JPH11188820A - Lining material and belt material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To render resistivity superior against separation between it and reinforcement fiber cloth and base material by specifying each tensile strength of a layer consisting of a fluorine-containing copolymer having a plurality of specific repetition units occupied at a specific rate, and a composite sheet surface consisting of glass woven fabric lying adjacent thereto. SOLUTION: A fluorine-containing copolymer is constituted of a repetition unit of formula I and a repetition unit of formula II (in the formula, X is a hydrogen atom or halogen atom, (m) is integers of 0 or 1, and (n) is an integral number of 1 or more). Herein, respective repetition units are made to have 94-60 mol.% and 6-40 mol.% occupied in terms of the total of both repetition units. Also, glass woven fabric is provided on the layer of a fluorine-containing copolymer or adjacent thereto. In addition, the tensile strength is made at least 25 kg/cm in a direction where tensile strength is minimum on the composite sheet surface. In this manner, resistivity can be done excellently with respect to separation between it and reinforcement glass woven fabric or base material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lining material and a belt material comprising a fluorinated copolymer layer and a glass woven fabric. More specifically, the present invention relates to a lining material having a high peeling resistance, in which a layer of a fluorine-containing copolymer and a glass woven fabric are strongly bonded, and a belt material having excellent durability.

[0002]

2. Description of the Related Art Conventionally, heat resistance, which is a characteristic of fluorine resin,
Utilizing chemical resistance, surface properties, antifouling properties, etc., for example, a composite material obtained by compounding a fiber material with polytetrafluoroethylene (PTFE) or a copolymer of tetrafluoroethylene and perfluoropropylvinylether (PFA). It has been used as a lining material. However, since PTFE and PFA are hard materials themselves, they have a drawback that when they are repeatedly exposed to heat, they peel off from the fiber material or peel off from the substrate to which the lining material is bonded. Also, when the above-described composite material is used as a belt material, it is exposed to heat generated by repeated bending or repeated frictional heat, and thus has a drawback of causing the same problem as the lining material.

[0003]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a lining material and a belt material using a specific fluororesin which have solved the above-mentioned disadvantages. Still another object of the present invention is to provide a lining material having excellent resistance to peeling from a reinforcing fiber cloth or a base material and a belt material having excellent durability. Still other objects and advantages of the present invention will become apparent from the following description.

[0004]

According to the present invention, the above objects and advantages of the present invention are as follows: (A) The following formula (1)

[0005]

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A repeating unit represented by the following formula and the following formula (2)

[0007]

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Wherein X is a hydrogen atom or a halogen atom, m is 0 or 1, and n is an integer of 1 or more, and is a repeating unit represented by the formula (1). A layer comprising a fluorine-containing copolymer in which the unit and the repeating unit of the formula (2) occupy 94 to 60 mol% and 6 to 40 mol%, respectively, based on the sum of both repeating units; and (B) a glass woven fabric; Here, the glass woven fabric is present adjacent to the layer (A) made of the above-mentioned fluorocopolymer and has a tensile strength of at least 25 kg / in the direction where the tensile strength is minimum on the composite sheet surface.
cm, which is achieved by a lining material or a belt material characterized by being composed of a composite sheet.

The fluorine-containing copolymer (A) used in the present invention comprises a repeating unit represented by the formula (1) and a compound represented by the formula (2):
And a repeating unit represented by

In the monomer unit represented by the above formula (1), X
Is a hydrogen atom or a halogen atom. Fluorine, chlorine,
Halogen atoms of bromine and iodine are employed. Also,
m is 0 or 1, and n is an integer of 1 or more. N is preferably in the range of 1 to 12, more preferably 1 to 8, for the reason that the fluorocopolymer in the present invention is easily produced, that is, for ease of polymerization.

The composition of each monomer unit represented by the above formulas (1) and (2) is such that the content of the monomer unit represented by the above formula (1) is 60 to 94 mol%. In order to improve the melt moldability of the copolymer, preferably 70 to
90 mol%, and the amount of the monomer unit represented by the formula (2) is 6 to 40 mol%, preferably 10 to 30 mol%.

The fluorinated copolymer used in the present invention is
The monomer units represented by the formulas (1) and (2) are randomly arranged. Since the fluorine-containing copolymer in the present invention is insoluble in various solvents, its molecular weight cannot be determined by ordinary means. However, the melt viscosity of the fluorinated copolymer in the present invention depends on the content and molecular weight of the monomer unit represented by the formula (2),
The molecular weight can be estimated from the melt viscosity.

When the amount of the monomer unit represented by the general formula (2) is in the range of 6 mol% to 10 mol%, the temperature is 350 ° C.
When the above-mentioned monomer unit is in the range of more than 10 mol% and 40 mol% or less, the melt viscosity measured at 200 ° C. becomes 10 ² to 10 ⁷ poise.
The range of ² to 10 ⁷ poise. In the fluorine-containing copolymer used in the present invention, those having a monomer unit represented by the general formula (2) in the range of 6 mol% to 10 mol% have a melting point of 290 to 325 ° C., preferably It is in the range of 290-320 ° C. The fluorine-containing copolymer having the above composition and used in the present invention has a thermal decomposition temperature in the range of 370 to 410 ° C.

The fluorine-containing copolymer of the present invention in which the monomer unit represented by the general formula (2) is 10 to 40 mol% does not show a clear melting point. Further, the fluorocopolymer of the present invention having the above composition has good transmittance of visible to ultraviolet light, and generally has an absorbance of light of 250 nm of 0.4 or less.

The fluorinated copolymer of the present invention has an infrared absorption spectrum (hereinafter referred to as IR) of 29.
-CH ₂ -group around 90 cm ^-1 , -900 cm ^-1
CH ₂ OCF ₂ — group, and —CF at around 1200 cm ⁻¹
_It has an absorption band based on a _2- group, and by confirming and quantifying these absorption bands, it is based on the fluorine-containing vinyl ether represented by the formula (2) as the fluorine-containing copolymer in the present invention. The content of monomer units can be determined.

Further, the structure of the side chain can be confirmed from a fragment generated by decomposition of the side chain by pyrolysis gas chromatography / mass spectrometry (hereinafter referred to as Py-GC / MS). For example, for the fluorinated copolymer used in Example 1, a fragment derived from a pentafluoropropyl group can be detected from Py-GC / MS. The fluorinated copolymer in the present invention may be produced by any method, but is particularly preferably produced by the following method.

That is, tetrafluoroethylene and the following formula (3): CF ₂ ＣＦCFO (CH ₂ ) _m (CF ₂ ) _n X (3) where m, n and X are defined above. This is a method in which a fluorine-containing vinyl ether represented by the following formula is dissolved in an organic solvent and copolymerized in the presence of a radical polymerization initiator.

Specific examples of the fluorinated vinyl ether represented by the above formula (2) used in the present invention are as follows. CF ₂ = CFOCH ₂ CF ₃ , CF ₂ = CFO
CH ₂ CF ₂ CF ₃ , CF ₂ ＣＦCFOCH ₂ CF ₂ CF ₂ H,
CF ₂ ＣＦCFOCH ₂ (CF ₂ ) ₂ CF ₃ , CF ₂ ＣＦCFOC
H ₂ (CF ₂ ) ₃ CF ₃ , CF ₂ ＣＦCFOCH ₂ (CF ₂ ) ₄ C
_{F 3, CF 2 = CFOCH 2} (CF 2) 5 CF 3, CF 2 = C
FOCH ₂ (CF ₂ ) ₆ CF ₃ , CF ₂ ＣＦCFOCH ₂ (CF
₂ ) ₇ CF ₃ , CF ₂ ＣＦCFOCH ₂ (CF ₂ ) Cl, CF ₂
ＣＦCFOCH ₂ (CF ₂ ) Br, CF ₂ ＣＦCFOCH ₂ CF
₂ CF ₂ Br, CF ₂ = CFOCH ₂ CF ₂ CF ₂ Cl, CF
₂ = CFOCH ₂ (CF ₂ ) ₂ CF ₂ Br, CF ₂ = CFOC
H ₂ (CF ₂ ) ₂ CF ₂ Cl, CF ₂ ＣＦCFOCH ₂ (C
F ₂ ) ₃ CF ₂ Br, CF ₂ ＣＦCFOCH ₂ (CF ₂ ) ₃ CF ₂
Cl or the like.

Next, copolymerization of the above-mentioned fluorine-containing vinyl ether and tetrafluoroethylene is carried out. As a copolymerization method, a solution polymer obtained by dissolving the above two monomers in an organic solvent is employed. As the solution polymerization method, the method disclosed in JP-A-2-276808 can be employed as it is.

In this method, by controlling the monomer composition to be substantially constant, the composition of the monomer units in the obtained copolymer can be made substantially the same as the monomer composition. As a method of making the monomer composition during polymerization almost constant, a method of performing polymerization with the monomer composition charged before polymerization without supplying the monomer during polymerization, or of the same composition as the monomer composition charged before polymerization is used. A method of supplying a monomer during polymerization is employed. Furthermore, the fluorinated copolymer obtained by the above method is reacted with a fluorinating agent such as fluorine gas,
A fluorine-containing copolymer in which at least a part of the hydrogen atoms present in the molecule has been replaced by fluorine atoms is also suitably used in the present invention.

The glass woven fabric (B) used in the present invention may be a woven fabric or a non-woven fabric. The woven fabric may be appropriately selected depending on the application, and examples thereof include plain weave, satin weave, twill weave, and imitation weave.

The lining material and belt material of the present invention are:
The layer of the above-mentioned fluorocopolymer (A) is present on at least one surface of the glass woven fabric, that is, on one or both surfaces, in a state of being bonded to the glass woven fabric. Further, if necessary depending on the application, a multilayer structure in which the fluorocopolymer (A) and the glass woven fabric (B) are alternately laminated and compounded may be used.
The lining material and the belt material of the present invention have a tensile strength of at least 25 kg / cm in a direction having a minimum tensile strength on the surface of each material. By having such a tensile strength, it is advantageously used as each of the above materials. The tensile strength is preferably at least 40 kg / cm, more preferably at least 65 kg / cm.
The lining material and the belt material of the present invention further include a JI
The flexural modulus measured according to SK7203 is preferably 5,000 kgf / cm ² or less, more preferably 4,000 kgf / cm ² or less, and particularly preferably 3,50 kgf / cm ² or less.
0 kgf / cm ² or less. The lining material and belt material of the present invention preferably have a thickness of, for example, 0.2 to 10 mm and 0.2 to 5 mm, respectively.

The lining material and the belt material of the present invention are:
For example, a film or sheet of the fluorocopolymer of the present invention is prepared, and a glass woven fabric is sandwiched between two of them, or one of them is placed on a glass woven fabric, and then heated or pressurized or heated. A method in which the fluorinated copolymer is melt-extruded and laminated on a glass woven fabric, and then heated and pressed as necessary. Further, a multilayer structure can be produced by repeating these methods. The heating temperature and pressurizing pressure depend on the type of the fluorinated copolymer or glass woven fabric used,
Although it is difficult to unconditionally define the lining material to be obtained, the thickness of the belt material, etc., generally, the heating temperature is 150 to 400 ° C., and the pressure is 1 to 100 kg.
/ Cm ² .

The lining material and belt material of the present invention have the inherent chemical resistance and weather resistance of the fluorinated copolymer, and have the excellent strength as described above. It can be advantageously used as a lining for manufacturing equipment and pipes, and also as a belt material in applications in which it comes into direct contact with various chemicals or in food-related applications where contamination is less likely.

Hereinafter, the present invention will be described in detail with reference to examples. The present invention is not limited by such embodiments.

[0026]

EXAMPLE 1 A glass woven fabric having a thickness of about 0.4 mm was obtained by copolymerizing tetrafluoroethylene and 2,2,3,3,3-pentafluoropropyltrifluorovinyl ether on both sides.
It was sandwiched between a film having a thickness of 0.1 mm made of a fluorine-containing resin having 3.8 mol% of a monomer derived from 2,2,3,3,3-pentafluoropropyltrifluorovinylether and heated at 270 ° C. Thereafter, the resultant was adhered under pressure at 15 kg / cm ² to produce a composite film. The tensile strength of the composite membrane is 110 kg / cm in one direction and 140 k / cm in the orthogonal direction.
g / cm ² . The flexural modulus is 3200 kg /
cm ² . A belt was formed by fusing both ends of the composite film, and a heating / cooling cycle test was performed at 0 ° C. to 150 ° C. while applying a tensile force. After repeating 1,000 times, no separation between the substrate and the resin was observed.

Example 2 On one side of a glass woven fabric having a thickness of about 0.8 mm, tetrafluorotetrafluoroethylene having monomer units derived from 1,2,3,3-tetrafluoropropyltrifluorovinylether was used. A composite film having a thickness of 2 mm was manufactured in the same manner as in Example 1 except that a copolymer of ethylene and 2,2,3,3-tetrafluoropropyltrifluorovinyl ether was fused. The tensile strength of the composite membrane was 800 in both orthogonal directions.
kg / cm, and the flexural modulus is 3400 kg / cm ²
Met. The glass woven fabric side of the composite film was sandblasted in advance using an epoxy adhesive to a thickness of about 3 mm.
Glued to the iron plate. Then, the heating / cooling cycle test at 0 to 150 ° C. was repeated 1000 times, but no peeling of the composite film and the iron plate was observed.

[0028]

The lining material of the present invention exhibits excellent resistance to peeling from a reinforcing glass woven fabric or a base material, and the belt material exhibits excellent durability.

Claims (1)

[Claims] (A) The following formula (1): And a repeating unit represented by the following formula (2): Wherein X is a hydrogen atom or a halogen atom, m is 0 or 1, and n is an integer of 1 or more, and the repeating unit of the above formula (1) and the above The repeating unit of the formula (2) is 94 to 60 mol% and 6 to 60 mol%, respectively, based on the sum of both repeating units.
A layer comprising a fluorine-containing copolymer occupying 40 mol%, and (B) a glass woven fabric, wherein the glass woven fabric is present adjacent to the layer (A) comprising the fluorine-containing copolymer, and The tensile strength is at least 25 kg / cm in a direction having the minimum tensile strength on the composite sheet surface;
A lining material or belt material comprising a composite sheet.