JP4720202B2 - Fluororesin layer laminate manufacturing method and fluororesin layer laminate - Google Patents

Description

The present invention relates to a method for producing a fluororesin layer laminate, a fluororesin layer laminate, and a fluororesin for extrusion lamination.

Since the fluororesin is excellent in heat resistance, chemical resistance, solvent resistance, weather resistance, electrical insulation, and the like, it is widely used and used in various fields such as automobiles and OA equipment. However, the fluororesin has a problem that mechanical strength and dimensional stability are insufficient depending on the application. A method for solving this problem without impairing the excellent characteristics of the fluororesin has been considered.

As a method for improving mechanical strength and dimensional stability while taking advantage of the excellent properties of a fluororesin, a method for obtaining a laminate of a fluororesin layer and another material has been studied. However, since the fluororesin has a low surface energy, there is a problem that the adhesive strength with the counterpart material is low.

As a method for producing a laminate of a fluororesin layer, there is a method of adhering the fluororesin layer and another material using an adhesive. However, this method using an adhesive has a problem in that sufficient adhesive strength cannot be obtained, and the obtained laminate tends to cause delamination due to a temperature change or the like. In order to overcome this problem, a method for producing a laminate containing no adhesive has been studied.

As a method for producing a laminate of a fluorine-containing resin layer without using an adhesive, a method using a material having a carbonate group at the end of a polymer chain or a side chain as a fluororesin (see, for example, Patent Document 1 and Patent Document 2), In addition, there is a method using a fluororesin having specific melt flow characteristics and infrared absorption characteristics (for example, see Patent Document 3).

In these methods that do not use an adhesive, a heat lamination method consisting of laminating a pre-made base film and a pre-made fluororesin film and sandwiching them with a hot roll, or two or more kinds of resins, respectively. Attempts have been made to use a coextrusion process that is melted in a separate cylinder and laminated and extruded in a die.

The laminate obtained by the thermal lamination method has a problem that the interlayer adhesion strength is small. Further, the co-extrusion method has a problem that a material having a melting point higher than that of a fluororesin such as polyimide or a material that does not melt by heat cannot be applied as a base material.

International Publication No. 98/58937 Pamphlet WO99 / 45044 pamphlet Japanese Patent Laid-Open No. 11-320770

An object of the present invention is to provide a method for producing a laminate having a high interlayer adhesive strength between a fluororesin layer and a substrate in view of the above-described present situation.

The present invention is a fluororesin layer laminate production method for producing a fluororesin layer laminate comprising a substrate (A) and a fluororesin layer (B) in contact with the substrate (A) by extrusion lamination. The extrusion lamination includes a step of extruding a fluororesin melt (Bp) obtained by melting a melt-processable fluororesin onto a substrate (Ap), and the melt-processable fluorine undergoing the melting Fluoropolymer layer lamination, wherein the fluoropolymer constituting the resin has an adhesive part, and the base material (Ap) has affinity or reactivity with the adhesive part. It is a body manufacturing method.

The present invention is a fluororesin layer laminate produced by the above fluororesin layer laminate production method.

The present invention is a fluororesin layer laminate comprising a base material (A) and a fluororesin layer (B) formed by melting a melt processable fluororesin and in contact with the base material (A), The fluoropolymer constituting the melt-processable fluororesin that has undergone the melting has an adhesive part, and the adhesive strength (x) between the substrate (A) and the fluororesin layer (B) is The control adhesive strength (x ₀ ) is a value greater than the control adhesive strength (x ₀ ), and the control adhesive strength (x ₀ ) is a fluororesin film (Bf) formed by melting the melt processable fluororesin and a substrate ( Ap) is a fluororesin layer laminate having an adhesive strength between the fluororesin film (Bf) and the base material (Ap) in a control laminate obtained by pressure bonding with heat lamination.

The present invention relates to a fluororesin for extrusion lamination for constituting a fluororesin melt (Bp) extruded on a substrate (Ap) in extrusion lamination, wherein the fluororesin for extrusion lamination is a fluororesin having an adhesive part. It is a fluororesin for extrusion lamination characterized by comprising a polymer.
The present invention is described in detail below.

The method for producing a fluororesin layer laminate of the present invention comprises producing a fluororesin layer laminate comprising a base material (A) and a fluororesin layer (B) in contact with the base material (A) by extrusion lamination. It is.

The extrusion lamination includes a step of extruding a fluororesin melt (Bp) obtained by melting a melt-processable fluororesin onto a substrate (Ap) (hereinafter sometimes referred to as “extrusion step”).
In the fluororesin layer laminate produced by the fluororesin layer laminate production method of the present invention, the fluororesin melt (Bp) becomes a fluororesin layer (B), and the base material (Ap) A).

In the present specification, the “fluororesin melt (Bp)” is obtained by melting a melt-processable fluororesin. (1) By melting the melt-processable fluororesin, the base material (Ap ) Extruded upward (this state can also be referred to as “immediately after extrusion”) and (2) the adhesive action between the substrate (Ap) and the substrate (Ap) It is a concept including the thing before it ends. On the other hand, in this specification, the fluororesin layer (B) constituting the fluororesin layer laminate is bonded to the base material (Ap) after the adhesive action with the base material (Ap) of (2) is completed. Is a concept different from the above fluororesin melt (Bp).

The fluoropolymer constituting the melt-processable fluororesin that has undergone the melting has an adhesive part. In the present specification, the “melt-processable fluororesin that has been melted” corresponds to the above (1) and (2). Although the fluoropolymer constituting the melt-processable fluororesin that has undergone the melting is the one before the adhesive action with the base material (Ap) of (2) is completed, it has an adhesive part. In the fluororesin layer (B) exhibiting adhesiveness with the base material (A) after the adhesive action with the base material (Ap) has been completed, a few adhesive sites at the adhesive interface remain. Although it may be, all or most is consumed by the adhesion | attachment action with a base material (Ap), and it hardly exists. In the present specification, a fluoropolymer having an adhesive site is sometimes referred to as an “adhesive fluoropolymer”. The adhesive fluoropolymer can be usually obtained by introducing an adhesive site in the production of the fluoropolymer by polymerization. In this case, the adhesive site is the melt-processable fluororesin prior to the melting. It can also be present in the constituent fluoropolymer.

In this specification, the said fluoropolymer is a polymer which has a fluorine-containing monomer unit derived from a fluorine-containing monomer in a principal chain. The fluoropolymer may further have or may not have a fluorine-free monomer unit derived from a fluorine-free monomer.
In the present specification, the “monomer unit” for the fluoropolymer means a part of the polymer molecular structure, which is derived from the monomer. For example, the tetrafluoroethylene unit is represented by —CF ₂ —CF ₂ —.

The fluorine-containing monomer is not particularly limited as long as it is a polymerizable compound having a fluorine atom. For example, tetrafluoroethylene [TFE], vinylidene fluoride [VdF], chlorotrifluoroethylene [CTFE], vinyl fluoride [ VF], hexafluoropropylene [HFP], hexafluoroisobutene, perfluoro (alkyl vinyl ether) [PAVE] s, the following general formula (i):
^{_{CH 2 = CX 1 (CF 2}} ) n X 2 (i)
(Wherein, X ¹ represents a hydrogen atom or a fluorine atom, X ² represents a hydrogen atom, a fluorine atom or a chlorine atom, and n represents an integer of 1 to 10). Etc.

The fluorine-free monomer is not particularly limited as long as it is a polymerizable compound having no fluorine atom, and examples thereof include ethylene [Et], propylene, 1-butene, 2-butene, vinyl chloride, vinylidene chloride and the like. It is done.

Examples of the fluoropolymer include the following copolymer (I) and the following copolymer (II).
(I) a copolymer obtained by polymerizing at least tetrafluoroethylene and ethylene,
(II) At least tetrafluoroethylene and the following general formula (ii)
^{_{CF 2 = CF-Rf 2 (}} ii)
(Wherein Rf ² represents —CF ₃ or —ORf ¹ , and Rf ¹ represents a perfluoroalkyl group having 1 to 5 carbon atoms) and is polymerized with at least one monomer represented by A copolymer.

Examples of the copolymer (I) include a copolymer comprising at least 20 to 80 mol% of tetrafluoroethylene units and 80 to 20 mol% of ethylene units.
In the present specification, the mol% for each monomer unit is derived from the adhesive site-containing monomer unit described later in the total number of moles of the monomer from which the monomer unit constituting the molecular chain of the copolymer is derived. The number of moles excluding the number of moles of the monomer to be used is 100 mole%, and is the ratio of each monomer unit in 100 mole%.
The mol% for each monomer unit is a value determined from a ¹⁹ F-NMR chart.

The copolymer (I) may have other monomer units derived from other copolymerizable monomers in addition to the tetrafluoroethylene unit and the ethylene unit in the main chain. As a monomer, the kind of monomer according to the use of the obtained fluororesin layer laminated body can be selected suitably, and it can use for copolymerization.
Examples of the other monomers include hexafluoropropylene, trichlorofluoroethylene, propylene, and the following general formula (iii):
CX ³ ₂ = CX ⁴ (CF ₂ ) _n X ⁵ (iii)
(Wherein, ^{X 3} and ^{X 4} are the same or different and each represents a hydrogen atom or fluorine atom, ^{X 5} represents a hydrogen atom, a fluorine atom or a chlorine atom, n is integer of 1 to 10. ), A monomer represented by the following general formula (iv):
^{_{CF 2 = CF-ORf 1 (}} iv)
(Wherein, Rf ¹ represents a perfluoroalkyl group having 1 to 5 carbon atoms), and one or more of these are usually used.
The other monomer units may have a ratio of 0 to 20 mol% out of 100 mol% of the monomer units constituting the molecular chain of the copolymer (I).

As the fluoropolymer, the copolymer (I) is preferable in that it is excellent in heat resistance, chemical resistance, weather resistance, electrical insulation, low chemical permeability, non-adhesiveness, etc., heat resistance, chemical resistance TFE / HFP / Et copolymer is more preferable in terms of excellent properties, weather resistance, electrical insulation, low chemical liquid permeability, non-adhesiveness, low-temperature processability, transparency, and the like. It is preferable that the HFP unit in the said TFE / HFP / Et copolymer is 5-20 mol%, a more preferable minimum is 8 mol%, and a more preferable upper limit is 17 mol%. In addition to the monomer units derived from TFE, HFP, and Et, the TFE / HFP / Et copolymer is a range that does not impair the preferred properties of the TFE / HFP / Et copolymer. You may have 1 type, or 2 or more types of monomers.

In the present specification, the “adhesive site” means a functional group having affinity or reactivity with the substrate (Ap).
In the present specification, “affinity” means a property showing an interaction with a base material (Ap) that does not lead to a change in chemical structure, such as hydrogen bond, van der Waals force, etc., and “reactivity” The term “has a property of changing a chemical structure such as a functional group”.

The adhesive site is usually one that the adhesive fluoropolymer has in the main chain or side chain.
The adhesive site is not particularly limited, and examples thereof include a carbon-carbon double bond, a carbonyl group [—C (═O)], a group having a carbonyl group, a bond, and the like. 1 type may be sufficient and 2 or more types may be sufficient.

Examples of the group or bond having a carbonyl group include a carbonate group, a halogenoformyl group, a formyl group, a carboxyl group, a carbonyloxy group [—C (═O) O—], and an acid anhydride group [—C (═O). ) O—C (═O) —], isocyanate group, amide group [—C (═O) —NH—], imide group [—C (═O) —NH—C (═O) —], urethane bond [—NH—C (═O) O—], carbamoyl group [NH ₂ —C (═O) —], carbamoyloxy group [NH ₂ —C (═O) O—], ureido group [NH ₂ —C (═O) —NH—], an oxamoyl group [NH ₂ —C (═O) —C (═O) —] and the like.
The group or bond having a carbonyl group is preferably a carbonate group, a halogenoformyl group, or the like from the viewpoint of easy introduction and high reactivity.

The carbonate group is a group having a bond represented by [—OC (═O) O—], and —OC (═O) O—R group (wherein R is an organic group, a group I atom, Represents a group II atom or a group VII atom). Examples of the organic group in R in the above formula include an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms having an oxygen molecule constituting an ether bond, and preferably 1 to 8 carbon atoms. Or an alkyl group having 2 to 4 carbon atoms and having an oxygen molecule constituting an ether bond. Examples of the carbonate group include —OC (═O) O—CH ₃ , —OC (═O) O—C ₃ H ₇ , —OC (═O) O—C ₈ H ₁₇ , —OC (═O ) O-CH ₂ CH ₂ OCH ₂ CH _{3 and the} like.

The halogenoformyl group is represented by —COY (wherein Y represents a group VII atom), and —COF, —COCl and the like are preferable.

The number of adhesive sites may be appropriately selected depending on the type, shape, application, required adhesive strength, difference in the type of fluoropolymer described below, etc., but usually the number of main chain carbon atoms is 1 × 10 ^6. 3 to 1000 per piece. When the number of carbonyl groups is counted, the number of the adhesive sites is usually 150 or more per 1 × 10 ⁶ main chain carbon atoms, preferably 250 or more, and more preferably 300 or more.
In the present specification, the number of the “adhesive sites” is measured by performing an infrared absorption spectrum analysis according to the method for measuring the number of carbonyl group-containing functional groups described in International Publication No. 99/45044 pamphlet. It is.

Examples of the adhesive fluoropolymer include a fluorine-containing ethylenic polymer having a carbonyl group-containing functional group described in International Publication No. 99/45044 pamphlet.
As described above, the adhesive fluoropolymer can be usually obtained by introducing an adhesive site when producing a fluoropolymer by polymerization, but the method for introducing the adhesive site is not particularly limited, For example, (1) a method of copolymerizing an adhesive site-containing monomer, (2) a functional group derived from a polymerization initiator such as a carboxyl group or a carbonate group at the end of a polymer chain in polymerization in an aqueous medium such as emulsion polymerization. And (3) a method to be possessed by changing the carbon-carbon single bond in the polymer chain to a double bond during the polymerization or by heating after the polymerization.
As the method of (1) above, for example, an adhesive site-containing monomer is mixed with a fluorine-containing monomer of the type and blending depending on the target melt-processable fluororesin and, optionally, a fluorine-free monomer by a known method. It can be obtained by polymerization.

The “adhesive site-containing monomer” means a polymerizable compound having an adhesive site and may or may not have a fluorine atom. In the present specification, the above-mentioned “fluorine-containing monomer” and “fluorine-free monomer” do not have the adhesive part.
Examples of the adhesive part-containing monomer include perfluoroacrylic acid fluoride, 1-fluoroacrylic acid fluoride, acrylic acid fluoride, and 1-trifluoromethacrylic acid fluoride when the adhesive part is a group having a carbonyl group or a bond. And monomers having fluorine such as perfluorobutenoic acid; monomers having no fluorine such as acrylic acid, methacrylic acid, acrylic acid chloride, and vinylene carbonate.
As a polymerization initiator used for introducing a carbonate group, diisopropyl peroxycarbonate, di-n-propyl peroxydicarbonate, t-butyl peroxyisopropyl carbonate, bis (4-t-butylcyclohexyl) peroxydi Examples thereof include carbonate and di-2-ethylhexyl peroxydicarbonate.

In the present specification, the base material (Ap) is a base material before causing an adhesive action with an adhesive site present in the fluororesin melt (Bp). In this respect, the fluororesin melt ( Bp) is a different concept from the base material (A) in which the adhesive action with the adhesive site is terminated and the fluororesin layer laminate exhibits the adhesiveness with the fluororesin layer (B). As said base material (Ap), what has a property which does not melt in melting | fusing point of the said melt-processable fluororesin is preferable.

The base material (Ap) has affinity or reactivity with the adhesive site of the fluoropolymer constituting the fluororesin melt (Bp).
It does not specifically limit as said base material (Ap), The base material which consists of resin, a metal, glass, a carbon material, a synthetic rubber, a natural fiber, paper etc. is mentioned. As said base material (Ap), a film, a plate-shaped body, etc. are preferable.

It does not specifically limit as resin in the said base material (Ap), Any of a thermoplastic resin and a thermosetting resin may be sufficient.
Examples of the thermoplastic resin and thermosetting resin include polyamide resin, polyester resin, polycarbonate resin, polyacetal resin, poly (meth) acrylate resin, styrene resin, ABS resin, polyvinyl chloride resin, ethylene vinyl alcohol resin, and cellulose resin. Examples include plastic, modified polyphenylene ether resin, polyimide resin, epoxy resin, unsaturated polyester resin, phenol resin, polyurethane resin, silicone resin, and the like, and polyimide resin is preferable.
It does not specifically limit as a metal in the said base material (Ap), For example, an aluminum-type metal, an iron-type metal, a copper-type metal, nickel, titanium, stainless steel etc. are mentioned.
It does not specifically limit as glass in the said base material (Ap), For example, foam glass, hard glass, soft glass etc. are mentioned.
Examples of the carbon material in the base material (Ap) include carbon fiber, graphite, and amorphous carbon.
As said base material (Ap), what consists of a polyimide resin is preferable, and it is more preferable that it is a polyimide film.

The base material (Ap) and / or the fluororesin melt (Bp) is appropriately blended with additives such as appropriate auxiliary agents, fillers, stabilizers, ultraviolet absorbers, pigments, etc., as long as their properties are not impaired. It may be what you did.
By blending the above additives, the thermal stability, surface hardness, abrasion resistance, weather resistance, and chargeability of the base material (A) and / or the fluororesin layer (B) constituting the resulting fluororesin layer laminate. Etc. can be improved.

The method for producing a fluororesin layer laminate of the present invention is to produce a fluororesin layer laminate by extrusion lamination, and the extrusion lamination is referred to as the above-described extrusion step (hereinafter, sometimes referred to as “extrusion step (a)”). In addition, the crimping step (b), in which the base material (Ap) and the fluororesin melt (Bp) extruded onto the base material (Ap) after the extrusion step are usually sandwiched between rolls, is obtained. It may also include a winding step (c) for winding the laminated product, and is usually performed in the order of the extrusion step (a), the crimping step (b), and the winding step (c).

In the extrusion lamination, the extrusion step (a) is a step of extruding the fluororesin melt (Bp) obtained by melting the melt processable fluororesin onto the base material (Ap) as described above.
In the extrusion step (a), the preferred temperature range varies depending on the composition of the base material (Ap) and the fluororesin melt (Bp) to be used, the thickness of the target fluororesin layer laminate, etc., but the interlayer adhesion strength In general, the lower limit is equal to or higher than the melting point of the melt processable fluororesin used for the fluororesin melt (Bp), and the upper limit is less than the decomposition temperature of the melt processable fluororesin. Perform in a certain temperature range.

In the extrusion step (a), the speed at which the fluororesin melt (Bp) is extruded onto the substrate (Ap) depends on the composition and thickness of the fluororesin melt (Bp) and the substrate (Ap) used. Although it can set suitably by thickness etc., it can carry out in the range of 0.1-100 m / min, for example.

The extrusion lamination, in particular, the extrusion step (a) is performed in an inert gas and / or the substrate is previously dried or preheated in that a fluororesin layer laminate having a high interlayer adhesion strength is obtained. It is preferable to remove the moisture. As will be described later, the extrusion lamination is considered to be characterized by exhibiting the adhesiveness of the adhesive site present in the fluororesin melt (Bp) by the extrusion process. It is considered that the above adhesiveness can be sufficiently exerted when it is carried out in the inside and / or when moisture is removed by previously drying or preheating the substrate. In order to improve the adhesion and stability of the laminate obtained by extrusion lamination, the laminate is laminated at a temperature that is higher than the melting point of the melt processability (thermal processability) fluororesin and lower than the decomposition temperature. Processing may be performed in an appropriate processing time depending on the shape of the body.

Each process condition other than the above-mentioned extrusion process (a) in the above-mentioned extrusion lamination depends on each component of the base material (Ap) and the fluororesin melt (Bp) to be used, the thickness of the target fluororesin layer laminate, etc. Accordingly, it can be appropriately set according to a known method.

Since the fluororesin layer laminate manufacturing method of the present invention is manufactured by performing the above extrusion lamination, a fluororesin layer laminate having a strong adhesive strength between the substrate (A) and the fluororesin layer (B) is obtained. It can be manufactured.
In the conventional method of laminating a film made of a fluororesin having an adhesive portion by performing thermal lamination, a laminate having a high interlayer adhesion strength was not obtained, but this was because of (1) moisture in the air, Oxygen, nitrogen, etc. acted on the surface of the fluororesin film and the adhesive strength of the adhesive part existing on the surface of the fluororesin film was reduced or partially lost. (2) During the cooling process during film formation or during film storage It is presumed that since the adhesive part is more easily oriented to the inside than the film surface, the adhesive part has failed to function for adhesion to other materials.
In the method for producing a fluororesin layer laminate of the present invention, in the extrusion lamination, the fluororesin melt (Bp) is obtained by melting a melt processable fluororesin, and thus in the fluororesin melt (Bp). It is considered that the adhesiveness of the adhesive part could be sufficiently exhibited by the extrusion process.
Further, in the method for producing a fluororesin layer laminate of the present invention, particularly when the base material (Ap) that does not melt at the melting point of the melt processable fluororesin is used, the coextrusion method cannot be used to laminate. A base material having a melting point higher than that of the fluororesin can be laminated.

The 1st fluororesin layer laminated body of this invention was manufactured with the above-mentioned fluororesin layer laminated body manufacturing method, It is characterized by the above-mentioned.
Since the 1st fluororesin layer laminated body of this invention is manufactured by the above-mentioned fluororesin layer laminated body manufacturing method, the base material (A) which comprises the said fluororesin layer laminated body, and the said fluororesin layer ( The adhesive strength with B) is greater than that of a laminate comprising a conventional base material (A) and a fluororesin layer (B).
The first fluororesin layer laminate of the present invention generally has the same properties as the second fluororesin layer laminate of the present invention described later. Hereinafter, although the 2nd fluororesin layer laminated body of this invention is demonstrated, this description corresponds also to the said 1st fluororesin layer laminated body of this invention. In the present specification, “the fluororesin layer laminate of the present invention” without “first” or “second” is the first fluororesin layer laminate of the present invention and the second of the present invention. And a fluororesin layer laminate.

The second fluororesin layer laminate of the present invention comprises a base material (A) and a fluororesin layer (B) formed by melting a melt processable fluororesin and in contact with the base material (A). It is a fluororesin layer laminate.

In the second fluororesin layer laminate of the present invention, the substrate (A) is derived from the substrate (Ap) before lamination. As said melt-processable fluororesin and said base material (Ap), the same thing as what was demonstrated in the fluororesin layer laminated body manufacturing method of this invention can be used, respectively. As the base material (A), those not melting at the melting point of the melt processable fluororesin are preferable, and those using a polyimide film are more preferable.
In the second fluororesin layer laminate of the present invention, the fluororesin layer (B) is formed by melting a melt processable fluororesin and is in contact with the base material (A). Is.
In the second fluororesin layer laminate of the present invention, the fluoropolymer that constitutes the melt-processable fluororesin that has undergone the melting has an adhesive part. As said adhesive part, the thing similar to what was demonstrated in the fluororesin layer laminated body manufacturing method of this invention, such as a carbon-carbon double bond, a carbonyl group, the group which has a carbonyl group, or a coupling | bonding, is mentioned, for example.

In the second fluororesin layer laminate of the present invention, the adhesive strength (x) between the substrate (A) and the fluororesin layer (B) is greater than the control adhesive strength (x ₀ ). It is shown.

The control adhesive strength (x ₀ ) is the fluorine in the control laminate formed by press-bonding the fluororesin film (Bf) formed by melting the melt processable fluororesin and the substrate (Ap) by thermal lamination. It is the adhesive strength between the resin film (Bf) and the substrate (Ap).
The pressure bonding in the thermal lamination depends on the type of the melt processable fluororesin and the base material (Ap), but the temperature at which the fluororesin melt (Bp) extruded in the extrusion lamination comes into contact with the base material (Ap); Although it can be performed by pressurizing under conditions according to the pressure in the pressure bonding step of extrusion lamination and the laminating speed in the pressure bonding step of extrusion lamination, the temperature is usually 10 ° C. higher than the melting point of the melt processable fluororesin. As mentioned above, it presses at the temperature which is below the decomposition temperature of a melt processable fluororesin.
The fluororesin film (Bf) is made of the above-mentioned fluoropolymer, but the fluororesin melt (in a molten state) in that it is obtained by film processing before the thermal lamination. Bp) is a different concept. Moreover, since the said fluororesin film (Bf) passed through the said film processing, it is thought that the adhesive activity of an adhesive part is lower than the said fluororesin melt (Bp).

In the present specification, the adhesive strength (x) and the reference adhesive strength (x ₀ ) are obtained by cutting a fluororesin layer laminate into a width of 10 mm, and peeling the fluororesin layer and the polyimide layer at the ends using a blade. This is the strength required when making a grip margin and peeling it 180 ° at a speed of 25 mm / min with a Tensilon universal testing machine.

The adhesive strength (x) varies depending on the composition, thickness, etc. of the base material (A) and the fluororesin layer (B) constituting the second fluororesin layer laminate of the present invention. It can be 2 times or more larger than the adhesive strength (x ₀ ), and further 5 times or more larger. For example, when the base material (A) is a polyimide film, the adhesive strength (x) is usually 1000 N / m or more, preferably 1500 N / m or more, and more preferably 2000 N / m or more.
Also in the first fluororesin layer laminate of the present invention, the adhesive strength (x) is greater than the control adhesive strength (x ₀₎ between the substrate (A) and the fluorine resin layer and (B) Can be shown.

For example, the second fluororesin layer laminate of the present invention is bonded by extrusion lamination including a step of extruding a fluororesin melt (Bp) obtained by melting a melt processable fluororesin onto a substrate (Ap). Can be obtained.

In the fluororesin layer laminate of the present invention, the thickness of each layer is selected according to the application and purpose and is not particularly limited. As the thickness of the substrate (A), for example, in the case of a packaging film, it is preferably 5 to 200 μm, more preferably 10 μm or more and 150 μm or less, and the thickness of the fluororesin layer (B) The thickness is preferably 5 to 200 μm, more preferably 10 μm to 100 μm.

The fluororesin layer laminate of the present invention may be a multilayer laminate comprising one or more other layers in addition to the base material (A) and the fluororesin layer (B). As said other layer, you may touch the outer surface of a base material (A), ie, a surface different from a contact surface with the said fluororesin layer (B), or a fluororesin layer (B) It may be in contact with an outer surface, that is, a surface different from the contact surface with the substrate (A), or may be in contact with both of them. As said other layer, a thermoplastic resin layer, a thermosetting resin layer, a metal foil etc. may be laminated | stacked by 1 layer or 2 layers or more, for example. As the material constituting the other layers, polyimide, copper, aluminum, stainless steel such as SUS, and the like are preferable.
In the method for producing a fluororesin layer laminate of the present invention described above, the multilayer laminate is a method of introducing the other layers together with the base material (Ap) and press-bonding; a method of using the laminate as the base material (Ap) A fluororesin layer laminate obtained from the fluororesin layer laminate production method of the present invention described above and the above-mentioned other layers can be produced by a known method.

As described above, the fluororesin layer laminate of the present invention can have an interlayer adhesion strength greater than the interlayer adhesion strength of the laminate obtained by thermal lamination. Materials that require mechanical strength, durability, etc., such as packaging materials; Signboards, building materials, exterior materials, roofing materials, waterproof sheets, roof waterproof sheets, building equipment, agricultural greenhouses, etc. It can be used as an interior material excellent in contamination resistance. Moreover, since the fluororesin layer laminate of the present invention has a fluororesin layer (B), it is necessary to have chemical resistance, such as a chemical solution bag and a chemical packaging material; a medical bag; a food packaging material; It can also be used for applications that require electrical characteristics, such as insulating tape, insulating layers for motors and generators for vehicles, flexible printed boards, semiconductor packages, and the like.
Furthermore, the fluororesin layer laminate of the present invention is a flexible disk plate, OA equipment housing, food processing equipment, cooking equipment, etc., devices and equipment that require antifouling, non-adhesive, and low friction properties; It can also be used in liquid crystal related materials such as oil repellent glass and liquid crystal displays; semiconductor related materials; automobile related materials; process materials such as release films.
When the fluororesin layer laminate of the present invention is the above-mentioned multilayer laminate, for example, a flexible printed board obtained by laminating a copper foil on a fluororesin layer of a laminate composed of polyimide resin and fluororesin; metal It can be used as a surface conductor with an insulating layer formed by laminating a metal foil on a fluororesin layer of a laminate composed of a foil and a fluororesin.

The fluororesin for extrusion lamination of the present invention is for constituting a fluororesin melt (Bp) that is extruded onto a substrate (Ap) in extrusion lamination.

Although it does not specifically limit as said extrusion lamination, What melt | dissolves a fluororesin melt (Bp) and includes the process extruded on a base material (Ap) is preferable.
The base material (Ap) is the same as described for the fluororesin layer laminate manufacturing method of the present invention.
The said fluororesin melt (Bp) is a thing of the molten state comprised from the fluororesin for extrusion laminations of this invention. As said fluororesin melt (Bp), what was demonstrated regarding the fluororesin layer laminated body manufacturing method of this invention is mentioned, for example.

The fluororesin for extrusion lamination of the present invention is made of a fluoropolymer having an adhesive site.
The adhesive part and the fluoropolymer are the same as those described for the method for producing a fluororesin layer laminate of the present invention.

As a fluororesin for extrusion lamination of this invention, it is preferable that a base material (Ap) is a polyimide film.

The fluoropolymer for extrusion lamination of the present invention is useful as a material for a fluororesin layer laminate having a high interlayer adhesive strength, such as the fluororesin layer laminate of the present invention, and is also suitable for the method for producing a fluororesin layer laminate of the present invention. It can be preferably used.

Since the fluororesin layer laminate manufacturing method of the present invention has the above-described configuration, it is excellent as a method for manufacturing a fluororesin layer laminate having a high interlayer adhesion strength. Moreover, since the fluororesin layer laminate of the present invention has the above-described configuration, it can be used for materials, equipment, and the like that have high interlayer adhesion strength and require mechanical strength, durability, and the like. Furthermore, since the fluororesin for extrusion lamination of the present invention has the above-described configuration, it can be preferably used as a material for a fluororesin layer laminate having a high interlayer adhesion strength.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

Synthesis Example 1 (Synthesis of melt processable fluororesin)
200L of pure water was put into a glass-lined autoclave with an internal volume of 820L, and the inside of the diameter was sufficiently replaced with nitrogen gas. It is. Next, 292 g of perfluoro (1,1,5-trihydro-1-pentene) [CH ₂ ═CF (CF ₂ ) ₃ H] was injected using nitrogen gas, the temperature in the tank was 35 ° C., and the stirring speed was It was kept at 200 rpm. Pressed until further comprising a tetrafluoroethylene 7.25 kg / cm ² G, then pressed until the ethylene 8kg / cm ² G.

Then, 1.9 kg of a 50 mass% methanol solution of di-n-propyl peroxydicarbonate was charged to initiate polymerization. Since the pressure in the tank decreases with the progress of polymerization, a mixed gas of tetrafluoroethylene / ethylene / hexafluoropropylene (molar ratio = 39.2: 43.6: 17.3) was additionally injected so that the polymerization pressure was 8 kg. Polymerization was continued while maintaining at / cm ² G, and CH ₂ ═CF (CF ₂ ) ₃ H 1100 g was divided into 20 portions and charged with a micropump during the polymerization for a total of 32 hours. After completion of the polymerization, the contents were collected and washed with water to obtain 95 kg of a powdered melt-processable fluororesin.

The following measurement was performed on the obtained melt-processable fluororesin.
(1) Monomer unit
¹⁹ F-NMR analysis was performed and measured.
(2) Carbonate number melt processable fluororesin powder was compression molded at room temperature to produce a film having a thickness of 0.05 to 0.2 mm. The obtained film was subjected to infrared absorption spectrum analysis, and the absorbance of the peak [1809 cm ⁻¹ (ν _C═O )] attributed to the carbonyl group in the carbonate group [—OC (═O) —O—] was measured. . From the obtained measured value, the number of carbonate groups per 1 × 10 ⁶ main chain carbon atoms was calculated based on the following formula.
N = 500 AW / εdf
A: Absorbance of ν _{C = O} ε: Molar absorbance coefficient [l · cm ⁻¹ · mol ⁻¹ ] at ν _C═O
(From the model compound, ε = 170.)
W: Composition average molecular weight calculated from the monomer composition d: Film density [g / cm ³ ]
f: Film thickness [mm] Measured with a micrometer.
The infrared absorption spectrum analysis was performed by scanning 40 times using a Perkin-Elmer FTIR spectrometer 1760X (manufactured by Perkin-Elmer). Absorbance analysis of ν _{C = O} was performed using Perkin-Elmer Spectrum for Windows Ver. Performed with 1.4C software.
(3) A melting point differential scanning calorimeter (manufactured by Seiko Co., Ltd.) was used to measure at a rate of temperature increase of 10 ° C./min.

The obtained melt processable fluororesin has a monomer unit of TFE / Et / HFP / [CH ₂ ═CF (CF ₂ ) ₃ H] = 38.9 / 45.9 / 14.8 / 0.4, The number of carbonate groups was 411 per 1 × 10 ⁶ main chain carbon atoms, and the melting point was 171.8 ° C.

Example 1
The following operation was performed using the extrusion laminator shown in the schematic diagram of FIG.
The melt processable fluororesin obtained in Synthesis Example 1 is heated and melted at 230 ° C. in an extruder (3), and then the fluororesin melt (Bp) when contacting with the polyimide film becomes 260 ° C. The film was extruded from the slit of the T die (4) whose temperature was set as described above. Furthermore, after laminating the fluororesin layer to a thickness of 100 μm on the polyimide film (Kapton 500H; manufactured by Toray DuPont, 125 μm thickness) fed from the base material feed section (5), a pressure roll (6 ) And the cooling roll (2).
The adhesive strength of the obtained fluororesin layer laminate (the thickness of the fluororesin layer; 100 μm, the thickness of the polyimide layer; 125 μm) was cut into a width of 10 mm, and the end of the fluororesin layer and the polyimide layer were cut using a blade. It was 2200 N / m when peeled 180 ° at a rate of 25 mm / min and measured using a Tensilon universal tester (Orientec).

Comparative Example 1
The following operation was performed using the thermal laminator shown in the schematic diagram of FIG.
A melt processable fluororesin film (100 μm thickness) obtained by molding using the melt processable fluororesin obtained in Synthesis Example 1 and a polyimide film (Kapton 500H; manufactured by Toray DuPont, 125 μm thickness) The laminate (the thickness of the fluororesin layer; the thickness of the fluororesin layer; inserted between the heating roll (10) and the pressure roll (9), which is 260 ° C. so that the polyimide film surface is on the heating roll (10) side. 100 μm, polyimide layer thickness; 125 μm).
It was 300 N / m when the adhesive strength of the laminated body obtained by carrying out similarly to Example 1 was measured.

From the above, the fluororesin layer laminate obtained from Example 1 has an adhesive strength exceeding 1000 N / m, but the laminate obtained from Comparative Example 1 has an adhesive strength of less than 500 N / m. I understood.

Since the fluororesin layer laminate manufacturing method of the present invention has the above-described configuration, it is excellent as a simple method for manufacturing a fluororesin layer laminate having a high interlayer adhesion strength. Moreover, since the fluororesin layer laminate of the present invention has the above-described configuration, it can be used for a material having high interlayer adhesion strength and requiring mechanical strength, durability, and the like. Furthermore, since the fluororesin for extrusion lamination of the present invention has the above-described configuration, it can be used as a suitable material for a fluororesin layer laminate having high interlayer adhesion strength.

1 is a schematic diagram of an extrusion laminator used in Example 1. FIG. 3 is a schematic diagram of a thermal laminator used in Comparative Example 1. FIG.

Explanation of symbols

1. 1. Laminate winding unit 2. Cooling roll Extruder 4. T-die 5. 5. Substrate delivery unit 6. pressure roll 7. Fluororesin film delivery section 8. Substrate delivery unit Pressure roll 10. 10. heating roll Laminate winding part

Claims (1)

A fluororesin layer laminate production method for producing a fluororesin layer laminate comprising a substrate (A) and a fluororesin layer (B) in contact with the substrate (A) by extrusion lamination,
The extrusion lamination includes a step of extruding a fluororesin melt (Bp) obtained by melting a melt processable fluororesin onto a substrate (Ap),
The fluoropolymer constituting the melt-processable fluororesin that has undergone the melting has an adhesive part,
The base material (Ap) is a polyimide film ,
The method for producing a fluororesin layer laminate , wherein the adhesive site is a carbon-carbon double bond, a carbonyl group, and / or a group or bond having a carbonyl group .

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