JP2020111696A - Liquid composition and method for producing laminate - Google Patents

Abstract

To provide a liquid composition that contains powder of a solvent-soluble fluoroolefin polymer and a predetermined tetrafluoro polymer, and can form a molding having excellent workability and adhesiveness without impairing the physical properties of both polymers, and a method for producing a laminate using the liquid composition.SOLUTION: A liquid composition contains powder of a solvent-soluble fluoroolefin polymer, and a fluoropolymer (P) having a tetrafluoroethylene-based unit and an oxygen-containing polar group, and a polar solvent.SELECTED DRAWING: None

Description

The present invention relates to a liquid composition containing a solvent-soluble fluoroolefin polymer, a predetermined fluoropolymer powder, and a polar solvent, and a method for producing a laminate using such a liquid composition.

Solvent-soluble fluoroolefin polymers such as polyvinylidene fluoride have excellent physical properties such as weather resistance, gas barrier properties, heat resistance, chemical resistance, electrochemical resistance, and mold release properties, and are liquid compositions dissolved in a solvent. It is used as a paint or coating agent.
Patent Document 1 describes a solution composition containing polyvinylidene fluoride and a solvent as a coating material for exterior building materials.
Patent Document 2 describes an electrode binder material composed of an organosol containing polyvinylidene fluoride and a solvent.

JP-A-2000-204337 International Publication No. 2012/002038

The solvent-soluble fluoroolefin-based polymer can form a dense film of the fluoroolefin-based polymer as a liquid composition on the surface of the substrate, but on the other hand, the adhesiveness and workability (flexibility such as bending workability and hardness) are There is a problem of being low. Therefore, in order to improve the adhesiveness with the base material, a treatment such as forming a primer layer on the base material surface may be required. In addition, when a component for improving the adhesiveness or the processability is added to the liquid composition, the state stability of the liquid composition may be deteriorated or the physical properties of the processed product formed may be deteriorated.
The present invention includes a solvent-soluble fluoroolefin-based polymer and a powder of a predetermined tetrafluoropolymer, and forms a molded article having excellent processability and strong adhesiveness without impairing the physical properties of both polymers. An object of the present invention is to provide a liquid composition that can be obtained and a method for producing a laminate using the liquid composition.

The present invention provides the following inventions.
[1] A liquid composition containing a solvent-soluble fluoroolefin polymer, a powder of a fluoropolymer (P) having a unit based on tetrafluoroethylene and an oxygen-containing polar group, and a polar solvent.
[2] The liquid composition according to [1], wherein the volume-based cumulative 50% diameter of the powder is 0.05 to 75 μm.
[3] The liquid composition according to [1] or [2], wherein the ratio of the mass of the fluoropolymer (P) to the mass of the solvent-soluble fluoroolefin polymer is 0.4 or less.
[4] The liquid composition according to any one of [1] to [3], wherein the fluoropolymer (P) has a melting temperature of 140 to 320°C.
[5] The liquid composition according to any one of [1] to [4], wherein the fluoropolymer (P) contains a unit based on the monomer having the oxygen-containing polar group.
[6] The liquid according to any one of [1] to [5], wherein the oxygen-containing polar group is at least one group selected from the group consisting of a hydroxyl group, a carbonyl group-containing group, an acetal group and an oxycycloalkane group. Composition.
[7] The solvent-soluble fluoroolefin-based polymer is at least one monomer selected from the group consisting of vinyl fluoride, vinylidene fluoride, chlorotrifluoroethylene and 1,3,3,3-tetrafluoropropene. The liquid composition according to any one of [1] to [6], which is a polymer containing a unit based on the above.
[8] The solvent-soluble fluoroolefin polymer is polyvinyl fluoride, polyvinylidene fluoride, polychlorotrifluoroethylene, a copolymer of vinylidene fluoride and tetrafluoroethylene, or vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene. The liquid composition according to any one of [1] to [7], which is a copolymer with.
[9] The liquid composition according to any one of [1] to [8], wherein the polar solvent is an ester, an amide, or a ketone.
[10] The liquid composition according to any one of [1] to [9], which contains a dispersant.
[11] The liquid composition according to any one of [1] to [10], which contains a dispersant, and the dispersant is a fluoropolyol having a fluorine content of 10 to 50 mass% and a hydroxyl value of 10 to 35 mgKOH/g. Stuff.
[12] The liquid composition according to any one of [1] to [11], which is an electrode binder material.
[13] The liquid composition according to any one of [1] to [11] is applied to the surface of a base material, the polar solvent is removed by heating to form a polymer layer, and the base material and the polymer layer are combined. Is a method for manufacturing a laminated body, in which a laminated body laminated in this order is obtained.

According to the present invention, a molded article that has excellent state stability such as dispersibility and storage stability, and that exhibits strong adhesiveness and good processability without impairing the physical properties of the solvent-soluble fluoroolefin polymer. There is provided a liquid composition capable of forming a film, and a method for producing a laminate using the liquid composition.

"Powder D50" is the volume-based cumulative 50% diameter, the particle size distribution is measured by the laser diffraction/scattering method, the cumulative volume is calculated with the total volume of the group of particles as 100%, and the cumulative volume is calculated on the cumulative curve. Is the particle size at the point where is 50%.
"Powder D90" is the volume-based cumulative 90% diameter, the particle size distribution is measured by the laser diffraction/scattering method, and the cumulative volume is calculated with the total volume of the group of particles as 100%, and the cumulative volume on the cumulative curve. Is the particle size at the point where is 90%.
The “unit based on a monomer” is a generic term for an atomic group directly formed by polymerizing one molecule of a monomer and an atomic group obtained by chemically converting a part of this atomic group. In the present specification, the unit based on the monomer is also simply referred to as “unit”.
The “viscosity of the liquid composition” is a value measured with a B-type viscometer at room temperature (25° C.) under the condition of a rotation speed of 30 rpm. The measurement is repeated three times, and the average value of the three measured values is used.
The "thixo ratio of the liquid composition" is a value calculated by dividing the viscosity η ₁ measured under the condition of the rotation speed of 30 rpm by the viscosity η ₂ measured under the condition of the rotation speed of 60 rpm. The measurement of each viscosity is repeated three times, and the average value of the three measured values is used.
"Polymer melting temperature" is the temperature corresponding to the maximum value of the melting peak of the polymer measured by the differential scanning calorimetry (DSC) method.
"Peel strength of laminated body" means fixing a position of 50 mm from one end in the longitudinal direction of the laminated body cut out in a rectangular shape (length 100 mm, width 10 mm), pulling speed 50 mm/min, one end in the longitudinal direction. Is the maximum load (N/cm) applied when the metal foil and the resin layer are separated from each other at 90° to the laminate.
"Standard specific gravity of polymer" is the standard specific gravity of a polymer measured according to ASTM D 4895.
The "melt flow rate" is a melt mass flow rate (MFR) defined in JIS K 7210-1:2014 (corresponding international standard ISO 1133-1:2011).

The liquid composition of the present invention has a unit based on tetrafluoroethylene (TFE) (hereinafter, also referred to as “TFE unit”) and a fluoropolymer (P) having an oxygen-containing polar group (hereinafter, also referred to as “F polymer”). ) Powder, a solvent-soluble fluoroolefin polymer (hereinafter, also referred to as “S polymer”), and a polar solvent. It can be said that the liquid composition of the present invention is a liquid composition in which the powder of the F polymer is dispersed in the solvent in which the S polymer is highly dissolved.
While the liquid composition of the present invention maintains easy coating properties, a molded article (including a molding site such as a polymer layer; the same applies hereinafter) formed from the liquid composition of the present invention exhibits the physical properties of the S polymer. While exhibiting strong adhesiveness and good processability.

The reason is not necessarily clear, but in addition to the fact that the S polymer and the F polymer are both fluoroolefin-based polymers when they are formed, and they are easily fused and bonded, the F polymer contains an oxygen-containing polar group. It has points.
That is, it is considered that the F polymer having an oxygen-containing polar group has high stability in a polar solvent due to its polarity and interacts with the S polymer to be highly stably dispersed. As a result, it is considered that the liquid composition of the present invention has improved state stability because the F polymer powder is uniformly dispersed.
Further, it is considered that in forming a molded article, the F polymer having an oxygen-containing polar group not only exhibits adhesiveness, but also promotes interaction between polymers, for example, formation of a matrix. It is considered that this interaction forms a state in which the respective polymer chains are likely to be uniformly entangled. As a result, it is considered that a molded article excellent in adhesiveness and processability was formed from the liquid composition of the present invention without impairing the properties of the S polymer.

The powder of the F polymer in the present invention (hereinafter, also referred to as “F powder”) may contain a component other than the F polymer, but it is preferable that the F polymer is the main component. The content of the F polymer in the F powder is preferably 80% by mass or more, and particularly preferably 100% by mass.
The D50 of the F powder is preferably 0.05 to 75 μm, more preferably 0.05 to 6 μm, and particularly preferably 0.1 to 4 μm. Preferred embodiments of D50 of the F powder include a mode of 0.1 μm or more and less than 1 μm and a mode of 1 μm or more and 4 μm or less.
The D90 of the F powder is preferably 8 μm or less, particularly preferably 6 μm or less. The D90 of the F powder is preferably 0.1 μm or more, particularly preferably 0.3 μm or more. As a preferable mode of D90 of F powder, a mode of 0.3 μm or more and less than 2 μm and a mode of 2 μm or more and 6 μm or less can be mentioned.
In this case, the dispersibility of the F powder and the interaction with the S polymer are good, and the physical properties of the liquid composition and the molded product are likely to be further improved. For example, when the D50 of the F powder is 0.1 μm or more and less than 1 μm, the dispersibility of the liquid composition is excellent, and a molded product having excellent mechanical strength such as stretching characteristics is easily obtained. When the D50 of the F powder is 1 μm or more and 4 μm or less, it is easy to obtain a molded product having excellent crack resistance.

The oxygen-containing polar group possessed by the F polymer in 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 end group, and may be surface-treated (radiation treatment, electron beam). Treatment, corona treatment, plasma treatment, etc.), and the former is preferable. The oxygen-containing polar group contained in the F polymer may be a group prepared by modifying a polymer having a group capable of forming an oxygen-containing polar group. The oxygen-containing polar group contained in the polymer end group can be obtained by adjusting the components (polymerization initiator, chain transfer agent, etc.) used in the polymerization of the polymer.
The oxygen-containing polar group in the present invention is a polar atomic group containing an oxygen atom. However, the oxygen-containing polar group in the present invention does not include the ester bond itself and the ether bond itself, but includes an atomic group containing these bonds as a characteristic group.
Oxygen-containing polar group, a hydroxyl group, at least one group preferably selected from the group consisting of carbonyl group-containing group, acetal group and oxy cycloalkane _{group, -CF 2 CH 2 OH, -C} (CF 3) 2 OH, 1,2-glycol group _{(-CH (OH) CH 2 OH} ), acetal _{groups,> C (O), -} CF 2 C (O) OH,> CFC (O) OH, carboxamido (-C (O ) NH ₂ etc.), an acid anhydride residue (-C(O)OC(O)-), a dicarboxylic acid residue (-CH(C(O)OH)CH ₂ C(O)OH, etc.), A carbonate group (-OC(O)O-), an epoxy group or an oxetanyl group is more preferable.
Further, from the viewpoint of not easily impairing the adhesiveness, crack resistance and physical properties of the S polymer of the molded product, the oxygen-containing polar group is a polar group and is a cyclic group or a ring-opening group thereof, a cyclic acid anhydride residue. , A cyclic carbonate group, a cyclic acetal group, a 1,2-dicarboxylic acid residue or a 1,2-glycol group are particularly preferred, and a cyclic acid anhydride residue is most preferred.

The F polymer includes a TFE unit and a unit (hereinafter, also referred to as “FAE”) based on hexafluoropropylene (HFP), perfluoro(alkyl vinyl ether) (hereinafter also referred to as “PAVE”) or fluoroalkyl ethylene (hereinafter also referred to as “FAE”). A polymer containing a “PAE unit”) and a unit based on a monomer having an oxygen-containing polar group (hereinafter, also referred to as “polar unit”) is preferable.
The proportion of TFE units is preferably 50 to 99 mol%, and particularly preferably 90 to 99 mol%, based on all the units constituting the F polymer.
The PAE unit is preferably a PAVE-based unit or a HFP-based unit, particularly preferably a PAVE-based unit. Two or more types of PAE units may be used.
The proportion of PAE units is preferably from 0 to 10 mol%, particularly preferably from 0.5 to 9.97 mol%, based on all units constituting the F polymer.

The _{PAVE, CF 2 = CFOCF 3 (} PMVE), CF 2 = CFOCF 2 CF 3, CF 2 = CFOCF 2 CF 2 CF 3 (PPVE), CF 2 = CFOCF 2 CF 2 CF 2 CF 3, CF 2 = CFO _{(CF 2) 8} F can be mentioned, PMVE or PPVE is preferred.
The _{FAE, CH 2 = CH (CF} 2) 2 F (PFEE), CH 2 = CH (CF 2) 3 F, CH 2 = CH (CF 2) 4 F (PFBE), CH 2 = CF (CF 2 _{) 3 H, CH 2 = CF} (CF 2) 4 H can be mentioned, PFEE or PFBE is preferred.
The proportion of PAE units is preferably 0.5 to 9.97 mol% based on all units constituting the F polymer.

The polar unit is a unit based on a monomer having an acid anhydride residue, a unit based on a monomer having a carbonate group, a unit based on a monomer having a cyclic acetal group, a unit based on a monomer having a 1,2-dicarboxylic acid residue, A unit based on a monomer having a 1,2-diol residue or a unit based on a monomer having a 1,3-diol residue is preferable, and a monomer unit having a cyclic acid anhydride residue or a monomer unit having a cyclic carbonate group is more preferable. A monomer unit having a cyclic acid anhydride residue is particularly preferable. The polarity unit may be one type or two or more types.
The proportion of the polar unit is preferably 0 to 5 mol% and particularly preferably 0.01 to 3 mol% based on all units constituting the F polymer.

The monomer having a cyclic acid anhydride residue is itaconic acid anhydride, citraconic acid anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride (also known as hymic acid anhydride; hereinafter also referred to as “NAH”) or maleic anhydride. Acids are preferred and NAH is especially preferred.
The proportion of the polar unit is preferably 0.01 to 3 mol% based on all units constituting the F polymer.
In addition, the F polymer in this case may further include units other than TFE units, PAE units, and polar units (hereinafter, also referred to as “other units”). The other unit may be one type or two or more types.
Examples of monomers forming other units include ethylene, propylene, vinyl chloride, vinylidene chloride, vinyl fluoride (VF), vinylidene fluoride (VDF), and chlorotrifluoroethylene (CTFE). Other units are preferably ethylene, VDF or CTFE, with ethylene being particularly preferred.
The proportion of other units in the F polymer is preferably 0 to 50 mol%, and particularly preferably 0 to 40 mol%, based on all units constituting the F polymer.
140-320 degreeC is preferable, as for the melting temperature of F polymer, 200-320 degreeC is more preferable, and 260-320 degreeC is especially preferable. In this case, the fusion bondability between the F polymer and the S polymer is balanced, the adhesiveness and workability of the molded product are further improved, and the physical properties of the S polymer are less likely to be impaired.

The S polymer in the present invention is a polymer containing a unit based on a fluoroolefin (hereinafter, also referred to as “F unit”) that is soluble in a polar solvent different from that of the F polymer, and contains an F unit but contains an oxygen-containing polar group. Polymers without are preferred.
The fluoroolefin in the S polymer is preferably VF, VDF, CTFE or 1,3,3,3-tetrafluoropropene, and particularly preferably VDF or CTFE. Two or more kinds of fluoroolefins may be used.
The S polymer is polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), a copolymer of vinylidene fluoride and tetrafluoroethylene, or vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene. Are preferred and PVDF is particularly preferred.
The ratio of the mass of the F polymer to the mass of the S polymer (content of F polymer/content of S polymer) in the present invention is preferably 0.4 or less, particularly preferably 0.15 or less. In this case, when it is within this range, the state stability of the liquid composition is further improved, and the adhesiveness, crack resistance and physical properties of the S polymer can be easily balanced.
The total content of the F polymer and the S polymer in the present invention is preferably 20 to 70% by mass, and particularly preferably 30 to 60% by mass.

The polar solvent in the present invention is a liquid at 25°C, and a polar organic solvent is preferable.
The polar solvent may be used alone or in combination of two or more.
The polar solvent is preferably amide, alcohol, sulfoxide, ester, ketone or glycol ether, more preferably ester, ketone or amide, particularly preferably ketone or amide.
Specific examples of the polar solvent include methanol, ethanol, isopropanol, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, diethyl ether, dioxane, ethyl lactate, ethyl acetate, Butyl acetate, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, ethylene glycol monoisopropyl ether, γ-butyrolactone, cellosolve (methyl cellosolve, ethyl cellosolve, etc.), ethyl acetate, Examples include isopropyl acetate, butyl acetate, and isobutyl acetate.

The polar solvent is more preferably methyl ethyl ketone, cyclohexanone or N-methyl-2-pyrrolidone. In this case, the solubility of the S polymer is increased and the F polymer is easily dispersed uniformly. Further, the state stability of the liquid composition is further improved, and the adhesiveness and workability of the molded product are likely to be further improved. When the liquid composition is used as the electrode binder material, the polar solvent is particularly preferably N-methyl-2-pyrrolidone.
The polar solvent is more preferably a compound having a boiling point of 80 to 275°C, further preferably a compound having a boiling point of 125 to 250°C. In this range, when the polar solvent is distilled off by heating from the liquid composition, the volatilization of the organic solvent and the formation of the molded article effectively proceed.

The liquid composition of the present invention preferably contains a dispersant from the viewpoint of improving the dispersibility of the powder and improving the moldability thereof. The components used in producing the polymer (for example, the surfactant used in emulsion-polymerizing the fluoroolefin) do not correspond to the dispersant in the present invention.
The dispersant is preferably a compound having a hydrophobic site and a hydrophilic site, and examples thereof include an acetylene-based surfactant, a silicone-based surfactant, and a fluorine-based surfactant. These dispersants are preferably nonionic.
The dispersant is preferably fluoroalcohol, more preferably fluoromonool or fluoropolyol.

10-50 mass% is preferable, as for the fluorine content of fluoromonool, 10-45 mass% is more preferable, and its 15-40 mass% is especially preferable.
The fluoromonool is preferably nonionic.
The hydroxyl value of fluoromonool is preferably 40 to 100 mgKOH/g, more preferably 50 to 100 mgKOH/g, and particularly preferably 60 to 100 mgKOH/g.

The fluoromonool is preferably a compound represented by the following formula (a).
Formula _{^{(a): R a - (}} OQ a) ma -OH
The symbols in the formulas have the following meanings.
R ^a represents a polyfluoroalkyl group containing a polyfluoroalkyl group or an etheric oxygen _{atom, -CH 2 (CF 2) 4} F, -CH 2 (CF 2) 6 F, -CH 2 CH 2 (CF 2 _{) 4 F, -CH 2 CH 2} (CF 2) 6 F, -CH 2 CF 2 OCF 2 CF 2 OCF 2 CF 3, -CH 2 CF (CF 3) CF 2 OCF 2 CF 2 CF 3, -CH 2 _{CF (CF 3) OCF 2 CF} (CF 3) OCF 3, or _{-CH 2 CF 2 CHFO (CF 2} ) 3 OCF 3 are preferred.
Q ^a represents an alkylene group having 1 to 4 carbon atoms, and is preferably an ethylene group (—CH ₂ CH ₂ —) or a propylene group (—CH ₂ CH(CH ₃ )—). Q ^a may be composed of two or more kinds of groups. When it is composed of two or more kinds of groups, the groups may be arranged in a random pattern or a block pattern.
ma shows the integer of 4-20 and the integer of 4-10 is preferable.
The hydroxyl group of fluoromonool is preferably a secondary hydroxyl group or a tertiary hydroxyl group, and particularly preferably a secondary hydroxyl group.

Examples of fluoro _{monool, F (CF 2) 6 CH} 2 (OCH 2 CH 2) 7 OCH 2 CH (CH 3) OH, F (CF 2) 6 CH 2 (OCH 2 CH 2) 12 OCH 2 _{CH (CH 3) OH, F} (CF 2) 6 CH 2 CH 2 (OCH 2 CH 2) 7 OCH 2 CH (CH 3) OH, F (CF 2) 6 CH 2 CH 2 (OCH 2 CH 2) 12 _{OCH 2 CH (CH 3) OH} , F (CF 2) 4 CH 2 CH 2 (OCH 2 CH 2) 7 OCH 2 CH (CH 3) OH and the like.
Such fluoromonool can be obtained as a commercially available product (such as "Fluowet N083" and "Fluowet N050" manufactured by Arkroma Co., Ltd.).

The fluorine content of the fluoropolyol is preferably 10 to 50% by mass, more preferably 10 to 45% by mass, and particularly preferably 15 to 40% by mass.
The fluoropolyol is preferably nonionic.
The hydroxyl value of the fluoropolyol is preferably 10 to 35 mgKOH/g, more preferably 10 to 30 mgKOH/g, and particularly preferably 10 to 25 mgKOH/g.
The weight average molecular weight of the fluoropolyol is preferably 2,000 to 80,000, particularly preferably 6,000 to 20,000.
The fluoropolyol is preferably a fluoropolyol containing units based on fluoro(meth)acrylate. In addition, "(meth)acrylate" is a general term for acrylate and methacrylate.

The fluoro(meth)acrylate is preferably a monomer represented by the following formula (f).
Formula ^{_{(f): CH 2 = CX}} f C (O) O-Q f -R f
The symbols in the formulas have the following meanings.
X ^f represents a hydrogen atom, a chlorine atom or a methyl group.
Q ^f represents an alkylene group having 1 to 4 carbon atoms or an oxyalkylene group having 2 to 4 carbon atoms.
R ^f represents a polyfluoroalkyl group having 1 to 6 carbon atoms, a polyfluoroalkyl group having 3 to 6 carbon atoms containing an etheric oxygen atom, or a polyfluoroalkenyl group having 4 to 12 carbon atoms, and —CF(CF _{3 ) (C (CF (CF 3} ) 2) (= C (CF 3) 2)), - C (CF 3) = C (CF (CF 3) 2) 2, - (CF 2) 4 F or - ( CF ₂ ) ₆ F is preferred.

Specific examples of the fluoro(meth)acrylate include CH ₂ ═CHC(O)OCH ₂ CH ₂ (CF ₂ ) ₄ F and CH ₂ ═C(CH ₃ )C(O)OCH ₂ CH ₂ (CF ₂ ) _{4. F, CH 2 = CHC (O} ) OCH 2 CH 2 (CF 2) 6 F, CH 2 = C (CH 3) C (O) OCH 2 CH 2 (CF 2) 6 F, CH 2 = CHC (O) _{OCH 2 CH 2 OCF (CF 3} ) (C (CF (CF 3) 2) (= C (CF 3) 2)), CH 2 = C (CH 3) C (O) OCH 2 CH 2 OC (CF 3 _{) = C (CF (CF 3} ) 2) 2, CH 2 = CHC (O) OCH 2 CH 2 CH 2 CH 2 OCF (CF 3) (C (CF (CF 3) 2) (= C (CF 3) _{2)), CH 2 = C} (CH 3) C (O) OCH 2 CH 2 CH 2 CH 2 OC (CF 3) = C (CF (CF 3) 2) 2 and the like.

Preferable specific examples of the fluoropolyol include copolymers of the monomer represented by the above formula (f) and the monomer represented by the following formula (o).
Formula ^{_{(o): CH 2 = CX}} o C (O) - (OZ o) mo -OH
The symbols in the formulas have the following meanings.
X ^o represents a hydrogen atom or a methyl group.
Z ^o represents an alkylene group having 1 to 4 carbon atoms.
mo is an integer of 3 to 200.
In addition, Z ^o may be composed of two or more kinds of groups. In this case, the arrangement of different alkylene groups may be random or block.
When the compound represented by the formula (o) is used, not only the dispersibility of the liquid composition is excellent, but also the physical properties such as wettability and adhesiveness of the molded product are easily improved.

Specific examples of the monomer represented by the formula (o) include CH ₂ ═CHCOO(CH ₂ CH ₂ O) ₈ OH, CH ₂ ═CHCOO(CH ₂ CH ₂ O) ₁₀ OH, CH ₂ ═CHCOO(CH _{2 CH 2 O) 12 OH, CH} 2 = CHCOOCH 2 CH 2 CH 2 CH 2 O (CH 2 CH 2 O) 8 OH, CH 2 = CHCOOCH 2 CH 2 CH 2 CH 2 O (CH 2 CH 2 O) 10 OH , CH ₂ ═CHCOOCH ₂ CH ₂ CH ₂ CH ₂ O(CH ₂ CH ₂ O) ₁₂ OH, CH ₂ ═C(CH ₃ )COO(CH ₂ CH(CH ₃ )O) ₈ OH, CH ₂ ═C( _{CH 3) COO (CH 2 CH} (CH 3) O) 12 OH, CH 2 = C (CH 3) COO (CH 2 CH (CH 3) O) 16 OH, CH 2 = C (CH 3) COOCH 2 CH _{2 CH 2 CH 2 O (CH} 2 CH (CH 3) O) 8 OH, CH 2 = C (CH 3) COOCH 2 CH 2 CH 2 CH 2 O (CH 2 CH (CH 3) O) 12 OH, CH _{2 = C (CH 3) COOCH} 2 CH 2 CH 2 CH 2 O (CH 2 CH (CH 3) O) 16 OH and the like.

The fluoropolyol may be composed only of a unit based on the monomer represented by the formula (f) and a unit based on the monomer represented by the formula (o), and may further include another unit. ..
The content of the units based on the monomer represented by the formula (f) with respect to all the units contained in the fluoropolyol is preferably 60 to 90 mol%, more preferably 70 to 90 mol%.
The content of the unit based on the monomer represented by the formula (o) is preferably 10 to 40 mol% and more preferably 10 to 30 mol% with respect to all the units contained in the fluoropolyol.
The total content of the units based on the monomer represented by the formula (f) and the monomer represented by the formula (o) is preferably 90 to 100 mol %, based on all units contained in the fluoropolyol, and 100 Mol% is more preferred.
The proportion of fluoroalcohol in the liquid composition of the present invention is preferably 10% by mass or less, more preferably 1% by mass or less, and particularly preferably 0.01% by mass or less. The lower limit of the ratio is usually more than 0%.

The liquid composition of the present invention may contain materials other than the F polymer, the S polymer, and the polar solvent. Other materials include thixotropic agents, fillers, defoamers, dehydrating agents, plasticizers, weathering agents, antioxidants, heat stabilizers, lubricants, antistatic agents, brighteners, colorants, conductive agents. , Release agents, surface treatment agents, viscosity modifiers, flame retardants, curing agents, curing aids. Other materials may or may not dissolve in the liquid composition.

Other materials include solvent-insoluble fluoropolymers, including copolymers of TFE and PAVE (PFA), copolymers of TFE and HFP (FEP), copolymers of TFE and ethylene (ETFE), low molecular weight polytetrafluoroethylene. Fluoroethylene (PTFE) is mentioned.
In addition to the homopolymer of TFE, the low molecular weight PTFE also includes so-called modified PTFE, which is a copolymer of a very small amount of comonomer (PAVE, HFP, FAE, etc.) and TFE. Further, PFA may include units based on monomers other than TFE and PAVE. The same applies to the other copolymers (FEP, ETFE) described above.
Melt viscosity at 380 ° C. of the solvent-insoluble type fluoropolymer, 1 × preferably ^{10 2 Pa · s~1 × 10 6} Pa · s, 1 × 10 3 Pa · s~1 × 10 6 Pa · s is more preferable. Further, the melting temperature thereof is preferably 260 to 340°C.
When the liquid composition of the present invention contains a solvent-insoluble fluoropolymer, the ratio of the mass of the solvent-insoluble fluoropolymer to the mass of the S polymer is preferably 0.4 or less, and particularly preferably 0.15 or less. The solvent-insoluble fluoropolymer is a polymer different from the F polymer and the S polymer.

Other materials include thermosetting resins (epoxy resin, thermosetting polyimide resin, polyimide precursor (polyamic acid), acrylic resin, phenol resin, polyester resin, polyolefin resin, modified polyphenylene ether resin, bismaleimide resin, and Functional cyanate ester resin, polyfunctional maleimide-cyanate ester resin, polyfunctional maleimide resin, vinyl ester resin, urea resin, diallyl phthalate resin, melanin resin, guanamine resin, melamine-urea co-condensation resin, etc.), hot melt Resin (polyester resin, polyolefin resin, styrene resin, polycarbonate, thermoplastic polyimide, polyarylate, polysulfone, polyallylsulfone, aromatic polyamide, aromatic polyetheramide, polyphenylene sulfide, polyallyl ether ketone, polyamideimide, liquid crystal Polyester, polyphenylene ether, etc.), reactive alkoxysilane, carbon black, and inorganic filler (such as lath microspheres and ceramic microspheres).

The viscosity of the liquid composition of the present invention is preferably 1 to 1000 mPa·s, more preferably 5 to 500 mPa·s, and particularly preferably 10 to 200 mPa·s. In this case, the dispersibility of the liquid composition and the coatability of the liquid composition are easily balanced.
The thixo ratio (η ₁ /η ₂₎ calculated by dividing the viscosity η ₁ of the liquid composition of the present invention measured at a rotation speed of 30 rpm by the viscosity η ₂ measured at a rotation speed of 60 rpm. ) Is preferably 0.8 to 2.2. In this case, it is easy to balance the dispersibility of the liquid composition with the processability such as the coatability of the liquid composition.

The liquid composition of the present invention can be produced by mixing F powder, S polymer and polar solvent. Specifically, it is preferable that the dispersion liquid containing the F powder and the polar solvent is mixed with the solution containing the S polymer and the polar solvent to prepare the mixture.
Upon mixing, the dispersion is preferably well dispersed. For example, when solid content is observed in the dispersion liquid, it is preferable that the dispersion liquid is subjected to a dispersion treatment using a homodisper immediately before mixing and further a dispersion treatment using a homogenizer to improve the dispersion state. .. In particular, when using a dispersion liquid stored at 0 to 40° C., it is preferable to perform the dispersion treatment.
The polar solvents in the dispersion and the solution are preferably the same polar solvent.

The liquid composition of the present invention has excellent state stability, and can form a molded product having excellent crack resistance and strong adhesiveness without impairing the physical properties of the S polymer.
When the liquid composition of the present invention is applied to the surface of a base material and heated to form a polymer layer containing an F polymer and an S polymer (hereinafter, also referred to as “polymer layer P”), a base material, It is possible to manufacture a laminate in which a polymer layer containing an F polymer and an S polymer is laminated in this order.
The ranges of the F polymer, the F powder, the S polymer and the polar solvent in the production of this laminate are the same as defined in the liquid composition of the present invention, including the preferable embodiments thereof. Further, the polymer layer P may be formed on at least one surface of the base material, the polymer layer P may be formed on only one surface of the base material, or the polymer layer P may be formed on both surfaces of the base material. ..

As a method for applying to the surface of the base material, a spray method, a roll coating method, a spin coating method, a gravure coating method, a micro gravure coating method, a gravure offset method, a knife coating method, a kiss coating method, a bar coating method, a die coating method, a fountain. Examples include the Mayer bar method and the slot die coating method.
The polymer layer P may be formed by heating, and is preferably heated in a temperature range of 100 to 300°C. The polymer layer P is preferably a polymer layer formed by melting an F polymer and an S polymer.

Examples of the method for heating the base material include a method using an oven, a method using a ventilation drying furnace, and a method of irradiating with heat rays (infrared rays).
The atmosphere for heating the substrate may be either under normal pressure or under reduced pressure. The atmosphere in the holding is any of an oxidizing gas (oxygen gas etc.), a reducing gas (hydrogen gas etc.) and an inert gas (helium gas, neon gas, argon gas, nitrogen gas etc.). It may be.
The heating time of the base material is usually 0.5 to 30 minutes.
The thickness of the polymer layer P is preferably 50 μm or less, more preferably 30 μm or less, and particularly preferably 10 μm or less. The thickness of the polymer layer P is preferably 0.1 μm or more, particularly preferably 4 μm or more. Within this range, the polymer layer P having excellent crack resistance can be easily formed without impairing the physical properties of the S polymer.
In the laminated body, the base material and the polymer layer P are firmly adhered to each other. The peel strength between the base material and the polymer layer P is preferably more than 12 N/cm, particularly preferably 15 N/cm or more. The upper limit of the peel strength is not particularly limited and is preferably 100 N/cm or less.

The base material is not particularly limited, and may be a metal base material such as copper, aluminum, or iron, a glass base material, a resin base material, a silicon base material, or a ceramic base material.
The shape of the base material is not particularly limited, and may be any of a planar shape, a curved surface shape, an uneven shape, and a foil shape, a plate shape, a film shape, or a fibrous shape.
Specific examples of the laminate also include a polyimide film in which the substrate is a polyimide film, and the polymer layer P formed from the liquid composition of the present invention is provided on at least one surface of the polyimide film.
An adhesive layer may be separately provided between the polyimide film and the polymer layer, but since the polymer layer P formed from the liquid composition of the present invention has excellent adhesiveness, the adhesive layer is not provided. May be.

A preferred embodiment of the polyimide film is 2,2′,3,3′- or 3,3′,4,4′-biphenyltetracarboxylic dianhydride (3,3′,4,4′-benzophenonetetra). Carboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, etc.) and other acid dianhydrides as the main component and paraphenylenediamine as the main component And a film of a polymer with the above components. A specific example of the polyimide film is Optical Type AF (manufactured by Kaneka North America).
Such a polyimide film is useful as an insulating coating. The mass is preferably 23.5 g/m ² or less, and the loop stiffness value is preferably 0.45 g/cm or more.
The thickness of the polymer layer P in the polyimide film is preferably 1 to 200 μm, particularly preferably 5 to 20 μm. The thickness of the polyimide film is particularly preferably 5 to 150 μm.

Such a polyimide film has excellent electrical insulation properties, abrasion resistance, hydrolysis resistance, etc., and can be used as a packaging material for electrically insulating tapes, electric cables or electric wires, for aerospace or electric vehicles, and electric wires. It can be used particularly preferably as a material or a cable material.
According to the present invention, it is possible to obtain a laminate having a polymer layer P which is excellent in crack resistance without impairing the physical properties of the S polymer and which also contains the F polymer and is excellent in adhesiveness. Therefore, a composite laminate in which another material is further laminated on the polymer layer P of the laminate can be manufactured.
When the surface of the polymer layer P of the laminated body and the second base material are pressure-bonded to each other, a composite laminated body in which the first base material, the polymer layer P, and the second base material are laminated in this order is obtained. can get.

The second base material is not particularly limited, and may be a metal base material such as copper, aluminum, or iron, a glass base material, a resin base material, a silicon base material, or a ceramic base material.
The shape of the second base material is not particularly limited, and may be any of a flat shape, a curved shape, and an uneven shape.
The property of the second base material may be any of foil, plate, film, and fiber.
Specific examples of the second base material include a heat resistant resin base material and a prepreg which is a precursor of a fiber reinforced resin plate.
A prepreg is a sheet-like base made by impregnating a base material (tow, woven fabric, etc.) of reinforcing fibers (glass fiber, carbon fiber, etc.) with a resin (thermosetting resin, thermoplastic resin, etc. described above). It is a material.
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, polyallylsulfone, aromatic polyamide, aromatic polyetheramide, polyphenylene sulfide, polyallyl ether ketone, polyamideimide, liquid crystalline polyester, and polytetrafluoroethylene. ..

As a method for pressure-bonding the surface of the polymer layer P of the laminate and the second base material, a thermocompression bonding method can be mentioned.
When the second base material is a prepreg, the pressure bonding temperature in the thermocompression bonding method is preferably 120 to 300°C, particularly preferably 160 to 220°C. Within this range, the polymer layer P and the prepreg can be firmly adhered while suppressing thermal deterioration of the prepreg.
When the second substrate is a heat resistant resin substrate, the thermocompression bonding temperature is preferably 300 to 400°C. Within this range, the polymer layer and the heat-resistant resin base material can be firmly bonded while suppressing the thermal deterioration of the heat-resistant resin base material.
The thermocompression bonding is preferably performed in a reduced pressure atmosphere, and particularly preferably performed in a vacuum degree of 20 kPa or less. In this range, it is possible to prevent bubbles from being mixed into the interfaces of the substrate, the polymer layer P, and the second base material in the composite laminate, and to suppress deterioration due to oxidation. Moreover, it is preferable that the temperature of the thermocompression bonding be raised after reaching the vacuum degree.
The pressure in thermocompression bonding is preferably 0.2 to 10 MPa. Within this range, the polymer layer P and the second base material can be firmly bonded while suppressing damage to the composite laminate.

When the liquid layer forming material for forming the second polymer layer is applied to the surface of the polymer layer P of the laminate to form the second polymer layer, the first base material, the polymer layer P, and the A composite laminate in which the two polymer layers are laminated in this order is obtained.
The liquid layer forming material is not particularly limited, and the liquid composition of the present invention may be used.
The method for forming the second polymer layer is also not particularly limited and can be appropriately determined depending on the properties of the liquid layer forming material used. For example, when the layer forming material is the liquid composition of the present invention, the second polymer layer can be formed under the same conditions as the method for forming the polymer layer P in the laminate. That is, when the layer forming material is the liquid composition of the present invention, the polymer layer P can be multi-layered to easily form a thicker polymer layer P.

Specific examples of the composite laminate obtained by such a production method include a composite laminate obtained by using the liquid composition of the present invention or a liquid composition containing F powder as a liquid layer forming material. Since the second polymer layer is formed on the polymer layer P exhibiting strong adhesiveness, a composite laminate having high peel strength can be obtained even by using the latter liquid composition. Such a composite laminate can also be suitably used as one mode of the above-mentioned resin-coated metal foil or insulating coating.
The polymer layer P in the laminate of the present invention has excellent crack resistance without impairing the physical properties of the S polymer. By removing the base material from the laminate, a polymer thin film containing an F polymer and an S polymer can be obtained. The polymer thin film is preferably a polymer thin film formed by melting an F polymer and an S polymer.

The method of removing the base material from the laminate is not particularly limited, and examples thereof include a method of peeling and removing the base material from the laminate, and a method of dissolving and removing the base material from the laminate. For example, when the base material is a copper foil, the base material surface of the laminate is brought into contact with an etching solution such as hydrochloric acid, the base material is dissolved and removed, and a polymer thin film is easily obtained.
The range of the polymer in the polymer thin film is the same as the definition in the liquid composition of the present invention, including the preferable embodiments thereof.
The thickness of the polymer thin film is preferably 50 μm or less, more preferably 30 μm or less, and particularly preferably 10 μm or less. The thickness of the polymer thin film is preferably 1 μm or more, and particularly preferably 4 μm or more. Within this range, the polymer thin film is more excellent in adhesiveness and crack resistance without impairing the physical properties of the S polymer.

The liquid composition of the present invention can be used as a binder material for electrodes.
The total content (solid content concentration) of the F polymer and the S polymer in the electrode binder is preferably 15 to 55 mass% with respect to the total amount.
The content of the polar solvent in the electrode binder is preferably 45 to 85 mass% with respect to the total amount.
In this case, when the electrode binder is mixed with the electrode active material and the like to prepare the electrode mixture, the viscosity of the electrode mixture becomes appropriate and not only the thick film coating on the current collector but also the electrode Dispersibility of the electrode active material and the like in the mixture is likely to be further improved.
When the liquid composition of the present invention is used as a binder for electrodes, it may contain components other than the F polymer, S polymer and polar solvent. The content of other components is preferably 10% by mass or less, and more preferably 1% by mass or less, based on the total amount of the binder for electrodes.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.
Various measuring methods are shown below.
<D50 and D90 of powder>
The powder was dispersed in water using a laser diffraction/scattering type particle size distribution measuring device (LA-920 measuring device manufactured by Horiba Ltd.) for measurement.
<Storage stability of liquid composition>
After leaving the liquid composition at 25° C. for 1 week, the state was visually confirmed and evaluated according to the following evaluation criteria.
◯: No sediment is confirmed, or sediment is confirmed but can be easily redispersed.
X: Sediment is confirmed and cannot be easily redispersed.

<Crack resistance of polymer layer>
After applying the liquid composition to the surface of a stainless steel plate (thickness 0.5 mm) having a vinyl tape attached to one end, slide the rod along the end and smooth it at 100° C. for 3 minutes for 3 minutes. It was dried once and further heated at 300° C. for 10 minutes. As a result, a polymer layer having an inclined thickness was formed on the surface of the stainless steel plate due to the thickness of the vinyl tape attached to the edges. This stainless steel plate was visually confirmed, and the film thickness of the polymer layer at the tip of the crack line generation portion (the portion where the polymer layer was thinnest) was measured using MINTEST3000 (manufactured by Electro Physik), and the following evaluation criteria were used. It was evaluated by.
◯: The thickness of the polymer layer at the tip where cracks occur is 50 μm or more.
X: The thickness of the polymer layer at the tip where cracks occur is less than 50 μm.

<Peel strength of laminate>
The position of 50 mm from one end in the length direction of the laminate cut out in a rectangular shape (length 100 mm, width 10 mm) was fixed, the pulling speed was 50 mm/min, and 90° to the laminate from one end in the length direction, The maximum load applied when the metal foil and the resin layer were peeled off was measured as the peeling strength (N/cm) and evaluated according to the following evaluation criteria.
Good: Peel strength is 10 N/cm or more.
X: Peel strength is less than 10 N/cm.

The materials used are shown below.
[powder]
Powder (1 ¹ ): Polymer (P ¹ ) containing 97.9 mol%, 0.1 mol% and 2.0 mol% of units based on TFE, units based on NAH and units based on PPVE in this order (melting point: Powder having a D50 of 0.3 μm and a D90 of 1.8 μm.
Powder (X ¹ ): A powder made of PTFE and having a D50 of 0.3 μm.
[Dispersant]
Fluoro _{Polyol: CH 2 = C (CH 3} ) C (O) OCH 2 CH 2 (CF 2) units based on ₆ F and _{CH 2 = C (CH 3)} C (O) (OCH 2 CH 2) a 23 OH A copolymer containing a base unit (fluorine content: 35% by mass, hydroxyl value: 19 mgKOH/g).

[Example 1] Production example of liquid composition (No. 1)
[Example 1-1] Production example of liquid composition 1 30 parts by mass of powder (1 ¹ ), 5 parts by mass of fluoropolyol, and 65 parts by mass of cyclohexinone were mixed to disperse the powder (1 ¹ ). A dispersion was obtained. A PVDF solution containing PVDF and cyclohexanone (PVDF content: 70% by mass), which is a standard commercially available PVDF coating composition, is mixed with the dispersion liquid, and 56% by mass of PVDF and a polymer (P ¹ ) are mixed. To obtain a cyclohexanone solution containing 6% by mass (Liquid composition 1. Ratio of mass of polymer (P ¹ ) to mass of PVDF: 0.11.). The storage stability was “◯” and the crack resistance was “◯”.
[Example 1-2] except for using the powder ^{(X 1)} in place of preparation powder liquid composition 2 ^{(1 1),} in the same manner as in Example 1-1, PVDF 56 mass%, PTFE 6 A cyclohexanone solution (mass% by mass, liquid composition 2. Ratio of mass of PTFE to mass of PVDF: 0.11) was obtained. The storage stability was “◯” and the crack resistance was “x”.

[Example 2] Production Example of Laminated Body [Example 2-1] Production Example of Laminated Body 1 Liquid composition 1 was applied to the surface of a copper foil, dried at 100°C for 10 minutes, and then heated at 300°C under an inert gas atmosphere. It was heated for 10 minutes and gradually cooled. Thus, a laminate having a copper foil and a polymer layer (thickness 5 μm) containing the polymer (P ¹ ) and PVDF formed on the surface of the copper foil was obtained. The peel strength was “◯”.
[Example 2-2] Production Example of Layered Product 2 A copper foil was formed on the surface of the copper foil in the same manner as in Example 2-1 except that the liquid composition 2 was used instead of the liquid composition 1. A laminate having a polymer layer containing PTFE and PVDF (thickness 5 μm) was obtained. The peel strength was "x".

Example 3 Production Example of Liquid Composition (Part 2)
30 parts by mass of powder (1 ¹ ), 5 parts by mass of fluoropolyol, and 65 parts by mass of N-methyl-2-pyrrolidone (NMP) were mixed to obtain a dispersion liquid in which powder (1 ¹ ) was dispersed. .. An NMP solution containing PVDF (PVDF content: 70% by mass) was mixed with the dispersion liquid to prepare an NMP solution containing 56% by mass of PVDF and 6% by mass of the polymer (P ¹ ) (liquid composition 3. PVDF. The ratio of the mass of the polymer (P ¹ ) to the mass of: 0.11) was prepared. When liquid composition 3 was used as a binder material for electrodes and graphite powder was mixed, a uniform slurry (electrode mixture) having high fluidity was obtained.

The liquid composition of the present invention can be used for producing molded products such as films, impregnated products (prepregs, etc.), laminated plates (metal laminates, etc.). INDUSTRIAL APPLICABILITY The liquid composition of the present invention is useful as a material for antenna parts, printed circuit boards, aircraft parts, automobile parts, sports equipment, food industry products, paints, cosmetics, and the like. Wires for electrical equipment, etc.), electrical insulation tape, insulation tape for oil drilling, printed circuit board materials, separation membranes (microfiltration membranes, ultrafiltration membranes, reverse osmosis membranes, ion exchange membranes, dialysis membranes, gas separation membranes, etc. ), electrode binders (for lithium secondary batteries, fuel cells, etc.), covers for copy rolls, furniture, automobile dashboards, home appliances, sliding members (load bearings, sliding shafts, valves, bearings, gears, cams) , Belt conveyors, food conveyor belts, etc.), tools (shovels, files, saws, saws, etc.), boilers, hoppers, pipes, ovens, baking molds, chutes, dies, toilet bowls, container coating materials. is there.

Claims (13)

A liquid composition comprising a solvent-soluble fluoroolefin-based polymer, a powder of a fluoropolymer (P) having a tetrafluoroethylene-based unit and an oxygen-containing polar group, and a polar solvent. The liquid composition according to claim 1, wherein the volume-based cumulative 50% diameter of the powder is 0.05 to 75 µm. The liquid composition according to claim 1 or 2, wherein the ratio of the mass of the fluoropolymer (P) to the mass of the solvent-soluble fluoroolefin-based polymer is 0.4 or less. The liquid composition according to any one of claims 1 to 3, wherein a melting temperature of the fluoropolymer (P) is 140 to 320°C. The liquid composition according to any one of claims 1 to 4, wherein the fluoropolymer (P) contains a unit based on a monomer having the oxygen-containing polar group. The liquid composition according to any one of claims 1 to 5, wherein the oxygen-containing polar group is at least one group selected from the group consisting of a hydroxyl group, a carbonyl group-containing group, an acetal group and an oxycycloalkane group. Stuff. The solvent-soluble fluoroolefin polymer has a unit based on at least one monomer selected from the group consisting of vinyl fluoride, vinylidene fluoride, chlorotrifluoroethylene and 1,3,3,3-tetrafluoropropene. The liquid composition according to any one of claims 1 to 6, which is a polymer containing the composition. The solvent-soluble fluoroolefin polymer is polyvinyl fluoride, polyvinylidene fluoride, polychlorotrifluoroethylene, a copolymer of vinylidene fluoride and tetrafluoroethylene, or vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene. The liquid composition according to any one of claims 1 to 7, which is a copolymer. The liquid composition according to claim 1, wherein the polar solvent is an ester, an amide, or a ketone. The liquid composition according to claim 1, further comprising a dispersant. The liquid composition according to any one of claims 1 to 10, comprising a dispersant, wherein the dispersant is a fluoropolyol having a fluorine content of 10 to 50% by mass and a hydroxyl value of 10 to 35 mgKOH/g. .. The liquid composition according to any one of claims 1 to 11, which is an electrode binder material. The liquid composition according to any one of claims 1 to 11 is applied to the surface of a base material, the polar solvent is removed by heating to form a polymer layer, and the base material and the polymer layer are separated from each other. A method for manufacturing a laminated body, in which a laminated body laminated in this order is obtained.