WO2020204081A1 - Multilayer body - Google Patents

Abstract

The present invention provides a multilayer body which has excellent alkali resistance and excellent interlayer adhesion at high temperatures.　A multilayer body which comprises a first crosslinked layer that contains a fluorine-containing polymer and a second crosslinked layer that contains a non-fluorine polymer, while optionally having a thin film, and which is configured such that the fluorine-containing polymer is composed of a copolymer that has a unit based on tetrafluoroethylene and a unit based on propylene or a copolymer that has a unit based on tetrafluoroethylene and a unit based on perfluoro(alkyl vinyl ether). With respect to the image of a cross-section of this multilayer body, said cross-section being perpendicular to the lamination surface of the multilayer body, the heights of recesses and projections of the line that is formed by the lamination surface of the multilayer body are from 3 μm to 40 μm; and if a T type peel test is performed at 100-200°C in accordance with JIS K6854-3 (1999), a material break occurs in the first crosslinked layer or in the second crosslinked layer.

Description

Laminate

The present invention relates to a laminate.

Fluorine rubber has excellent heat resistance, chemical resistance, oil resistance, weather resistance, etc., and is therefore suitable for use in harsh environments where general-purpose rubber cannot be applied.
Examples of the fluororubber include a crosslinked product of a copolymer having a unit based on vinylidene fluoride and a unit based on hexafluoropropylene (hereinafter, also referred to as FKM), a unit based on tetrafluoroethylene and a unit based on propylene. Cross-linked products of copolymers (hereinafter, also referred to as FEPM), cross-linked products of copolymers having units based on tetrafluoroethylene and units based on perfluoro (alkyl vinyl ether) (hereinafter, also referred to as FFKM), etc. are known. Has been done.

Since fluorine rubber is generally expensive, a laminate in which fluorine rubber and non-fluorine rubber are laminated has been proposed (Patent Document 1). Patent Document 1 discloses a rubber laminate obtained by vulcanizing and adhering a vulcanizable rubber composition composed of a fluororubber and a quaternary ammonium salt derivative of triazinethiol and a vulcanizable rubber composition other than fluororubber. ing.

Japanese Patent Application Laid-Open No. 05-320453

However, the rubber laminate described in the examples of Patent Document 1 is a rubber laminate of FKM and non-fluorinated rubber, and has insufficient alkali resistance. Therefore, the rubber laminate described in the examples of Patent Document 1 is not suitable for use in a high-alkali usage environment such as a rubber hose for fuel for automobiles.

Generally, fluororubbers such as FEPM and FFKM are superior in alkali resistance to FKM. However, according to the present inventor, in order to improve the alkali resistance, the laminate obtained by laminating FEPM or FFKM and non-fluorinated rubber has reduced adhesiveness between each layer, that is, interlayer adhesiveness, and has a high temperature of about 150 ° C. Below, it was found that peeling may occur at the interface of each layer.

The present invention provides a laminate having excellent alkali resistance and interlayer adhesion under high temperature.

The present invention has the following aspects.
[1] A laminate having a first crosslinked layer containing a crosslinked product of a fluorine-containing polymer and a second crosslinked layer containing a crosslinked product of a non-fluorinated polymer.
The fluorine-containing polymer is a copolymer having a unit based on tetrafluoroethylene and a unit based on propylene, or a copolymer having a unit based on tetrafluoroethylene and a unit based on perfluoro (alkyl vinyl ether).
In the image of the cross section perpendicular to the laminated surface of the laminated body, the height of the unevenness of the line formed by the laminated surface of the laminated body is 3 μm to 40 μm, and the T type specified in JIS K6854-3: 1999. A laminate in which material breakage occurs in the first crosslinked layer or the second crosslinked layer when the peeling test is performed at a temperature of 100 to 200 ° C.
However, the laminated surface of the laminated body includes the interface between the first and second crosslinked layers adjacent to each other, or the first and second crosslinked layers adjacent to each other via a thin film. The height of the unevenness of the line formed by the laminated surface of the laminated body, which is an interface existing between the above, is a value measured by the following method. (1) Using a scanning electron microscope, at a magnification of 1000 times, the cross section perpendicular to the laminated surface of the laminated body is 90 μm perpendicular to the laminated surface of the laminated body × parallel to the laminated surface of the laminated body. An image is obtained by photographing a range of 120 μm. (2) One end and the other end of the line formed by the laminated surface of the laminated body, which can be visually recognized in the image, are connected by a line (hereinafter referred to as line 1). (3) Two lines parallel to line 1 are added (hereinafter, one of the two lines is referred to as line 2 and the other is referred to as line 3).
However, the line 2 and the line 3 sandwich the line 1 and include all the lines formed by the laminated surfaces of the laminated body existing in the image, and the distance between the two lines. Is arranged so as to be the shortest. (4) The value obtained by converting the distance between the line 2 and the line 3 into the length of the laminated surface of the actual laminated body is defined as the "height of the unevenness of the line formed by the laminated surface of the laminated body".
[2] The first crosslinked layer is a crosslinked layer produced from a first composition containing a fluorine-containing polymer, a crosslinking agent, and a crosslinking aid.
The laminate according to [1], wherein the second crosslinked layer is a crosslinked layer produced from a second composition containing a non-fluorine polymer and a crosslinking agent.
[3] The laminate according to [1] or [2], which further has a thin layer.
[4] The laminate according to any one of [1] to [3], wherein the second crosslinked layer further contains a crosslinking aid.
[5] In the laminated body, when the length is 60 mm and the width is 25 mm and the thickness is arbitrary, the height of the unevenness is 10 points of intersections of lines that divide the length into 6 equal parts and the width into 3 equal parts. The laminate according to any one of [1] to [4], which is an average value when three arbitrary intersections are selected and the height of the unevenness at the arbitrary intersection is measured.
[6] The laminate according to any one of [1] to [5], wherein the copolymer having a unit based on tetrafluoroethylene and a unit based on propylene further has an iodine atom.
[7] The laminate according to any one of [1] to [6], wherein the copolymer having a unit based on tetrafluoroethylene and a unit based on perfluoro (alkyl vinyl ether) further has an iodine atom.
[8] The copolymer having a unit based on tetrafluoroethylene and a unit based on propylene further has a unit based on a monomer having two or more polymerizable unsaturated bonds [1] to [7]. ] The laminate according to any one of.
[9] A copolymer having a unit based on tetrafluoroethylene and a unit based on perfluoro (alkyl vinyl ether) further has a unit based on a monomer having two or more polymerizable unsaturated bonds. The laminate according to any one of 1] to [8].
[10] The laminate according to [8] or [9], wherein the unit based on the monomer having two or more polymerizable unsaturated bonds is a compound represented by the following formula 4.
CR ¹ R ² = CR ^3- R ⁴ -CR ⁵ = CR ⁶ R ⁷ ... Equation 4
In formula 4, R ¹ , R ² , R ³ , R ⁵ , R ⁶ , and R ⁷ are independently hydrogen atoms, fluorine atoms, or methyl groups, and R ⁴ is an alkylene group having 1 to 25 carbon atoms. , An alkylene group having 1 to 25 carbon atoms and having an ethereal oxygen atom, a fluoroalkylene group having 1 to 25 carbon atoms, and a fluoroalkylene group having 1 to 25 carbon atoms and having an ethereal oxygen atom. It is a group having or an oxygen atom.
[11] A rubber hose using the laminate according to [1] to [10].

According to the present invention, a laminate having excellent alkali resistance and interlayer adhesion under high temperature can be obtained.

It is a scanning electron micrograph of the cross section perpendicular to the laminated surface of the laminated body obtained in Example 4 of Example.

The meanings of the following terms in the present specification are as follows.
By "monomer" is meant a compound having a polymerizable unsaturated bond. Examples of the polymerizable unsaturated bond include a double bond and a triple bond between carbon atoms.
The "unit based on a monomer" is a general term for an atomic group directly formed by polymerizing one molecule of a monomer and an atomic group obtained by chemically converting a part of the atomic group. .. A "monomer-based unit" is also referred to as a "monomer unit". A unit based on a specific monomer may be described by adding a "unit" to the name or abbreviation of the specific monomer. For example, tetrafluoroethylene is abbreviated as "TFE", and a unit based on tetrafluoroethylene is also referred to as "TFE unit".
The “storage shear modulus G'” is a value measured at a temperature of 100 ° C., an amplitude of 0.5 ° C., and a frequency of 50 times / minute according to ASTM D5289 and D6204.
The "ethery oxygen atom" is an oxygen atom existing once between carbon atoms.
"Rubber" means rubber exhibiting properties as defined by JIS K 6200 (2008) and is distinguished from "resin".

<Laminated body>
The laminate of the present invention is a laminate having a first crosslinked layer containing a crosslinked product of a fluoropolymer described later and a second crosslinked layer containing a crosslinked product of a non-fluoropolymer, and has the above-mentioned fluorine-containing weight. A copolymer having a TFE unit and a propylene unit (hereinafter, also referred to as copolymer 1) or a copolymer having a TFE unit and a perfluoro (alkyl vinyl ether) (hereinafter, also referred to as PAVE) unit (hereinafter, also referred to as PAVE). , Also referred to as copolymer 2).
Details of the method for producing the laminate of the present invention will be described later.
In the laminate of the present invention, when the T-type peeling test specified in JIS K6854-: 1999 was performed at a temperature of 100 to 200 ° C., the material was broken at the first crosslinked layer or the second crosslinked layer. Occurs.
Further, in the laminated body of the present invention, the height of the unevenness of the line formed by the laminated surface of the laminated body (hereinafter, also referred to as the height of the unevenness) is 3 μm or more in the image of the cross section perpendicular to the laminated surface. It is 40 μm.

The method for measuring the height of the unevenness is as follows.
(1) Using a scanning electron microscope (hereinafter, also referred to as SEM), at a magnification of 1000 times, the cross section is perpendicular to the laminated surface of the laminated body, and 90 μm × laminated perpendicular to the laminated surface of the laminated body. An image is obtained by photographing a range of 120 μm parallel to the laminated surface of the body. (2) One end and the other end of the line formed by the laminated surface of the laminated body, which can be visually recognized in the above image, are connected by a line (hereinafter referred to as line 1). (3) Two lines parallel to line 1 are added (hereinafter, one of the two lines is referred to as line 2 and the other is referred to as line 3).
However, the line 2 and the line 3 sandwich the line 1 and include all the lines formed by the laminated surfaces of the laminated body existing in the image, and the distance between the two lines. Is arranged so as to be the shortest. (4) The value obtained by converting the distance between the line 2 and the line 3 into the length on the laminated surface of the actual laminated body is defined as the “height of unevenness”.

The SEM used for measuring the height of the unevenness is not particularly limited.
When observing a reflected electron image using an SEM, it is possible to clarify the laminated surface of the first crosslinked layer containing a fluorine-containing polymer and the second crosslinked layer containing a non-fluorinated polymer by adjusting the contrast. it can.

It is preferable that the image taken by the SEM has a scale.

In the image taken by SEM, the height of the unevenness of the laminated body of the present invention is 3 μm to 40 μm. The height of the unevenness of the laminated body of the present invention is preferably 4 μm or more. Further, the height of the unevenness of the laminated body of the present invention is preferably 20 μm or less, more preferably 10 μm or less, and most preferably 7 μm or less.
When the height of the unevenness is 3 μm or more, it is considered that the contact area between the first crosslinked layer and the second crosslinked layer becomes large, and the interlayer adhesiveness is excellent.
When the height of the unevenness is 40 μm or less, the first crosslinked layer is relatively uniformly present in the laminated body, so that the alkali resistance can be sufficiently exhibited.

The laminated body of the present invention can also be imaged by photographing a cross section thereof using an atomic force microscope (hereinafter, also referred to as AFM). When AFM is used, the difference in physical properties obtained from the surface information of the first crosslinked layer containing a fluorine-containing polymer and the second crosslinked layer containing a non-fluorinated polymer can be obtained as an image of light and dark, and the light and dark can be obtained. Binarization is possible by dividing the gradation. The binarized position is set to the center level divided by gradation, so that an image with clear contrast can be obtained and the laminated surface can be easily read.

In the image taken by SEM or AFM, the visible unevenness of the line formed by the laminated surface of the laminated body indicates that the laminated surface of the laminated body has unevenness, and the height thereof is the height of the laminated surface. It shows the height of the unevenness that exists in.
The larger the height of the unevenness of the line formed by the laminated surface of the laminated body, the larger the unevenness exists on the laminated surface, that is, the surface area of the first crosslinked layer and the second crosslinked layer becomes large, and the first Since it is considered that the contact area between the crosslinked layer and the second crosslinked layer becomes large, the laminate of the present invention has excellent interlayer adhesiveness.

In the image of the cross section of the laminated body of the present invention, the height of the unevenness of the line formed by the laminated surface of the laminated body is an average value when a plurality of points on the laminated surface of the laminated body are measured (hereinafter, average uneven height). It can also be expressed as (also written as).
The measurement points for calculating the average uneven height are preferably 3 to 6 points.
Further, it is preferable that the measurement point is not an edge of the laminated body but an inner point. Since the edges of the laminated surface of the laminated body may be affected by the manufacturing process, significant measurement results may not be obtained.
As a specific example, in the laminated body of the present invention, when the length is 60 mm and the width is 25 mm and the thickness is arbitrary, out of 10 points of intersections of lines that divide the length into 6 equal parts and the width into 3 equal parts. The average value when three arbitrary intersections are selected and the height of the unevenness at the arbitrary intersection is measured can be used as the average uneven height of the laminated body.

The laminate of the present invention has a first crosslinked layer containing a crosslinked product of a fluorine-containing polymer described later and a second crosslinked layer containing a crosslinked product of a non-fluorinated polymer described later.
The laminated body of the present invention is preferably, but is not limited to, a laminated body having a two-layer structure of a first crosslinked layer and a second crosslinked layer. That is, the laminate of the present invention may have a thin layer other than the first crosslinked layer and the second crosslinked layer. The thickness of the thin film is preferably 0.01 to 1 μm. The thickness of the thin film is more preferably 0.1 μm or more. Further, the thickness of the thin film is more preferably 0.5 μm or less. When the thickness of the thin film is within the above range, it is difficult to inhibit the co-crosslinking between the first composition and the second composition. The co-crosslinking will be described later. Examples of the thin layer include an adhesive thin layer existing between both layers, a thin layer made of a thermoplastic resin, and a metal thin film, which will be described later.
Further, the laminate of the present invention may have a plurality of first crosslinked layers and a plurality of second crosslinked layers.

Since the interlayer adhesiveness is superior, the first crosslinked layer is produced from the first composition containing a fluorine-containing polymer described later, and the second crosslinked layer is a second composition containing a non-fluorinated polymer described later. It is preferably produced from the crosslinked product of.

<Manufacturing method of laminated body>
The method for producing a laminate of the present invention produces a laminate having a layer of a first composition described later and a layer of a second composition described later, followed by the first composition and the second composition. A method of reacting the composition to produce a laminate having a first crosslinked layer and a second crosslinked layer is preferable.

In a preferred method for producing a laminate of the present invention, the first composition contains a fluoropolymer composed of the copolymer 1 or the copolymer 2, a cross-linking agent, and a cross-linking aid, and the second composition is It contains a non-fluoropolymer and a cross-linking agent, and optionally contains a cross-linking aid.
Details of the fluorine-containing polymer, non-fluorine polymer, cross-linking agent, and cross-linking aid will be described later.

The following (1) is a preferable manufacturing method for obtaining a laminate having an uneven height of 3 μm to 40 μm and having excellent interlayer adhesion between the first crosslinked layer and the second crosslinked layer at high temperatures. The method of (4) can be mentioned.

(1) Adjustment of Crosslinking Aid In the method for producing a laminate of the present invention, the second composition contains a crosslinking aid, and the first composition and the second composition share a common crosslinking aid. It is preferable to include it. When the second composition contains a cross-linking aid and the first composition and the second composition contain a common cross-linking aid, the common cross-linking aid reacts with the common cross-linking agent. It is considered that the cross-linking reaction at the interface between the first composition and the second composition is likely to proceed.

Here, "does not contain a common cross-linking aid" means that when the second composition contains a cross-linking aid, any of the cross-linking aids contained in the first composition is the second composition. It means that it is a compound different from any of the cross-linking aids contained. The case where the second composition does not contain a cross-linking aid corresponds to the case where the first composition and the second composition do not contain a common cross-linking aid.

(2) Adjustment of SP Value of Polymer In the method for producing a laminate of the present invention, the SP value of the fluorinated polymer contained in the first composition and the non-fluorinated polymer contained in the second composition are used. The absolute value of the difference from the SP value is preferably 0 to 10 (J / cm ³ ) ^1/2 . The absolute value of the difference between the SP value of the fluorinated polymer contained in the first composition and the SP value of the non-fluorinated polymer contained in the second composition is 5 (J / cm ³ ) ^1/2 or less. Is more preferable, and 2 J / cm ³ ) ^1/2 or less is further preferable. When the absolute value of the difference between the SP value of the fluorine-containing polymer and the SP value of the non-fluorine polymer is within the above range, the compatibility between the fluorine-containing polymer and the non-fluorine polymer is good, and the first Since it is considered that the fluorine-containing polymer in the composition and the non-fluorine polymer in the second composition easily form a primary bond, interlayer adhesion between the first crosslinked layer and the second crosslinked layer of the laminate is considered. The sex is even better.

The SP value δT referred to in the present invention is a solubility parameter of Hildebrand. The SP value δT (J / cm ³ ) ^1/2 is calculated from the HSP value.
The HSP value referred to in the present invention is the solubility parameter of Hansen, which is the dispersion term δD (J / cm ³ ) ^1/2 , the polar term δP (J / cm ³ ) ^1/2 , and the hydrogen bond term δH (J / cm). ³ ) ^{Consists of 1/2} .
The relationship between the SP value and the HSP value is expressed by the following formula (i).
^{δT 2 = δD 2+ δP 2 +} δH 2 (i)

δD, δP, and δH are calculated from the results of the solubility evaluation test. The solubility test is performed by the method shown below.
Approximately 5 mL of a solvent having a known solubility parameter was collected in a glass vial, approximately 0.2 g of the sample was added, and the mixture was allowed to stand at 25 ° C. for 72 hours. The mass change rate Q is measured for those that have not collapsed.
The mass change rate Q is calculated by the following formula (ii).
Q = {W (after) / W (before)} x 100 (%) (ii)
However, W (after) is the mass of the sample before the test, and W (before) is the mass of the sample after the test.

Solvents with known solubility parameters include acetic acid, acetone, acetonitrile, n-butyl acetate, chloroform, cyclohexane, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), ethyl acetate, methyl ethyl ketone (MEK), and methyl isobutyl ketone. (MIBK), dichloromethane, propylene carbonate, propylene glycerol monomethyl ether (PM), propylene glycerol monomethyl ether acetate (PMA), tetrahydrofuran (THF), toluene, fluorobenzene, p-fluoroanisole, 2,2,2-trifluoroethanol , Perfluorohexane. The presence or absence of disintegration is confirmed for all the above-mentioned solvents, and the mass change rate Q is measured for those that do not disintegrate.

The results of the above measurements were plotted on a three-dimensional graph, and δD, δP, and δH were calculated by the Hansen sphere method. For the calculation, Hansen Solubility Parameter in Practice (HSPiP) ver. The Data Points mode in the Genetic Algorithm option of the 5.0.08 Sphere program was used.
The SP value δT was calculated from the obtained values of δD, δP, and δH and the formula (i).

The SP values of the first composition and the second composition can be appropriately adjusted by aligning the SP values of the polymers or adding additives described later.
In the method for producing a laminate of the present invention, the absolute value of the difference between the SP value of the fluorinated polymer contained in the first composition and the SP value of the non-fluorinated polymer contained in the second composition is 0. -10 (J / cm ³ ) ^1/2 is preferable.

(3) Adjustment of Crosslinking Degree of Composition In the method for producing a laminate of the present invention, the crosslinking degree of the first composition is preferably 5 to 150. The degree of cross-linking of the first composition is more preferably 10 or more, further preferably 20 or more. Further, the degree of cross-linking of the first composition is more preferably 100 or less.
The degree of cross-linking of the second composition is preferably 5 to 300. The degree of cross-linking of the second composition is more preferably 10 or more, further preferably 30 or more. Further, the degree of cross-linking of the composition of 2 is more preferably 210 or less, further preferably 170 or less.

The degree of cross-linking is defined by the following equation 3.
Crosslinkability = MH-ML ・ ・ ・ Equation 3
However, MH is the maximum value of torque when a cross-linking test is performed with a rubber processing analyzer (RPA: rubber process analyzer), which is a kind of cross-linking characteristic measuring instrument, and ML is the minimum value of torque. The degree of cross-linking described in the present specification is a value measured using an RPA-2000 (manufactured by Alpha Technologies), which is a rubber processing analyzer (RPA).

The degree of cross-linking is a measure of the cross-linking reactivity of the composition that can be cross-linked, and the larger the value of the degree of cross-linking, the more cross-linking points and the better the cross-linking reactivity. When laminating a composition having high cross-linking reactivity, it has excellent interlayer adhesion.

When the degree of cross-linking of the first composition is not less than the lower limit of the above range, the cross-linking reactivity is excellent. Excellent for.
When the degree of cross-linking of the second composition is at least the lower limit of the above range, the interlayer adhesiveness is excellent. Therefore, a laminate having excellent interlayer adhesiveness can be produced. Excellent for.
The degree of cross-linking can be adjusted, for example, by the amount of cross-linking aid.

In the method for producing a laminate of the present invention, the absolute value of the difference between the degree of cross-linking of the first composition and the degree of cross-linking of the second composition is preferably 0 to 200. The absolute value of the difference between the degree of cross-linking of the first composition and the degree of cross-linking of the second composition is more preferably 150 or less. When the absolute value of the difference between the degree of cross-linking of the first composition and the degree of cross-linking of the second composition is within the above range, the fluorine-containing polymer in the first composition and the second composition Since it is considered that the non-fluorine polymer easily forms a primary bond, the interlayer adhesiveness between the first crosslinked layer and the second crosslinked layer of the laminate is further excellent.

(4) Adjustment of Polymer Viscosity In the method for producing a laminate of the present invention, the Mooney viscosity of the fluorine-containing polymer contained in the first composition is preferably 10 to 300. The Mooney viscosity of the fluorine-containing polymer contained in the first composition is more preferably 30 or more, further preferably 50 or more. The Mooney viscosity of the fluorine-containing polymer contained in the first composition is more preferably 200 or less, and even more preferably 120 or less.
The Mooney viscosity of the non-fluorinated polymer contained in the second composition is preferably 5 to 120. The Mooney viscosity of the non-fluorinated polymer contained in the second composition is more preferably 10 or more, further preferably 20 or more. The Mooney viscosity of the non-fluorinated polymer contained in the second composition is more preferably 110 or less, further preferably 70 or less.

When the Mooney viscosity of the fluorine-containing polymer contained in the first composition is at least the lower limit of the above range, the processability is excellent, and when it is at least the upper limit of the above range, the fluorine-containing polymer has a non-fluorine weight at the interface. It is easy to mix with the coalescence, and it is considered that the fluorine-containing polymer in the first composition and the non-fluorine polymer in the second composition easily form a primary bond, so that the interlayer adhesiveness is excellent.

When the Mooney viscosity of the non-fluorine polymer contained in the second composition is at least the lower limit of the above range, the processability is excellent, and when it is at least the upper limit of the above range, the non-fluorine polymer contains fluorine at the interface. Since it is considered that the polymer is easily mixed with the polymer and the fluorine-containing polymer in the first composition and the non-fluorine polymer in the second composition are likely to form a primary bond, the interlayer adhesiveness is excellent.

The Mooney viscosity of the fluorine-containing polymer is L with a diameter of 38.1 mm and a thickness of 5.54 mm according to JIS K6300-1: 2013 using a Mooney viscometer (SMV-201 manufactured by Shimadzu Corporation). It is a value measured by using a mold rotor and setting a preheating time of 1 minute and a rotor rotation time of 4 minutes at 100 ° C.

In the method for producing a laminate of the present invention, the absolute value of the difference between the Mooney viscosity of the fluorinated polymer contained in the first composition and the Mooney viscosity of the non-fluorinated polymer contained in the second composition is 0 to 200 is preferable. The absolute value of the difference between the Mooney viscosity of the fluorinated polymer contained in the first composition and the Mooney viscosity of the non-fluorinated polymer contained in the second composition is more preferably 100 or less, further preferably 75 or less. .. When the absolute value of the difference between the Mooney viscosity of the fluorine-containing polymer contained in the first composition and the Mooney viscosity of the non-fluorinated polymer contained in the second composition is within the above range, the fluorine-containing weight at the interface Since it is considered that the coalescence and the non-fluorinated polymer are easily mixed, and the fluoropolymer in the first composition and the non-fluorinated polymer in the second composition are likely to form a primary bond, the first of the laminates is The interlayer adhesiveness between the first crosslinked layer and the second crosslinked layer is further excellent.

(First composition)
The first composition contains a fluorinated polymer, a copolymer 1 or a copolymer 2, and a cross-linking agent and a cross-linking aid. The first composition may contain other components as long as the effects of the present invention are not impaired.

The crosslinked product of the copolymer 1 or the copolymer 2 is a crosslinked product of a copolymer (FKM) having a hexafluoropropylene (hereinafter, also referred to as HFP) unit and a vinylidene fluoride (hereinafter, also referred to as VdF) unit. It has excellent alkali resistance and steam resistance compared to products.

(Copolymer 1)
The copolymer 1 is a copolymer having a TFE unit and a propylene unit.
The copolymer 1 may further have other monomer units, if necessary, as long as the effects of the present invention are not impaired.

Examples of the other monomer in the copolymer 1 include a monomer having two or more polymerizable unsaturated bonds (hereinafter, also referred to as DVE), PAVE, and perfluoro (oxaalkyl vinyl ether) (hereinafter, POAVE). (Note) is illustrated.

When DVE is copolymerized with TFE and propylene, a copolymer 1 having a branched chain is obtained. When the copolymer 1 further has DVE units, it has mechanical properties such as cross-linking reactivity, tensile strength of the cross-linked product, and compression set characteristics at high temperature, as well as rubber physical properties at low temperature of the cross-linked product (hereinafter, low temperature characteristics). Also referred to as) is excellent.

As the DVE, at least one selected from the group consisting of the compound 4 represented by the following formula 4, the compound 5 represented by the following formula 5, and the compound 6 represented by the following formula 6 is preferable.
CR ¹ R ² = CR ^3- R ⁴ -CR ⁵ = CR ⁶ R ⁷ ... Equation 4
CR ⁸ R ⁹ = CR ^10- OCO-R ^11- COO-CR ¹² = CR ¹³ R ¹⁴ ... Equation 5
CR ¹⁵ R ¹⁶ = CR ¹⁷ COOCH = CH ₂ ... Equation 6

However, R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁷ are independent hydrogen atoms and fluorine atoms, respectively. Alternatively, they are methyl groups, and R ⁴ and R ¹¹ are independently an alkylene group having 1 to 25 carbon atoms, an alkylene group having 1 to 25 carbon atoms and having an ethereal oxygen atom, and 1 carbon atom. Fluoroalkylene groups of up to 25, fluoroalkylene groups having 1 to 25 carbon atoms and having ethereal oxygen atoms, or oxygen atoms, and R ¹⁵ and R ¹⁶ are independently hydrogen atoms and carbon atoms, respectively. It is an alkyl group having 1 to 10 or an alkyl group having 1 to 10 carbon atoms and having an ethereal oxygen atom.

Examples of the compound 4 having an etheric oxygen atom include divinyl ethers, allyl vinyl ethers, butenyl vinyl ethers, fluoro (divinyl ethers), fluoro (allyl vinyl ethers), and fluoro (butenyl vinyl ethers).

Compound 4, from the viewpoint of enhancing the crosslinking reactivity and heat ^resistance, it is preferred that ^{R 1, R 2, R 3} , R 5, R 6 and ^{R 7} are each independently a fluorine atom or a hydrogen ^{atom, R} 1, It is more preferable that all of R ² , R ³ , R ⁵ , R ⁶ and R ⁷ are fluorine atoms.

When R ⁴ is not an oxygen atom, the alkylene group or fluoroalkylene group of R ⁴ may be linear or branched chain. However, the alkylene group or fluoroalkylene group of R ⁴ is preferably linear. The number of carbon atoms of R ⁴ is preferably 2 to 15. The number of carbon atoms of R ⁴ is more preferably 3 or more. Further, the number of carbon atoms of R ⁴ is more preferably 8 or less, further preferably 6 or less, and particularly preferably 5 or less. R etheric number of oxygen atoms in the ^4, 0-4 are preferred. Etheric oxygen atoms in R ⁴ is more preferably 1 or more. Further, etheric oxygen atoms in R ⁴ is 2 or less being more preferred. When R ⁴ is these preferred embodiments, the mechanical properties such as the tensile strength of the crosslinked product of the copolymer 1 and the compression set characteristics at high temperature are further excellent.

The R ^4, heat resistance, in terms of polymer suppressing coloration, fluoroalkylene group preferably having no or oxygen atom having an oxygen atom at both ends, and more preferably perfluoroalkylene groups as the fluoroalkylene group.

Specific examples of the compound 4 include divinyl ethers such as allyl vinyl ether, butenyl vinyl ether, and 1,4-butanediol divinyl ether, CH ₂ = CH (CF ₂ ) ₆ CH = CH ₂ (hereinafter, also referred to as C6DV). , CF ₂ = CFO (CF ₂ ) ₂ OCF = CF ₂ , CF ₂ = CFO (CF ₂ ) ₃ OCF = CF ₂ (hereinafter also referred to as C3DVE), CF ₂ = CFO (CF ₂ ) ₄ OCF = CF ₂ (Hereinafter, also referred to as C4DVE.), CF ₂ = CFO (CF ₂ ) ₆ OCF = CF ₂ , CF ₂ = CFO (CF ₂ ) ₈ OCF = CF ₂ , CF ₂ = CFO (CF ₂ ) ₂ OCF (CF ₃ ) _{) CF 2 OCF = CF 2,} CF 2 = CFO (CF 2) 2 O (CF (CF 3) CF 2 O) 2 CF = CF 2, CF 2 = CFOCF 2 O (CF 2 CF 2 O) 2 CF = _{CF 2, CF 2 = CFO (} CF 2 O) 3 (CF (CF 3) CF 2 O) 2 CF = CF 2, CF 2 = CFOCF 2 CF (CF 3) O (CF 2) 2 OCF (CF 3) Examples thereof include fluoro (divinyl ethers) such as CF ₂ OCF = CF ₂ , CF ₂ = CFO CF ₂ CF ₂ O (CF ₂ O) ₂ CF ₂ CF ₂ OCF = CF ₂ , allyl vinyl ethers, and butenyl vinyl ethers.
Among these, C6DV, C3DVE, and C4DVE are more preferable, and C3DVE and C4DVE are even more preferable, because the low temperature characteristics are further excellent while maintaining the mechanical properties of the crosslinked product of the copolymer 1.

Examples of the compound 5 include divinyl esters, alkyl vinyl esters, fluoro (divinyl esters) and fluoro (alkyl vinyl esters).
In compound 5, it is preferable that R ⁸ , R ⁹ , R ¹⁰ , R ¹² , R ¹³ and R ¹⁴ are hydrogen atoms.

Examples of R ¹¹ include the same groups as R ⁴ . The same applies to the preferable range of the number of carbon atoms. The number of etheric oxygen atoms in R ¹¹ is preferably 0 to 1, and more preferably 0.
A preferable specific example of the compound 5 is divinyl adipate, which is a divinyl ester.

As the compound 6, a compound in which R ¹⁶ is a hydrogen atom is preferable, and a compound in which R ¹⁶ and R ¹⁷ are hydrogen atoms is more preferable.
Preferable specific examples of Compound 6 include vinyl crotonic acid and vinyl methacrylate. Among these, vinyl crotonic acid is more preferable as the compound 6.

For DVE, one type may be used alone, or two or more types may be used in combination. When the copolymer 1 has DVE units, the ratio of the DVE units is preferably 0.01 to 3 mol% with respect to the total of all the units constituting the copolymer 1. The ratio of DVE units is more preferably 1 mol% or less, still more preferably 0.5 mol% or less, based on the total of all the units constituting the copolymer 1. When the ratio of DVE units is not more than the lower limit of the above range, the mechanical properties such as the tensile strength of the crosslinked product of the copolymer 1 and the compression set at a high temperature are further excellent. When the ratio of DVE units is not more than the upper limit of the above range, cracking when stress such as bending is applied at high temperature is surely prevented while maintaining excellent physical properties of the crosslinked product of the copolymer 1. It can be further reduced.

Compound 7 is exemplified as PAVE.
CF ₂ = CF- ^{OR f1} ... Equation 7
However, R ^f1 is a perfluoroalkyl group having 1 to 10 carbon atoms.

The perfluoroalkyl group of R ^f1 may be linear or branched. The number of carbon atoms of the perfluoroalkyl group is preferably 1 to 8. The number of carbon atoms of the perfluoroalkyl group is more preferably 6 or less, further preferably 5 or less, and particularly preferably 3 or less.

Specific examples of PAVE include perfluoro (methyl vinyl ether) (hereinafter, also referred to as PMVE), perfluoro (ethyl vinyl ether) (hereinafter, also referred to as PEVE), and perfluoro (propyl vinyl ether) (hereinafter, also referred to as PPVE). ) Is illustrated. One type of PAVE may be used alone, or two or more types may be used in combination. Of these, PMVE is preferable.

When the copolymer 1 has PAVE units, the ratio of the PAVE units is preferably 3 to 60 mol% with respect to the total of all the units constituting the copolymer 1. The ratio of PAVE units is more preferably 5 mol% or more, still more preferably 10 mol% or more, based on the total of all the units constituting the copolymer 1. The ratio of PAVE units is more preferably 57 mol% or less, still more preferably 40 mol% or less, based on the total of all the units constituting the copolymer 1. When the PAVE unit of the copolymer 1 is within the above range, the chemical resistance (alkaline, etc.) is further excellent.

Examples of POAVE include compound 8 represented by the formula 8.
CF ₂ = CF- (OCF ₂ CF ₂ ) _n- (OCF ₂ ) _m- (OC ₃ F ₆ ) _p- OR ^f2 ... Equation 8

However, R ^f2 is a perfluoroalkyl group having 1 to 4 carbon atoms, n is an integer of 0 to 3, m is an integer of 0 to 4, p is an integer of 0 to 4, and n + m + p is. It is an integer from 1 to 7.

Note that n, m, and p represent the numbers of (OCF ₂ CF ₂ ), (OCF ₂ ), and (OC ₃ F ₆ ), respectively. Therefore, Equation 8 does not represent the order of arrangement of (OCF ₂ CF ₂ ) _n , (OCF ₂ ) _m , (OC ₃ F ₆ ) _{p, and} each of n, m, and p is 2 or more. In the case, (OCF ₂ CF ₂ ) _n , (OCF ₂ ) _m , (OC ₃ F ₆ ) _p does not represent the block arrangement of (OCF ₂ CF ₂ ), (OCF ₂ ), (OC ₃ F ₆ ). .. That is, (OCF ₂ CF ₂ ), (OCF ₂ ), and (OC ₃ F ₆ ) are arranged in any order.

In R ^f2 , the perfluoroalkyl group may be linear or branched. The carbon number of R ^f2 is preferably 1 to 3.
C ₃ F ₆ may be linear or branched.
When n is 0, m is preferably 3 or 4.
When n is 1, m is preferably an integer of 2 to 4.
When n is 2 or 3, m is preferably 0.
n is preferably an integer of 1 to 3.
When the carbon number, n and m of R ^f2 are within the above ranges, the productivity of the copolymer 1 is improved, and the low temperature characteristics of the crosslinked product of the copolymer 1 are excellent.

Specific examples of the compound 8 include the following compounds.
_{CF 2 = CF-OCF 2 CF} 2 -OCF 2 -OCF 2 -OCF 2 -OCF 2 -OCF 3 ( hereinafter, also referred to as C9PEVE.)
_{CF 2 = CF-OCF 2 CF} 2 -OCF 2 -OCF 2 -OCF 3 ( hereinafter, also referred to as C7PEVE.)
_{CF 2 = CF-OCF 2 CF} 2 -OCF 2 CF 2 -OCF 2 CF 3 ( hereinafter, also referred to as EEAVE.)
_{CF 2 = CF-OCF 2 CF} 2 -OCF 2 CF 2 -OCF 2 CF 2 -OCF 2 CF 3 ( hereinafter, also referred to as EEEAVE.)
CF ₂ = CF-OCF ₂ -OCF ₃
CF ₂ = CF-OCF ₂ -OCF ₂ CF ₃
CF ₂ = CF-OCF ₂ CF (CF ₃ ) -OCF ₂ CF (CF ₃ ) -OCF ₂ CF ₂ CF _{3
CF 2 = CF-OCF 2 -OCF} 2 -OCF 3
CF ₂ = CF-OCF ₂ CF ₂ -OCF ₃
CF ₂ = CF-OCF ₂ CF ₂ -OCF ₂ CF ₃
CF ₂ = CF-OCF ₂ CF (CF ₃ ) -OCF ₂ CF ₂ CF ₃

As the compound 8, C9PEVE, C7PEVE, EEAVE, and EEEAVE are preferable because the productivity of the copolymer 1 is improved and the low temperature characteristics of the crosslinked product of the copolymer 1 are excellent.
In addition, these compounds can be produced by the method described in International Publication No. 00/56694 using the corresponding alcohol as a raw material.

The other monomer is not particularly limited as long as it is a compound copolymerizable with TFE and propylene. Specifically, HFP, VdF, chlorotrifluoroethylene, vinyl fluoride, pentafluoropropylene, perfluorocyclobutene, ethylene having a perfluoroalkyl group (for example, CH ₂ = CHCF ₃ , CH ₂ = CHCF ₂ CF ₃ , _{CH 2 = CHCF 2 CF 2 CF} 3, CH 2 = CHCF 2 CF 2 CF 2 CF 3, CH 2 = CHCF 2 CF 2 CF 2 CF 2 CF 3 , etc.) a monomer having a fluorine atom such as, ethylene, isobutylene , Alpha-olefins such as penten, methyl vinyl ethers, ethyl vinyl ethers, propyl vinyl ethers, vinyl ethers such as butyl vinyl ethers, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl esters such as vinyl caprylate, etc. Examples of monomers that do not.

As another monomer, a monomer having an iodine atom may be used. When a monomer having an iodine atom is copolymerized, an iodine atom is introduced into the copolymer 1.
Examples of the monomer having an iodine atom include iodine ethylene, 4-iodo-3,3,4,4-tetrafluoro-1-butene, 2-iodo-1,1,2,2-tetrafluoro-1-vinyloxyetane. , 2-Iodine ethyl vinyl ether, allyl iodide, 1,1,2,3,3,3-hexafluoro-2-iodo-1- (perfluorovinyloxy) propane, 3,3,4,5,5,5- Hexafluoro-4-iodopentene, iodotrifluoroethylene, 2-iodoperfluoro (ethyl vinyl ether) are exemplified.

As the other monomer, one type may be used alone, or two or more types may be used in combination.
When the copolymer 1 has other monomer units, the ratio of the other monomer units is preferably 0.001 to 10 mol% with respect to the total of all the units constituting the copolymer 1. The ratio of the other monomer units is more preferably 0.01 mol% or more with respect to the total of all the units constituting the copolymer 1. Further, the ratio of the other monomer units is more preferably 3 mol% or less, still more preferably 1 mol% or less, based on the total of all the units constituting the copolymer 1.

The copolymer 1 preferably has an iodine atom from the viewpoint of excellent crosslinkability. From the viewpoint of cross-linking reactivity, the iodine atom is preferably bonded to at least the end of the polymer chain of the copolymer 1. The end of the polymer chain means both the end of the main chain and the end of the branched chain.

The copolymer 1 having an iodine atom is a method of copolymerizing a monomer having an iodine atom as another monomer or a method of producing the copolymer 1 by using a chain transfer agent having an iodine atom described later. It can be manufactured by the above.

The iodine atom content of the copolymer 1 is preferably 0.01 to 5.0% by mass with respect to the total mass of the copolymer 1. The iodine atom content of the copolymer 1 is more preferably 0.05% by mass or more with respect to the total mass of the copolymer 1. The iodine atom content of the copolymer 1 is more preferably 2.0% by mass or less, still more preferably 1.0% by mass or less, based on the total mass of the copolymer 1. When the content of iodine atoms is within the above range, the cross-linking reactivity is further excellent, and the mechanical properties of the cross-linked product are further excellent.

The storage shear elastic modulus G'of the copolymer 1 is preferably 50 kPa to 600 kPa. The storage shear elastic modulus G'of the copolymer 1 is more preferably 100 kPa or more, and further preferably 200 kPa or more. The storage shear elastic modulus G'of the copolymer 1 is more preferably 500 kPa or less, and further preferably 400 kPa or less. When the storage shear modulus G'is large, the molecular weight of the polymer is large, and the density of entanglement of molecular chains is also high. When the storage shear modulus G'of the copolymer 1 is within the above range, the tensile strength and mechanical properties of the crosslinked product of the copolymer 1 are further excellent.

As the copolymer 1, any of the following copolymers X1 to X8 is preferable. Any one of these copolymers may be used alone, or two or more thereof may be used in combination.

X1, X2, X4, X5, X6, and X8 are more preferable because the crosslinked product of the copolymer 1 is further excellent in mechanical properties, heat resistance, chemical resistance (alkali resistance, etc.), oil resistance, and weather resistance. X1, X5 and X8 are more preferable, and X1 and X5 are particularly preferable.

X1: A combination of a TFE unit and a propylene unit (hereinafter, also referred to as a P unit).
X2: A combination of TFE units, P units, and VdF units.
X3: A combination of TFE units, P units, and PPVE units.
X4: A combination of TFE units, P units, and PMVE units.
X5: A combination of TFE units, P units, and 4 units of compound.
X6: A combination of TFE unit, P unit, compound 4 unit, and VdF unit.
X7: Combination of TFE unit, P unit, compound 4 unit, and PPVE unit.
X8: A combination of TFE unit, P unit, compound 4 unit, and PMVE unit.

The molar ratio or ratio of each unit constituting each of the copolymers X1 to X8 is preferably within the following numerical range. When the ratio of each unit constituting each of the copolymers X1 to X8 is within the following numerical range, the crosslinked product of the copolymer 1 has mechanical properties, heat resistance, chemical resistance (alkali resistance, etc.), and oil resistance. Excellent in properties and weather resistance.

The ratio of TFE units is 30 to 99 mol% and the ratio of P units is 1 to 70 mol% with respect to the total of all the units constituting X1: X1. More preferably, the ratio of TFE units is 30 to 70 mol% and the ratio of P units is 30 to 70 mol% with respect to the total of all the units constituting X1. More preferably, the ratio of TFE units is 40 to 60 mol% and the ratio of P units is 40 to 60 mol% with respect to the total of all the units constituting X1.
X2: The ratio of TFE units is 40 to 59 mol%, the ratio of P units is 40 to 59 mol%, and the ratio of VdF units is 1 to 10 mol% with respect to the total of all the units constituting X2.
X3: The ratio of TFE units is 30 to 60 mol%, the ratio of P units is 10 to 40 mol%, and the ratio of PPVE units is 10 to 40 mol% with respect to the total of all the units constituting X3.
X4: The ratio of TFE units is 30 to 60 mol%, the ratio of P units is 10 to 40 mol%, and the ratio of PMVE units is 10 to 40 mol% with respect to the total of all the units constituting X4.
X5: The ratio of TFE units is 40 to 59.99 mol%, the ratio of P units is 40 to 59.99 mol%, and the ratio of 4 compounds is 0.01 to 3 with respect to the total of all the units constituting X5. Mol%.
X6: The ratio of TFE units is 40 to 58.99 mol%, the ratio of P units is 40 to 58.99 mol%, and the ratio of 4 compounds is 0.01 to 3 with respect to the total of all the units constituting X6. The ratio of mol% and VdF unit is 1 to 10 mol%.
X7: The ratio of TFE units is 30 to 60 mol%, the ratio of P units is 10 to 40 mol%, the ratio of 4 compounds is 0.01 to 3 mol%, and PPVE with respect to the total of all the units constituting X7. The unit ratio is 10-40 mol%.
X8: The ratio of TFE units is 30 to 60 mol%, the ratio of P units is 10 to 40 mol%, the ratio of 4 compounds is 0.01 to 3 mol%, and PMVE to the total of all the units constituting X8. The unit ratio is 10-40 mol%.

When the copolymer 1 is a binary copolymer composed of TFE units and P units, the molar ratio [TFE units / P units] between the TFE units and the P units is preferably 30/70 to 99/1. , 30/70 to 70/30 is more preferable, and 40/60 to 60/40 is even more preferable. When the molar ratio of the TFE unit to the P unit is within the above range, the mechanical properties, heat resistance, chemical resistance (alkali resistance, etc.), oil resistance and weather resistance of the crosslinked product are further excellent.
The total of the ratio of TFE units and the ratio of P units is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 99 mol% or more, based on the total of all the units constituting the copolymer 1. .. When the total of the ratio of TFE units and the ratio of P units to the total of all the units constituting the copolymer 1 is within the above numerical range, the mechanical properties, heat resistance, chemical resistance (alkali resistance, etc.) of the crosslinked product are high. ), Oil resistance and weather resistance are even better.

(Copolymer 2)
The copolymer 2 is a copolymer having a TFE unit and a PAVE unit.
As the PAVE unit contained in the copolymer 2, the above-mentioned 7 units of the compound are preferable.

In R ^f1 of compound 7, the perfluoroalkyl group may be linear or branched. The carbon number of R ^f1 is preferably 1 to 5 and more preferably 1 to 3 from the viewpoint of improving the productivity of the copolymer 2.

Preferred specific examples of compound 7 include PMVE, PEVE, PPVE, CF ₂ = CF-O-CF ₂ CF ₂ CF ₂ CF ₃ .
As the compound 7, PMVE, PEVE, and PPVE are preferable from the viewpoint of improving the productivity of the copolymer 2.

The copolymer 2 preferably has at least one of a POAVE unit and a DVE unit.
The above-mentioned compound 8 is exemplified as POAVE.

The preferred R ^f2 aspect of the compound 8 in the copolymer 2 and the preferred ranges of n and m are the same as those of the compound 8 represented by the formula 8 in the copolymer 1.
When the carbon number, n and m of R ^f2 are within the above-mentioned preferable ranges, the productivity of the copolymer 2 is improved, and the low temperature characteristics of the crosslinked product of the copolymer 2 are excellent.

Specific examples of the compound 8 in the copolymer 2 include the same compounds as the compound 8 represented by the formula 8 in the copolymer 1.

As the compound 8, C9PEVE, C7PEVE, EEAVE, and EEEAVE are preferable because the productivity of the copolymer 2 is improved and the low temperature characteristics of the crosslinked product of the copolymer 2 are excellent.
In addition, these compounds can be produced by the method described in International Publication No. 00/56694 using the corresponding alcohol as a raw material.

When the copolymer 2 has a DVE unit, it is excellent in low temperature characteristics as well as mechanical properties such as tensile strength of the crosslinked product and compression set characteristics at high temperature.
Examples of the polymerizable unsaturated bond include a carbon atom-carbon atom double bond and a triple bond, and a double bond is preferable. The number of polymerizable unsaturated bonds is preferably 2 to 6, more preferably 2 or 3, and particularly preferably 2.
The DVE is preferably a perfluoro compound.

As the DVE, at least one selected from the group consisting of compound 4, compound 5, and compound 6 in the copolymer 1 is preferable.

The copolymer 2 may further have a unit based on another monomer, if necessary, as long as the effect of the present invention is not impaired.
Examples of other monomers in the copolymer 2 include fluorine atoms and monomers having a halogen atom other than fluorine atoms (bromotrifluoroethylene, iodotrifluoroethylene, etc.), and monomers having a fluorine atom and a nitrile group. (CF ₂ = CFO (CF ₂ ) ₅ CN, perfluoro (8-cyano-5-methyl-3,6-dioxa-1-octene), etc.) are exemplified.

The ratio of TFE units in the copolymer 2 is preferably 35 to 75 mol% with respect to the total of all the units constituting the copolymer 2. The ratio of TFE units is more preferably 40 mol% or more, still more preferably 50 mol% or more, based on the total of all the units constituting the copolymer 2.

The ratio of PAVE units in the copolymer 2 is preferably 25 to 65 mol% with respect to the total of all the units constituting the copolymer 2. The ratio of PAVE units is more preferably 60 mol% or less, further preferably 57 mol% or less, and most preferably 40 mol% or less, based on the total of all the units constituting the copolymer 2.

The ratio of POAVE units in the copolymer 2 is preferably 3 to 57 mol% with respect to the total of all the units constituting the copolymer 2. The ratio of POAVE units is more preferably 5 mol% or more, still more preferably 8 mol% or more, based on the total of all the units constituting the copolymer 2. The ratio of POAVE units is more preferably 40 mol% or less, still more preferably 30 mol% or less, based on the total of all the units constituting the copolymer 2.

The ratio of DVE units in the copolymer 2 is preferably 0.01 to 1 mol% with respect to the total of all the units constituting the copolymer 2. The ratio of DVE units is more preferably 0.05 mol% or more with respect to the total of all the units constituting the copolymer 2. The ratio of DVE units is more preferably 0.5 mol% or less, still more preferably 0.3 mol% or less, based on the total of all the units constituting the copolymer 2.

The ratio of units based on other monomers in the copolymer 2 is preferably 0 to 5 mol% with respect to the total of all the units constituting the copolymer 2. The ratio of the units based on the other monomers is more preferably 3 mol% or less, still more preferably 2 mol% or less, based on the total of all the units constituting the copolymer 2.

When the ratio of the TFE unit, the PAVE unit, the POAVE unit, the DVE unit and the unit based on other monomers in the copolymer 2 is within the above range, the rubber physical properties of the crosslinked product of the copolymer 2 are maintained. The low temperature characteristics, alkali resistance, and interlayer adhesion between the first crosslinked layer and the second crosslinked layer of the laminate at high temperatures are further excellent.

The copolymer 2 preferably has more iodine atoms from the viewpoint of further excellent crosslinkability. The iodine atom is preferably bonded to the end of the polymer chain of the copolymer 2. The term "terminal of a polymer chain" is a concept that includes both the end of a main chain and the end of a branched chain.

The iodine atom content is preferably 0.01 to 1.5% by mass, more preferably 0.01 to 1.0% by mass, based on the copolymer 2. When the content of iodine atoms is within the above range, the crosslinkability of the copolymer 2 is further excellent.

The storage shear elastic modulus G'of the copolymer 2 is preferably 100 kPa to 600 kPa.
The storage shear elastic modulus G'of the copolymer 2 is more preferably 200 kPa or more. Further, the storage shear elastic modulus G'of the copolymer 2 is more preferably 500 kPa or less, and further preferably 400 kPa or less. When the storage shear modulus G'is large, the molecular weight of the polymer is large, and the density of entanglement of molecular chains is also high. When the storage shear elastic modulus G'of the copolymer 2 is within the above range, the tensile strength and the mechanical properties of the crosslinked product of the copolymer 2 are further excellent.

(Method for producing copolymer)
The copolymer 1 can be produced, for example, by polymerizing a monomer component containing TFE and propylene in the presence of a radical polymerization initiator. If necessary, the monomer component for producing the copolymer 1 may contain at least one selected from the group consisting of PAVE, DVE and other monomers in the copolymer 1. The copolymer 1 can be produced, for example, by the methods disclosed in International Publication No. 2009/112022, International Publication No. 2010/053056, and the like.

The copolymer 2 can be produced, for example, by polymerizing a monomer component containing TFE and PAVE in the presence of a radical polymerization initiator. The monomer component for producing the copolymer 2 may contain POAVE, DVE and other monomers in the copolymer 2, if necessary. The copolymer 2 can be produced, for example, by the method disclosed in International Publication No. 2010/082633 and the like.

(Ingredients contained in the first composition)
The first composition contains a cross-linking agent and a cross-linking aid as additives together with the fluorine-containing polymer. In addition, the first composition preferably further contains an antioxidant. The first composition may also contain a polymer other than the fluorine-containing polymer of the present invention and a component other than the above-mentioned additive.

Examples of the cross-linking agent include organic peroxides, polyols, polyamines, triazines, imidazoles, anilines, and ammonium salts. Among these, organic peroxides are preferable because they are excellent in productivity, heat resistance, and chemical resistance.

Examples of organic peroxides include dibenzoyl peroxide, bis (α, α-dimethylbenzyl) peroxide, di (tert-butyl) peroxide, tert-butylperoxyacetate, tert-butylperoxyisopropyl carbonate, and tert-butylper. Oxybenzoate, 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexin-3, α, α'- Examples thereof include bis (tert-butylperoxy) -diisopropylbenzene, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, and bis (α, α-dimethylbenzyl) peroxide. These may be used alone or in combination of two or more.

The content of the cross-linking agent in the first composition is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the copolymer 1 or the copolymer 2. The content of the cross-linking agent in the first composition is more preferably 0.1 part by mass or more with respect to 100 parts by mass of the copolymer 1 or the copolymer 2. The content of the cross-linking agent is more preferably 7 parts by mass or less with respect to 100 parts by mass of the copolymer 1 or the copolymer 2. When the content of the organic peroxide is within the above range, the interlayer adhesiveness between the first crosslinked layer and the second crosslinked layer at a high temperature is further excellent.

Examples of the cross-linking aid include compounds having two or more unsaturated bonds in one molecule. Specific examples of the cross-linking aid include triallyl cyanurate, triallyl isocyanurate, bismaleimide, ethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, trimethylolpropane trimetaacrylate, and divinylbenzene. To. Of these, triallyl cyanurate and triallyl isocyanurate are preferable.

The content of the cross-linking aid in the first composition is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the copolymer 1 or the copolymer 2. The content of the cross-linking aid is more preferably 0.5 parts by mass or more with respect to 100 parts by mass of the copolymer 1 or the copolymer 2. The content of the cross-linking aid is more preferably 7 parts by mass or less with respect to 100 parts by mass of the copolymer 1 or the copolymer 2. When the content of the cross-linking aid is within the above range, the physical properties such as hardness and heat resistance of the cross-linked product of the copolymer 1 or the copolymer 2 are excellent.

In the method for producing a laminate of the present invention, it is preferable that at least one of the first composition and the second composition contains an antioxidant. This makes it easier to manufacture a laminate in which the tensile strength and elongation at the time of cutting, which are the physical properties of fluororubber, are sufficiently maintained in practical use.

As the antioxidant, a compound having a phenolic hydroxyl group is preferable.
Examples of the compound having a phenolic hydroxyl group include bisphenol A, bisphenol AF, phenol, cresol, p-phenylphenol, m-phenylphenol, o-phenylphenol, allylphenol, p-hydroxybenzoic acid, and ethyl p-hydroxybenzoate. Illustrated. Among these, o-phenylphenol is more preferable.

When the first composition contains an antioxidant, the content of the antioxidant is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the copolymer 1 or the copolymer 2. The content of the antioxidant is more preferably 3 parts by mass or less, still more preferably 2 parts by mass or less, based on 100 parts by mass of the copolymer 1 or the copolymer 2.

In the present invention, it is also preferable to add a nitrogen-containing compound such as amine or imine to the first composition as a processing aid. By blending the nitrogen-containing compound in the first composition, the interlayer adhesiveness between the first crosslinked layer and the second crosslinked layer at a high temperature can be further improved.

Specific examples of the nitrogen-containing compound include 1,8-diazabicyclo [5.4.0] undecene-7, 1,5-diazabicyclo [4.3.0] nonen-5, 1,4-diazabicyclo [2.2]. .2] Octane, triethylamine, tributylamine, diphenylamine, piperidine, morpholine, pyridine, benzotriazole, p-dimethylaminopyridine are exemplified.

The blending amount of the nitrogen-containing compound in the first composition is preferably 0.01 to 2 parts by mass, preferably 0.01 to 2.0 parts by mass with respect to 100 parts by mass of the copolymer 1. The blending amount of the nitrogen-containing compound is more preferably 0.05 parts by mass or more with respect to 100 parts by mass of the copolymer 1. Further, the blending amount of the nitrogen-containing compound is more preferably 1.0 part by mass or less with respect to 100 parts by mass of the copolymer 1.

Examples of other components include fluoropolymers other than copolymer 1 and copolymer 2 (hereinafter, also referred to as other fluoropolymers), and additives other than the above.

Examples of other fluorine-containing polymers include copolymers having HFP units and VdF units and not having P units, and copolymers having HFP units, VdF units and TFE units and having no P units. To.

When the first composition contains another fluorinated polymer, the content of the other fluorinated polymer is preferably 50 parts by mass or less with respect to 100 parts by mass of the fluorinated copolymer in the present invention.

Further, the first composition may contain a relatively small amount of the non-fluorine polymer with respect to the fluorine-containing polymer. Examples of the non-fluorine polymer include the non-fluorine polymer contained in the second composition. When the first composition contains a small amount of non-fluorinated polymer, the affinity at the interface between the layer of the first composition and the layer of the second composition is improved, and the layer of the first composition and the layer of the first composition are used. It is considered that the cross-linking reaction at the interface with the layer of the second composition is likely to proceed.

When the first composition contains a non-fluorinated polymer, the content of the non-fluorinated polymer in the first composition with respect to the total amount of the fluoropolymer and the non-fluorinated polymer is preferably 30% by mass or less. More preferably, it is 15% by mass or less.

Examples of additives other than the above include fillers, processing aids, dispersion aids, plasticizers, softeners, antiaging agents, adhesive aids, and cross-linking accelerators.

Fillers include carbon black, fumed silica, wet silica, fine quartz powder, asbestos soil, zinc flower, basic magnesium carbonate, activated calcium carbonate, magnesium silicate, aluminum silicate, titanium dioxide, talc, and mica powder. Examples thereof include aluminum sulfate, calcium sulfate, barium sulfate, asbestos, graphite, wallastonite, molybdenum disulfide, carbon fiber, aramid fiber, various whiskers, and glass fiber.

Examples of processing aids include fatty acid derivatives such as sodium stearate, stearic acid amide, calcium stearate, and oleic acid glyceride, stearic acid, phosphoric acid derivatives, natural waxes, and synthetic waxes.

Examples of the dispersion aid include higher fatty acids and metal amine salts thereof.
Examples of the plasticizer include phthalic acid derivatives, adipic acid derivatives, and sebacic acid derivatives.
Examples of the softener include lubricating oil, process oil, coal tar, and castor oil.
Examples of the antiaging agent include phenylenediamine, hinderedamine, phosphate, quinoline, cresol, and dithiocarbamate metal salt.
Examples of the adhesion aid include a silane coupling agent and a titanate-based coupling agent.

Examples of the cross-linking accelerator include oxides of divalent metals such as magnesium oxide, calcium oxide, zinc oxide and lead oxide, and compounds having a guanidine structure.
In addition, a colorant, an ultraviolet absorber, a flame retardant, an oil resistance improver, a foaming agent, a scorch inhibitor, a tackifier, a lubricant and the like can be blended as needed.

When the first composition contains the copolymer 2 and further contains a metal oxide, the cross-linking reaction facilitates rapid and reliable progress.
The metal oxide is preferably a monovalent or divalent metal oxide.
Specific examples of the monovalent or divalent metal oxide include zinc oxide, magnesium oxide, sodium oxide, calcium oxide, barium oxide, lead oxide, and copper oxide.
The content of the metal oxide is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the copolymer 2. The content of the metal oxide is more preferably 0.5 parts by mass or more with respect to 100 parts by mass of the copolymer 2. Further, the content of the metal oxide is more preferably 6 parts by mass or less with respect to 100 parts by mass of the copolymer 2. When the content of the metal oxide is within the above range, the hardness of the crosslinked product of the first composition is excellent.

The first composition is obtained by a kneading method using a kneading device such as a roll, a kneader, a Banbury mixer, or an extruder, and comprises a copolymer 1 or a copolymer 2, a cross-linking agent, a cross-linking aid, and if necessary, another. It can be prepared by mixing with the ingredients.

(Second composition)
The second composition contains a cross-linking agent as an additive together with the non-fluorine polymer, and optionally contains a cross-linking aid. The second composition may contain other additives as long as the effects of the present invention are not impaired.

The non-fluorine polymer is not particularly limited as long as it is a polymer that can be used as a raw material for crosslinked rubber (non-fluorine rubber) that does not contain a fluorine atom. The non-fluorinated polymer is preferably crosslinked with an organic peroxide. As described above, the Mooney viscosity of the non-fluorinated polymer is preferably 5 to 120. The Mooney viscosity of the non-fluorinated polymer contained in the second composition is more preferably 10 or more, further preferably 20 or more. The Mooney viscosity of the non-fluorinated polymer contained in the second composition is more preferably 110 or less, further preferably 70 or less.

Examples of non-fluorine rubber include the rubber containing no fluorine atom described in JIS K6297: 2005. Specifically, acrylic rubber (ACM), ethylene acrylic rubber (AEM), ethylene propylene diene rubber (EPDM), silicone rubber, ethylene propylene rubber (EPM), ethylene vinyl acetate rubber (EVM), chloroprene rubber (CR), butyl rubber. (IIR), isoprene rubber (IR), butadiene rubber (BR), chlorinated polyethylene rubber (CM), chlorosulfonated polyethylene rubber (CSM), chlorinated polyethylene rubber (CPE) are exemplified. Examples of the silicone rubber include dimethyl silicone rubber (MQ), methyl vinyl silicone rubber (VMQ), and methyl phenyl silicone rubber (PMQ). One of these may be used, or two or more thereof may be mixed and used.

Examples of the polymer which is a raw material of commercially available ACM include Nipol (registered trademark) AR31 (manufactured by Zeon Corporation).
Examples of the polymer which is a raw material of commercially available AEM include VAMAC (registered trademark) DP and VAMAC (registered trademark) G (manufactured by The Chemours Company).
Examples of the polymer which is a raw material of commercially available EVM include Denka ER (registered trademark) 5300 and Denka ER (registered trademark) 8401 (manufactured by Denka).
Examples of the polymer which is a raw material of commercially available EPDM include Esplen (registered trademark) EPDM and the like (manufactured by Sumitomo Chemical Co., Ltd.).
Examples of the polymer which is a raw material of commercially available silicone rubber include KE971TU (manufactured by Shinetsu Silicone Co., Ltd.) and KE951U (manufactured by Shinetsu Silicone Co., Ltd.).

As the cross-linking agent in the second composition, the same cross-linking agent as the cross-linking agent in the first composition is exemplified.
The content of the cross-linking agent in the second composition is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the non-fluorinated polymer. The content of the cross-linking agent is more preferably 0.1 part by mass or more with respect to 100 parts by mass of the non-fluorinated polymer. The content of the cross-linking agent is more preferably 6 parts by mass or less with respect to 100 parts by mass of the non-fluorinated polymer. When the content of the cross-linking agent is within the above range, the interlayer adhesiveness between the first cross-linking layer and the second cross-linking layer at a high temperature is further excellent.

When the second composition contains a cross-linking aid, the cross-linking aid in the second composition is exemplified by the same cross-linking aid as the cross-linking aid in the first composition.
When the second composition contains a cross-linking aid, the content of the cross-linking aid in the second composition is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the non-fluorinated polymer. The content of the cross-linking aid in the second composition is more preferably 0.5 parts by mass or more, still more preferably 1 part by mass or more, based on 100 parts by mass of the non-fluorinated polymer. The content of the cross-linking aid in the second composition is more preferably 10 parts by mass or less with respect to 100 parts by mass of the non-fluorinated polymer. When the content of the cross-linking aid is within the above range, the interlayer adhesiveness between the first cross-linking layer and the second cross-linking layer at a high temperature is further excellent.

As described above, the second composition preferably contains an antioxidant, like the first composition. As the antioxidant contained in the second composition, the same antioxidant as the antioxidant in the first composition is exemplified. The antioxidant contained in the second composition may be the same antioxidant as the antioxidant contained in the first composition, or may be a different antioxidant.
When the second composition contains an antioxidant, the content of the antioxidant is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the non-fluorinated polymer described later. The content of the antioxidant is more preferably 3 parts by mass or less, still more preferably 2 parts by mass or less, based on 100 parts by mass of the non-fluorinated polymer.

In the present invention, it is also preferable to add a nitrogen-containing compound such as amine or imine to the second composition as a processing aid. By blending the nitrogen-containing compound in the second composition, the interlayer adhesiveness between the first crosslinked layer and the second crosslinked layer at a high temperature can be further improved. Examples of the nitrogen-containing compound include the same nitrogen-containing compound as the nitrogen-containing compound in the first composition.
The blending amount of the nitrogen-containing compound in the second composition is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 2.0 parts by mass with respect to 100 parts by mass of the non-fluorinated polymer. The blending amount of the nitrogen-containing compound is more preferably 0.05 parts by mass or more with respect to 100 parts by mass of the copolymer 2. Further, the blending amount of the nitrogen-containing compound is more preferably 1 part by mass or less with respect to 100 parts by mass of the copolymer 2.

As the additive in the second composition, the same additive as the additive in the first composition is exemplified.
In addition, the second composition may contain a relatively small amount of the fluorine-containing polymer with respect to the non-fluorine polymer. The fluorine-containing polymer is not limited to the copolymer 1 and the copolymer 2 contained in the first composition, and may be other fluorine-containing polymers. When the second composition contains a small amount of a fluorine-containing polymer, the affinity at the interface between the layer of the first composition and the layer of the second composition is improved, and the layer of the first composition and the layer of the first composition are used. It is considered that the cross-linking reaction at the interface with the layer of the second composition is likely to proceed.

When the second composition contains a fluorinated polymer, the content of the fluorinated polymer in the second composition with respect to the total amount of the non-fluorinated polymer and the fluorinated polymer is preferably 30% by mass or less. More preferably, it is 15% by mass or less.

The second composition is prepared by mixing a non-fluorine polymer and a cross-linking agent, and if necessary, a cross-linking aid and an additive by a kneading method using the same kneading device as the first composition. it can.

(Laminating method)
The method of laminating the layer of the first composition and the layer of the second composition is not particularly limited.
In the method for producing a laminate of the present invention, the layer of the first composition and the layer of the second composition are laminated in an uncrosslinked state to form an uncrosslinked laminate, which is then crosslinked to form a first composition. To form a crosslinked structure within each layer of the layer of the material and the layer of the second composition, and to form a crosslinked structure between the layers of the first composition and the layer of the second composition. That is, co-crosslinking is preferable. When co-crosslinked, the interlayer adhesiveness between the first crosslinked layer and the second crosslinked layer of the laminate obtained by the method for producing a laminate of the present invention at high temperature is further excellent.

When co-crosslinking, it is preferable to add an organic peroxide as a cross-linking agent for the first composition and the second composition. As a result, the interlayer adhesiveness between the first crosslinked layer and the second crosslinked layer of the laminate obtained by the method for producing a laminate of the present invention at high temperatures is further excellent.
When sulfur is used as the cross-linking agent, co-crosslinking is also referred to as co-vulcanization.

Examples of the method for reacting the first composition and the second composition in the uncrosslinked laminate include a method of heating and a method of irradiating ultraviolet rays.
As a method of reacting the first composition with the second composition, a method of heating is preferable. Specific examples of the heating method include heat press crosslinking, steam crosslinking, and hot air crosslinking.

For example, a method can be adopted in which the primary cross-linking is performed by heating at 100 to 400 ° C. for several seconds to 24 hours, and then the secondary cross-linking is performed by heating at 100 to 300 ° C. for 30 minutes to 48 hours. Secondary cross-linking is not essential, but by performing secondary cross-linking, the mechanical properties, compression set, and other properties of the cross-linked product can be further stabilized or further improved.

As a specific method for producing a laminate of the present invention, the first composition and the second composition are co-extruded to obtain an uncrosslinked laminate, and then the uncrosslinked laminate is reacted. A method of forming a sheet of the first composition and a second composition, respectively, and heat-pressing the sheet of the first composition and the sheet of the second composition to bond them together. An example is a method by injection molding in which the composition and the second composition are injected into a mold or the like.

In the method for producing a laminate of the present invention, it is preferable that the first crosslinked layer and the second crosslinked layer are in direct contact with each other. However, in order to improve the adhesiveness, an adhesive may be applied between the layers as long as the co-crosslinking between the first composition and the second composition is not hindered, and an adhesive thin layer is formed between the layers. It may be laminated. As the adhesive, a silane coupling agent is preferable, and specific examples thereof include vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-aminopropyltriethoxysilane, and 3-glycidoxypropyltriethoxysilane. Will be done.

(Mechanism of action)
The laminate of the present invention described above is excellent in alkali resistance because the first composition contains a copolymer having TFE units and P units or a copolymer having TFE units and PAVE units. Further, in the laminated body of the present invention, since the height of the unevenness of the line formed by the laminated surface of the laminated body is 3 to 40 μm, the interlayer adhesiveness at high temperature is excellent.

<Use>
Since the laminate of the present invention does not peel off at high temperatures, it is suitable as a component used at high temperatures.

The laminate of the present invention is suitable for, for example, a hose. The hose made of the laminated body of the present invention (hereinafter referred to as a laminated rubber hose) may have a layer other than the first crosslinked layer and the second crosslinked layer. In this specification, the hose and the tube are referred to as "hose" without distinction.

In the laminated rubber hose, by using the first crosslinked layer as the innermost layer, a laminated rubber hose having an inner surface having heat resistance, chemical resistance, oil resistance, weather resistance, alkali resistance and steam resistance can be obtained. Further, by using the first crosslinked layer as the outermost layer, a laminated rubber hose having an outer surface having heat resistance, chemical resistance, oil resistance, weather resistance, alkali resistance and steam resistance can be obtained.

Examples of the use of the laminated rubber hose include rubber hoses for transportation equipment such as automobiles, ships, and aircraft, liquid crystal equipment, semiconductor equipment, food manufacturing equipment, analytical equipment, chemical plant equipment, and nuclear plant equipment. ..

Specific examples include turbocharger hoses, PCV hoses, oil return hoses, exhaust gas hoses, EGR hoses, oil hoses, sterilization hoses, sterilization hoses, fuel hoses, oil resistant rubber hoses, combustion gas resistant rubber hoses, and brake oil resistance. Rubber hose, chemical resistant rubber hose, freon resistant rubber hose, heat resistant air rubber hose, rubber hose for gas heat pump, hydraulic brake hose, engine oil hose, radiator hose, vacuum hose, vapor hose, ATF hose, water piping hose, steam piping hose Illustrated.

In addition, the laminated rubber hose is also excellent in resistance to liquids, especially oil and coolant (LLC), and is suitable for oil piping, coolant liquid piping, and the like.
Further, since the laminated rubber hose is also excellent in resistance to strongly basic compounds, it is also used as a member of a urea SCR system in which an aqueous urea solution such as AdBlue (registered trademark), which is strongly basic, is used.

The method for manufacturing the laminated rubber hose is not particularly limited. For example, the laminated rubber hose is formed by co-extruding the first composition and the second composition into a tubular shape to obtain an uncrosslinked laminate, and reacting the first composition with the second composition. can get.
Alternatively, after the first composition or the second composition is extruded into a tubular shape, the second composition or the first composition is extruded on the surface thereof to obtain an uncrosslinked laminate. By reacting this, a laminated rubber hose in which the inner layer is composed of the first crosslinked layer or the second crosslinked layer and the outer layer is composed of the second crosslinked layer or the first crosslinked layer is obtained.

In addition to the two-layer rubber hose in which the inner layer is composed of a first crosslinked layer or a second crosslinked layer and the outer layer is composed of a second crosslinked layer or a first crosslinked layer, the laminated rubber hose has a first Alternatively, it may be a multilayer rubber hose having a layer composed of a second crosslinked layer, a three-layer rubber hose having a reinforcing fiber layer on the surface of the outer layer, or the like. Further, as long as the co-crosslinking between the first composition and the second composition is not hindered, an adhesive thin layer such as an adhesive and heat are formed between the first cross-linking layer and the second cross-linking layer. It may have a layer made of a plastic resin and a metal thin film. Examples of the reinforcing fibers of the laminated rubber hose include para-aramid fibers and meta-aramid fibers. Examples of commercially available products include Technora (manufactured by Teijin Limited) and Nomex (manufactured by The Chemours Company).

The thickness of the first crosslinked layer composed of the first composition and the second crosslinked layer composed of the crosslinked product of the second composition in the laminate of the present invention is not particularly limited.
For example, when the laminate of the present invention is used as a laminated rubber hose for automobiles, the thickness of the first crosslinked layer is preferably 0.1 to 100 mm, more preferably 0.15 to 50 mm, and particularly 0.2 to 30 mm. preferable.
The thickness of the second crosslinked layer is preferably 0.1 to 100 mm. The thickness of the second crosslinked layer is more preferably 0.15 to 50 mm, particularly preferably 0.2 to 30 mm.

For example, when the laminate of the present invention is used as a laminated rubber hose for a plant, the thickness of the first crosslinked layer is preferably 0.2 to 200 mm, more preferably 0.2 to 100 mm, particularly 0.2 to 20 mm. preferable.
When the laminated body of the present invention is used as a laminated rubber hose for a plant, the thickness of the second crosslinked layer is preferably 0.2 to 200 mm. The thickness of the above is more preferably 0.2 to 100 mm, and particularly preferably 0.2 to 50 mm.

The laminate of the present invention can be used, for example, as a rubber roll.
Examples of the use of the rubber roll include a rubber roll for a film, a rubber roll for papermaking, a rubber roll for plywood, and a rubber roll for steel.

When the laminate of the present invention is used as an industrial laminated rubber roll, the thickness of the first crosslinked layer is preferably 0.1 to 20000 mm, more preferably 0.15 to 10000 mm, and particularly preferably 0.2 to 1000 mm. .. The thickness of the second crosslinked layer is preferably 0.1 to 20000 mm, more preferably 0.15 to 10000 mm, and particularly preferably 0.1 to 1000 mm.
The ratio of the thickness of the first crosslinked layer to the total thickness of the first crosslinked layer and the second crosslinked layer in the laminate of the present invention is preferably 10 to 90%, preferably 25 to 75%. More preferred.

The laminate of the present invention can be used, for example, as a sealing material.
Examples of the sealing material include O-rings, V-rings, gaskets, and packings.
For example, when the laminate of the present invention is used as a sealing material, the thickness of the first crosslinked layer is preferably 0.1 to 100 mm, more preferably 0.15 to 50 mm, and particularly preferably 0.2 to 30 mm. The thickness of the second crosslinked layer is preferably 0.1 to 100 mm, more preferably 0.15 to 50 mm, and particularly preferably 0.2 to 30 mm.

The laminate of the present invention can be used, for example, as a wire covering material.
In the coated electric wire of the present invention, the electric wire covering material formed on the outer periphery of the core wire is not only formed in direct contact with the core wire but also indirectly formed on the outer periphery via another layer between the coated electric wire and the core wire. It may be the one. Specifically, the coated wire of the present invention is not only an insulated wire in which the laminate of the present invention is used as a wire coating material and is a conductor or a core wire is directly coated, but also the laminated body of the present invention is used as an outer layer as a wire coating material. Also includes such wires, such as cables with sheaths and wire harnesses. Examples of the cable include a sensor cable and a power cable.
The conductor is not particularly limited, and examples thereof include various plated wires such as copper, copper alloys, aluminum and aluminum alloys, tin plating, silver plating, and nickel plating, stranded wires, superconductors, and plated wires for semiconductor element leads.

When the laminate of the present invention is used as an electric wire coating material, the thickness of the first crosslinked layer is preferably 0.1 to 10 mm, more preferably 0.15 to 5 mm, and particularly preferably 0.2 to 3 mm. The thickness of the second crosslinked layer is preferably 0.1 to 10 mm, more preferably 0.15 to 5 mm, and particularly preferably 0.2 to 3 mm.

The laminate of the present invention can be used for, for example, a belt, anti-vibration rubber, and a diaphragm in addition to the above-mentioned uses.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by the following description.

<Measurement method>
(Copolymerization composition of copolymer 1)
The proportion (mol%) of each unit constituting each copolymer 1 was determined by ¹⁹ F-nuclear magnetic resonance (NMR) analysis, fluorine content analysis, and infrared absorption spectrum analysis.

(Iodine content of copolymer 1)
The iodine content of the copolymer 1 was quantified by a device combining an automatic sample combustion device, an ion chromatograph pretreatment device (manufactured by Mitsubishi Chemical Analytech Co., Ltd., AQF-100 type), and an ion chromatograph.

(Storage shear modulus G'of copolymer 1)
Using a rubber processing analyzer (RPA-2000 manufactured by Alpha Technologies, Inc.), measurements were taken at a temperature of 100 ° C., an amplitude of 0.5 ° C., and a frequency of 50 times / minute according to ASTM D5289 and D6204.

(Moony viscosity of copolymer 1 and non-fluorine polymer)
Preheating time at 100 ° C. using a Mooney viscometer (SMV-201 manufactured by Shimadzu Corporation) and an L-shaped rotor with a diameter of 38.1 mm and a thickness of 5.54 mm according to JIS K6300-1: 2013. The measurement was performed with the rotor rotation time set to 4 minutes for 1 minute.

(SP value of copolymer 1, non-fluorine polymer)
The method for measuring the SP value is as described above.

(Crosslink degree of the first composition and the second composition)
When a rubber processing analyzer (RPA-2000 manufactured by Alpha Technologies Co., Ltd.) was used, the maximum value of torque was MH and the minimum value of torque was ML. The degree of cross-linking is indicated by the value obtained by subtracting ML from MH (MH-ML).

(Cross section of laminated body)
The laminate of the present invention was cut by the cryo-ultra microtome method in a direction perpendicular to the laminate surface. The equipment used for cutting is an ultramicrotome (Leica EM UC 6 manufactured by Leica Microsystems) and a frozen section preparation system (Leica EM FC 6 manufactured by Leica Microsystems). After coating the exposed cross section with carbon by about 15 nm, SEM (manufactured by Hitachi High-Technologies Corporation, SU8230) is used to make the cross section perpendicular to the laminated surface of the laminated body and perpendicular to the laminated surface of the laminated body. An image was obtained by photographing a range of 120 μm parallel to the laminated surface of the 90 μm × laminated body. The observation conditions at this time are an accelerating voltage: 2 kV or 5 kV, a detector condition: SE (LA100) or YAGBSE, and the magnification is 1000 times.
The method of defining the height of unevenness is as follows.
(1) One end and the other end of the line formed by the laminated surface of the laminated body, which can be visually recognized in the obtained image, are connected by a line (hereinafter referred to as line 1).
(2) Two lines parallel to line 1 are added (hereinafter, one of the two lines is referred to as line 2 and the other is referred to as line 3).
However, the line 2 and the line 3 sandwich the line 1 and include all the lines formed by the laminated surfaces of the laminated body existing in the image, and the distance between the two lines. Is arranged so as to be the shortest.
(3) The value obtained by converting the distance between the line 2 and the line 3 into the length on the laminated surface of the actual laminated body is defined as the “height of unevenness”.

<Each ingredient>
Copolymer 1-A: Corresponding to copolymer 1, a copolymer having TFE units and P units, and the ratio of TFE units to the total of all the units constituting copolymer 1-A is 56 mol%. The ratio of P units is 44 mol%, G'= 280 kPa, Mooney viscosity = 91, SP value = 8.8 (J / cm ³ ) ^1/2 , and iodine atom is 0.4 with respect to the total mass of the copolymer. Contains% by mass. Copolymer 1-A can be produced by the method disclosed in International Publication No. 2009/112022.

Non-fluorine polymer A: AEM raw material, VAMAC (registered trademark) DP, manufactured by The Chemours, Mooney viscosity = 20, SP value = 18.5 (J / cm ³ ) ^1/2
Non-fluorine polymer B: Raw material for silicone rubber, KE951U, manufactured by Shinetsu Silicone Co., Ltd., Mooney viscosity = 17, SP value = 15 (J / cm ³ ) ^1/2
Non-fluorine polymer C: Raw material for EPDM, Esplen (registered trademark) E 501A, manufactured by Sumitomo Chemical Co., Ltd., Mooney viscosity = 43, SP value = 16.8 (J / cm ³ ) ^1/2

Crosslinking agent A: Organic peroxide, α, α'-bis (tert-butylperoxy) -diisopropylbenzene), Luperox® F40P-SP2 (manufactured by Arkema).
Crosslinking agent B: Organic peroxide, α, α'-bis- (tert-butylperoxy) diisopropylbenzene, Parkardox 14 (product name), manufactured by Kayaku Akzo.
Crosslinking agent C: Organic peroxide, bis (α, α-dimethylbenzyl) peroxide, Parkmill (registered trademark) D, manufactured by Nichiyu Co., Ltd. Crosslinking aid: Triallyl isocyanurate, 1,3,5-triallyl isocyanurate , TAIC (registered trademark), manufactured by Mitsubishi Chemical Co., Ltd.

Antioxidant: o-phenylphenol, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.
Carbon Black A: THENMAX N-990 (product name), manufactured by Canarb Limited.
Carbon Black B: FEF, Asahi # 60 Carbon (product name), manufactured by Asahi Carbon Co., Ltd.

Processing aid A: Fatty acid derivative, calcium stearate, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.
Processing aid B: Higher fatty acid, stearic acid, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.
Processing aid C: Fatty acid derivative, Emaster 510P (product name), manufactured by RIKEN Vitamin Co., Ltd.
Processing aid D: Nitrogen-containing compound, Lipomin 18D (product name), manufactured by Lion Specialty Chemicals.
Processing aid E: Phosphoric acid derivative, Phosphanol RL-210 (product name), manufactured by Toho Chemical Industry Co., Ltd.
Processing aid F: Fatty acid derivative, oleic acid glyceride, Rikemar XO-100 (product name), manufactured by RIKEN Vitamin Co., Ltd.

Anti-aging agent: Hindertoamine, Nocrack CD (product name), manufactured by Ouchi Shinko Chemical Industry Co., Ltd. Crosslink accelerator manufactured by Kagaku Kogyo Co., Ltd .: Zinc oxide, manufactured by Shodo Kagaku Co., Ltd.
Softener: Process oil, Diana process oil PW (product name) 90, manufactured by Idemitsu Kosan.

<Preparation of the first composition and the second composition>
With the mass ratio formulations shown in Tables 1 and 2, two rolls were used to uniformly knead each compounding agent to prepare a first composition and a second composition, respectively. The degree of cross-linking (MH-ML) of each composition was measured by the above method. The results are shown in Table 1. In Table 1, the column of "RPA condition" shows the cross-linking condition when MH-ML was measured using a rubber processing analyzer (RPA-2000 manufactured by Alpha Technologies). For example, "170 ° C. x 12 min" means that the first composition or the second composition was reacted at 170 ° C. for 12 minutes.

 

 

<Examples 1 to 10>
Table 3 shows the combinations of the first composition and the second composition in Examples 1 to 10.
A laminate was produced from a laminate in which the first composition and the second composition shown in Table 3 were combined. Specifically, the first composition and the second composition are respectively molded into dimensions of 125 mm in length × 30 mm in width × 1.1 mm in thickness, laminated in the combination shown in Table 2, and at 70 ° C. for 5 minutes. Preliminary press molding was performed under the conditions of. Then, steam vulcanization was carried out under the cross-linking conditions shown in the table to obtain a laminate of Examples 1 to 10 having a first cross-linking layer and a second cross-linking layer having a length of 120 mm, a width of 25 mm and a thickness of 2 mm. At this time, a release film having a length of 60 mm and a width of 30 mm is sandwiched between the layer of the first composition and the layer of the second composition, and half of the laminate in the length direction is not adhered. And said.
The grips of the laminates of Examples 1 to 10 were set in a T-type peeling tester (JIS K6854-3: 1999), and the laminate was peeled off at a speed of 50 mm / min at a temperature of 150 ° C. to form a first crosslink. The delamination state between the layer and the second crosslinked layer was visually observed, and the interlayer adhesiveness under high temperature was evaluated.
The interlayer adhesion of the laminated body in which the material is broken without peeling off is judged as "◎", and a part of the laminated surface is peeled off, but a part of the material is broken. The interlayer adhesiveness of the laminated body under high temperature was judged to be "◯", and the interlayer adhesiveness of the laminated body having peeled laminated surfaces under high temperature was judged to be "x". The evaluation results are shown in Table 3. In the T-type peeling test, when the peeling surface is broken, it means that the interlayer adhesiveness is good, and when the laminated surface is peeled off, it means that the interlayer adhesiveness is low.

 

Table 4 shows the height of the unevenness of the laminates of Examples 1 to 4.

 

In the laminates of Examples 1, 3 and 4, since the laminated surface was not peeled off and the material was broken in the T-type peeling test at a temperature of 150 ° C., the first crosslinked layer and the second crosslinked layer were broken. It was shown that and were chemically linearly combined.
It is considered that this is because the height of the unevenness of the laminated body of Example 1 is 3 μm or more, the surface area of the laminated surface of the laminated body is large, and there are many parts having a linear combination.
Further, when the T-type peeling test was performed on the laminated body of Example 1 at a temperature of 25 ° C., it was confirmed that the laminated surface was not peeled off in any of the laminated bodies and the interlayer adhesiveness was excellent.

The laminate of Example 2 was inferior in interlayer adhesiveness at high temperatures. It is considered that this is because the height of the unevenness of the laminated body of Example 2 is less than 3 μm and the surface area of the laminated surface of the laminated body is small.

The laminate obtained by the method for producing a laminate of the present invention and the laminate of the present invention are suitable for materials such as O-rings, sheets, gaskets, oil seals, diaphragms, V-rings, etc., in addition to hoses. In addition, heat-resistant and chemical-resistant sealing materials, heat-resistant and oil-resistant sealing materials, wire coating materials, sealing materials for semiconductor devices, corrosion-resistant rubber coatings, sealing materials for urea-based greases, rubber coatings, calendar sheets, sponges, rubber rolls, etc. Oil drilling members, heat dissipation sheet, solution bridge, rubber sponge bearing seal (urea grease resistant, etc.), lining (chemical resistant), automotive insulating sheet, endoscopic packing (amine resistant), mono pump, bellows hose (calendar) Sheet processed products), water heater packings or valves, fenders (marine civil engineering, ships), fibers and non-woven fabrics (protective clothing, etc.), base sealants, rubber gloves, button switches, food container packings, water cylinder packings Applications are exemplified.
The entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2019-072277 filed on April 04, 2019 are cited here as the disclosure of the specification of the present invention. It is something to incorporate.

Claims (11)

1. A laminate having a first crosslinked layer containing a crosslinked product of a fluorine-containing polymer and a second crosslinked layer containing a crosslinked product of a non-fluorinated polymer.
   The fluorine-containing polymer is a copolymer having a unit based on tetrafluoroethylene and a unit based on propylene, or a copolymer having a unit based on tetrafluoroethylene and a unit based on perfluoro (alkyl vinyl ether).
   In the image of the cross section perpendicular to the laminated surface of the laminated body, the height of the unevenness of the line formed by the laminated surface of the laminated body is 3 μm to 40 μm, and the T type specified in JIS K6854-3: 1999. A laminate in which material breakage occurs in the first crosslinked layer or the second crosslinked layer when the peeling test is performed at a temperature of 100 to 200 ° C.
   However, the laminated surface of the laminated body includes the interface between the first and second crosslinked layers adjacent to each other, or the first and second crosslinked layers adjacent to each other via a thin film. The height of the unevenness of the line formed by the laminated surface of the laminated body, which is an interface existing between the above, is a value measured by the following method. (1) Using a scanning electron microscope, at a magnification of 1000 times, the cross section perpendicular to the laminated surface of the laminated body is 90 μm perpendicular to the laminated surface of the laminated body × parallel to the laminated surface of the laminated body. An image is obtained by photographing a range of 120 μm. (2) One end and the other end of the line formed by the laminated surface of the laminated body, which can be visually recognized in the image, are connected by a line (hereinafter referred to as line 1). (3) Two lines parallel to line 1 are added (hereinafter, one of the two lines is referred to as line 2 and the other is referred to as line 3).
   However, the line 2 and the line 3 sandwich the line 1 and include all the lines formed by the laminated surfaces of the laminated body existing in the image, and the distance between the two lines. Is arranged so as to be the shortest. (4) The value obtained by converting the distance between the line 2 and the line 3 into the length of the laminated surface of the actual laminated body is defined as the "height of the unevenness of the line formed by the laminated surface of the laminated body".
2. The first cross-linking layer is a cross-linking layer produced from a first composition containing a fluorine-containing polymer, a cross-linking agent, and a cross-linking aid.
   The laminate according to claim 1, wherein the second crosslinked layer is a crosslinked layer produced from a second composition containing a non-fluorine polymer and a crosslinking agent.
3. The laminate according to claim 1 or 2, further comprising a thin layer.
4. The laminate according to any one of claims 1 to 3, wherein the second crosslinked layer further contains a crosslinking aid.
5. In the laminated body, when the length is 60 mm and the width is 25 mm and the thickness is arbitrary, the height of the unevenness is out of 10 points of intersections of lines that divide the length into 6 equal parts and the width into 3 equal parts. The laminate according to any one of claims 1 to 4, which is an average value when three arbitrary intersections are selected and the height of the unevenness at the arbitrary intersection is measured.
6. The laminate according to any one of claims 1 to 5, wherein the copolymer having a unit based on tetrafluoroethylene and a unit based on propylene further has an iodine atom.
7. The laminate according to any one of claims 1 to 6, wherein the copolymer having a unit based on tetrafluoroethylene and a unit based on perfluoro (alkyl vinyl ether) further has an iodine atom.
8. Any one of claims 1 to 7, wherein the copolymer having a unit based on tetrafluoroethylene and a unit based on propylene further has a unit based on a monomer having two or more polymerizable unsaturated bonds. The laminate according to the item.
9. Claims 1 to 1, wherein the copolymer having a unit based on tetrafluoroethylene and a unit based on perfluoro (alkyl vinyl ether) further has a unit based on a monomer having two or more polymerizable unsaturated bonds. Item 8. The laminate according to any one of 8.
10. The laminate according to claim 8 or 9, wherein the unit based on the monomer having two or more polymerizable unsaturated bonds is a compound represented by the following formula 4.
    CR ¹ R ² = CR ^3- R ⁴ -CR ⁵ = CR ⁶ R ⁷ ... Equation 4
    In formula 4, R ¹ , R ² , R ³ , R ⁵ , R ⁶ , and R ⁷ are independently hydrogen atoms, fluorine atoms, or methyl groups, and R ⁴ is an alkylene group having 1 to 25 carbon atoms. , An alkylene group having 1 to 25 carbon atoms and having an ethereal oxygen atom, a fluoroalkylene group having 1 to 25 carbon atoms, and a fluoroalkylene group having 1 to 25 carbon atoms and having an ethereal oxygen atom. It is a group having or an oxygen atom.
11. A rubber hose using the laminate according to claims 1 to 10.
    
    
    
    
    
    
    

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