JP3400847B2 - Method for producing cross-linked amorphous fluoropolymer and amorphous fluoropolymer solution composition - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to a main chain or terminal cyano group in the side chain of the polymer, have a crosslinking site consisting of amidine groups or imide-yl amidine group, and a fluorine-containing lipid in the main chain
The amorphous fluorine-containing polymer to have a aliphatic ring structure relates to a method for cross-linking.

[0002]

2. Description of the Related Art Fluororesin is excellent in chemical resistance, low dielectric property, low surface energy, non-adhesiveness, weather resistance, and chemical heat resistance (high thermal decomposition temperature). It is used in various applications that cannot be used. In JP-A-1-13125 JP CF ₂ = CFO (C
It is known that F ₂ ) _n CF═CF ₂ undergoes cyclopolymerization to give a polymer having a cyclic structure and being soluble in a solvent and having a low refractive index and a low dielectric constant.

Although these polymers have high thermal decomposition temperatures, they are 69 when the glass transition temperature (T _g ) is n = 1.
Since the temperature is 108 ° C. even in the case of ° C. and n = 2, there is a problem that the heat distortion temperature is not so high and it is insufficient for use at high temperature. In order to eliminate such drawbacks of the polymer having a fluorinated alicyclic structure and to give a crosslinked product having an improved heat distortion temperature that can withstand high temperature use, it is clear that the following method is effective. Has become.

[0004] Sunawa Chi, a polymer having a maleimide group in the molecule, in the molecule has a fluorinated aliphatic ring structure -
And a polymer having a NH ₂ group by crosslinking by heating, have found the present applicant that the polymer to overcome the aforementioned drawbacks can be obtained. By doing so, the mechanical heat resistance was considerably improved, but two kinds of polymers having different end groups had to be prepared.

[0005]

In order to overcome the above-mentioned drawbacks, the present invention uses a solution of an amorphous fluorine-containing polymer such as a polymer having a fluorine-containing alicyclic structure, which is mechanically treated at a high temperature. A method for producing a cross-linked product having improved heat resistance , and
Beauty shall be the object of providing an amorphous fluorine-containing polymer solution composition to a new purpose.

[0006]

The present invention SUMMARY OF], the main chains or terminal to a cyano group in the side chain of the polymer, have a amidine group or an imide-yl amidine group, and a fluorine-containing aliphatic ring structure in its main chain
Have the amorphous fluorine-containing polymer to have a granulation method producing a fluorine-containing polymer obtained by crosslinking, characterized in that to triazine ring forming reaction, and the main chain or terminal to a cyano group in the side chain of the polymer and, and it contains a main chain Ru <br/> to have a fluorinated aliphatic ring structure amorphous fluorine-containing polymer and amidine group-containing compound or imide yl amidine group-containing compound, fluorine-containing polymer solution composition objects, and have a cyano group at the end of the main chain or side chain of the polymer, and main chain fluorinated aliphatic ring
Providing a fluorine-containing polymer solution composition containing a catalyst which promotes the triazine ring formation reaction by trimerization of amorphous fluorine-containing polymer and a cyano group have a structure.

The fluorine-containing polymer used in the present invention has a cyano group, an amidine group or an imidoylamidine group at the end of the main chain or side chain of the polymer and has a fluorine-containing main chain.
It is a solvent-soluble polymer having an alicyclic structure . A preferred example is an amorphous fluorine-containing polymer which is a polymer soluble in a fluorine-containing solvent and has a fluorine-containing alicyclic structure in the main chain of the polymer. The polymer main chain preferably has a fluorinated alicyclic structure in a repeating unit obtained by polymerizing a monomer.

[0008]

An amorphous fluoropolymer having a fluorine-containing alicyclic structure in its main chain (hereinafter referred to simply as an amorphous fluoropolymer
Also note. ) , CF ₂ ═CFO (CF ₂ ).
Examples thereof include cyclized polymers of _n CF ═CF ₂ (n = 1 to 3), perfluoro (2,2-dimethyl-1,3-dioxole) or homopolymers of perfluoro-1,3-dioxole. Copolymers using a plurality of these monomers are also suitable. Also, a copolymer of these monomers and a monomer such as tetrafluoroethylene can be used if it is amorphous .

[0010]

[0011]

[0012] The molecular weight of the obtained that fluoropolymer used in the present invention varies depending on the polymer composition and application, the average molecular weight of the number average or weight average of approximately 1000 to ⁷ for use as a coating material, in particular 10 ^{4 to} 5 x 1
0 ⁶ is preferable.

[0013] If the molecular weight is too small, the polymer or is brittle, there is a case where properties such as excellent heat resistance of the original fluoropolymer may be impaired. Also, does the molecular weight exceed 10 ⁶ ?
It is not always easy to obtain or synthesize a polymer soluble in a solvent. Basically, polymer be soluble in the solvent solution viscosity 10 ⁶ c P (centipoise) or less, the upper limit of preferably 10 ⁵ c P or less, more preferably 10 ⁴ c P less value, if the molecular weight There is no.

[0014] The average molecular weight of the light scattering method and osmometry, that will directly obtained by a method by melt viscoelasticity. Further, if making a calibration curve using the data obtained in advance those methods, by measuring the gel permeation chromatography and intrinsic viscosity [eta], Ru calculated Siu molecular weight.
That it will also determined by analysis of the terminal groups by infrared absorption spectrum and nuclear magnetic resonance spectra. In the case of an amorphous perfluoropolymer having a ring structure in the main chain, perfluoro (2
-Butyltetrahydrofuran) has an intrinsic viscosity [η] measured at 30 ° C. of 0.02 to 5 dl / g, especially 0.05
Polymers of up to 1 dl / g are preferred.

As a method for introducing a cyano group into a polymer, 1) a method in which a cyano group-containing monomer is radically copolymerized, 2) an alkoxycarbonyl group introduced at the end of a side chain or a main chain is converted into an amide with ammonia. Then, it is dehydrated with phosphorus pentoxide, trifluoroacetic anhydride / pyridine or the like and converted into a cyano group.

Examples of the cyano group-containing monomer include perfluoro (3,6-dioxa-4-methyl-7-octenonitrile), perfluoro (4,7-dioxa-5-methyl-8-nonenonitrile) and perfluoro. (5,8-dioxa-6-methyl-9-decenonitrile), perfluoro (5-oxa-6-heptenonitrile), perfluoro (6-oxa-7-octenonitrile), perfluoro (7-oxa-8). -Nonenonitrile), perfluoro (2,5-dimethyl-4,7-dioxa-8-nonenonitrile) and other cyano group-containing vinyl ethers, perfluoro (3-butenonitrile), perfluoro (4-pentenonitrile), perfluoro Cyano group-containing α-olefins such as (5-hexenonitrile) and perfluoroacrylonitrile Ru example Siu.

[0017] It is preferable that two or more cyano groups on average are introduced into one molecule of the polymer. When an alkoxycarbonyl group is introduced into the side chain and then converted into a cyano group, the alkoxycarbonyl group is obtained by copolymerizing a monomer having a structure in which the cyano group in the above-mentioned cyano group-containing monomer is substituted with an alkoxycarbonyl group. It is introduced by doing.

In the present invention, an amidine group (-C (= NH) NH ₂ ) or an imidoylamidine group (-C (= NH) N = C (NH ₂ )) is added to the terminal of the main chain or side chain of the polymer.
- amorphous fluorine-containing polymer having a) may be the end of the main chain or side chain of the polymer obtained by reacting the amorphous fluorine-containing polymer with ammonia having a cyano group.

[0019] As the solvent to dissolve the fluoropolymer described above, Ru illustrated Siu the following aprotic fluorine-containing compound.
For example, perfluorobenzene, pentafluorobenzene, 1,3-bis (trifluoromethyl) benzene,
1,4-bis (trifluoromethyl) polyfluoro aromatic compounds such as benzene, perfluorotributylamine, polyfluoroalkyl trialkylamine compound, such as perfluorotripropylamine, perfluorohexane, perfluorooctane, perfluoro decane, Perfluorododecane, perfluoro-2,7-dimethyloctane, 1,1,2-trichloro-1,2,2-trifluoroethane, 1,1,1-trichloro-2,2,2-trifluoroethane, 1,3-dichloro-1,1,2,2
3-pentafluoropropane, 1,1,1,3-tetrachloro-2,2,3,3-tetrafluoropropane,
1,1,3,4-tetrachloro-1,2,2,3,4
4-hexafluorobutane, perfluoro-1,2-dimethylhexane, perfluoro-1,3-dimethylhexane, 2H, 3H-perfluoropentane, 1H-perfluorohexane, 1H-perfluorooctane, 1H
-Perfluorodecane, 1H, 1H, 1H, 2H, 2H
-Perfluorohexane, 1H, 1H, 1H, 2H, 2
H-perfluorooctane, 1H, 1H, 1H, 2H,
2H-perfluorodecane (hereinafter referred to as compound A
U ) 3H, 4H-perfluoro-2-methylpentane, 2H, 3H-perfluoro-2-methylpentane,
1H-1,1-dichloroperfluoropropane, 1H-
Polyfluoroalkane compounds such as 1,3-dichloroperfluoropropane, perfluorodecalin, perfluorocyclohexane, polyfluorocycloalkane compounds such as perfluoro-1,3,5-trimethylcyclohexane, perfluoro-2-butyltetrahydrofuran, etc. polyfluoro cyclic ether compounds, fluorine-containing but a low molecular weight polyether that it used alone or in combination, Ru earthenware pots also used a wide range of compounds in addition to these.

In the present invention, in the case of a polymer having an amidine group or an imidoylamidine group, if the solvent is an aprotic fluorine-containing solvent alone, it tends to cause high viscosity or gelation. In this case, the amount of the protic fluorinated compound is 0.01 per 100 parts by weight of the aprotic fluorinated compound.
50 parts by weight, Ru preferably reduced viscosity when added 0.1 to 20 parts by Siu. If it can dissolve the polymer, but it may also be used protic fluorine-containing compound alone.

[0021] trifluoroethanol as flop protic fluorine-containing compound, 2,2,3,3,3-pentafluoro-pro Pano Lumpur, 2- (perfluorobutyl) ethanol, 2- (perfluorohexyl) ethanol ( Less than,
It is called compound B. ) , 2- (perfluorooctyl) ethanol, 2- (perfluorodecyl) ethanol, 2
-(Perfluoro-3-methylbutyl) ethanol, 1
H, 1H, 3H-tetrafluoro-1-propanol,
1H, 1H, 5H-octafluoro-1-pentanol, 1H, 1H, 7H-dodecafluoro-1-heptanol, 1H, 1H, 9H-hexadecafluoro-1-nonanol, 2H-hexafluoro-2-propanol,
Fluorine-containing alcohols such as 1H, 1H, 3H-hexafluoro-2-butanol, trifluoroacetic acid, perfluoropropanoic acid, perfluorobutanoic acid, perfluoropentanoic acid, perfluorohexanoic acid, perfluoroheptanoic acid, perfluorooctane Fluorine-containing carboxylic acids such as acids, perfluorononanoic acid, perfluorodecanoic acid, 3H-tetrafluoropropanoic acid, 5H-octafluoropentanoic acid, 7H-dodecafluoroheptanoic acid, 9H-hexadecafluorononanoic acid, and these fluorine-containing carboxylic acids amides of carboxylic acids, trifluoromethanesulfonic acid, Ru cormorants using a fluorine-containing sulfonic acids such as heptadecafluorooctanesulfonic acid.

[0022] The solvent of the fluorine-containing polymer solution, in the coating applications, boiling point is not more 300 ° C. or less at 1 mmHg, is used as a 20 ° C. or higher at 1 atm. Preferably, it is 40 to 300 ° C. at 1 atmospheric pressure.

[0023] In the present invention, by heating the polymer having a cyano group at the terminal of the main chain or side chain in the presence of a catalyst which promotes the triazine ring forming reaction, before Symbol polymer and amidine group-containing compound Moshiku Is heated by heating a mixture with an imidoylamidine group-containing compound, or by heating a polymer obtained by converting the cyano group of the polymer into an amidine group or an imidoylamidine group by ammonia , A crosslinked polymer having a triazine ring having improved mechanical heat resistance at high temperature can be obtained. The heating temperature is 100 ° C to 400 ° C, preferably 200 ° C to 3
50 ° C is adopted.

A cyano group at the end of the main chain or side chain of the polymer
Containing amorphous fluorine-containing polymer having
After coating the substrate with the elementary polymer solution,
By bringing it into contact with gas, it is possible to
A combined coating film can be formed on the substrate. Further, after coating the solution of the cyano group-containing polymer on the substrate ,
100 ° C to 400 ° C, preferably 200 ° C to 350 ° C
Then, a coating film of a crosslinked polymer having a triazine ring can be obtained by contacting with ammonia gas .

Examples of the amidine group-containing compound and imidoylamidine group-containing compound include compounds represented by the following chemical formulas. Other than Ru cormorants used wide range of compounds having an amidine group or an imide-yl amidine group.

[0026]

[Chemical 1]

The catalyst which promotes the triazine ring forming reaction, i.e. as a catalyst for promoting a triazine ring forming reaction by trimerization of a cyano group, an organic peroxide catalyst, bisazo compounds based catalyst, such as a transition metal compound catalyst is used To be Transition metal compound type catalyst is preferably used, and specifically, zinc, manganese, perfluoro carboxylates such as cobalt,, etc. Ru illustrative Siu. In addition to copper also, silver, Ru cormorants with mosquito <br/> Domiu beam of any number of the transition metal compound. In particular, perfluorocarboxylic acid salts are preferable because they have good solubility in a fluorine-containing solvent. Moreover, that would be allowed to proceed a crosslinking reaction I by the addition of a peroxide, such as tert- butyl hydroperoxide. In the field of semiconductors , the cross-linked amorphous fluoropolymer obtained by the present invention is used in the semiconductor field as a sealing material for transistors, ICs, LSIs and multi-chip modules, buffer coat films, passivation films , interlayer insulating films. Ru apply Siu in. Particularly in these applications, the amorphous fluoropolymer is obtained by the present invention when it is necessary to maintain the shape at a high temperature of 200 ° C. or higher in the semiconductor manufacturing process.
Amorphous fluoropolymers are useful.

On the other hand, the present inventionAmorphous fluorine-containing polymer obtained by
CoalescingAre not limited to the above applicationsNaUsed for purposesU
It Windows, doors, show windows, solar cells, solar heat
Water bottle, personal computer, TV, video playback
As an anti-reflective film for displays such as display devices and video recorders
UseUIt

The display is a liquid crystal, CRT, Ru applied Siu to various methods such as a plasma method. That it will be used in a pollution protecting device called pellicle used for dust adhesion prevention on a photomask and a reticle in the semiconductor manufacturing lithography process. Other than Ru applied Siu, such as in a variety of applications optical fiber and water and oil repellent coating.

[0030]

EXAMPLES "Synthesis Example 1 (Synthesis of a Polymer Having a Cyano Group)" 132 g of perfluoro (butenyl vinyl ether) and perfluoro (3,6-dioxa-4-methyl-7) were placed in a 1000 cm ³ flask under a nitrogen atmosphere. -Octenonitrile) 3.28 g, 15% by weight of diisopropyl peroxydicarbonate 1,1,2-trichloro-1,2,2
-Trifluoroethane (R-113) solution 3.06
g , 2.4 g of R-113 and 720 g of pure water were added, the system was replaced with nitrogen gas three times, and then suspension polymerization was carried out at 40 ° C. for 40 hours.

As a result, 60 g of an amorphous fluoropolymer having a cyano group was obtained. The perfluoro (2-
Intrinsic viscosity [η] at 30 ° C. in butyltetrahydrofuran was 0.24 dl / g. Perfluoro (3,6-dioxa-4-methyl-7-octenyl Roh nitrile) units by NMR was Tsu see that has been introduced 1.2 mol% in the copolymer. When the infrared absorption spectrum of this fluoropolymer was measured, absorption by a cyano group was observed at 2260 cm ^-1 .

Example 1 The fluoropolymer of Synthesis Example 1 was dissolved in compound A / 2,2,2-trifluoroethanol (weight ratio 99.5 / 0.5) to give a solution having a concentration of 5% by weight. Was prepared. Ammonia gas was blown into the solution at room temperature for 10 minutes to convert the cyano group into an amidine group. A cast film was prepared in a nitrogen atmosphere, the temperature was gradually raised, and the temperature was kept at 300 ° C. for 2 hours.

In the infrared absorption spectrum, absorption by the triazine ring was observed at 1560 cm ^-1 . 2,2,2 in the solvent
-When trifluoroethanol was not added, the solution became highly viscous and cast molding was difficult, but formation of triazine ring was observed by the same heat treatment. Solvent Pas <br/> Furuoro tri-butylamine / compound B (weight ratio 95 /
Also in the case of 5), formation of a triazine ring was similarly confirmed.

[0034] dissolved in "Example 2" Synthesis Example 1 of the fluoropolymer perfluorotributylamine butylamine <br/> amine / compound B (weight ratio 95/5), concentration 15
A wt% solution was prepared. After blowing the room temperature for 10 min ammonia gas into the solution, it was spin-coated on a silicon wafer, was crosslinked 1 hour heat treatment at 300 ° C..
In accordance with JIS K5400, put a checkerboard-shaped scratch 3
It heat-processed at 50 degreeC for 1 hour. It was confirmed by microscope observation that the state of the cross-cut did not change before and after the heat treatment at 350 ° C.

Comparative Example 1 A perfluoro ( butenyl vinyl ether ) homopolymer (intrinsic viscosity [η]: 0.24 dl / g) was spin-coated on a silicon wafer and heat-treated at 300 ° C. for 10 minutes.
In accordance with JIS K 5400, put a checkerboard-shaped scratch 2
When heat-treated at 50 ° C. for 1 hour, fusion of resin between cross-cuts was observed.

[0036] dissolved in "Example 3" Synthesis Example 1 of the fluoropolymer perfluorotributylamine butylamine <br/> amine / compound B (weight ratio 95/5), concentration of 12
A wt% solution was prepared. 0.15 parts by weight of C ₈ F ₁₇ C (= NH) NH ₂ was added to 100 parts by weight of the solution, and spin-coated on a silicon wafer. 350 ° C
After cross-linking by heat treatment in accordance with JIS K5400, it was heat-treated at 350 ° C. for 1 hour with a checkerboard-shaped scratch. It was confirmed by microscope observation that the state of the cross-cut did not change before and after the heat treatment at 350 ° C. The heat treatment at 400 ° C. did not change the state of the cross, and no fusion between the crosses was observed.

Example 4 Instead of C ₈ F ₁₇ C (= NH) NH ₂ , (C ₈ F ₁₇ CO 2
Example 3 except that 0.36 parts by weight of O) ₂ Zn was added.
The same experiment was conducted, but the result was the same.

[0038] "Example 5" was a fluorine-containing polymer of Synthesis Example 1 was dissolved in perfluorotributylamine butylamine <br/> Min prepare a 12 wt% solution. After spin coating on a silicon wafer, it was contacted with ammonia gas and heat-treated at 350 ° C. for 2 hours. The state of the cross-cuts before and after the heat treatment at 350 ° C. was observed in the same manner as in Example 3, but no fusion between the cross-cuts due to the melt flow of the polymer was observed.

[0039] The fluorine-containing polymer of the "Example 6" Synthesis Example 1 to prepare a film having a thickness of 100 microns m by heat pressing. It was immersed in R-113 and ammonia gas was blown into it for 3 hours. Film and dried removed, was measured for infrared absorption spectrum, the absorption of the amidine group was observed at 1655 cm ^-1.
This film is placed in an oven and gradually heated to 180
When heat-treated at 0 ° C. for 2 hours, absorption by the triazine ring was observed at 1560 cm ⁻¹ . 3 more of this film
When heated at 00 ° C. for 2 hours, there was no change in absorption at 1560 cm ⁻¹ .

Example 7 The ammonia-treated solution of Example 1 was spin-coated on a silicon wafer and heat-treated at 350 ° C. for 1 hour in a nitrogen atmosphere. 15 in infrared absorption spectrum (FT-IR)
Absorption of the triazine ring by the crosslinking reaction was confirmed at 60 cm ^-1 . Further, to produce a pore pore size 2.mu. m by etching has been heat treated for one hour again 350 ° C., the change in shape of the hole was observed. Similar tests for poly (perfluoro)
( Butenyl vinyl ether ) ) ([η]: 0.24), it was observed that the holes were collapsed by the heat treatment after etching.

[0041]

Applying a fluorine-containing polymer solution composition of the present invention, the coating of amorphous fluorine-containing polymer having a fluorine-containing Motoabura aliphatic ring structure obtained by heat-treating are crosslinked, high temperature Has excellent mechanical properties and is not easily deformed by external pressure.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-3-172311 (JP, A) JP-A-49-61119 (JP, A) JP-A-59-109546 (JP, A) JP-A-6- 56936 (JP, A) JP-A-2-191613 (JP, A) JP-A-6-136218 (JP, A) JP-A-2-147614 (JP, A) US Patent 3546186 (US, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 14/18-14/28 C08F 8/30-8/32 C08F 16/32 C08F 216/14-216/20

Claims (3)

(57) [Claims] 1. A polymer of the main chain or terminal to a cyano group of the side chain, have a amidine group or an imide-yl amidine group, or
One of the main chain amorphous fluorine-containing polymer to have a fluorinated aliphatic ring structure, a manufacturing method of an amorphous fluorine-containing polymer obtained by crosslinking, characterized in that to triazine ring forming reaction. 2. A main chain or at the end of the side chain have a cyano group, and amorphous fluorine-containing polymer and amidine group-containing compound to have a fluorinated aliphatic ring structure in its main chain of the polymer or imidoyl An amorphous fluoropolymer solution composition containing an amidine group-containing compound. 3. A polymer backbone or have a cyano group at the end of the side chain, and triazine by trimerization of amorphous fluorine-containing polymer and a cyano group to have a fluorinated aliphatic ring structure in its main chain the amorphous fluorine-containing polymer solution composition containing a catalyst which promotes the ring-forming reaction.