ³ -R _f ¹³¹ X ⁴
(Wherein X ³ is a hydrogen atom, fluorine atom or CH ₃ , R _f ¹³¹ is a fluoroalkylene group, perfluoroalkylene group, fluoropolyoxyalkylene group or perfluoropolyoxyalkylene group, and X ⁴ is an iodine atom. Or a bromine atom)
Formula _{(14): CF 2 = CFO} (CF 2 CF (CF 3) O) m (CF 2) n -X 5
(Wherein, m is an integer of 0 to 5, n is an integer of 1 to 3, and X ⁵ is a cyano group, a carboxyl group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or —CH ₂ I). The fluoromonomer represented, and
Formula _{(15): CH 2 = CFCF} 2 O (CF (CF 3) CF 2 O) m (CF (CF 3)) n -X 6
(Wherein, m is an integer of 0 to 5, n is an integer of 1 to 3, X ⁶ is a cyano group, a carboxyl group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or —CH ₂ OH). Fluoromonomer, and
General formula (16): CR ¹⁶² R ¹⁶³ = CR ¹⁶⁴ -Z-CR ¹⁶⁵ = CR ¹⁶⁶ R ¹⁶⁷
(Wherein R ¹⁶² , R ¹⁶³ , R ¹⁶⁴ , R ¹⁶⁵ , R ¹⁶⁶ and R ¹⁶⁷ are the same or different and are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Z is linear or branched. An alkylene group having 1 to 18 carbon atoms, a cycloalkylene group having 3 to 18 carbon atoms, an alkylene group having 1 to 10 carbon atoms or an oxyalkylene that is at least partially fluorinated Group or
_{- (Q) p -CF 2 O-} (CF 2 CF 2 O) m (CF 2 O) n -CF 2 - (Q) p -
(Wherein, Q is an alkylene group or an oxyalkylene group, p is 0 or 1, m / n is 0.2 to 5), and the molecular weight is 500 to 10,000 (par) A fluoropolyoxyalkylene group; It is preferably at least one selected from the group consisting of monomers represented by

X ³ is preferably a fluorine atom. Rf ¹²¹ and Rf ¹³¹ are preferably a perfluoroalkylene group having 1 to 5 carbon atoms. R ¹²¹ is preferably a hydrogen atom. X ⁵ is preferably a cyano group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or —CH ₂ I. X ⁶ is preferably a cyano group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or —CH ₂ OH.

Examples of the monomer giving a crosslinking _{site, CF 2 = CFOCF 2 CF (} CF 3) OCF 2 CF 2 CN, CF 2 = CFOCF 2 CF (CF 3) OCF 2 CF 2 COOH, CF 2 = CFOCF 2 CF (CF 3) _{OCF 2 CF 2 CH 2 I,} CF 2 = CFOCF 2 CF 2 CH 2 I, CH 2 = CFCF 2 OCF (CF 3) CF 2 OCF (CF 3) CN, CH 2 = CFCF 2 OCF (CF 3) CF 2 OCF (CF ₃ ) COOH, CH ₂ = CFCF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) CH ₂ OH, CH ₂ = CHCF ₂ CF ₂ I, CH ₂ = CH (CF ₂ ) ₂ CH = CH ₂ CH ₂ ═CH (CF ₂ ) ₆ CH═CH ₂ and CF ₂ ═CFO (CF ₂ ) ₅ CN At least one is preferable, and CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CN is more preferable.

The fluoropolymer preferably has a cyano group. When the fluorine-containing polymer has a cyano group, the dendrimer acts more suitably as a crosslinking agent, and a molded product having excellent heat resistance can be obtained.
The cyano group can be introduced into the fluorine-containing polymer by a monomer that gives a crosslinking site as described above. Moreover, as another method, it can also introduce | transduce by the method as described in international publication 00/05959 pamphlet.
The fluorinated polymer having a cyano group preferably contains 0.1 to 5.0 mol%, and preferably 0.2 to 2.0 mol% of a monomer that gives a crosslinking site with respect to all monomer units. More preferred. In this case, it is preferable that the monomer which gives a crosslinking site is a monomer having a cyano group.

The fluorine-containing elastomer preferably has a glass transition temperature of −70 ° C. or higher, more preferably −60 ° C. or higher, and more preferably −50 ° C. or higher from the viewpoint of excellent compression set at high temperatures. Further preferred. Moreover, it is preferable that it is 5 degrees C or less from the point that cold resistance is favorable, It is more preferable that it is 0 degrees C or less, It is still more preferable that it is -3 degrees C or less.

The above glass transition temperature is obtained by using a differential scanning calorimeter (manufactured by METTLER TOLEDO, DSC822e) to obtain a DSC curve by heating 10 mg of the sample at 10 ° C./min. It can be determined as the temperature indicating the midpoint of the two intersections of the extended line and the tangent at the inflection point of the DSC curve.

The fluorine-containing elastomer preferably has a Mooney viscosity ML (1 + 20) at 170 ° C. of 30 or more, more preferably 40 or more, and still more preferably 50 or more from the viewpoint of good heat resistance. Further, in terms of good workability, it is preferably 150 or less, more preferably 120 or less, and even more preferably 110 or less.

The fluorine-containing elastomer preferably has a Mooney viscosity ML (1 + 20) at 140 ° C. of 30 or more, more preferably 40 or more, and still more preferably 50 or more from the viewpoint of good heat resistance. Moreover, it is preferable that it is 180 or less at a point with favorable workability, It is more preferable that it is 150 or less, It is still more preferable that it is 110 or less.

The fluorine-containing elastomer preferably has a Mooney viscosity ML (1 + 10) at 100 ° C. of 10 or more, more preferably 20 or more, and still more preferably 30 or more from the viewpoint of good heat resistance. Further, in terms of good workability, it is preferably 120 or less, more preferably 100 or less, and still more preferably 80 or less.

The Mooney viscosity can be measured according to JIS K6300 at 170 ° C. or 140 ° C. and 100 ° C. using a Mooney viscometer MV2000E type manufactured by ALPHA TECHNOLOGIES.

The partially fluorinated elastomers and perfluoroelastomers described above can be produced by conventional methods, but the resulting polymer has a narrow molecular weight distribution and is easy to control the molecular weight, and an iodine atom or bromine atom is introduced at the terminal. From the point that can be made, an iodine compound or a bromine compound can also be used as a chain transfer agent. Examples of the polymerization method performed using an iodine compound or a bromine compound include a method of performing emulsion polymerization in an aqueous medium while applying pressure in the presence of an iodine compound or a bromine compound in a substantially oxygen-free state. (Iodine transfer polymerization method). Representative examples of the iodine compound or bromine compound to be used include, for example, the general formula:
R ¹³ I _x Br _y
(Wherein x and y are each an integer of 0 to 2 and satisfy 1 ≦ x + y ≦ 2, and R ¹³ is a saturated or unsaturated fluorohydrocarbon group having 1 to 16 carbon atoms or chlorofluoro A hydrocarbon group or a hydrocarbon group having 1 to 3 carbon atoms which may contain an oxygen atom). By using an iodine compound or a bromine compound, an iodine atom or a bromine atom may be introduced into the polymer and may also function as a crosslinking point.

Examples of the iodine compound and bromine compound include 1,3-diiodoperfluoropropane, 2-iodoperfluoropropane, 1,3-diiodo-2-chloroperfluoropropane, 1,4-diiodoperfluorobutane, , 5-Diiodo-2,4-dichloroperfluoropentane, 1,6-diiodoperfluorohexane, 1,8-diiodoperfluorooctane, 1,12-diiodoperfluorododecane, 1,16-diiodo perfluoro hexadecane, diiodomethane, 1,2-diiodoethane, 1,3-diiodo -n- _{propane, CF 2 Br 2, BrCF 2} CF 2 Br, CF 3 CFBrCF 2 Br, CFClBr 2, BrCF 2 CFClBr, CFBrClCFClBr, BrCF 2 CF ₂ CF ₂ Br, BrCF CFBrOCF _3, 1-bromo-2-iodoperfluoroethane, 1-bromo-3-iodoperfluoropropane, 1-bromo-4-iodoperfluorobutane, 2-bromo-3-iodoperfluorobutane, 3-bromo -4-iodoperfluorobutene-1, 2-bromo-4-iodoperfluorobutene-1, monoiodomonobromo and diiodomonobromo substituents of benzene, and (2-iodoethyl) and (2-bromoethyl) ) Substituents and the like, and these compounds may be used alone or in combination with each other.

Among these, 1,4-diiodoperfluorobutane, 1,6-diiodoperfluorohexane, and 2-iodoperfluoropropane are used from the viewpoint of polymerization reactivity, crosslinking reactivity, availability, and the like. Is preferred.

It is preferable that the said composition contains the dendrimer of the said cage-type silsesquioxane of 0.5-100 mass parts with respect to 100 mass parts of said fluoropolymers. More preferably, it is 5-50 mass parts, More preferably, it is 5-25 mass parts. If the cage silsesquioxane is too little, the reinforcing property is poor, and if the cage silsesquioxane has too much dendrimer, it is too hard and the sealability may be lowered.

The composition may further contain a general crosslinking agent. Examples of the crosslinking agent include crosslinking agents used in peroxide crosslinking, polyol crosslinking, polyamine crosslinking, triazine crosslinking, oxazole crosslinking, imidazole crosslinking, and thiazole crosslinking.

The crosslinking agent used in peroxide crosslinking may be an organic peroxide that can easily generate a peroxy radical in the presence of heat or a redox system. Specifically, for example, 1,1-bis (t- Butylperoxy) -3,5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α , Α-bis (t-butylperoxy) -p-diisopropylbenzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t -Butylperoxy) -hexyne-3, benzoyl peroxide, t-butylperoxybenzene, 2,5-dimethyl-2,5-di (benzoyl peroxide) C) Hexane, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, 1,3-bis (t-butylperoxyisopropyl) benzene, and the like. In general, the type and amount of the organic peroxide are selected in consideration of the amount of active —O—O—, decomposition temperature and the like.

As the crosslinking aid which can be used in this case, it may be a compound having reaction activity with respect to peroxy radicals and polymer radicals, for example _{CH 2 = CH-, CH 2 =} CHCH 2 -, CF 2 And polyfunctional compounds having a functional group such as ═CF—. Specifically, for example, triallyl cyanurate, triallyl isocyanurate (TAIC), triacryl formal, triallyl trimellitate, N, N′-n-phenylene bismaleimide, dipropargyl terephthalate, diallyl phthalate, tetraallyl Terephthalate amide, triallyl phosphate, bismaleimide, fluorinated triallyl isocyanurate (1,3,5-tris (2,3,3-trifluoro-2-propenyl) -1,3,5-triazine 2,4 6-trione), tris (diallylamine) -S-triazine, triallyl phosphite, N, N-diallylacrylamide, 1,6-divinyldodecafluorohexane, and the like.

Examples of the crosslinking agent used for polyol crosslinking include polyhydric alcohol compounds such as bisphenol A and bisphenol AF.

Examples of the crosslinking agent used for polyamine crosslinking include polyvalent amine compounds such as hexamethylenediamine carbamate, N, N′-dicinnamylidene-1,6-hexanediamine, and 4,4′-bis (aminocyclohexyl) methanecarbamate.

Examples of the crosslinking agent used for triazine crosslinking include organotin compounds such as tetraphenyltin and triphenyltin.

As a crosslinking agent used for oxazole crosslinking, imidazole crosslinking, and thiazole crosslinking, for example, the general formula (20):

(In the formula, R ⁴ represents —SO ₂ —, —O—, —CO—, an alkylene group having 1 to 6 carbon atoms, a perfluoroalkylene group having 1 to 10 carbon atoms, a single bond, or

R ⁵ and R ⁶ are each —NH ₂ and the other is —NHR ⁷ , —NH ₂ , —OH or —SH, and R ⁷ is a hydrogen atom, a fluorine atom or a monovalent group An organic group, preferably R ⁵ is —NH ₂ and R ⁶ is —NHR ⁷ . Preferable specific examples of the alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and the like. As the perfluoroalkylene group having 1 to 10 carbon atoms, Is

Etc. These compounds are known as examples of bisdiaminophenyl compounds in JP-B-2-59177, JP-A-8-120146, etc.), Bisaminophenol-based crosslinking agent, bisaminothiophenol-based crosslinking agent, general formula (21):

A bisamidrazone crosslinking agent represented by the general formula (22):

(Wherein R _f ³ is a C 1-10 perfluoroalkylene group),
Or general formula (23):

(Wherein n is an integer of 1 to 10), and the like. These bisaminophenol-based crosslinking agents, bisaminothiophenol-based crosslinking agents, bisdiaminophenyl-based crosslinking agents, etc. are those conventionally used for crosslinking systems having a cyano group as a crosslinking point. It reacts with the group to form an oxazole ring, a thiazole ring and an imidazole ring to give a cross-linked product.

As a particularly preferred crosslinking agent, a compound having a plurality of 3-amino-4-hydroxyphenyl groups or 3-amino-4-mercaptophenyl groups, or the general formula (24):

(Wherein R ⁴ , R ⁵ and R ⁶ are the same as above), and specific examples thereof include 2,2-bis (3-amino-4-hydroxyphenyl) hexa Fluoropropane (generic name: bis (aminophenol) AF), 2,2-bis (3-amino-4-mercaptophenyl) hexafluoropropane, tetraaminobenzene, bis-3,4-diaminophenylmethane, bis-3 , 4-diaminophenyl ether, 2,2-bis (3,4-diaminophenyl) hexafluoropropane, 2,2-bis [3-amino-4- (N-phenylamino) phenyl] hexafluoropropane, 2, 2-bis [3-amino-4- (N-methylamino) phenyl] hexafluoropropane, 2,2-bis [3-amino-4- (N-ethylamino) ) Phenyl] hexafluoropropane, 2,2-bis [3-amino-4- (N-propylamino) phenyl] hexafluoropropane, 2,2-bis [3-amino-4- (N-perfluorophenylamino) ) Phenyl] hexafluoropropane, 2,2-bis [3-amino-4- (N-benzylamino) phenyl] hexafluoropropane, and the like.

Among these, the crosslinking agent is 2,2-bis [3-amino-4- (N-phenylamino) phenyl] hexafluoropropane from the viewpoint of heat resistance, steam resistance, amine resistance, and good crosslinkability. Is preferred.

The general crosslinking agent is preferably 0.05 to 10 parts by mass and more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the fluoropolymer.

The composition may contain a general filler.

Examples of the general filler include imide fillers having an imide structure such as polyimide, polyamideimide, and polyetherimide; polyarylate, polysulfone, polyethersulfone, polyphenylene sulfide, polyetheretherketone, polyetherketone, polyoxy Organic fillers made of engineering plastics such as benzoate (excluding compound (a)), metal oxide fillers such as aluminum oxide, silicon oxide and yttrium oxide, metal carbides such as silicon carbide and aluminum carbide, silicon nitride and aluminum nitride Examples thereof include inorganic fillers such as metal nitride filler, aluminum fluoride, and carbon fluoride.

Among these, aluminum oxide, yttrium oxide, silicon oxide, polyimide, and carbon fluoride are preferable from the viewpoint of the shielding effect of various plasmas.

Moreover, you may mix | blend the said inorganic filler and organic filler individually or in combination of 2 or more types.

The amount of the general filler is preferably 0.5 to 100 parts by mass, more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the fluoropolymer.

In particular, in fields where high purity and non-staining properties are not required, it is possible to add ordinary additives, such as fillers, processing aids, plasticizers, colorants, etc., which are blended into the fluorine-containing polymer composition as necessary. One or more conventional crosslinking agents and crosslinking aids different from those described above may be blended.

The said composition can be prepared by mixing said each component using a normal polymer processing machine, for example, an open roll, a Banbury mixer, a kneader, etc. In addition, it can be prepared by a method using a closed mixer. The composition can be suitably used as a molding material for obtaining a molded product by molding, and can also be suitably used as a molding material for obtaining a molded product by cross-linking molding.

A method for obtaining a preform using the composition as a molding material may be a conventional method, and may be a known method such as a method of heat-compressing with a mold, a method of press-fitting into a heated mold, or a method of extruding with an extruder. Can be done. In the case of an extruded product such as a hose or an electric wire, a molded product can be obtained by performing heat crosslinking with steam after extrusion.

As the crosslinking conditions,

(Standard crosslinking conditions)
Kneading method: Roll kneading press cross-linking: oven cross-linking at 180 ° C. for 30 minutes: 290 ° C. for 18 hours.

The present invention is also a molded article obtained from the above composition.
Since the molded product of the present invention is obtained by using the dendrimer as a crosslinking agent, it has excellent heat resistance. Furthermore, it is excellent in plasma resistance.
Therefore, it can be suitably used as a sealing material for a semiconductor manufacturing apparatus that requires heat resistance, in particular, a semiconductor manufacturing apparatus. Examples of the sealing material include O-ring, square ring, gasket, packing, oil seal, bearing seal, lip seal and the like.
In addition, it can also be used as various polymer products used in semiconductor manufacturing equipment, such as diaphragms, tubes, hoses, various rubber rolls, and belts. It can also be used as a coating material and a lining material.

The semiconductor manufacturing apparatus referred to in the present invention is not particularly limited to an apparatus for manufacturing a semiconductor, and is widely used as a semiconductor that requires a high degree of cleanness, such as an apparatus for manufacturing a liquid crystal panel or a plasma panel. This includes all manufacturing equipment used in the field, and examples include the following.

(1) etching apparatus dry etching apparatus plasma etching apparatus reactive ion etching apparatus reactive ion beam etching apparatus sputter etching apparatus ion beam etching apparatus wet etching apparatus ashing apparatus (2) cleaning apparatus dry etching cleaning apparatus UV / O ₃ cleaning apparatus ion Beam cleaning device Laser beam cleaning device Plasma cleaning device Gas etching cleaning device Extraction cleaning device Soxhlet extraction cleaning device High temperature high pressure extraction cleaning device Microwave extraction cleaning device Supercritical extraction cleaning device (3) Exposure device Stepper coater / developer (4) Polishing device CMP apparatus (5) film forming apparatus CVD apparatus sputtering apparatus (6) diffusion / ion implantation apparatus oxidation diffusion apparatus ion implantation apparatus

The molded article of the present invention exhibits excellent performance as a sealing material for, for example, a CVD apparatus, a plasma etching apparatus, a reactive ion etching apparatus, an ashing apparatus, or an excimer laser exposure machine.

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

なお、ＰＯＳＳは、下記式：

で表される化合物である。 Synthesis Example 1 (Manufacture of a cage silsesquioxane dendrimer having ortho-phenylenediamine at the end)
A cage-type silsesquioxane dendrimer having metaphenylenediamine at the terminal is described in Polym. Chem. , 2015, 6, 4758-4765. Produced by the method described. Using the resulting dendrimer, a third-generation terminal orthodiamine dendrimer was synthesized in the same manner by the procedure represented by the following formula.

In addition, POSS is the following formula:

It is a compound represented by these.

Synthesis Example 2 (Manufacture of a cage silsesquioxane dendrimer having metaphenylenediamine at the terminal)
A third generation terminal metaphenylenediamine cage silsesquioxane dendrimer is described in Polym. Chem. , 2015, 6, 4758-4765. Produced by the method described.

Example 1
Fluorine-containing elastomer (TFE / PMVE / CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CN (CNVE) = 59.4 / 40.1 / 0.5 (molar ratio), 100 parts by mass, After mixing 10 parts by mass of the third-generation terminal orthophenylenediamine dendrimer obtained in Synthesis Example 1 in 1500 parts by mass of a fluorine-containing solvent, the fluorine-containing solvent was volatilized at room temperature to obtain a fluorine-containing elastomer composition. The fluorine-containing solvent used was R-318 (manufactured by Daikin Industries, Ltd., main component: C ₄ F ₈ Cl ₂ ).

The obtained fluorine-containing elastomer composition was heated in an oven at 180 ° C. for 30 minutes to obtain a molded product.
About the obtained molded article, the gel fraction evaluation mentioned later and the measurement of 50% mass reduction | decrease temperature were performed. The results of gel fraction evaluation and the measurement results of 50% mass reduction temperature are shown in Table 1.

Comparative Example 1
A fluorine-containing elastomer composition was obtained in the same manner as in Example 1 except that no dendrimer was added. A molded product was obtained from the obtained fluorine-containing elastomer composition in the same manner as in Example 1. About the obtained molded article, the gel fraction evaluation mentioned later and the measurement of 50% mass reduction temperature were performed. The results of gel fraction evaluation and the measurement results of 50% mass reduction temperature are shown in Table 1.

Comparative Example 2
A fluorine-containing elastomer composition was obtained in the same manner as in Example 1 except that the components of the fluorine-containing elastomer composition were changed as shown in Table 1. A molded product was obtained from the obtained fluorine-containing elastomer composition in the same manner as in Example 1. About the obtained molded article, the gel fraction evaluation mentioned later and the measurement of 50% mass reduction | decrease temperature were performed. The results of gel fraction evaluation and the measurement results of 50% mass reduction temperature are shown in Table 1.

(Gel fraction evaluation)
After the molded products obtained in Example 1 and Comparative Examples 1 and 2 were immersed in a fluorine-containing solvent at 40 ° C. for 18 hours, the remaining gel was obtained by removing the sol dissolved in the fluorine-containing solvent. It is dried at 200 ° C. for 48 hours to remove the fluorine-containing solvent in the gel, the dry weight of the gel is measured, and the gel fraction is calculated by the following formula.
Gel fraction (%) = (gel content dry weight) / (initial dry weight) × 100
The results are shown in Table 1.

(50% mass loss temperature)
Using a thermal mass meter (TG-DTA6200, manufactured by Seiko Instruments Inc.), the mass change was measured under the conditions of air 200 ml / min, temperature rising rate 10 ° C./min, temperature range 20 to 600 ° C., and the temperature when the mass decreased by 50%. Was measured. The results are shown in Table 1.

Example 2
Fluorine-containing elastomer (TFE / PMVE / cyano group-containing monomer = 59.4 / 40.1 / 0.5 (molar ratio)), 100 parts by mass, the third generation terminal obtained in Synthesis Example 1 10 parts by mass of orthodiamine dendrimer and 0.8 parts by mass of the crosslinking agent 2,2-bis [3-amino-4- (N-phenylamino) phenyl] hexafluoropropane were premixed in 1500 parts by mass of a fluorine-containing solvent. After that, the fluorine-containing solvent was volatilized at 60 ° C., and kneaded with an open roll to obtain a fluorine-containing elastomer composition, wherein the fluorine-containing solvent was R-318 (manufactured by Daikin Industries, Ltd., main component: C ₄ F ₈ Cl ₂ ) was used.

The obtained fluorine-containing elastomer composition was subjected to crosslinking by pressing at 180 ° C. for 30 minutes, and then oven-crosslinked in an oven at 290 ° C. over 18 hours to obtain a molded product.
The obtained molded product was evaluated for plasma resistance described later. The results of the plasma resistance evaluation are shown in Table 2.

Comparative Example 3
A fluorine-containing elastomer composition was obtained in the same manner as in Example 2 except that the third generation terminal orthodiamine dendrimer obtained in Synthesis Example 1 was not blended. A molded product was obtained from the obtained fluorine-containing elastomer composition in the same manner as in Example 2. The obtained molded product was evaluated for plasma resistance described later. The results of the plasma resistance evaluation are shown in Table 2.

(Plasma resistance evaluation)
Part of the molded product obtained in Example 2 and Comparative Example 3 was covered with a Kapton electrical insulating tape, and subjected to oxygen plasma and CF ₄ plasma irradiation treatment under the following conditions. The amount of etching was measured by measuring the level difference. The results are shown in Table 2.

Oxygen plasma irradiation conditions:
Gas flow rate: 16sccm
RF output: 400W
Pressure: 2.6Pa
Etching time: 30 minutes CF ₄ plasma irradiation conditions:
Gas flow rate: 16sccm
RF output: 400W
Pressure: 2.6Pa
Etching time: 30 minutes

Etching amount measurement:
Using a laser microscope VK-9700 manufactured by Keyence Corporation, the level difference between the coated surface and the exposed surface was measured to examine the etching amount.

Claims (9)

A cage-type silsesquioxane dendrimer represented by the general formula (1).
General formula (1):

(In the general formula (1), R ^{1 to} R ⁸ are represented by the following formula (2):

It is an organic group containing the terminal group represented by these. In the formula, R ⁹ is the same or different and is —NH ₂ , —NHR ¹⁰ , —OH or —SH, and R ¹⁰ is a fluorine atom or a monovalent organic group. ) The dendrimer according to claim 1, which has a particle size of 0.5 to 15 nm. The dendrimer according to claim 1 or 2, wherein the generation number is 1-8. A composition comprising a fluorine-containing polymer and the dendrimer according to claim 1, 2 or 3. The composition according to claim 4, wherein the fluorine-containing polymer has a cyano group. The composition according to claim 4 or 5, wherein the fluorine-containing polymer is a fluorine-containing elastomer. The composition of Claim 4, 5 or 6 containing the dendrimer represented by 0.5-100 mass parts General formula (1) with respect to 100 mass parts of fluoropolymers. The composition according to claim 4, 5, 6, or 7, which is a molding material. A molded article obtained from the composition according to claim 4, 5, 6, 7 or 8.