JP6789521B2 - Dendrimer, composition and molded product - Google Patents

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 thus are used in the fields of aerospace, semiconductor manufacturing equipment, chemical plants, and the like. Widely used as a sealing material in harsh environments.

When a molded product such as a sealing material is manufactured, a cross-linking agent is used in the composition for forming the molded product. For example, Patent Document 1 discloses a seal for a semiconductor manufacturing apparatus composed of a composition consisting of 1 to 10 parts by weight of an organic peroxide as a cross-linking agent with respect to 100 parts by weight of a fluorine-based elastomer.

Japanese Unexamined Patent Publication No. 06-302527

An object of the present invention is to provide a novel compound capable of providing a molded product having excellent heat resistance and plasma resistance while acting as a cross-linking agent. It is also an object of the present invention to provide a composition capable of providing a molded product having excellent heat resistance and plasma resistance without using a general cross-linking agent, and while being produced without using a general cross-linking agent. An object of the present invention is to provide a molded product having excellent heat resistance and plasma resistance.

As a result of diligent studies by the present inventors, a dendrimer of silsesquioxane having a specific structure acts as a cross-linking agent, and a molded product obtained by using the above-mentioned 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 dendrimer of cage-type silsesquioxane represented by the general formula (1).
General formula (1):

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

It is an organic group containing a terminal group represented by. In the formula, R ⁹ is the same or different, -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 a fluoropolymer and the above-mentioned dendrimer.

The fluoropolymer preferably has a cyano group.

The fluoropolymer is preferably a fluoroelastomer.

The composition of the present invention preferably contains 0.5 to 100 parts by mass of a dendrimer represented by the general formula (1) with respect to 100 parts by mass of the fluoropolymer.

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

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

Since the dendrimer of the present invention has the above-mentioned structure, it is possible to obtain a molded product having excellent heat resistance and plasma resistance while acting as a cross-linking agent.
The composition of the present invention can be crosslinked without using a general cross-linking agent, and can provide a molded product having excellent heat resistance and plasma resistance.
The molded product of the present invention is excellent in heat resistance and plasma resistance even though a general cross-linking 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-type silsesquioxane dendrimer represented by the general formula (1). The dendrimer of the present invention can act as a cross-linking agent and provide a molded product having excellent heat resistance. Further, the molded product obtained by using the dendrimer of the present invention as a cross-linking agent is also excellent in plasma resistance. Therefore, the molded product obtained by using the dendrimer of the present invention as a cross-linking agent is particularly suitable as a sealing material for semiconductor manufacturing equipment and the like.
General formula (1):

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

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

The organic group containing a terminal group represented by the above formula (2) is preferably an alkyl group, an alkoxy group or a phenyl group containing a terminal group represented by the above formula (2).
The alkyl group and the alkoxy group preferably have 1 to 1000 carbon atoms, more preferably 1 to 600 carbon atoms, and further preferably 1 to 400 carbon atoms. When the number of carbon atoms is 2 or more, the 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.
The R ^{1 to} R ⁸ may include a cyclic structure such as an aromatic ring other than the benzene ring contained in the terminal group. Further, the above R ^{1 to} R ⁸ may contain 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 contain a cyclic structure such as an aromatic ring other than the benzene ring contained in the terminal group. Since R ^{1 to} R ⁸ contain 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 the terminal functional groups face outward, so that the heat resistance , Excellent plasma resistance.
More preferably, R ^{1 to} R ⁸ include a terminal group represented by the formula (2), an alkylene group or an oxyalkylene group, and a 2 to 6-valent benzene ring. The benzene ring is more preferably trivalent. The alkylene group and the oxyalkylene group may have 1 to 10 carbon atoms, respectively, and preferably 1 to 5 carbon atoms.
In addition, when referring to "n-valent benzene ring" in this specification, it means that n hydrogen atoms of a 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, further preferably 5 nm or more, and more preferably 10 nm or less. preferable. The particle size can be adjusted according to the types of R ^{1 to} R ⁸ .

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

As the dendrimer of the cage-type silsesquioxane, in the general formula (1), R ^{1 to} R ⁸ are independently represented by the following general formula (2) (hereinafter, "terminal group T"). Also called.) Included.

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, -NH ₂ , -NHR ¹⁰ , -OH or -SH, and R ¹⁰ is a fluorine atom or a monovalent organic group.
The monovalent organic group represented by R ^10, for example, aliphatic hydrocarbon group, a phenyl group or a benzyl group. Specifically, for example, at least one of R ¹⁰ is a lower alkyl group having 1 to 10 carbon atoms such as -CH ₃ , -C ₂ H ₅ , -C ₃ H ₇ , and particularly 1 to 6; -CF ₃ , -. C ₂ F ₅ , -CH ₂ F, -CH ₂ CF ₃ , -CH ₂ C ₂ F _5, and other hydrogen atom-containing lower alkyl groups with 1 to 10 carbon atoms, especially 1 to 6; phenyl group; benzyl group;- C ₆ F ₅ , -CH ₂ C ₆ F ₅ or other fluorine atom substituted with 1 to 5 hydrogen atoms for a phenyl or benzyl group; -C ₆ H _5-n (CF ₃ ) _n , -CH ₂ A phenyl or 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.
Since the cross-linking reactivity is good, 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 containing the above-mentioned specific terminal group T, and also has excellent heat resistance and plasma resistance of a molded product obtained from the composition containing the dendrimer of the present invention. Can be an invention.

Examples of the dendrimer of the cage-type 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 divalent groups independently represented by -NH-CO-, -O-CO-, -O-, -CO- or -OCH _2- . L ¹ and L ² are preferably divalent groups represented by -NH-CO-.

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

Equation (3):

As the dendrimer of the cage-type silsesquioxane, in the general formula (1), it is preferable that all of R ^{1 to} R ⁸ contain a terminal group T and a trivalent group B, and a trivalent group. B is bonded to the silicon atom of the cage-type silsesquioxane via a divalent group A represented by-(CH ₂ ) _l- 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-type silsesquioxane via the above divalent group A, and the terminal group T is divalent via the trivalent group B. It is more preferable that it is bonded to the group A of. A plurality of trivalent groups B may be bonded to form a regular repeating structure.

As the dendrimer of the cage-type silsesquioxane, those having 1 to 8 generations are preferable, and those having 1 to 6 generations 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 ) _l −NH-CO− (l is an integer of 1 to 5).

Each of the above structures corresponds to a 1st to 5th generation dendrimer.

As an example, the structures of R ^{1 to} R ⁸ possessed by the second generation dendrimer are specifically shown in the following equation.

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.
Illustrating the structure of ^R 1 to R ⁸ having dendrimer second generation 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 the present invention can be produced by a known method except for the following points.
The dendrimer of the present invention has a terminal group of the formula (2) at the end. For example, when R ⁹ in the formula (2) is −NH ₂ , the dendrimer of the present invention is a cage-type silsesquioxane dendrimer having _two NHs at the terminal, and 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. When R ⁹ is a terminal group other than −NH ₂ , the corresponding reaction may be used in the same manner as appropriate. The reaction conditions may be set as appropriate.

The composition of the present invention is characterized by containing a fluoropolymer and a dendrimer of the above-mentioned cage-type silsesquioxane having a specific structure.

As the fluoropolymer, a fluoroelastomer is preferable because it is excellent in sealing property, 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.

Examples of the partially fluorinated elastomer include vinylidene fluoride (VdF) -based fluororubber, tetrafluoroethylene (TFE) / propylene (Pr) -based fluororubber, and tetrafluoroethylene (TFE) / propylene / vinylidene fluoride (VdF) -based fluororubber. , Ethylene / hexafluoropropylene (HFP) -based fluororubber, ethylene / hexafluoropropylene (HFP) / vinylidene fluoride (VdF) -based fluororubber, ethylene / hexafluoropropylene (HFP) / tetrafluoroethylene (TFE) -based fluororubber And so on. Among them, at least one selected from the group consisting of vinylidene fluoride-based fluororubber and tetrafluoroethylene / propylene-based fluororubber is preferable.

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, it is a copolymer consisting 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 according to the type of monomer.

Examples of at least one other monomer copolymerizable with the above vinylidene fluoride include tetrafluoroethylene [TFE], hexafluoropropylene [HFP], fluoroalkyl vinyl ether, chlorotrifluoroethylene [CTFE], and trifluoroethylene. Trifluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, hexafluoroisobutene, vinyl fluoride, general formula (6): CH ₂ = CFRf ⁶¹ (in the formula, Rf ⁶¹ is a linear chain having 1 to 12 carbon atoms. Or a fluoromonomer represented by a branched fluoroalkyl group), general formula (7): CH ₂ = CH- (CF ₂ ) _n- X ² (in the formula, X ² is H or F, and n is 3 to 3 to Fluoromonomers represented by (an integer of 10), monomers such as monomers giving a cross-linking site; non-fluorinated monomers such as ethylene, propylene, and alkyl vinyl ethers can be mentioned. 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 a fluoroalkyl vinyl ether,
General formula (8): CF ₂ = CF-ORf ⁸¹
(In the formula, Rf ⁸¹ represents a perfluoroalkyl group having 1 to 8 carbon atoms.)
General 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, and 2 to 6 carbon atoms containing 1 to 3 oxygen atoms. Fluoromonomer represented by (is a linear or branched perfluorooxyalkyl group), and
General formula (11): CF ₂ = CFO (CF ₂ CF (Y ¹¹ ) O) _m (CF ₂ ) _n F
(In the formula, Y ¹¹ represents a fluorine atom or a trifluoromethyl group. M is an integer of 1 to 4. n is an integer of 1 to 4.) Selected from the group consisting of fluoromonomers. It is preferable that there is at least one species.
The fluoromonomer represented by the general formula (8) is more preferable.

Specific examples of the vinylidene fluoride-based fluororubber are represented by VdF / HFP-based rubber, VdF / HFP / TFE-based rubber, VdF / CTFE-based rubber, VdF / CTFE / TFE-based rubber, and VDF / general formula (6). Fluoromonomer-based rubber, VDF / fluoromonomer / TFE-based rubber represented by the general formula (6), VDF / perfluoro (methyl vinyl ether) [PMVE] -based rubber, VDF / PMVE / TFE-based rubber, VDF / PMVE / Examples include TFE / HFP-based rubber. As the fluoromonomer-based rubber represented by VDF / general formula (6), VDF / CH ₂ = CFCF _3- based rubber is preferable, and as the fluoromonomer / TFE-based rubber represented by VDF / general formula (6), it is preferable. VDF / TFE / CH ₂ = CFCF ₃ rubber is preferable.

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 CH ₂ = CFCF ₃ It is more preferable that the copolymer is composed of 20 to 50 mol%.

The tetrafluoroethylene / propylene fluororubber is preferably a copolymer composed of 45 to 70 mol% of tetrafluoroethylene, 55 to 30 mol% of propylene, and 0 to 5 mol% of fluoromonomer that provides a crosslinked site. ..

The fluorine-containing elastomer may be a perfluoroelastomer. Examples of the perfluoroepolymer include TFE / general formulas (8), (10) or (11) fluoromonomer copolymers and TFE / general formulas (8), (10). ) Or (11), at least one selected from the group consisting of a fluoromonomer / a monomer copolymer giving a cross-linking site is preferable.
In the case of a TFE / PMVE copolymer, the composition is preferably 45-90 / 10-55 (mol%), more preferably 55-80 / 20-45, and even more preferably 55-. It is 70/30 to 45.
In the case of a monomer copolymer giving a TFE / PMVE / cross-linking site, it is preferably 45-89.9 / 10-54.9 / 0.01-4 (mol%), more preferably 55-77. It is 9/20 to 49.9 / 0.1 to 3.5, and more preferably 55 to 69.8 / 30 to 44.8 / 0.2 to 3.
In the case of the fluoromonomer copolymer represented by the general formula (8), (10) or (11) having a TFE / carbon number of 4 to 12, it is preferably 50 to 90/10 to 50 (mol%). , More preferably 60 to 88/12 to 40, and even more preferably 65 to 85/15 to 35.
In the case of a monomer copolymer having a TFE / fluoromonomer represented by the general formula (8), (10) or (11) having 4 to 12 carbon atoms / a cross-linking site, preferably 50 to 89.9 / 10 -49.9 / 0.01-4 (mol%), more preferably 60-87.9 / 12-39.9 / 0.1-3.5, even more preferably 65-84. It is .8 / 15 to 34.8 / 0.2 to 3.
If it is out of the range of these compositions, the property as a rubber elastic body is lost, and the property tends to be close to that of a resin.
In the perfluoroelastomer containing TFE, the monomer that gives the cross-linking site does not have to be a perfluoromonomer.

Examples of the perfluoroepolymer include TFE / a fluoromonomer represented by the general formula (11) / a fluoromonomer copolymer giving a cross-linking site, TFE / a 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 TFE / fluoromonomer represented by the general formula (8) / a monomer copolymer giving a cross-linking site. Is preferable.

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

The monomer that gives a cross-linking site is a monomer (cure site monomer) having a cross-linking group that gives a cross-linking site to the fluoropolymer for forming a cross-link with a cross-linking agent.

As a monomer that gives a cross-linking 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 , X ⁴ is an iodine atom or a bromine atom)
General formula (13): CX ³ ₂ = CX ^3- R _f ¹³¹ X ⁴
(In the formula, X ³ is a hydrogen atom, a fluorine atom or CH ₃ , R _f ¹³¹ is a fluoroalkylene group, a perfluoroalkylene group, a fluoropolyoxyalkylene group or a perfluoropolyoxyalkylene group, and X ⁴ is an iodine atom. Or a fluoromonomer represented by (or a bromine atom),
General formula (14): CF ₂ = CFO (CF ₂ CF (CF ₃ ) O) _m (CF ₂ ) _n −X ⁵
(In the formula, 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). Represented fluoromonomer and
General formula (15): CH ₂ = CFCF ₂ O (CF (CF ₃ ) CF ₂ O) _m (CF (CF ₃ )) _n −X ⁶
(In the formula, m is an integer of 0 to 5, n is an integer of 1 to 3, and 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
(In the formula, R ¹⁶² , R ¹⁶³ , R ¹⁶⁴ , R ¹⁶⁵ , R ¹⁶⁶ and R ¹⁶⁷ are the same or different alkyl groups having a hydrogen atom or 1 to 5 carbon atoms. Z is a linear or branched alkyl group. An alkylene group having 1 to 18 carbon atoms, a cycloalkylene group having 3 to 18 carbon atoms, or at least a partially fluorinated alkylene group having 1 to 10 carbon atoms or an oxyalkylene group which may have an oxygen atom in the form. Group or
− (Q) _p −CF ₂ O − (CF ₂ CF ₂ O) _m (CF ₂ O) _n − CF ₂ − (Q) _p −
(In the formula, 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 10000 (par). It is a fluoropolyoxyalkylene group. ) Is preferably at least one selected from the group consisting of monomers.

X ³ is preferably a fluorine atom. Rf ¹²¹ and Rf ¹³¹ are preferably perfluoroalkylene groups 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.

As the monomers giving the cross-linking 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 It is preferable that at least one selected from the group consisting of CN, CF ₂ = CFOCF ₂ CF ( CF ₃ ) OCF ₂ CF ₂ CN is more preferable.

The fluoropolymer preferably has a cyano group. When the fluoropolymer has a cyano group, the dendrimer acts more preferably as a cross-linking agent, and a molded product having excellent heat resistance can be obtained.
The cyano group can be introduced into the fluoropolymer by the above-mentioned monomer giving a cross-linking site. As another method, it can be introduced by the method described in Pamphlet No. 00/05959.
The fluoropolymer having a cyano group preferably contains 0.1 to 5.0 mol% of a monomer giving a cross-linking site with respect to all the monomer units, and preferably contains 0.2 to 2.0 mol%. More preferred. In this case, the monomer that gives the cross-linking site is preferably 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 temperature. More preferred. Further, from the viewpoint of good cold resistance, it is preferably 5 ° C. or lower, more preferably 0 ° C. or lower, and even more preferably -3 ° C. or lower.

The glass transition temperature is determined by using a differential scanning calorimeter (DSC822e, manufactured by METTLER TOLEDO) to raise the temperature of 10 mg of the sample at 10 ° C./min to obtain a DSC curve, which is the base before and after the secondary transition of the DSC curve. It can be obtained as the temperature indicating the midpoint of the intersection of the extension line of the line and the tangent line at the turning 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 further preferably 50 or more, in terms of good heat resistance. Further, in terms of good workability, it is preferably 150 or less, more preferably 120 or less, and further 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 further preferably 50 or more, in terms of good heat resistance. Further, in terms of good workability, it is preferably 180 or less, more preferably 150 or less, and further preferably 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 further preferably 30 or more, in terms of good heat resistance. Further, in terms of good workability, it is preferably 120 or less, more preferably 100 or less, and further preferably 80 or less.

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

The above-mentioned partially fluorinated elastomer and perfluoroelastomer can be produced by a conventional method, but the obtained polymer has a narrow molecular weight distribution and the molecular weight can be easily controlled, and an iodine atom or a bromine atom is introduced at the terminal. Iodine compounds or bromine compounds can also be used as the chain transfer agent from the viewpoint of the above. Examples of the polymerization method using an iodine compound or a bromine compound include a method of performing emulsion polymerization in an aqueous medium under pressure in the presence of an iodine compound or a bromine compound in a substantially anoxic state. (Iodine transfer polymerization method). Typical examples of the iodine compound or bromine compound used include, for example, the general formula:
R ¹³ I _x Br _y
(In the formula, x and y are integers of 0 to 2, respectively, and satisfy 1 ≦ x + y ≦ 2, and R ¹³ is a saturated or unsaturated fluorohydrocarbon group having 1 to 16 carbon atoms or chlorofluoro. Examples thereof include a compound represented by a hydrocarbon group or a hydrocarbon group having 1 to 3 carbon atoms and 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 also function as a cross-linking point.

Examples of the iodine compound and the bromine compound include 1,3-diiodoperfluoropropane, 2-iodoperfluoropropane, 1,3-diiodo-2-chloroperfluoropropane, 1,4-diiodoperfluorobutane, and 1 , 5-Diode-2,4-dichloroperfluoropentane, 1,6-diiodoperfluorohexane, 1,8-diiodoperfluorooctane, 1,12-diiodoperfluorododecane, 1,16-diiodine 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 ₂ CFBrOCF ₃ , 1-bromo-2-iodoperfluoroethane, 1-bromo- ₃ -iodoperfluoropropane, 1-bromo-4-iodoperfluorobutane, 2-bromo-3-3 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 viewpoints of polymerization reactivity, cross-linking reactivity, availability, and the like. Is preferable.

The composition preferably contains 0.5 to 100 parts by mass of the cage-type silsesquioxane dendrimer with respect to 100 parts by mass of the fluoropolymer. It is more preferably 5 to 50 parts by mass, and further preferably 5 to 25 parts by mass. If the amount of cage-type silsesquioxane is too small, the reinforcing property is poor, and if the amount of cage-type silsesquioxane is too large, the sealability may be deteriorated.

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

The cross-linking agent used in the peroxide cross-linking may be an organic peroxide that can easily generate a peroxy radical in the presence of heat or an oxidation-reduction 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) -hexin-3, benzoyl peroxide, t-butylperoxybenzene, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxymaleic acid, t-butyl Peroxyisopropyl carbonate, 1,3-bis (t-butylperoxyisopropyl) benzene and the like can be mentioned. Generally, the type and amount of organic peroxide used are selected in consideration of the amount of activity-O-O-, decomposition temperature, and the like.

Further, the cross-linking aid that can be used in this case may be a compound having a reaction activity with respect to a peroxy radical and a polymer radical, for example, CH ₂ = CH −, CH ₂ = CHCH ₂ −, CF _2. = Examples thereof include polyfunctional compounds having a functional group such as CF-. Specifically, for example, triallyl cyanurate, triallyl isocyanurate (TAIC), triacrylic formal, triallyl trimerite, N, N'-n-phenylene bismaleimide, dipropagil 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 cross-linking agent used for cross-linking the polyol include polyhydric alcohol compounds such as bisphenol A and bisphenol AF.

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

Examples of the cross-linking agent used for triazine cross-linking include organic tin compounds such as tetraphenyltin and triphenyltin.

Examples of the cross-linking agent used for oxazole cross-linking, imidazole cross-linking, and thiazole cross-linking include the general formula (20):

(In the formula, R ⁴ is -SO _2- , -O-, -CO-, an alkylene group having 1 to 6 carbon atoms, a perfluoroalkylene group having 1 to 10 carbon atoms or a single bond, or

R ⁵ and R ⁶ are groups represented by, one of which is -NH ₂ and the other of which are -NHR ⁷ , -NH ₂ , -OH or -SH, and R ⁷ is a hydrogen atom, a fluorine atom or a monovalent group. It is an organic group, preferably R ⁵ is -NH ₂ and R ⁶ is -NHR ⁷ . Preferred 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 a perfluoroalkylene group having 1 to 10 carbon atoms. Is

And so on. These compounds are known as examples of bisdiaminophenyl compounds in JP-A-2-59177, JP-A-8-12146, etc.), and are bisdiaminophenyl-based cross-linking agents. Bisaminophenol-based cross-linking agent, bis-aminothiophenol-based cross-linking agent, general formula (21):

Bisamidrazone-based cross-linking agent represented by, general formula (22):

(In the formula, R _f ³ is a perfluoroalkylene group having 1 to 10 carbon atoms),
Or general formula (23):

Examples thereof include a bisamide oxime-based cross-linking agent represented by (in the formula, n is an integer of 1 to 10). These bisaminophenol-based cross-linking agents, bis-aminothiophenol-based cross-linking agents, bis-diaminophenyl-based cross-linking agents, etc. have conventionally been used for cross-linking systems using a cyano group as a cross-linking point, but carboxyl groups and alkoxycarbonyls have been used. It also reacts with groups to form oxazole rings, thiazole rings, and imidazole rings, giving crosslinked products.

Particularly preferred cross-linking agents include compounds 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, R} 6, are the same in a said) a compound represented by, and the like, specifically, for example, 2,2-bis (3-amino-4-hydroxyphenyl) hex 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, 2,2-bis [3-amino-4- (N-phenylamino) phenyl] hexafluoropropane as a cross-linking agent from the viewpoint of heat resistance, steam resistance, amine resistance, and good cross-linking property. Is preferable.

The general cross-linking 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 above composition may contain a general filler.

Examples of the general filler include imide-based fillers having an imide structure such as polyimide, polyamideimide, and polyetherimide; polyarylate, polysulfone, polyethersulfone, polyphenylenesulfide, polyetheretherketone, polyetherketone, and 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, aluminum nitride and the like. Examples thereof include metal nitride fillers, aluminum fluoride, and inorganic fillers such as carbon fluoride.

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

Further, the above-mentioned inorganic filler and organic filler may be blended alone or in combination of two or more.

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

Especially in fields where high purity and non-staining properties are not required, it is possible to add usual additives to be added to the fluoropolymer composition, such as fillers, processing aids, plasticizers, and colorants, if necessary. It is possible to add one or more commonly used cross-linking agents or cross-linking aids different from the above.

The composition can be prepared by mixing each of the above components using a conventional polymer processing machine, for example, an open roll, a Banbury mixer, a kneader, or the like. In addition, it can also be prepared by a method using a closed mixer. The above composition can be suitably used as a molding material for molding to obtain a molded product, and can also be suitably used as a molding material for cross-linking to obtain a molded product.

The method of obtaining the preformed body using the above composition as a molding material may be an ordinary method, and may be a known method such as a method of heating and compressing with a mold, a method of press-fitting into a heated mold, and a method of extruding with an extruder. Can be done. In the case of extruded products such as hoses and electric wires, molded products can be obtained by heat-crosslinking with steam after extrusion.

The above cross-linking conditions include

(Standard cross-linking conditions)
Kneading method: Roll kneading Press crosslinking: 180 ° C. for 30 minutes Oven crosslinking: 290 ° C. for 18 hours, unless otherwise specified, crosslinking is carried out under these conditions.

The present invention is also a molded product obtained from the above composition.
Since the molded product of the present invention is obtained by using the above dendrimer as a cross-linking agent, it has excellent heat resistance. Furthermore, it is also excellent in plasma resistance.
Therefore, it can be suitably used as a sealing material for semiconductor manufacturing equipment, particularly semiconductor manufacturing equipment, which is particularly required to have heat resistance. Examples of the sealing material include O-rings, square-rings, gaskets, packings, oil seals, bearing seals, lip seals 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, but is a wide range of semiconductors that require a high degree of cleanliness, such as an apparatus for manufacturing a liquid crystal panel or a plasma panel. It includes all manufacturing equipment used in the field, and examples thereof include the following.

(1) Etching equipment Dry etching equipment Plasma etching equipment Reactive ion etching equipment Reactive ion beam etching equipment Sputter etching equipment Ion beam etching equipment Wet etching equipment Ashing equipment (2) Cleaning equipment Dry etching cleaning equipment UV / O ₃ cleaning equipment Ion Beam cleaning equipment Laser beam cleaning equipment Plasma cleaning equipment Gas etching cleaning equipment Extraction cleaning equipment Socksley Extraction cleaning equipment High temperature and high pressure extraction cleaning equipment Microwave extraction cleaning equipment Supercritical extraction cleaning equipment (3) Exposure equipment Stepper coater / developer (4) Polishing equipment CMP device (5) Formation device CVD device Sputtering device (6) Diffusion / ion injection device Oxidation diffusion device Ion injection device

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

Next, the present invention will be described with reference to examples, but 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 (Production of a cage-type silsesquioxane dendrimer having orthophenylenediamine at the end)
A cage-type silsesquioxane dendrimer having a metaphenylenediamine at the end was polymerized. Chem. , 2015, 6, 4758-4765. Manufactured by the method described. Using the obtained 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.

Synthesis Example 2 (Production of cage-type silsesquioxane dendrimer having metaphenylenediamine at the end)
The dendrimer of the third generation terminal metaphenylenediamine cage-type silsesquioxane was polymerized. Chem. , 2015, 6, 4758-4765. Manufactured 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), with respect to 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. . Here, the fluorine-containing solvent, R-318 (Daikin Industries Ltd., main _component: C ₄ F 8 Cl ₂₎ was used.

The obtained fluorine-containing elastomer composition was heated in an oven at 180 ° C. for 30 minutes to obtain a molded product.
The obtained molded product was evaluated for gel fraction and 50% mass reduction temperature, which will be described later. Table 1 shows the results of the gel fraction evaluation and the measurement results of the 50% mass reduction temperature.

Comparative Example 1
A fluorine-containing elastomer composition was obtained in the same manner as in Example 1 except that no dendrimer was added. From the obtained fluorine-containing elastomer composition, a molded product was obtained in the same manner as in Example 1. The obtained molded product was evaluated for gel fraction and 50% mass reduction temperature, which will be described later. Table 1 shows the results of the gel fraction evaluation and the measurement results of the 50% mass reduction temperature.

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. From the obtained fluorine-containing elastomer composition, a molded product was obtained in the same manner as in Example 1. The obtained molded product was evaluated for gel fraction and 50% mass reduction temperature, which will be described later. Table 1 shows the results of the gel fraction evaluation and the measurement results of the 50% mass reduction temperature.

(Gel fraction evaluation)
The molded products obtained in Example 1 and Comparative Examples 1 and 2 are immersed in a fluorine-containing solvent at 40 ° C. for 18 hours, and then the remaining gel content is obtained by removing the sol component dissolved in the fluorine-containing solvent. The gel 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 dry weight) / (initial dry weight) x 100
The results are shown in Table 1.

(50% mass reduction temperature)
Using a thermogravimetric meter (TG-DTA6200 manufactured by Seiko Instruments), measure the mass change under the conditions of air 200 ml / min, heating rate 10 ° C / min, and temperature range 20 to 600 ° C, and the temperature when the mass is reduced 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 terminal of the third generation obtained in Synthesis Example 1 10 parts by mass of orthodiamine dendrimer and 0.8 parts by mass of cross-linking agent 2,2-bis [3-amino-4- (N-phenylamino) phenyl] hexafluoropropane are premixed in 1500 parts by mass of a fluorine-containing solvent. Then, the fluorinated solvent was volatilized at 60 ° C. and kneaded with an open roll to obtain a fluorinated elastomer composition. The fluorinated 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 pressed at 180 ° C. for 30 minutes for cross-linking, and then further cross-linked in an oven at 290 ° C. for 18 hours to obtain a molded product.
The obtained molded product was evaluated for plasma resistance, which will be 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. From the obtained fluorine-containing elastomer composition, a molded product was obtained in the same manner as in Example 2. The obtained molded product was evaluated for plasma resistance, which will be described later. The results of the plasma resistance evaluation are shown in Table 2.

(Plasma resistance evaluation)
A part of the molded product obtained in Example 2 and Comparative Example 3 was coated with Kapton electrical insulating tape, and oxygen plasma and CF ₄ plasma irradiation treatment was performed under the following conditions to obtain a coated surface and an exposed surface. The amount of etching was examined by measuring the step difference. The results are shown in Table 2.

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

Etching amount measurement:
Using a laser microscope VK-9700 manufactured by KEYENCE CORPORATION, the step between the covered surface and the exposed surface was measured to determine 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 the following formula (2):

It is an organic group containing a terminal group represented by. In the formula, R ⁹ is the same or different, -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, wherein the dendrimer has a particle size of 0.5 to 15 nm. The dendrimer according to claim 1 or 2, wherein the number of generations is 1 to 8. A composition comprising a fluoropolymer and the dendrimer according to claim 1, 2 or 3. The composition according to claim 4, wherein the fluoropolymer has a cyano group. The composition according to claim 4 or 5, wherein the fluoropolymer is a fluoroelastomer. The composition according to claim 4, 5 or 6, which contains a dendrimer represented by the general formula (1) of 0.5 to 100 parts by mass with respect to 100 parts by mass of the fluoropolymer. The composition according to claim 4, 5, 6 or 7, which is a molding material. A molded product obtained from the composition according to claim 4, 5, 6, 7 or 8.