JP3029323B2 - Fluoropolymer composition for coating and use thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluoropolymer composition suitable for coating and its use.

[0002]

2. Description of the Related Art Fluororesins are used in various applications that cannot be used with general-purpose plastics because of their excellent solvent resistance, low dielectric properties, low surface energy, non-adhesion, weather resistance, and the like. . In many cases, despite the fact that the surface properties of fluororesins are required, most resins are insoluble in solvents and coating is not possible, so products are obtained by cutting, melt molding, etc. Yes,
It has become very expensive.

[0003] Polyvinylidene fluoride is known to be dissolved in a polar solvent such as dimethylformamide at high temperatures, since the solvent is very has limited, also is no charge partial solubility can be used, a uniform and transparent It is difficult to obtain a coating film. Further, since the fluororesin has non-adhesiveness, the adhesiveness to the substrate tends to be insufficient, and in order to improve this, the substrate is roughened or the fluororesin is changed to Na.
/ Etching with naphthalene.

In recent years, fluororesins comprising a copolymer of fluoroolefin and vinyl ether or vinyl ester have been developed and used as coating agents and paints soluble in general-purpose solvents. Because it is a copolymer, solvent resistance, non-stickiness,
Characteristics of the fluorine resin such as a low refractive index did not exactly charged minute.

On the other hand, an example in which a fluorinated polymer having a ring structure in the main chain is obtained by cyclopolymerization of perfluorodiene is described in SPE Trans . , 3,231 (1963) and American Chem. Soc. , Polyme
r Preprints, 7, 1, 112 (1966)
However, there is a problem that the method for synthesizing a polymer under high pressure requires γ-ray irradiation, and the solubility in a solvent is insufficient and only a dilute solution can be obtained. It was not used as a fluororesin solution.

[0006] Even when coating is performed using a solution of such a polymer, adhesion to an inorganic base such as glass, ceramics, silicon, aluminum, copper, silver, stainless steel or an organic base such as plastic or rubber is possible. However, it was not always sufficient and was not suitable for practical use.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to overcome the aforementioned disadvantages of the prior art.

[0008]

The present invention SUMMARY OF] has been made to solve the problems described above, the polymer and at least one coupling group of the fluorine-containing aliphatic ring structure in a closed-Perilla within the molecule An object of the present invention is to provide a fluorine-containing polymer composition for coating, comprising a solvent that dissolves the polymer.

The fluoropolymer in the composition of the present invention has an aliphatic ring structure. For example, Chemical Formula 1, Chemical Formula 2, Chemical Formula 3
Or a compound having a ring structure as shown in Chemical formula 4 (In Chemical formula 1, Chemical formula 2, Chemical formula 3 and Chemical formula 4, k is 0 to 5,
m is 0 to 4, n is 0 to 1, k + m + n is 1 to 6, r ,
p and q are each 0 to 5, r + p + q is 1 to 6, and R is F
Or CF ₃ , R ¹ Is F or CF ₃ , R ² Is F or CF ₃ ).

[0010]

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[0011]

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[0012]

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[0013]

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[0014]Chemical formula 5, chemical 6, chemical 7, chemical 8, chemical 9 or
Is 10Polymers having a ring structure such as
You.HoweverHowever, the content of the present invention is limited to only these.Rena
No.

[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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In the present invention, the polycyclic resin having a specific ring structure
The following two methods are used to produce the mer . However, the book
Invention Lena have limited thereto preparation.

1. By cyclopolymerization

[0023]

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[0024]

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[0025]

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2. Using cyclic monomers

[0027]

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In the above, a polymer having a perfluoroaliphatic ring structure has been exemplified. However, in the present invention, a polymer in which a part of the above-mentioned fluorine atom is substituted by another hydrogen atom or an organic group, or a metathesis is used. Those having a ring structure such as those obtained by polymerization, such as Chemical formulas 15 and 16, can also be mentioned.

[0029]

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[0030]

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The invention polymer having a specific ring structure in is obtained more smoothly and advantageously above such cyclization Polymerization, in particular, has a polymerizable different two polymerizable groups in the molecule one or by number of atoms of a straight portion of the connecting chain connecting these two polymerizable groups used monomer is 2 to 7, even without employing an ultra high-pressure conditions and the large dilution conditions,
Ru obtained allowed to proceed smoothly advantageously cyclic polymerization by suppressing the gelation of the polymer.

As a monomer suitable for cyclization polymerization as described above, first, it is desirable to have two carbon-carbon multiple bonds having different polymerizabilities. Usually, a carbon-carbon double bond is employed. For example, a fluorine-containing monomer that has two multiple bonds that are not symmetrical, has a vinyl group and an allyl group, a vinyl ether group and a vinyl group, a fluorine-containing multiple bond and a hydrocarbon multiple bond, a perfluoro multiple bond and a partially fluorinated multiple bond such as the monomer, and the like.

Second, it is desirable that the straight-chain portion of the connecting chain connecting these two carbon-carbon multiple bonds has 2 to 7 atoms. When the number of atoms in the linear portion of the linking chain is 0 to 1, cyclization polymerization hardly occurs, and the same applies to the case where the number is 8 or more. Usually, the case where the number of atoms is 2 to 5 is preferable. Also, linking chain is not limited to linear, may have a side chain structure or cyclic structure, constituting atoms in addition is not limited to carbon atoms, O, S, contain such heteroatoms N also not good.

Third, those having a fluorine content of 10% by weight or more are desirable. If the fluorine content is too low, the specificity of the fluorine atom is hardly exhibited. Of course, perfluoro monomer is preferably employed.

Specific examples of the specific fluorine-containing monomer include those listed in Chemical formulas 17 and 18.

[0036]

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[0037]

Embedded image CF ₂ = CFOCF ₂ CF = CF ₂ , CF ₂ = CFOCF ₂ CF ₂ CF = CF ₂ , CF ₂ = CFOCF ₂ CF = CH ₂ , CF ₂ = CFOCF ₂ CF (CF ₃ ) CF = CF ₂ , CF ₂ = CFOCF ₂ OCF ₂ CF = CF ₂ , CF ₂ = CFOCF ₂ CF ₂ CH = CH ₂ , CF ₂ = CFOCF ₂ (CH ₂ ) _x NHCOCH = CH ₂ (where x is an integer of 0 to 3) , CF ₂ = CFOCF ₂ CF ₂ C (CF ₃ ) = CF ₂ , CF ₂ = CFO (CF ₂ ) ₂ CF = CFCF ₃ , CF ₂ = CFOCF ₂ CF ₂ OCF = CFCl, CF ₂ = CFCONHC (CF ₃ ) ₂ CH ₂ CH = CH ₂ , CF ₂ = CFCF ₂ CF ₂ CH = CH ₂ , CF ₂ = CFCF ₂ CF (CF ₃ ) CH = CH ₂ , CF ₂ = CHOCH ₂ CH ₂ CF = CF ₂ , CH ₂ = CFCOOCH ₂ CH ₂ CF = CF ₂ , CH ₂ = C (CF ₃ ) COOCH ₂ CH ₂ CF = CF ₂ , CH ₂ = CHOCH ₂ CH ₂ CF ₂ CF = CF ₂ , CH ₂ = CFCOOCH (CF ₃ ) CH ₂ CF = CF ₂

[0038] The present invention Contact Itewa, CF ₂ = CFO- made having one vinyl ether group polymerization reactivity, cyclic polymerization of, in terms of such gelling inhibition is preferably used, in particular,
Perfluoroallyl vinyl ether (CF ₂ ＣＦCFOC
F ₂ CF = CF ₂₎ and perfluoro butenyl vinyl ether _{(CF 2 = CFOCF 2 CF 2} CF = CF 2)
Is a preferred example.

The above-mentioned monomer components may be used alone or in combination of two or more, and may be further used in combination with other copolymer components so as not to impair the essence of these components. No problem .

The other monomer to be copolymerized is not particularly limited as long as it is a monomer having radical polymerizability, and a wide range of fluorine-containing, hydrocarbon-based and the like can be exemplified. Of course, these other are monomers may be allowed to the specific monomer and radical copolymerization capable of introducing cyclic structures polymerization alone, rows above copolymerization reaction in combination of two or more appropriate Align also good.

[0041] The present invention your information, it is usually desirable to select the fluorinated monomers such as fluoroolefins, fluoroalkyl vinyl ether as the other monomers. For example, tetrafluoroethylene, perfluoro (methyl vinyl ether), perfluoro (propyl vinyl ether), or carboxymethyl like perfluorovinyl ether containing such functional groups hexyl group and Sul e groups are preferred embodiments, vinylidene fluoride , Vinyl fluoride, chlorotrifluoroethylene and the like.

As the copolymer composition, the composition of the cyclic structure is preferably 20% or more, in order to make use of the characteristics of the specific fluorinated aliphatic ring structure aimed at in the present invention, and preferably 40 % or more.
% Is more preferable.

Further, since the fluoropolymer in the composition of the present invention has a coupling group, a coating film strongly adhered to the substrate can be obtained without impairing properties such as transparency.
Simply adding a coupling agent to a solution of a polymer having a fluorinated aliphatic ring structure does not sufficiently improve the adhesion. In addition, the method of treating the surface of the base material with a coupling agent is not necessarily sufficient in terms of durability such as water resistance, and the performance of a polymer having a fluorinated aliphatic ring structure such as a low dielectric constant is not sufficient. It may not be fully available.

The coupling group in the present invention is -M
R ¹ _na R ² _a [M is Si, Ti, selected from Z r Contact and Al, R ¹ is a halogen atom, a hydroxyl group, an amino group, aminoxy group, a ketoxime group, an amido group and -OR ³ (R
³ is a monovalent organic group, R ² is a monovalent organic group, n is 2 or 3, a is selected from 0, 1, and 2 (however, when n is 2, a is selected from 0 and 1)]]. Such coupling groups are considered to excellent adhesion for containing highly reactive groups with an inorganic base that -MR ¹ is obtained.

[0045] Here, preferred examples of R ¹ include chlorine Hara
Child, a halogen atom such as fluorine atom, a hydroxyl group, an alkoxy group, an alkoxy-substituted alkoxy group, a hydroxyalkyl group, an acyloxy group, aminoxy group, a ketoxime group, an amino group, an amide group and the like.

In particular, considering the stability of the composition, the reactivity with the inorganic substrate, the influence of the reaction by-products, etc.
A degree of alkoxy groups is preferred. When the composition has such an alkoxy group, the stability of the composition is good, and by-products generated during coating have almost no adverse effect. Further, as long as R ¹ is within the above-mentioned range, two or more kinds of R ¹ bonded to one M may be different.

As M , Si is particularly preferably used because it exhibits extremely strong adhesiveness to the inorganic substrate without impairing the transparency.

[0048] Further, although R ² is a monovalent organic group, -M
R ² need not be reactive. Such <br/> alkyl groups as R ^2, allyl group and the like.
Such a group is preferably a group having about 1 to 10 carbon atoms.

[0049] As such coupling groups, trimethoxysilyl group, triethoxysilyl group, methyldimethoxysilyl group, triethoxy titanium group, and etc. tributoxy zirconium group.

As a method for introducing a coupling group into a fluoropolymer, a fluoropolymer having a reactive group such as a carboxyl group, an alkoxycarbonyl group, or a hydroxyl group may be added to X-MR ¹ _na R ² _a ( In the formula, X is a chlorine atom, an amino group, an aminoalkyl group, a ureido group, a glycidoxy group,
Epoxy group, isocyanate group, an alkyl or vinyl group having at least one functional atom or group of acryloyl group, M, R ^1, R ^2, n,
a is the same as described above. ) In and a method of reacting a compound I Table.

Here, the fluoropolymer having a reactive group can be produced in the same manner as in the production of the fluoropolymer having a fluorinated ring structure described above. That is, fluoroaliphatic by the polymerization was usually an organic peroxy compound initiator
By producing a fluorine-containing polymer having a family ring structure, -CH ₂ COOH, fluorine-containing polymer having a reactive group such as -CH ₂ COOCH ₃ obtained at the end.

When producing a fluorinated polymer having a fluorinated aliphatic ring structure, CF ₂ ＣＦCFOCF ₂ C
The reactive group can be positively introduced by copolymerizing a monomer having a reactive group such as F (CF ₃ ) O— (CF ₂ ) ₃ —COOCH ₃ .

[0053] coupling group is introduced by reacting the compound having such reactive fluorine-containing polymer coupling group Ki each described above with a group. This reaction is preferably performed at a temperature of about 10 to 50 ° C. for about 2 to 5 hours.

When producing a fluorine-containing polymer having a fluorine-containing aliphatic ring structure, it is preferable to copolymerize a monomer having a coupling group with a radical polymerizable group such as vinyltrimethoxysilane and vinyltriethoxysilane. Can introduce a coupling group.

When the degree of introduction of the coupling group is too small, the effect of improving the adhesion and the like is too small,
If the amount is too large, the intrinsic properties of the polymer having a fluorinated aliphatic ring structure may be reduced, or the stability of the composition may be deteriorated to cause gelation. Therefore, it is preferable to appropriately select the amount of the coupling group to be introduced depending on the purpose. In general, the adhesion is improved if one coupling group is introduced per polymer molecule.

Further, even if all of the polymers having a fluorinated aliphatic ring structure present in the composition are not polymers having a coupling group, the adhesion is improved. For example, if the polymer having a fluorinated aliphatic ring structure contained in the composition has about 1/20 (weight ratio) of a polymer having at least one coupling group, the adhesion is sufficiently improved. .

The polymer having a fluorinated aliphatic ring structure has an intrinsic viscosity (hereinafter abbreviated as [η]) of 0.1 to 0.1 as measured at 30 ° C. in perfluoro (2-butyltetrahydrofuran). 1.5 dl / g, especially 0.1 dl / g
Those having a density of 2 to 0.35 dl / g are preferably employed.
Mechanical strength small again ones at room temperature or high temperature [eta] is undesirably low. In addition, those having a large [η] have a high viscosity when used as a coating composition, making the coating operation difficult.

In the present invention, examples of the solvent for dissolving the polymer having a fluorinated aliphatic ring structure include the following.

[0059] polyfluoro aromatic compound perfluoro benzene, perfluorotripropylamine, perfluorotributylamine, tri scan (polyfluoroalkyl) such perfluorotripentylamine amine, perfluorohexane, perfluorooctane, perfluoro fluoro decane, (perfluoro--n- octyl) ethane, perfluoro (2,3,5-trimethylene Ruhe hexane) like poly fluoroalkanes, (perfluoro--n- octyl)
Polyfluoroalkenes such as ethylene and hexafluoropropylene trimer; polyfluorocycloalkanes such as perfluorocyclohexane and perfluorodecalin; and polyfluorocyclic ethers such as perfluoro (2-butyl-tetrahydrofuran).

[0060] Further, as a solvent, it may be used in the form of alone or in combination with solvents Ki Each of the above. Further, chlorofluorocarbons such as trichlorotrifluoroethane and dichlorodifluoromethane, hydrochlorofluorocarbons such as dichlorotetrafluoropropane, low molecular weight fluorinated polyethers, hydrocarbons, alcohols and other organic solvents may be used as a mixed solvent.

When a solvent having a high boiling point is used as the solvent, the evaporation rate is reduced, and a clean coating film can be obtained. On the other hand, when a solvent having a low boiling point is used, the viscosity of the composition becomes low, and the coating workability is improved.

Various solvents can be selected according to the purpose. Usually, those having a boiling point of 50 ° C. or higher, particularly 150 ° C. or higher are suitably employed. The upper limit of the boiling point of the solvent used is not particularly limited, but is usually about 250 ° C. If the boiling point is too high, it is not suitable for coating.

In the composition of the present invention, if the concentration of the polymer having a fluorinated aliphatic ring structure is 0.1% by weight or more, a coating film can be formed. Here, it is not necessary that all of the polymers having a fluorinated aliphatic ring structure be polymers having a coupling group. As described above, 1/20 (weight ratio) thereof, preferably 1/1.
If about 0 is a polymer having a coupling group, good adhesion is achieved. The concentration of the polymer having a fluorinated aliphatic ring structure used here and hereinafter is the total concentration of the polymer having no coupling group and the polymer having the coupling group.

Further, it is possible to form a thin film by decreasing the concentration of the polymer having a fluorinated aliphatic ring structure, and to form a thick film by increasing the concentration. The concentration is appropriately selected depending on the purpose,
Usually, it is selected from the range of 0.1 to 30% by weight, preferably 0.5 to 20% by weight.

[0065] In the compositions of the present invention, an acidic substance and a carboxyl group such as hydrofluoric acid contained in the composition, sul
It is preferable that the number of acidic groups such as e-group is as small as possible. When these large amount of presence, your electrical properties of the coating film
Good beauty water resistance may decrease, or invite corrosion of the coated article surface. Also, if the acidic substance and the acidic group is a large amount present, decreases the stability of the coupling groups, and in the introduction reaction of the coupling groups, the preparation of the composition, increase in viscosity during storage, the gel Strong tendency to occur.

[0066] Hereinafter the acidic substance Oyo beauty acidic group 10 ppm, in particular be in 5ppm or less preferred in enhancing the stability of the composition. Oyo acidic substances which may be present in the composition beauty as the acidic group hydrofluoric acid, an inorganic acid such as hydrochloric acid,
Polymerization initiator, an organic acid derived from the surfactant, etc., a carboxyl group attached to the polymer, such as e group.
Therefore, as the reactive group in the above-mentioned polymer, an alkoxycarbonyl group is preferable to a carboxyl group.

For the purpose of improving the stability of the composition,
It is also possible to add an acid acceptor such as a trialkylamine.

Coating using the composition of the present invention includes brushing, doctor blade, bar coater,
Any of the usual coating methods such as application using a flow coater, spray coating, spin coating and the like can be employed. In particular, when smoothness is required, it is preferable to employ spin coating.

The article formed with the coating layer of the fluoropolymer composition for coating of the present invention has excellent properties such as low dielectric constant, low reflectivity, transparency and chemical resistance.

The fluorine-containing polymer composition for coating of the present invention can be used as an optical fiber clad material, a lens, a mirror, a solar cell, an optical disk, a touch panel, a semiconductor element, a hybrid IC, a liquid crystal cell, a printed circuit board, a photosensitive drum, a film capacitor, a glass. Optical coatings such as windows and various films, protective coatings in the electrical field, syringes, pipettes,
Thermometer, beaker such, a petri dish, the medical field, the field of chemistry, such as a graduated cylinder, other solder mask, solder resist, rubber, protection of plastic, weather, anti-fouling coat, fiber, protective coat of cloth 帛, sealant of the antifouling coat, As an IC encapsulant, it can be applied to uses such as rust preventive paints, resin adhesion inhibitors, and ink adhesion inhibitors. Among them, it can be advantageously used particularly for applications requiring transparency, such as an optical fiber clad material and an optical window coating material.

Further, it can be advantageously used as an interlayer insulating film and a protective film in a semiconductor element and an integrated circuit device.
It is possible to obtain a semiconductor device integrated circuit device having a high response speed and a small number of malfunctions, utilizing characteristics such as low water absorption, low dielectric constant, and high heat resistance of a fluororesin.

[0072]

EXAMPLES Next, Synthesis Examples (Examples 1 to 3) of the present invention , Examples
(Examples 4 to 8 and 10 to 15), Comparative Examples (Examples 9 and 16)
Specifically described further on, this description is not intended to limit the present invention.

[0073] Example 1 (Synthesis of fluorine-containing Polymerization body A-1) 35 g of perfluoro (allyl vinyl ether), trichlorotrifluoroethane 5g (hereinafter, abbreviated as R113), 150 g of ion-exchanged water, and 35 mg of (C ₃ F ₇ COO) ₂ was used as a polymerization initiator in an inner volume of 2
It was placed in a 00 ml pressure-resistant glass autoclave. After the inside of the system was replaced with nitrogen three times, suspension polymerization was performed at 26 ° C. for 23 hours. As a result, 28 g of a polymer was obtained.

When the infrared absorption spectrum of this polymer was measured, it was found that the 1
There was no absorption around 660 cm ^-1 and 1840 cm ^-1 .
Further, absorption of -COOH was observed at 1810 cm ^-1 . ¹⁹ F dissolving the polymer in perfluorobenzene -
When the NMR spectrum was measured, a spectrum showing the following repeating structure was obtained.

[0075]

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Next, the compound present in the fluoropolymer is
It was replaced by COOH to -COOCH _3. This polymer 3.
5 g of perfluoro (2-butyltetrahydrofuran)
0.1 g of N- ( β-aminoethyl ) -γ-aminopropyltrimethoxysilane was added to the solution dissolved in 46.5 g.
Was added. The system was replaced with N ₂ and stirred at room temperature for 3 hours to obtain a fluoropolymer A-1.

When the infrared absorption spectrum of the obtained polymer was measured, it was found that -C existing in the original fluoropolymer was present.
No absorption of OOCH ₃ at 1800 cm ⁻¹
-Absorption was observed at 1730 cm ^-1 . Also, [η]
Was 0.32 dl / g.

Example 2 (Synthesis of Fluoropolymer A-2) Instead of N- ( β-aminoethyl ) -γ-aminopropyltrimethoxysilane in Example 1, γ -glycidoxypropyltrimethoxysilane was used. Except for the above, a fluorine-containing polymer A-2 was obtained in the same manner as in Example 1. [Η] of this polymer
Was 0.32 dl / g.

Example 3 (Synthesis of Fluoropolymers A-3 and A-4 ) 50 g of perfluoro ( butenyl vinyl ether ) , R
113 7 g of, 210g of ion-exchanged water, methanol 30g and diisopropyl peroxydicarbonate carbonate Ne as a polymerization initiator - bets 130 mg, was placed in a pressure glass autoclave having an internal volume of 300 ml. After purging the system with nitrogen three times, suspension polymerization was performed at 40 ° C. for 23 hours. As a result, 40 g of polymer A-3 was obtained. [Η] of this polymer was 0.30 dl / g.

When the infrared absorption spectrum of this polymer was measured, it was found that the 1
There was no absorption around 660 cm ^-1 and 1840 cm ^-1 .
Additionally, ¹⁹ F - Toko filtration Example 1 measured NMR spectra
As in the above, a spectrum corresponding to the ring structure was obtained.

Next, the -C present in the fluoropolymer is
It was replaced by OOH to -COOCH _3. This polymer 4g was dissolved in perfluoro (tributylamine) 58 g solution was heated at 50 ° C. 10 hours resulted in the removal of HF, to afford the free fluorine ion concentration 1ppm following solutions. Γ
- aminopropyltriethoxysilane 0.05g was added, and the system was replaced with nitrogen, to give a fluoropolymer A-4 and 3 hours stirred at room temperature.

[0082] The infrared absorption spectrum of the obtained polymer was measured, 1800c due to -COOCH ₃
The absorption at m ^-1 is reduced by 20% compared to the original fluoropolymer, and the absorption of -CONH- is 1,730 cm ^-1.
Was recognized.

The polymer A-3 had a 10% thermal decomposition temperature of 475 ° C., a water absorption of 0.01% or less, a dielectric constant at 23 ° C. of 2.2 (60 Hz to 1 MHz), and a volume resistance of 10 ^17. Ω
Cm or more, [η] was 0.30 dl / g.

Examples 4 to 8 Fluoropolymers A-1 and A-2 synthesized in Examples 1 and 2 are shown in Table 1 below. [ The numbers in the table are parts by weight, B-1 is perfluoro (2-butyltetrahydrofuran) ), B-2 is perfluorotributylamine ] .

Next, using these fluoropolymer compositions, a glass plate was coated with a bar coater and then dried by heating to obtain a transparent coating film having a thickness of 5 μm .

The adhesion of the coating film to glass was evaluated by a grid test. The adhesion after immersion in boiling water for 2 hours was evaluated in the same manner. The results are shown in Table 2 [ The numbers in the table are grid test (JIS D0202)
4.15) Maximum number of remaining coating films: 10
0, minimum 0 ] .

[0087] EXAMPLE 9 fluoropolymer A-1 of Synthesis N-(beta-aminoethyl)-.gamma.-aminopropyltrimethoxysilane synthesized without adding the fluorine-containing polymer of a fluorine-containing polymer A
The same procedure as in Example 4 was performed, except that -1 was used instead .

[0088]

[Table 1]

[0089]

[Table 2]

[0090] EXAMPLE 10 The fluorine-containing polymer composition shown in (optical fiber clad material) Table 3 (B-2 is a perfluorotributylamine) was applied to the periphery of the silica fibers, the result of applying the optical fiber cladding material (fiber Are shown in Table 3.

[0091]

[Table 3]

[0092] fluorine-containing polymer used in Example 10, exhibit excellent properties as an optical fiber cladding full Tsu containing content low high for the refractive index, also has high transparency. Furthermore, in order to excellent adhesion between the core material, even a small transmission loss due to interfacial peeling.

Examples 11 to 15 Fluoropolymers A-1 and A synthesized in Examples 1, 2 and 3
Using -2 and A- 4, a composition was prepared according to Table 4 (the numbers in the table are parts by weight, and the solvent was perfluorotributylamine). These compositions were stable with no increase in viscosity observed after storage at 50 ° C. for 10 hours.

Next, using these fluoropolymer compositions, spin coating was performed on various base plates at 2000 rpm, and drying was performed at 80 to 180 ° C. for 1 hour.
A smooth coating film was obtained. As a substrate, glass, silicon,
A silicon nitride film and aluminum were used. Next, a moisture resistance test of the adhesion of the obtained coating film to the substrate was performed.

The evaluation of adhesiveness was made according to JIS D0202.
Performed according to No. 15, and the number of squares remaining intact on the substrate was counted. The evaluation of the adhesion was performed at the initial stage and after the moisture resistance test. Moisture resistance test (pressure cooker test: PCT)
The conditions were 125 ° C. and 2.3 atm. Tables 5 to 8 show the test results. The numbers in the table represent the number of squares remaining intact.

Example 16 Using the fluoropolymer A-3 synthesized in Example 3, a composition shown in Table 4 (the numbers in the table are parts by weight, and the solvent was perfluorotributylamine) was prepared. Then, Example 11
In the same manner as in the above, the adhesiveness to the substrate was evaluated. Table 5
8 shows the test results.

[0097]

[Table 4]

[0098]

[Table 5]

[0099]

[Table 6]

[0100]

[Table 7]

[0101]

[Table 8]

[0102]

The fluorine-containing polymer composition of the present invention has excellent solvent resistance, chemical resistance, low surface energy, low refractive index, low water absorption, low dielectric constant, high heat resistance, etc. This has an effect that a coating film having excellent essential properties, extremely high transparency, and strong adhesion to a substrate can be easily provided.

──────────────────────────────────────────────────続 き Continuation of front page (51) Int.Cl. ⁷ Identification code FI C09D 147/00 C09D 165/00 165/00 201/02 201/02 G02B 6/00 386 G02B 6/00 386 C03C 25/02 B (72) Inventor Masao Unoki 1150 Hazawa-cho, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture Asahi Glass Co., Ltd.Examiner of the Central Research Laboratory Masakatsu Kondo (56) References JP-A-10-152631 (JP, A) (JP, A) JP-A-62-199612 (JP, A) JP-A-62-101625 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 129/10 C09D 127 / 12 C09D 129/14 C09D 145/00 C09D 147/00 C09D 165/00 CA (STN) CAOLD (STN) REGISTRY (STN) WPIDS (STN)

Claims (8)

(57) [Claims] 1. A fluorine-containing aliphatic ring structure of polymer and the coating fluorinated polymer composition comprising a solvent which dissolves the polymer having at least one coupling group in the molecule of organic perilla. 2. A polymer having a fluorinated aliphatic ring structure and
And a solvent that dissolves the polymer.
At least 1/20 (weight) of the polymer having an aromatic ring structure
Ratio) has at least one coupling group in the molecule.
Fluoropolymer composition for coating which is a polymer having
object. 3. A polymer having a fluorinated aliphatic ring structure,
3. The polymer according to claim 1, which is a polymer having a ring structure in a main chain.
The fluoropolymer composition for coating according to the above. 4. A coupling group is -MR ¹ _na R ² _a [however, M is Si, Ti, selected from Z r Contact and Al, R ¹
Is a halogen atom, a hydroxyl group, an amino group, an aminooxy group,
Selected from a ketoxime group, an amide group and —OR ³ (R ³ is a monovalent organic group), R ² is a monovalent organic group, n is 2 or 3, and a is 0, 1, and 2. (Where n is 2, a is selected from 0 and 1)]. The fluorine-containing polymer composition for coating according to claim 1, 2 or 3. 5. The fluoropolymer composition for coating according to claim 1 , wherein the solvent is a solvent having a boiling point of 50 to 250 ° C. 6. acidic substance and an acid group contained in the composition is 10ppm or less claims 1-5 for coating the fluorine-containing polymer composition according <br/> to any one of. 7. An article having a coating layer of the fluoropolymer composition for coating according to any one of claims 1 to 6 . 8. Koti according to any one of claims 1 to 6
An optical fiber having a cladding layer made of a fluoropolymer composition for coating.