CN113227216A - Powder dispersion, method for producing laminate, method for producing polymer film, and method for producing coated woven fabric - Google Patents

Powder dispersion, method for producing laminate, method for producing polymer film, and method for producing coated woven fabric Download PDF

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Publication number
CN113227216A
CN113227216A CN201980085923.2A CN201980085923A CN113227216A CN 113227216 A CN113227216 A CN 113227216A CN 201980085923 A CN201980085923 A CN 201980085923A CN 113227216 A CN113227216 A CN 113227216A
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powder
polymer
dispersion
powder dispersion
laminate
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山边敦美
细田朋也
笠井涉
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AGC Inc
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Asahi Glass Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene

Abstract

The invention provides a powder dispersion, a method for manufacturing a laminate using the powder dispersion, a method for manufacturing a polymer film, and a method for manufacturing a coated fabric, wherein the powder dispersion comprises a non-hot-melt polytetrafluoroethylene powder or a hot-melt fluoropolymer powder and a predetermined tetrafluoroethylene polymer powder, and can form a molded article having excellent processability and exhibiting strong adhesiveness without impairing the physical properties of the two polymers. The powder dispersion of the present invention comprises: a powder (1) of a fluoropolymer having tetrafluoroethylene-based units and oxygen-containing polar groups, a powder (21) of non-fusible polytetrafluoroethylene or a powder (22) of a fusible fluoropolymer, and an aqueous medium.

Description

Powder dispersion, method for producing laminate, method for producing polymer film, and method for producing coated woven fabric
Technical Field
The present invention relates to a powder dispersion, a method for producing a laminate, a method for producing a polymer film, and a method for producing a coated woven fabric
Background
Fluoroolefin polymers such as Polytetrafluoroethylene (PTFE), a copolymer (PFA) of tetrafluoroethylene and perfluoro (alkyl vinyl ether), and a copolymer (FEP) of tetrafluoroethylene and hexafluoropropylene are excellent in physical properties such as mold release properties, electrical characteristics, water/oil repellency, chemical resistance, weather resistance, and heat resistance, and are used in various industrial applications by utilizing their physical properties.
Among them, when a powder dispersion liquid obtained by dispersing a powder of a fluoroolefin polymer in a solvent is applied to the surface of various substrates, the properties of the fluoroolefin polymer can be imparted to the surface, and therefore, the powder dispersion liquid is useful as a coating agent (see patent documents 1 and 2).
Documents of the prior art
Patent document
Patent document 1: international publication No. 2018/016644
Patent document 2: international publication No. 2008/018400
Disclosure of Invention
Technical problem to be solved by the invention
Fluoroolefin-based polymers each have inherent properties.
It is known that non-fusible polytetrafluoroethylene has specific physical properties represented by fibrillar properties. It is considered that when a dispersion in which a powder of non-heat-fusible polytetrafluoroethylene and a powder of a heat-fusible fluoroolefin polymer such as PFA or FEP are mixed is used, a molded article having both of the physical properties of the two polymers can be formed.
However, the dispersion has a low dispersibility, and when the dispersion is adjusted to a uniform dispersion, or the dispersion is redispersed after a lapse of time, or a dispersion treatment such as application of a shear stress is performed to further incorporate other components, the non-heat-fusible polytetrafluoroethylene is fibrillated and is thereby deteriorated, which has a technical problem that the dispersibility and the moldability are deteriorated.
Further, molded articles formed from the dispersion have a technical problem that mechanical strength such as crack resistance and adhesiveness are not yet sufficient. In particular, when the thickness of the molded article is increased or the molded article is subjected to drawing, the crack resistance and the adhesiveness are still insufficient.
On the other hand, a hot-melt fluoropolymer such as modified PTFE, PFA, FEP, or the like has excellent heat resistance, chemical resistance, and the like, and also has excellent moldability, as in PTFE. However, the adhesiveness and processability (flexibility such as stretchability and bending processability) of the molded article to other materials are still insufficient, and this tendency is particularly remarkable in a molded article formed from an aqueous dispersion of a powder of a hot-melt fluoropolymer. Further, when a component for improving adhesiveness and processability is added to the aqueous dispersion, there is a problem that the dispersion state of the dispersion is lowered and the physical properties of the fluoropolymer of the molded article are lowered.
An object of the present invention is to provide a powder dispersion containing a powder of non-fusible polytetrafluoroethylene or a powder of fusible fluoropolymer, and a powder of a predetermined tetrafluoro polymer, which can form a molded article having excellent processability and exhibiting strong adhesiveness without impairing the physical properties of the two polymers, a method for producing a laminate using the powder dispersion, a method for producing a polymer film, and a method for producing a coated woven fabric.
Technical scheme for solving technical problem
The present invention has the following technical contents.
< 1 > a powder dispersion comprising: a powder (1) of a fluoropolymer having tetrafluoroethylene-based units and oxygen-containing polar groups, a powder (21) of non-fusible polytetrafluoroethylene or a powder (22) of a fusible fluoropolymer, and an aqueous medium.
< 2 > the powder dispersion as described in < 1 >, wherein the powder (1) has a cumulative 50% diameter on a volume basis of 0.01 to 75 μm, and the powder (21) or the powder (22) has a cumulative 50% diameter on a volume basis of 0.01 to 100 μm.
The powder dispersion liquid of < 3 > such as < 1 > or < 2 > wherein the mass ratio of the content of the fluoropolymer to the content of the non-hot-melt polytetrafluoroethylene or the content of the hot-melt fluoropolymer is 0.4 or less.
The powder dispersion of any one of < 4 > to < 1 > -3 > wherein the fluoropolymer has a melting temperature of 140-320 ℃.
The powder dispersion as described in any of < 5 > to < 4 >, wherein the fluoropolymer contains units based on the monomer having the oxygen-containing polar group.
The powder dispersion as described in any of < 6 > to < 5 >, wherein the oxygen-containing polar group is a hydroxyl-containing group or a carbonyl-containing group.
The powder dispersion of any one of < 7 > to < 6 >, wherein the non-fusible polytetrafluoroethylene has fibrillating properties.
The powder dispersion of any one of < 8 > to < 7 >, wherein the hot-melt fluoropolymer is a modified polytetrafluoroethylene, a copolymer of tetrafluoroethylene and perfluoro (alkyl vinyl ether), or a copolymer of tetrafluoroethylene and hexafluoropropylene.
The powder dispersion of any one of < 9 > to < 1 > -8 > comprising both the powder (21) of the non-fusible polytetrafluoroethylene and the powder (22) of the fusible fluoropolymer.
The powder dispersion of any one of < 10 > to < 1 > < 9 >, which further comprises an acetylene-based surfactant, a silicone-based surfactant or a fluorine-based surfactant.
The powder dispersion of any one of < 11 > to < 10 >, wherein the dispersion further contains a fluorine-based surfactant, and the fluorine-based surfactant is a fluorinated monohydric alcohol or a fluorinated polyhydric alcohol.
< 12 > a method for producing a laminate, which comprises applying the powder dispersion as described in any one of < 1 > -11 > to the surface of a substrate, and heating to remove the aqueous medium to form a polymer layer, thereby obtaining a laminate in which a substrate layer comprising the substrate and the polymer layer are laminated in this order.
< 13 > a method for producing a polymer film, which comprises applying the powder dispersion as defined in any one of < 1 > -11 > to a surface of a substrate, removing the aqueous medium by heating to form a polymer layer, thereby obtaining a laminate in which a base layer comprising the substrate and the polymer layer are sequentially laminated, and removing the base layer from the laminate, thereby obtaining a polymer film comprising the polymer layer.
< 14 > a method for producing a coated woven fabric, which comprises impregnating a woven fabric with the powder dispersion as defined in any one of < 1 > to < 11 > and drying the woven fabric to obtain a woven fabric coated with a polymer layer.
Effects of the invention
The invention provides a powder dispersion which is excellent in state stability such as dispersibility and storage stability and can form a molded article which is less likely to crack and exhibits strong adhesiveness without impairing the physical properties of non-fusible polytetrafluoroethylene, and a powder dispersion which is excellent in state stability and can form a molded article which exhibits strong adhesiveness and good processability without impairing the physical properties of a fusible fluoropolymer. Also disclosed are a method for producing a laminate, a method for producing a polymer film, and a method for producing a coated woven fabric, each using the powder dispersion.
Detailed Description
"D50 of the powder" means a cumulative 50% diameter on a volume basis, and means a particle size distribution measured by a laser diffraction/scattering method, and a cumulative curve obtained by taking the total volume of the particle group as 100% is a point on the cumulative curve where the cumulative volume reaches 50%.
"D90 of the powder" means a cumulative 90% diameter on a volume basis, and means a particle size distribution measured by a laser diffraction/scattering method, and a cumulative curve obtained by taking the total volume of the particle group as 100% is a point on the cumulative curve where the cumulative volume reaches 90%.
The "unit" in the polymer may be a radical formed directly from a monomer by polymerization, or a radical obtained by treating a polymer obtained by polymerization by a predetermined method to convert a part of the structure. In addition, units based on monomer A are also referred to as monomer A units.
The "viscosity of the powder dispersion" is a value measured at room temperature (25 ℃) at 30rpm using a B-type viscometer. The measurement was repeated 3 times, and the average of the 3 measurements was taken.
"thixotropic ratio of powder dispersion" means a viscosity eta measured at a rotation speed of 30rpm1Divided by the viscosity eta determined at a speed of 60rpm2The calculated value. The measurement of each viscosity was repeated 3 times, and the average of the 3 measurements was taken.
The "melting temperature (melting point) of a polymer" means a temperature corresponding to the maximum value of the melting peak of the polymer measured by a Differential Scanning Calorimetry (DSC) method.
The "peel strength of the laminate" means the maximum load (N/cm) applied when the metal foil and the resin layer are peeled from the laminate at 90 ° from the other end in the longitudinal direction at a stretching speed of 50 mm/min by fixing the laminate at a position 50mm apart from one end in the longitudinal direction of the laminate cut into a rectangular shape (100 mm in length and 10mm in width).
"Standard specific gravity of a polymer" is the standard specific gravity of a polymer measured according to ASTM D4895.
"melt flow rate" is JIS K7210-1: 2014 (corresponding to the Melt Flow Rate (MFR) specified in International Specification ISO 1133-1: 2011).
The powder dispersion of the present invention (present dispersion) comprises: a powder (1) comprising Tetrafluoroethylene (TFE) -based units (TFE units) and an oxygen-containing polar group-containing polymer (hereinafter also referred to as "F polymer"), a powder (21) of non-fusible polytetrafluoroethylene (hereinafter also referred to as "non-fusible PTFE") or a powder (22) of a fusible fluoropolymer (hereinafter also referred to as "M polymer"), and an aqueous medium.
The present dispersion can also be said to be a dispersion in which the powder (1) and the powder (21) or the powder (22) are dispersed in the form of particles in an aqueous medium containing water as a main component.
In addition, the F polymer, the non-heat-fusible PTFE, and the M polymer are different polymers from each other.
The molded article (including molded parts such as polymer layers, the same applies hereinafter) formed from the dispersion has the specific properties of each fluoropolymer, such as the fibrillating property of non-heat-fusible PTFE and the processability of a heat-fusible fluoropolymer, and exhibits strong adhesiveness and crack resistance.
The reason is not clear, but the following is considered.
In the present dispersion containing the powder (21), both the non-fusible PTFE and the F polymer are polymers containing TFE units, and they interact with each other, and therefore, they are easily fused and joined. Further, it is considered that since the F polymer has an oxygen-containing polar group, it has high stability in an aqueous medium, and also interacts with non-heat-fusible PTFE, thereby improving the dispersion stability of the powder thereof. As a result, it is considered that the two powders are stably and uniformly dispersed in the aqueous medium, and the state stability of the present dispersion is excellent.
Further, it is considered that the F polymer having an oxygen-containing polar group not only exhibits adhesiveness but also promotes interaction between polymers, for example, promotes formation of a matrix, when a molded article is formed. It is considered that the interaction causes each polymer chain to be easily entangled uniformly. As a result, it is considered that a molded article having excellent adhesiveness and crack resistance can be formed from the dispersion without impairing the properties of the non-heat-fusible PTFE.
On the other hand, in the present dispersion liquid containing the powder (22), both the M polymer and the F polymer are polymers having fluorine atoms, and they interact with each other and are easily welded and joined. Further, it is considered that since the F polymer has an oxygen-containing polar group, its stability in an aqueous medium is high, and interaction with the M polymer also occurs, thereby improving the dispersion stability of its powder. As a result, it is considered that the two powders are stably and uniformly dispersed in the aqueous medium, and the state stability of the present dispersion is excellent.
Further, it is considered that the F polymer having an oxygen-containing polar group not only exhibits adhesiveness but also promotes interaction between polymers, for example, promotes formation of a matrix, when a molded article is formed. It is considered that the interaction causes each polymer chain to be easily entangled uniformly. As a result, it is considered that a molded article having excellent adhesiveness and processability can be formed from the dispersion without impairing the properties of the M polymer.
The powder (1) of the present invention is a powder comprising an F polymer, preferably a powder composed of an F polymer. The content of the F polymer in the powder (1) is preferably 80% by mass or more, and particularly preferably 100% by mass.
D50 in the powder (1) is preferably 0.01 to 75 μm, more preferably 0.05 to 6 μm, and still more preferably 0.1 to 4 μm. Suitable forms of D50 in the powder (1) include a form of 0.1 μm or more and less than 1 μm and a form of 1 μm or more and 4 μm or less.
D90 in powder (1) is preferably 8 μm or less, more preferably 6 μm or less. D90 in powder (1) is preferably 0.1 μm or more, more preferably 0.3 μm or more. Suitable forms of D90 in the powder (1) include a form of 0.3 to less than 2 μm and a form of 2 to 6 μm.
In this case, the dispersion stability of the dispersion and the physical properties of the molded article can be further improved. For example, when D50 of powder (1) is 0.1 μm or more and less than 1 μm, the dispersibility thereof is more excellent, and a molded article excellent in mechanical strength such as tensile properties can be easily obtained. When D50 of powder (1) is 1 to 4 μm, a molded article having excellent crack resistance can be easily obtained.
The oxygen-containing polar group of the F polymer of the present invention may be contained in a unit based on a monomer having an oxygen-containing polar group, may be contained in a polymer terminal group, and may be contained in the polymer by surface treatment (radiation treatment, electron beam treatment, corona treatment, plasma treatment, or the like), and the first is preferable. The oxygen-containing polar group of the F polymer may be a group obtained by modifying a polymer having a group capable of forming an oxygen-containing polar group. The oxygen-containing polar group contained in the polymer terminal group can be obtained by adjusting components (a polymerization initiator, a chain transfer agent, and the like) used in polymerization of the polymer.
The oxygen-containing polar group is a polar atomic group containing an oxygen atom. However, the oxygen-containing polar group does not include an ester bond itself and an ether bond itself, but includes an atomic group contained with these bonds as characteristic groups.
The oxygen-containing polar group is preferably at least 1 group selected from the group consisting of a hydroxyl-containing group, a carbonyl-containing group, an acetal group and an oxirane group, more preferably a hydroxyl-containing group or a carbonyl-containing group, and still more preferably-CF2CH2OH、-C(CF3)2OH, 1, 2-diol group (-CH (OH) CH2OH)、-CF2C (O) OH, > CFC (O) OH, carboxamide (-C (O) NH)2Etc.), acid anhydride residue (-C (O) OC (O) -), imide residue (-C (O) NHC (O) -, etc.), dicarboxylic acid residue (-CH (C (O) OH) CH2C (O) OH, etc.) or a carbonate group (-OC (O) O-).
The oxyalkylene group is preferably an epoxy group or an oxetane group.
In addition, the oxygen-containing polar group is a cyclic group or a ring-opening group thereof as a polar group, and a cyclic acid anhydride residue, a cyclic imide residue, a cyclic carbonate group, a cyclic acetal group, a1, 2-dicarboxylic acid residue, or a1, 2-diol group is particularly preferable, and a cyclic acid anhydride residue is most preferable, from the viewpoint of not impairing the adhesiveness and crack resistance of the molded article and the physical properties of the polymer.
The F polymer is preferably a polymer comprising TFE units, and units based on Hexafluoropropylene (HFP) or perfluoro (alkyl vinyl ether) (hereinafter also referred to as "PAVE") or fluoroalkyl ethylene (hereinafter also referred to as "FAE units") (hereinafter also referred to as "PAE units"), and units based on monomers having an oxygen-containing polar group (hereinafter also referred to as "polar units").
The proportion of the TFE unit in the total units constituting the F polymer is preferably 50 to 99 mol%, more preferably 90 to 99 mol%.
The PAE units are preferably PAVE-based units or HFP-based units, more preferably PAVE-based units. The number of PAE units may be 2 or more.
The proportion of the PAE unit in the total units constituting the F polymer is preferably 0.5 to 9.97 mol%.
As PAVE, CF is mentioned2＝CFOCF3(PMVE)、CF2＝CFOCF2CF3、CF2＝CFOCF2CF2CF3(PPVE)、CF2＝CFOCF2CF2CF2CF3、CF2＝CFO(CF2)8F, preferably PMVE or PPVE.
As FAE, CH may be mentioned2＝CH(CF2)2F(PFEE)、CH2＝CH(CF2)3F、CH2＝CH(CF2)4F(PFBE)、CH2＝CF(CF2)3H、CH2＝CF(CF2)4H, preferably PFEE or PFBE.
The polar unit is preferably a unit based on a monomer having an acid anhydride residue, a carbonate group, a cyclic acetal group, a1, 2-dicarboxylic acid residue, a1, 2-diol residue, or a1, 3-diol residue, more preferably a unit based on a monomer having a cyclic acid anhydride residue or a cyclic carbonate group, and still more preferably a unit based on a monomer having a cyclic acid anhydride residue. The number of the polar units may be 1 or 2 or more.
The monomer having a cyclic acid anhydride residue is preferably itaconic anhydride, citraconic anhydride, 5-norbornene-2, 3-dicarboxylic anhydride (alias: nadic anhydride; hereinafter also referred to as "NAH") or maleic anhydride, and more preferably NAH.
The proportion of the polar unit in the total units constituting the F polymer is preferably 0.01 to 3 mol%.
In addition, the F polymer in this case may further contain a unit (hereinafter also referred to as "other unit") other than the TFE unit, the PAE unit, and the polar unit. The number of other units may be 1 or 2 or more.
Examples of the monomer forming the other unit include ethylene, propylene, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride (VDF), and Chlorotrifluoroethylene (CTFE). The other unit is preferably ethylene, VDF or CTFE, more preferably ethylene.
The proportion of the other units in the F polymer in the total units constituting the F polymer is preferably 0 to 50 mol%, more preferably 0 to 40 mol%.
The melting temperature of the F polymer is preferably 140 to 320 ℃, more preferably 200 to 320 ℃, and further preferably 260 to 320 ℃. In this case, the fusion bondability between the F polymer and the non-heat-fusible PTFE is balanced, and the adhesiveness and crack resistance of the molded article are further improved, and the physical properties of the non-heat-fusible PTFE are not easily damaged.
The dispersion liquid may contain the powder (21) or the powder (22), may contain only the powder (21), may contain only the powder (22), or may contain both the powder (21) and the powder (22).
The powder (21) is a powder containing non-hot-melt PTFE, preferably a powder composed of non-hot-melt PTFE. The content of the non-heat-fusible PTFE in the powder (21) is preferably 80% by mass or more, and more preferably 100% by mass. In the present specification, components (such as a surfactant) used for producing the non-heat-fusible PTFE are not included in components other than the non-heat-fusible PTFE.
The powder (22) of the present invention is a powder containing an M polymer, and preferably a powder composed of an M polymer. The content of the M polymer in the powder (22) is preferably 80% by mass or more, more preferably 100% by mass.
D50 of the powder (21) is preferably 0.01 to 100. mu.m, more preferably 0.1 to 10 μm. A preferable form of D50 of the powder (21) is 0.1 to 1 μm.
D90 of powder (21) is preferably 200 μm or less, more preferably 20 μm or less. D90 of powder (21) is preferably 0.1 μm or more, more preferably 0.2 μm or more. A specific preferable form of D90 in the powder (21) is 0.1 to 2 μm.
In this case, the dispersibility of the powder (1) and the interaction between the powders are improved, and the physical properties of the dispersion and the molded article are easily further improved.
Suitable forms of the relationship between D50 in powder (1) and D50 in powder (21) include a form in which D50 in powder (1) is 0.1 μm or more and less than 1 μm or more and 4 μm or less, and D50 in powder (21) is 0.1 μm or more and 1 μm or less. In the former form, the dispersion has excellent dispersibility, and a molded article having excellent mechanical strength such as tensile properties can be easily obtained. In the latter form, a molded article excellent in crack resistance can be easily obtained.
D50 of the powder (22) is preferably 0.01 to 100 μm, more preferably 0.1 to 10 μm. A preferable form of D50 of the powder (22) is 0.1 to 1 μm.
D90 of the powder (22) is preferably 200 μm or less, more preferably 20 μm or less. D90 of powder (22) is preferably 0.1 μm or more, more preferably 0.2 μm or more. A preferable form of D90 of the powder (22) is 0.1 to 2 μm. In this case, the dispersibility of the powder (22) and the interaction with the powder (1) become good, and the adhesiveness and the crack resistance of the molded article and the physical properties of the M polymer are easily further improved.
Suitable forms of the relationship between D50 in powder (1) and D50 in powder (22) include a form in which D50 in powder (1) is 0.1 μm or more and less than 1 μm, a form in which D50 is 1 μm or more and 4 μm or less, and a form in which D50 in powder (22) is 0.1 μm or more and 1 μm or less. In the former form, the dispersion has excellent dispersibility, and a molded article having excellent mechanical strength such as tensile properties can be easily obtained. In the latter form, a molded article excellent in crack resistance can be easily obtained.
The non-heat-fusible PTFE is Polytetrafluoroethylene (PTFE), and contains a modified PTFE which is a copolymer of TFE and a very small amount of a comonomer (PAVE, HFP, FAE, or the like) in addition to a homopolymer of TFE.
As described above, the molded article obtained from the dispersion exhibits strong adhesiveness and crack resistance, and the fibrous surface properties and porosity of the molded article of non-heat-fusible PTFE are not easily impaired.
The proportion of TFE units in the non-fusible PTFE in the total units is preferably 99.5 mol% or more, and more preferably 99.9 mol% or more.
The non-heat-fusible PTFE is preferably a polymer obtained by emulsion polymerization of TFE in water. The non-heat-fusible PTFE powder is a powder in which a polymer obtained by emulsion polymerization of TFE in water is dispersed in water in the form of particles. When the powder is used, the powder dispersed in water may be used as it is, or the powder may be recovered from water and used.
Non-heat-fusible PTFE is widely available from commercial products in the form of powder and dispersion thereof.
The non-hot-melt PTFE preferably has fibrillar properties. If the fibrillicity is present, the porous film can be more easily produced by the stretching treatment. The non-heat-fusible PTFE having fibril properties means PTFE in which an unfired polymer powder can be extruded in a paste form. That is, the term "PTFE" refers to PTFE having strength and ductility in a molded product obtained by paste extrusion.
The number average molecular weight of the non-heat-fusible PTFE is preferably from 30 to 30000 ten thousand, more preferably from 50 to 2500 ten thousand.
The standard specific gravity as an index of the average molecular weight of the non-heat-fusible PTFE is preferably 2.14 to 2.22, more preferably 2.15 to 2.21.
The melt viscosity of the non-heat-fusible PTFE at 380 ℃ is preferably 1X 109Pa · s or more. The upper limit of the melt viscosity is usually 1X 1010Pa·s。
When at least one of the number average molecular weight, standard specific gravity and melt viscosity of the non-fusible PTFE is within the above range, the fibrillating property of the non-fusible PTFE becomes better, and a molded article having more excellent mechanical properties and the like can be formed. In this case, the stability of the state of the dispersion liquid can be improved more easily.
The M polymer is a polymer containing a unit based on a fluoroolefin different from the F polymer (hereinafter also referred to as "F unit"), and preferably a polymer having no oxygen-containing polar group containing the F unit.
The proportion of the F unit in the M polymer in the whole unit is preferably 50.0 mol% or more, more preferably 99.5 mol% or more, and still more preferably 99.9 mol% or more.
The fluoroolefin in the M polymer is preferably TFE or VDF, more preferably TFE. The fluoroolefin may be 2 or more.
The M polymer is preferably a copolymer of TFE and PAVE (PFA), a copolymer of TFE and HFP (FEP), a copolymer of TFE and ethylene (ETFE), a homopolymer of VDF (PVDF), or a low molecular weight PTFE, more preferably a low molecular weight PTFE.
In addition to the homopolymer of TFE, low molecular weight PTFE includes a modified PTFE which is a copolymer of TFE with a very small amount of a comonomer (PAVE, HFP, FAE, or the like). In addition, PFAs can comprise units based on monomers other than TFE and PAVE. The same applies to the other copolymers (FEP, ETFE, PVDF).
As a suitable form of the M polymer, low molecular weight PTFE or modified PTFE can be mentioned.
In this case, the melt viscosity of the M polymer at 380 ℃ is preferably 1X 102～1×106Pa · s, more preferably 1X 103～1×106Pa·s。
In this case, the melting temperature of the polymer is preferably 321 to 340 ℃, more preferably 325 to 335 ℃.
In this case, the melt flow rate of the polymer is preferably 1 to 10g/10 min, more preferably 1 to 5g/10 min.
When at least one of the melt viscosity, melt flow rate, and melt temperature of the low molecular weight PTFE or modified PTFE is within the above range, a molded article having more excellent physical properties (processability, mechanical strength, etc.) of the PTFE can be formed. In this case, the interaction between the powder (22) and the powder (1) in the dispersion is improved, and the stability of the state of the dispersion is more easily improved.
The low molecular weight PTFE may be a high molecular weight PTFE (melt viscosity of 1X 10)9～1×1010Pa · s) or more, or PTFE obtained by polymerizing TFE to produce PTFE by adjusting a chain transfer agent (polymers described in international publication nos. 2018/026012, 2018/026017, etc.) (see japanese patent laid-open publication nos. 2009-1745, 2010/114033, 2015-2320)82, etc.).
A suitable example of the low molecular weight PTFE is PTFE having a number average molecular weight (Mn) of 20 ten thousand or less calculated according to the following formula (1).
Mn＝2.1×1010×ΔHc-5.16…(1)
In the formula (1), Δ Hc represents the heat of crystallization (cal/g) of the PTFE measured by differential scanning calorimetry.
The Mn of the low molecular weight PTFE is preferably 10 or less, more preferably 5 ten thousand or less. The Mn of the low molecular weight PTFE is preferably 1 ten thousand or more.
In addition, PFA or FEP is one suitable form of the M polymer.
In this case, the melt viscosity of the M polymer at 380 ℃ is preferably 1X 102～1×104Pa · s, more preferably 1X 102～1×103Pa·s。
In this case, the melt flow rate of the M polymer is preferably 5 to 30g/10 min, more preferably 5 to 20g/10 min.
In this case, the melting temperature of the M polymer is preferably 260 to 320 ℃, more preferably 280 to 310 ℃.
When at least one of the melt viscosity, melt flow rate and melting temperature of PFA or FEP falls within the above range, not only can a molded article having more excellent physical properties (processability, mechanical strength, etc.) of PFA or FEP be formed, but also the state stability of the dispersion can be more easily improved.
The M polymer is preferably a polymer obtained by emulsion polymerization of a fluoroolefin in water. The powder of the M polymer is a powder in which a polymer obtained by emulsion polymerization of a fluoroolefin in water is dispersed in water in the form of particles. When the powder is used, the powder dispersed in water may be used as it is, or the powder may be recovered from water and used.
The M polymer may be modified by surface treatment (radiation treatment, electron beam treatment, corona treatment, plasma treatment, etc.). Examples of the surface treatment method include those described in international publication No. 2018/026012 and international publication No. 2018/026017.
M polymers are widely available from commercial sources as powders and dispersions thereof.
The dispersion may contain only non-hot-melt PTFE, only M polymer, or both non-hot-melt PTFE and M polymer. In addition, each polymer is preferably contained in a powder form.
When the dispersion contains both non-heat-fusible PTFE and M polymer, the D50 of the powder of non-heat-fusible PTFE (powder (21)) is preferably 0.1 to 1 μ M, and the D90 thereof is preferably 0.1 to 2 μ M. In this case, D50 of the M polymer powder (22)) is preferably 0.1 to 1 μ M, and D90 thereof is preferably 0.1 to 2 μ M.
In this case, the mass ratio of the content of the F polymer to the content of the non-heat-fusible PTFE or the content of the M polymer in the present dispersion is preferably 0.4 or less, and more preferably 0.15 or less. In this case, the interaction between the powders is improved, the stability of the state of the dispersion is further improved, and the adhesiveness and crack resistance of the molded article and the physical properties of the polymers are easily balanced.
In this case, the total content of the non-heat-fusible PTFE and the M polymer is preferably 20 to 70% by mass, and more preferably 30 to 60% by mass.
From the viewpoint of improving the dispersibility of each powder and improving the moldability thereof, the dispersion preferably contains a dispersant. Further, the components used in the production of the polymer (for example, the surfactant used in the emulsion polymerization of the fluoroolefin) do not belong to the dispersant of the present invention.
The dispersant is preferably a compound having a hydrophobic site and a hydrophilic site, and examples thereof include acetylene surfactants, silicone surfactants, and fluorine surfactants. These dispersants are preferably nonionic.
The dispersant is preferably a fluoroalcohol, more preferably a fluoromonohydric alcohol or a fluoropolyhydric alcohol.
The fluorine content of the fluorinated monool is preferably 10 to 50% by mass, more preferably 10 to 45% by mass, and further preferably 15 to 40% by mass.
The fluorinated monoalcohol is preferably nonionic.
The hydroxyl value of the fluorinated monool is preferably 40 to 100mgKOH/g, more preferably 50 to 100mgKOH/g, and still more preferably 60 to 100 mgKOH/g.
The fluorinated monoalcohol is preferably a compound represented by the following formula (a).
Formula (a): ra-(OQa)ma-OH
The symbols in the formula represent the following meanings.
RaRepresents a polyfluoroalkyl group or a polyfluoroalkyl group containing an etheric oxygen atom, preferably-CH2(CF2)4F、-CH2(CF2)6F、-CH2CH2(CF2)4F、-CH2CH2(CF2)6F、-CH2CF2OCF2CF2OCF2CF3、-CH2CF(CF3)CF2OCF2CF2CF3、-CH2CF(CF3)OCF2CF(CF3)OCF3or-CH2CF2CHFO(CF2)3OCF3。
QaAn alkylene group having 1 to 4 carbon atoms, preferably an ethylene group (-CH)2CH2-) or propylene (-CH)2CH(CH3)-)。QaMay be composed of 2 or more groups. When the group is composed of 2 or more groups, the arrangement of the groups may be random or block.
ma represents an integer of 0 to 20, preferably an integer of 4 to 10.
The hydroxyl group of the fluoromonoalcohol is preferably a secondary hydroxyl group or a tertiary hydroxyl group, and particularly preferably a secondary hydroxyl group.
Specific examples of the fluoromonohydric alcohol include F (CF)2)6CH2(OCH2CH2)7OCH2CH(CH3)OH、F(CF2)6CH2(OCH2CH2)12OCH2CH(CH3)OH、F(CF2)6CH2CH2(OCH2CH2)7OCH2CH(CH3)OH、F(CF2)6CH2CH2(OCH2CH2)12OCH2CH(CH3)OH、F(CF2)4CH2CH2(OCH2CH2)7OCH2CH(CH3)OH。
The fluorinated monool is commercially available as "Fluowet N083" or "Fluowet N050" manufactured by Okara Kabushiki Kaisha (アークロマ Co., Ltd.).
The fluorine content of the fluorinated polyol is preferably 10 to 50% by mass, more preferably 10 to 45% by mass, and still more preferably 15 to 40% by mass.
The fluoropolyol is preferably nonionic.
The hydroxyl value of the fluorinated polyol is preferably 10 to 35mgKOH/g, more preferably 10 to 30mgKOH/g, and still more preferably 10 to 25 mgKOH/g.
The weight average molecular weight of the fluoropolyol is preferably 2000 to 80000, more preferably 6000 to 20000.
The fluorinated polyol is preferably a fluorinated polyol comprising units based on a fluoro (meth) acrylate. In addition, "(meth) acrylate" refers to a generic name of acrylate and methacrylate.
The fluoro (meth) acrylate is preferably a monomer represented by the following formula (f).
Formula (f): CH (CH)2＝CXfC(O)O-Qf-Rf
The symbols in the formula represent the following meanings.
XfRepresents a hydrogen atom, a chlorine atom or a methyl group.
QfRepresents an alkylene group having 1 to 4 carbon atoms or an oxyalkylene group having 2 to 4 carbon atoms.
RfRepresents a C1-6 polyfluoroalkyl group, a C3-6 polyfluoroalkyl group containing an etheric oxygen atom, or a C4-12 polyfluoroalkyl group, preferably-CF (CF)3)(C(CF(CF3)2)(＝C(CF3)2))、-C(CF3)＝C(CF(CF3)2)2、-(CF2)4F or- (CF)2)6F。
Specific examples of the fluoro (meth) acrylate include CH2＝CHC(O)OCH2CH2(CF2)4F、CH2＝C(CH3)C(O)OCH2CH2(CF2)4F、CH2＝CHC(O)OCH2CH2(CF2)6F、CH2＝C(CH3)C(O)OCH2CH2(CF2)6F、CH2＝CHC(O)OCH2CH2OCF(CF3)(C(CF(CF3)2)(＝C(CF3)2))、CH2＝C(CH3)C(O)OCH2CH2OC(CF3)＝C(CF(CF3)2)2、CH2＝CHC(O)OCH2CH2CH2CH2OCF(CF3)(C(CF(CF3)2)(＝C(CF3)2))、CH2＝C(CH3)C(O)OCH2CH2CH2CH2OC(CF3)＝C(CF(CF3)2)2。
Suitable examples of the fluoropolyol include copolymers of a monomer represented by the above formula (f) and a monomer represented by the following formula (o).
Formula (o): CH (CH)2＝CXoC(O)-(OZo)mo-OH
The symbols in the formula represent the following meanings.
XoRepresents a hydrogen atom or a methyl group.
ZoAn alkylene group having 1 to 4 carbon atoms, preferably an ethylene group (-CH)2CH2-)。
mo is an integer of 1 to 200, preferably an integer of 4 to 30.
In addition, ZoMay be composed of 2 or more groups. In this case, the arrangement of the different alkylene groups may be random or block.
The use of the compound represented by the formula (o) not only makes the dispersion excellent in dispersibility, but also makes it easy to particularly improve physical properties such as wettability and adhesiveness of a molded article.
Specific examples of the monomer represented by the formula (o) include CH2＝CHCOO(CH2CH2O)8OH、CH2＝CHCOO(CH2CH2O)10OH、CH2＝CHCOO(CH2CH2O)12OH、CH2＝CHCOOCH2CH2CH2CH2O(CH2CH2O)8OH、CH2＝CHCOOCH2CH2CH2CH2O(CH2CH2O)10OH、CH2＝CHCOOCH2CH2CH2CH2O(CH2CH2O)12OH、CH2＝C(CH3)COO(CH2CH(CH3)O)8OH、CH2＝C(CH3)COO(CH2CH(CH3)O)12OH、CH2＝C(CH3)COO(CH2CH(CH3)O)16OH、CH2＝C(CH3)COOCH2CH2CH2CH2O(CH2CH(CH3)O)8OH、CH2＝C(CH3)COOCH2CH2CH2CH2O(CH2CH(CH3)O)12OH、CH2＝C(CH3)COOCH2CH2CH2CH2O(CH2CH(CH3)O)16OH。
The fluoropolyol may be composed of only a unit based on the monomer represented by the formula (f) and a unit based on the monomer represented by the formula (o), or may further contain other units.
The content of the unit based on the monomer represented by the formula (f) is preferably 60 to 90 mol%, more preferably 70 to 90 mol%, based on the total units contained in the fluorinated polyol.
The content of the unit based on the monomer represented by the formula (o) is preferably 10 to 40 mol%, more preferably 10 to 30 mol% with respect to the total units contained in the fluorinated polyol.
The total content of the unit based on the monomer represented by the formula (f) and the unit based on the monomer represented by the formula (o) is preferably 90 to 100 mol%, more preferably 100 mol%, based on the total units contained in the fluorinated polyol.
The proportion of the fluoroalcohol in the present dispersion is preferably 10% by mass or less, more preferably 1% by mass or less, and still more preferably 0.01% by mass or less. The lower limit of the above proportion is usually more than 0%.
The aqueous medium of the present invention is a dispersion medium of the dispersion liquid, and water is the main component.
The aqueous medium may be composed of water alone or water and a water-soluble compound.
Among them, as the water-soluble compound, a compound which is liquid at 25 ℃, does not react with each polymer or has extremely low reactivity and can be easily removed by heating or the like is preferable. The aqueous medium preferably contains 95% by mass or more of water, more preferably 99% by mass or more of water, and still more preferably 100% by mass of water.
The proportion of the aqueous medium in the dispersion is preferably 15 to 65% by mass, more preferably 25 to 50% by mass. Within this range, the dispersion is excellent in coatability, and the resulting molded article is less likely to suffer from appearance defects.
The present dispersion may contain other materials than the F polymer, the non-heat-fusible PTFE or M polymer, and the aqueous medium. Examples of the other materials include thixotropy imparting agents, fillers, antifoaming agents, dehydrating agents, plasticizers, weather-resistant agents, antioxidants, heat stabilizers, lubricants, antistatic agents, whitening agents, colorants, conductive agents, mold release agents, surface treatment agents, viscosity modifiers, and flame retardants. Other materials may or may not be soluble in the present dispersion.
Examples of the other material other than the F polymer, the non-heat-fusible PTFE, and the M polymer include thermosetting resins (epoxy resins, thermosetting polyimide resins, polyimide precursor (polyamic acid), acrylic resins, phenol resins, polyester resins, polyolefin resins, modified polyphenylene ether resins, bismaleimide resins, polyfunctional cyanate resins, polyfunctional maleimide-cyanate resins, polyfunctional maleimide resins, vinyl ester resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, melamine-urea copolycondensation resins, and the like), heat-fusible resins (polyester resins, polyolefin resins, styrene resins, polycarbonates, thermoplastic polyimides, polyarylates, polysulfones, polyallyl sulfones, aromatic polyamides, aromatic polyetheramides, and the like, Polyphenylene sulfide, polyallylether, polyamideimide, liquid crystalline polyester, polyphenylene ether, etc.), reactive alkoxysilane, carbon black, and inorganic filler (hollow inorganic microspheres such as glass microspheres and ceramic microspheres).
The viscosity of the dispersion is preferably 1 to 1000 mPas, more preferably 5 to 500 mPas, and further preferably 10 to 200 mPas.
The thixotropic ratio of the dispersion is preferably 0.8 to 2.2.
In this case, the dispersibility and coatability of the dispersion are easily balanced.
The present dispersion can be produced by mixing the powder (1) with the powder (21) or the powder (22). Specifically, it is preferably produced by mixing a dispersion (p1) containing the powder (1) and an aqueous medium with a dispersion (p2) containing the powder (21) or the powder (22) and an aqueous medium.
The dispersion liquid (p1) and the dispersion liquid (p2) are preferably mixed in a state in which each dispersion liquid is well dispersed. For example, when it is confirmed that the solid matter is settled in the dispersion liquid (p1), it is preferable to disperse the dispersion liquid (p1) by a homomixer immediately before mixing and further disperse the dispersion liquid by a homogenizer so as to improve the dispersion state. Particularly, when the dispersion (p1) stored at 0 to 40 ℃ is used, it is preferable to perform the dispersion treatment.
The aqueous medium (dispersion medium) of each of the dispersion (p1) and the dispersion (p2) is preferably water.
The dispersion liquid is excellent in dispersion stability and storage stability and also excellent in handling properties. The dispersion can form a molded article having excellent crack resistance and exhibiting strong adhesiveness without impairing the physical properties of non-heat-fusible PTFE or M polymer.
The present dispersion is applied to the surface of a base material, and heated to form a polymer layer containing an F polymer and a non-heat-fusible PTFE or M polymer, whereby a laminate in which a base material layer and a polymer layer composed of the above base material are sequentially laminated can be produced.
The ranges of the F polymer, powder (1), non-heat-fusible PTFE, M polymer, powder (21), powder (22), and aqueous medium in the laminate, including their suitable forms, are the same as defined in the present dispersion. The polymer layer may be formed on at least one surface of the base material layer, may be formed on only one surface of the base material layer, or may be formed on both surfaces of the base material layer.
Examples of the method for coating the surface of the base material include a spray method, a roll coating method, a spin coating method, a gravure coating method, a microgravure coating method, a gravure offset coating method, a knife coating method, a kiss coating method (キスコート method), a bar coating method, a die coating method, a jet meyer bar coating method (ファウンテンメイヤーバー method), and a slit die coating method.
The polymer layer can be formed by heating, and it is preferable to heat the base material to a temperature at which the aqueous medium volatilizes (a temperature range of 100 to 300 ℃), more preferable to heat the base material to a temperature at which the aqueous medium volatilizes (100 to 300 ℃) and further preferable to heat the base material to a temperature at which the non-heat-fusible PTFE is baked (300 to 400 ℃).
That is, the polymer layer in the case of using the present dispersion liquid containing non-heat-fusible PTFE is preferably a polymer layer containing an F polymer and obtained by baking non-heat-fusible PTFE. In this case, the non-heat-fusible PTFE may be partially or completely subjected to the firing treatment.
In addition, the polymer layer in the case of using the present dispersion liquid containing the M polymer is preferably a polymer layer containing the F polymer and having the M polymer melt-processed. In this case, the M polymer may be partially or completely melt-processed.
Examples of the method of heating the substrate include a method using an oven, a method using a through-air drying oven, and a method of irradiating heat rays (infrared rays).
The atmosphere for heating the substrate may be either normal pressure or reduced pressure. The atmosphere for holding may be any of an oxidizing gas (oxygen, etc.), a reducing gas (hydrogen, etc.), and an inert gas (helium, neon, argon, nitrogen, etc.).
The heating time of the substrate is usually 0.5 to 30 minutes.
The thickness of the polymer layer is preferably 50 μm or less, more preferably 30 μm or less, and further preferably 10 μm or less. The thickness of the polymer layer is preferably 0.1 μm or more, particularly preferably 4 μm or more. Within this range, a polymer layer having excellent crack resistance can be easily formed without impairing the physical properties of the non-heat-fusible PTFE or M polymer.
In the laminate, the base material layer and the polymer layer are firmly bonded. The peel strength between the base material layer and the polymer layer is preferably 10N/cm or more, and particularly preferably 15N/cm or more. The upper limit of the above peel strength is usually 100N/cm.
The material of the substrate may be any of metals such as copper, aluminum, iron, nickel, zinc, and alloys thereof, glass, resin, silicon, and ceramics.
The shape of the substrate may be any of a planar shape, a curved shape, and an uneven shape, or may be any of a foil shape, a plate shape, a film shape, and a fiber shape.
As a specific example of the laminate, a metal foil with a polymer layer in which a metal foil is used as a base material and a metal foil layer composed of a metal foil and a polymer layer are sequentially provided can be cited. An adhesive layer may be separately provided between the metal foil layer and the polymer layer, but the adhesive layer may not be provided because the polymer layer has excellent adhesiveness.
Suitable examples of the metal foil include copper foils such as rolled copper foil and electrolytic copper foil. In the laminate, the thickness of the metal foil is preferably 3 to 18 μm, and the thickness of the polymer layer is preferably 1 to 50 μm.
When a patterned circuit is formed on the copper foil layer, the laminate can be used as a printed wiring board having a polymer layer as an electrical insulating layer.
As a specific example of the laminate, a laminate film in which the base material is a polyimide film and the polymer layer formed from the present dispersion is provided on at least one surface of a polyimide layer formed from a polyimide film, and more specifically, a laminate film in which the polymer layer formed from the present dispersion is provided on both surfaces of a polyimide layer can be cited.
An adhesive layer may be separately provided between the polyimide layer and the polymer layer, but the adhesive layer may not be provided because the polymer layer formed from the present dispersion has excellent adhesion.
As a suitable form of the polyimide film, a film of a polymer of a component containing 2,2 ', 3, 3' -or 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride (e.g., 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride, etc.) as a main component and a component containing p-phenylenediamine as a main component can be cited. Specific examples of the polyimide film include an atmospheric type af (manufactured by bellied north america corporation, カネカノースアメリカ).
The polyimide film described above can be used as an insulating coating body. The weight of the weight is preferably 23.5g/m2The ring stiffness is preferably 0.45g/cm or more.
In the laminated film, the thickness of the polymer layer is preferably 1 to 200 μm, more preferably 5 to 20 μm. The thickness of the polyimide layer (polyimide film) is preferably 5 to 150 μm.
The laminate film is excellent in electrical insulation, abrasion resistance, hydrolysis resistance and the like, and can be used as an electrical insulating tape, a cable or a packaging material for an electric wire, and particularly suitable as a material for an electric wire or a material for an electric cable for aerospace use or electric automobile use.
Since the laminate of the present invention has a polymer layer containing the F polymer and having excellent adhesiveness, it is also possible to laminate another material on the polymer layer of the laminate to produce a composite laminate.
When the polymer layer surface of the laminate is pressure-bonded to the 2 nd base material, a composite laminate in which the 1 st base material layer (original base material layer of the laminate), the polymer layer, and the 2 nd base material layer composed of the 2 nd base material are sequentially laminated can be obtained.
The material of the 2 nd substrate may be any of metals such as copper, aluminum, iron, nickel, zinc, alloys thereof, glass, resin, silicon, and ceramics.
The shape of the 2 nd substrate is not particularly limited, and may be any of a planar shape, a curved shape, and an uneven shape, or may be any of a foil shape, a plate shape, a film shape, and a fiber shape.
Specific examples of the 2 nd substrate include a heat-resistant resin substrate, a prepreg which is a precursor of a fiber-reinforced resin plate, and the like.
The prepreg is a sheet-like substrate obtained by impregnating a substrate (e.g., chopped jute, woven fabric, etc.) of reinforcing fibers (e.g., glass fibers, carbon fibers, etc.) with a resin (e.g., the above-described thermosetting resin, thermoplastic resin, etc.).
The heat-resistant resin substrate is preferably a film containing a heat-resistant resin, and may be a single layer or a multilayer.
Examples of the heat-resistant resin include polyimide, polyarylate, polysulfone, polyarylsulfone, aramid, aromatic polyetheramide, polyphenylene sulfide, polyaryletherketone, polyamideimide, liquid crystalline polyester, and PTFE.
As a method of pressure-bonding the surface of the polymer layer of the laminate to the 2 nd substrate, a thermal pressure-bonding method is exemplified.
The pressure welding temperature when the No. 2 base material is prepreg is preferably 160-220 ℃.
The pressing temperature when the No. 2 base material is a heat-resistant resin base material is preferably 300 to 400 ℃.
The thermocompression bonding is preferably performed in a reduced pressure atmosphere, and particularly preferably in a vacuum degree of 20kPa or less. Within this range, incorporation of air bubbles into each interface in the composite laminated body can be suppressed, and degradation due to oxidation can be suppressed. In the thermocompression bonding, it is preferable to raise the temperature after the degree of vacuum is reached.
The pressure of the hot pressing is preferably 0.2-10 MPa.
When a liquid layer forming material for forming the 2 nd polymer layer is applied to the surface of the polymer layer of the laminate to form the 2 nd polymer layer, a composite laminate in which the 1 st base material layer, the polymer layer, and the 2 nd polymer layer are sequentially laminated can be obtained.
The liquid layer forming material is not particularly limited, and the present dispersion may be used.
The method for forming the 2 nd polymer layer is not particularly limited, and may be appropriately determined depending on the properties of the liquid layer-forming material used. For example, when the layer forming material is the present dispersion liquid, the 2 nd polymer layer can be formed under the same conditions as the method for forming the polymer layer in the laminate. That is, if the layer forming material is the present dispersion, it is easy to form a polymer layer into a plurality of layers and form a thicker polymer layer.
Specific examples of the composite laminate obtained by the above-described production method include composite laminates obtained using the present dispersion or a dispersion containing an F polymer as a liquid layer forming material. Since the 2 nd polymer layer is formed on the polymer layer exhibiting strong adhesiveness, a composite laminate having high peel strength can be obtained even when the latter dispersion is used.
According to the laminate of the present invention, it can be said that a polymer layer having excellent crack resistance can be formed without impairing the physical properties of the respective polymers. By removing the base material layer from the laminate, a polymer film uniformly containing each polymer can be obtained.
Among the polymer films containing non-hot-melt PTFE, the non-hot-melt PTFE containing the F polymer is preferably a polymer film subjected to firing treatment. In this case, the non-heat-fusible PTFE may be partially or completely subjected to the firing treatment.
Among the polymer films containing the M polymer, the M polymer containing the F polymer is preferably a polymer film subjected to firing treatment. In this case, the M polymer may be partially or completely fired.
Examples of the method for removing the base material layer from the laminate include a method for peeling and removing the base material layer from the laminate, and a method for dissolving and removing the base material layer from the laminate. For example, in the case where the base layer is made of a copper foil, when the surface of the laminate on the base layer side is brought into contact with an etching solution such as hydrochloric acid, the base layer is dissolved and removed, and a polymer film made of the polymer layer alone can be easily obtained.
The scope of the polymer in the polymer film includes that its suitable morphology is as defined in the present dispersion.
The thickness of the polymer film is preferably 50 μm or less, more preferably 30 μm or less, and further preferably 10 μm or less. The thickness of the polymer film is preferably 1 μm or more, more preferably 4 μm or more. Within this range, the polymer film is more excellent in adhesiveness and crack resistance without impairing the physical properties of each polymer.
When the woven fabric is impregnated with the dispersion and then dried, a coated woven fabric, which is a woven fabric coated with a polymer layer, can be obtained.
The woven fabric is a heat-resistant woven fabric that can resist drying, preferably a glass fiber woven fabric, a carbon fiber woven fabric, an aramid fiber woven fabric, or a metal fiber woven fabric, more preferably a glass fiber woven fabric or a carbon fiber woven fabric, and further preferably a woven fabric made of JIS R3410: a plain-woven glass fiber woven fabric composed of E glass yarn for electrical insulation as defined in 2006. The woven fabric may be treated with a silane coupling agent from the viewpoint of improving the adhesion between the woven fabric and the polymer layer.
The total content of the F polymer and the non-heat-fusible PTFE or M polymer in the coated woven fabric is preferably 30 to 80% by mass.
Examples of the method for impregnating a woven fabric with the dispersion include a method of immersing a woven fabric in the dispersion and a method of applying the dispersion to a woven fabric. The number of dipping times in the former method and the number of coating times in the latter method may be 1 time or 2 or more times, respectively. Since the present dispersion liquid containing the F polymer having excellent adhesiveness with other materials is used, a coated woven fabric having a high polymer content in which the woven fabric and the polymer are strongly adhered can be obtained even if the number of dipping times or the number of application times is small.
The method of drying the woven fabric may be appropriately determined depending on the type of the aqueous medium contained in the dispersion, and for example, when the aqueous medium is composed of only water, a method of passing the woven fabric through a ventilation drying oven in an atmosphere of 80 to 120 ℃ may be mentioned.
The polymer may be fired when the woven fabric is dried. The method of firing the polymer may be appropriately determined depending on the type of each polymer, and for example, a method of passing the woven fabric through a through-air drying oven in an atmosphere of 300 to 400 ℃. Further, the drying of the woven fabric and the firing of the polymer may be performed in one step.
Since the polymer layer contains the F polymer, the obtained coated woven fabric has excellent characteristics such as high adhesion between the polymer layer and the woven fabric, high surface smoothness, and less variation. The laminate obtained by thermally pressing the coated woven fabric and the metal foil has high peel strength and is not easily warped, and therefore, is suitable as a printed board material.
The present dispersion impregnated with the woven fabric may be applied to the surface of a base material and dried by heating to form a coated woven fabric layer comprising the F polymer, the non-heat-fusible PTFE or M polymer, and the woven fabric. In this way, a laminate can be produced in which a base layer composed of the base material and a coated fabric layer are sequentially laminated. The form is not particularly limited, and if the present dispersion liquid impregnated with the woven fabric is applied to a part of the inner wall surface of a molded article such as a tank, a pipe, a container, etc., and the molded article is heated while being rotated, a coating woven fabric layer can be formed on the entire inner wall surface of the molded article. The method for producing a coated woven fabric of the present invention is also useful as a method for lining the inner wall surface of a molded article such as a tank, a duct, a container, or the like.
Examples
The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
The various measurement methods are shown below.
< D50 and D90 of powder >
The powder was dispersed in water and measured using a laser diffraction/scattering particle size distribution measuring device ("LA-920 measuring instrument" manufactured by horiba ltd. (horiba japan).
< storage stability of powder Dispersion >
The powder dispersion was left at 25 ℃ for 1 week, and the state was visually confirmed, and evaluated according to the following evaluation criteria.
Good: no sediment was found.
And (delta): sediment was found but redispersed after shaking by hand.
X: sediment was found and light was not redispersed by shaking by hand.
< crack resistance of Polymer layer >
A stainless steel plate (thickness: 0.5mm) having a vinyl tape attached to one end edge thereof was coated with a powder dispersion on the surface thereof, and the rod was slid along the end edge, then dried 3 times for 3 minutes at 100 ℃ and further heated at 340 ℃ for 10 minutes. Thereby, a polymer layer having an inclined thickness caused by the thickness of the vinyl tape attached to the end edge is formed on the surface of the stainless steel plate. The thickness of the polymer layer at the tip of the crack line generation portion (the portion where the polymer layer is the thinnest) was measured by using MINITEST3000(Electro Physik corporation, manufactured by Electro Physik corporation) by visually checking the stainless steel sheet, and the evaluation was performed according to the following evaluation criteria.
Good: the thickness of the polymer layer at the crack-generating end is 10 μm or more.
And (delta): the thickness of the polymer layer at the crack-generating end is 5 μm or more and less than 10 μm.
X: the thickness of the polymer layer at the crack-generating front end is less than 5 μm.
< peel strength of laminate >
The position 50mm away from one end in the longitudinal direction of the laminate cut into a rectangular shape (length: 100mm, width: 10mm) was fixed, the metal foil layer and the polymer layer were peeled from the other end in the longitudinal direction at 90 ° to the laminate at a stretching speed of 50 mm/min, and the maximum load applied at the time of peeling was measured and evaluated as the peel strength (N/cm) according to the following evaluation criteria.
Good: the peel strength is 10N/cm or more.
X: the peel strength is less than 10N/cm.
The materials used are as follows.
[ Polymer and powder thereof ]
F, polymer 1: a copolymer comprising TFE-based units, NAH-based units and PPVE-based units in this order in the order of 97.9 mol%, 0.1 mol% and 2.0 mol% (melting point: 300 ℃ C.)
Polymer a 1: copolymer having no oxygen-containing polar group comprising TFE-based unit and PPVE-based unit in this order of 98.0 mol% and 2.0 mol% (melting point: 305 ℃ C.)
P Polymer 1: non-hot-melt PTFE having fibrillating properties, which contains 99.9 mol% or more of units based on TFE (standard specific gravity: 2.18, melt viscosity at 380 ℃ C.: 3.0X 10)9Pa·s)
M Polymer 1: hot-melt modified PTFE comprising 99.5 mol% or more of a TFE-based unit and a very small amount of a PFBE-based unit (melt viscosity at 380 ℃ C.: 1X 10)6Pa·s)
F, powder 11: powder of F Polymer 1 (D50: 1.7 μm, D90: 3.8 μm)
F, powder 12: powder of F Polymer 1 (D50: 0.3 μm, D90: 1.8 μm) [ obtained by subjecting F powder 11 to wet jet milling ]
Powder a 1: powder of Polymer A1 (D50: 0.3 μm, D90: 1.5 μm)
P powder 1: powder of P Polymer 1 (D50: 0.3 μm) [ P powder 1 available in the form of an aqueous Dispersion of P powder 1]
M, powder 1: m powder of Polymer 1 (D50: 0.3 μ M) [ M powder 1 is available as an aqueous dispersion of M powder 1]
[ dispersing agent ]
FM1：F(CF2)6CH2(OCH2CH2)7OCH2CH(CH3) OH (fluorine content: 34 mass%, hydroxyl value: 78mgKOH/g)
FP 1: comprising being based on CH2＝C(CH3)C(O)OCH2CH2(CF2)6Units of F and based on CH2＝C(CH3)C(O)(OCH2CH2)23A copolymer of OH units (fluorine content: 35% by mass, hydroxyl value: 19mgKOH/g)
Example 1 production of powder Dispersion
Example 1-1 preparation of Dispersion 1
A dispersion containing 30 parts by mass of the F powder 12, 5 parts by mass of the fluoromonohydric alcohol 1, and 65 parts by mass of water was mixed with an aqueous dispersion containing 50% by mass of the P powder 1. Thereby, a powder dispersion 1 in which each powder was dispersed in water and which contained 90 mass% of the P polymer 1 and 10 mass% of the F polymer 1 relative to the total amount of the P polymer 1 and the F polymer 1 was obtained (content of the F polymer 1/content of the P polymer 1: 0.11).
Examples 1-2 to 1-9 production of powder dispersions 2 to 9
Powder dispersions 2 to 9 were obtained in the same manner as in example 1-1, except that the type of powder and the type of dispersant were changed. The evaluation results of the kind of each powder dispersion and its storage stability are collectively shown in table 1 below.
[ Table 1]
Example (number of Dispersion) Using powders Dispersing agent Storage stability
1-1·(1) F powder 12+ P powder 1(0.11) FM1 ○
1-2·(2) F powder 11+ P powder 1(0.11) FM1 △
1-3·(3) F powder 12+ P powder 1(0.11) FP1 ○
1-4·(4) F powder 11+ P powder 1(0.11) FP1 △
1-5·(5) F powder 12+ M powder 1(0.11) FM1 ○
1-6·(6) F powder 11+ M powder 1(0.11) FM1 △
1-7·(7) F powder 12+ M powder 1(0.11) FP1 ○
1-8·(8) F powder 11+ M powder 1(0.11) FP1 △
1-9·(9) Powder A1+ P powder 1(0.11) FP1 ×
The number in parentheses in the powder column is F powder or the proportion of powder A11 in the total weight of the powder
Example 2 production of laminate
Example 2-1 production example of laminate 1
The powder dispersion 1 was applied to the surface of a copper foil, dried at 100 ℃ for 10 minutes, fired at 340 ℃ for 10 minutes in an inert gas atmosphere, and then slowly cooled. Thereby, a laminate (polymer layer-bearing copper foil) 1 having a copper foil layer composed of a copper foil and a polymer layer (thickness: 5 μm) containing P polymer 1 and F polymer 1 formed on the surface of the copper foil layer was obtained.
Examples 2-2 to 2-9 production of laminates 2 to 9
Laminates 2 to 9 were obtained in the same manner as in example 2-1, except that the kind of the powder dispersion was changed.
The results of evaluation of the crack resistance of the powder dispersions 1 to 4 and 9 and the results of evaluation of the peel strength of the laminates 1 to 9 are collectively shown in the following table 2.
[ Table 2]
Example (number of dispersions andlaminated bodySequence number) Crack resistance Strength of glass
2-1·(1) ○ ○
2-2·(2) ○ ○
2-3·(3) △ ○
2-4·(4) ○ ○
2-5·(5) Not determined ○
2-6·(6) Not determined ○
2-7·(7) Not determined ○
2-8·(8) Not determined ○
2-9·(9) × ×
Example 3 production of Polymer film
Example 3-1 production example of Polymer film 3
The powder dispersion 3 was applied to the surface of a copper foil, dried at 100 ℃ for 10 minutes, fired at 340 ℃ for 10 minutes in an inert gas atmosphere, and then slowly cooled. Thereby, a laminate 1 having a copper foil layer composed of a copper foil and a polymer layer containing P polymer 1 and F polymer 1 formed on the surface of the copper foil layer was obtained. The operations of coating, drying, and firing of the powder dispersion 3 were repeated on the polymer layer surface of the laminate under the same conditions. Thereby, the thickness of the polymer layer was increased to 30 μm. Thereafter, the copper foil layer of the laminate was removed with hydrochloric acid to obtain a polymer film 3 containing P polymer 1 and F polymer 1.
Example 3-2 production of Polymer film 4 and Polymer films 7 to 9
In the same manner as in example 3-1 except that the kind of the powder dispersion was changed, the polymer film 4 was obtained from the powder dispersion 4, the polymer film 7 was obtained from the powder dispersion 7, the polymer film 8 was obtained from the powder dispersion 8, and the polymer film 9 was obtained from the powder dispersion 9.
The polymer film 3, the polymer film 4, and the polymer film 9 are all porous films, and the breaking strength in the stretching treatment is the polymer film 3, the polymer film 4, and the polymer film 9 in this order from large to small.
Further, the polymer film was subjected to a stretching treatment (stretching ratio: 200%), a stretched film 3 was obtained from the polymer film 3, a stretched film 4 was obtained from the polymer film 4, and a stretched film 9 was obtained from the polymer film 9. Each of the stretched films is a porous film, and when the open pore state is compared, the pore diameter distribution is in the order of stretched film 3, stretched film 4, and stretched film 9 from small to large, and a dense porous film is formed in this order.
The polymer film 7, the polymer film 8, and the polymer film 9 have breaking strengths in the order of the polymer film 7, the polymer film 8, and the polymer film 9 from high to low. Further, as a result of repeated bending tests of the respective films, it was found that the number of times until the films were broken was as small as the polymer films 7, 8 and 9.
Example 4 production of Polymer film (2)
A dispersion containing 30 parts by mass of the F powder 12, 5 parts by mass of FM1, and 65 parts by mass of water, an aqueous dispersion containing 50% by mass of the M powder 1, and an aqueous dispersion containing 50% by mass of the P powder 1 were mixed. Thereby, a powder dispersion liquid in which each powder was dispersed in water and which contained 10 mass% of M Polymer 1, 10 mass% of F Polymer 1, and 80 mass% of P Polymer 1 with respect to the total amount of M Polymer 1, F Polymer 1, and P Polymer 1 was obtained (content of F Polymer 1/content of M Polymer 1: 1.0).
The powder dispersion was applied to the surface of a copper foil, dried at 100 ℃ for 10 minutes, fired at 340 ℃ for 10 minutes in an inert gas atmosphere, and then slowly cooled. Thereby, a laminate having a copper foil layer composed of a copper foil and a polymer layer formed on the surface of the copper foil layer was obtained. The operations of coating, drying, and firing of the powder dispersion were repeated on the polymer layer surface of the laminate under the same conditions. Thereby, the thickness of the polymer layer was increased to 30 μm. Thereafter, the copper foil layer of the laminate was removed with hydrochloric acid to obtain a polymer film containing M polymer 1, F polymer 1, and P polymer 1. The polymer film was subjected to a stretching treatment (stretching ratio: 200%) to obtain a dense porous film having a small pore size distribution.
Possibility of industrial utilization
The dispersion can be used for the production of molded articles such as films, impregnated articles (prepregs and the like), laminates (metal laminates with resin copper foils and the like), and molded articles for applications requiring releasability, electrical characteristics, water and oil repellency, chemical resistance, weather resistance, heat resistance, smoothness, abrasion resistance and the like. The molded article obtained from the dispersion can be used as an antenna member, a printed circuit board, an airplane member, an automobile member, a sports equipment, a food industry product, a paint, a cosmetic, and the like, and specifically, can be used as an electric wire coating material (an airplane electric wire or the like), an electrically insulating tape, an oil drilling insulating tape, a printed circuit board material, a separation membrane (a microfiltration membrane, an ultrafiltration membrane, a reverse osmosis membrane, an ion exchange membrane, a dialysis membrane, a gas separation membrane or the like), an electrode adhesive (a lithium secondary battery, a fuel cell or the like), a copying roll, furniture, an automobile instrument panel, a cover for home appliances or the like, a sliding member (a load bearing, a sliding shaft, a valve, a bearing, a gear, a cam, a belt conveyor, a food conveyor belt or the like), a tool (a shovel, a file, a awl, a saw or the like), a boiler, a hopper, a pipeline, an oven, a baking mold, a baking machine, chutes, moulds, toilets, container coverings.

Claims (14)

1. A powder dispersion comprising: a powder (1) of a fluoropolymer having tetrafluoroethylene-based units and oxygen-containing polar groups, a powder (21) of non-fusible polytetrafluoroethylene or a powder (22) of a fusible fluoropolymer, and an aqueous medium.
2. The powder dispersion according to claim 1, wherein the powder (1) has a cumulative 50% by volume diameter of 0.01 to 75 μm, and the powder (21) or the powder (22) has a cumulative 50% by volume diameter of 0.01 to 100 μm.
3. The powder dispersion liquid according to claim 1 or 2, wherein a mass ratio of the content of the fluoropolymer to the content of the non-thermofusible polytetrafluoroethylene or the content of the thermofusible fluoropolymer is 0.4 or less.
4. The powder dispersion according to any one of claims 1 to 3, wherein the fluoropolymer has a melting temperature of 140 to 320 ℃.
5. The powder dispersion liquid according to any one of claims 1 to 4, wherein the fluoropolymer comprises units based on a monomer having the oxygen-containing polar group.
6. The powder dispersion liquid according to any one of claims 1 to 5, wherein the oxygen-containing polar group is a hydroxyl-containing group or a carbonyl-containing group.
7. The powder dispersion as claimed in any one of claims 1 to 6, wherein the non-fusible polytetrafluoroethylene has fibrillating properties.
8. The powder dispersion according to any one of claims 1 to 7, wherein the hot-melt fluoropolymer is a modified polytetrafluoroethylene, a copolymer of tetrafluoroethylene and perfluoro (alkyl vinyl ether), or a copolymer of tetrafluoroethylene and hexafluoropropylene.
9. The powder dispersion according to any one of claims 1 to 8, wherein it comprises both a powder (21) of the non-thermofusible polytetrafluoroethylene and a powder (22) of the thermofusible fluoropolymer.
10. The powder dispersion liquid according to any one of claims 1 to 9, further comprising an acetylene-based surfactant, a silicone-based surfactant, or a fluorine-based surfactant.
11. The powder dispersion liquid according to any one of claims 1 to 10, further comprising a fluorine-based surfactant which is a fluorinated monohydric alcohol or a fluorinated polyhydric alcohol.
12. A method for producing a laminate, which comprises applying the powder dispersion according to any one of claims 1 to 11 onto a surface of a substrate, and heating to remove the aqueous medium to form a polymer layer, thereby obtaining a laminate in which a substrate layer comprising the substrate and the polymer layer are sequentially laminated.
13. A method for producing a polymer film, which comprises applying the powder dispersion as defined in any one of claims 1 to 11 onto a surface of a substrate, heating to remove the aqueous medium to form a polymer layer, thereby obtaining a laminate in which a base material layer comprising the substrate and the polymer layer are sequentially laminated, and removing the base material layer from the laminate, thereby obtaining a polymer film comprising the polymer layer.
14. A method for producing a coated woven fabric, which comprises impregnating a woven fabric with the powder dispersion according to any one of claims 1 to 11, and drying the woven fabric to obtain a woven fabric coated with a polymer layer.
CN201980085923.2A 2018-12-25 2019-12-19 Powder dispersion, method for producing laminate, method for producing polymer film, and method for producing coated woven fabric Pending CN113227216A (en)

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