Classifications

• • 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
• • 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
  • C08J3/12—Powdering or granulating
  • C08J3/124—Treatment for improving the free-flowing characteristics
• • 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
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
• • 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
• • 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
  • C08J2327/00—Characterised by the use 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; Derivatives of such polymers
  • C08J2327/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
  • C08J2327/12—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene

Definitions

• the present invention comprises a high-viscosity composition containing powder particles of a tetrafluoroethylene-based polymer and a liquid medium, a method for producing such a high-viscosity composition, and tetrafluoroethylene-based polymer particles dispersed from the high-viscosity composition.
• the present invention relates to a method for producing the resulting dispersion.
• the tetrafluoroethylene polymer is excellent in physical properties such as electrical insulation, water repellency, oil repellency, chemical resistance, and heat resistance. Therefore, the dispersion liquid in which the powder is dispersed in water or an oil-based solvent is useful as a material for forming a resist, an adhesive, an electrically insulating layer, a lubricant, an ink, a paint, and the like.
• the tetrafluoroethylene polymer has a low surface energy, and the particles constituting the powder (hereinafter, also referred to as “powder particles”) tend to aggregate with each other. Therefore, it is difficult to obtain a low-viscosity dispersion having excellent dispersion stability.
• Patent Document 1 discloses a non-aqueous dispersion liquid using an additive from the viewpoint of improving the dispersibility of the dispersion liquid and adjusting the physical characteristics of the dispersion liquid.
• the dispersion liquid described in Patent Document 1 is not yet sufficient in terms of dispersion stability.
• foaming becomes intense during the preparation of the dispersion, and dispersion stability may decrease due to aggregation.
• the surface smoothness of the coating film or molded product obtained from such a dispersion liquid may be deteriorated.
• the present inventors have studied a method for producing such a dispersion in order to obtain a dispersion having excellent dispersion stability of the powder particles from a tetrafluoroethylene polymer powder having a small specific surface area, and have completed the present invention. rice field.
• the dispersion liquid containing the powder particles of the tetrafluoroethylene-based polymer and further containing other functional materials is a coating film or molded product formed from the dispersion liquid.
• other functional materials inorganic filler, polymer or resin different from the tetrafluoroethylene-based polymer, etc.
• the physical properties of other functional materials can be imparted.
• the affinity between the tetrafluoroethylene polymer and other functional materials is generally low, and the dispersion stability tends to be further lowered in such a dispersion.
• An object of the present invention is to provide a highly viscous composition such as a paste which is a precursor of a dispersion liquid, which contains powder particles of a tetrafluoroethylene polymer and a liquid medium, and a method for producing the same. Further, the present invention comprises a powder particle of a tetrafluoroethylene polymer, a polar polymer, and a liquid medium having a polarity, and a more highly viscous composition such as a wet powder which is a precursor of a dispersion liquid, and a method for producing the same. The purpose is to provide.
• an object of the present invention is to provide a dispersion having excellent dispersion stability, which comprises diluting the highly viscous composition with a liquid medium to produce a dispersion in which powder particles of a tetrafluoroethylene polymer are dispersed. do.
• the present invention has the following aspects.
• [1] Contains particles and a liquid medium derived from a tetrafluoroethylene polymer powder having a specific surface area of 25 m 2 / g or less, a solid content concentration of 40% by mass or more, a temperature of 25 ° C., and a rotation speed.
• the composition of [1] which further contains a polymer or resin other than the tetrafluoroethylene polymer, which is soluble in the liquid medium.
• a composition comprising, having a viscosity of 10,000 to 100,000 Pa ⁇ s as measured by a capillograph with a temperature of 25 ° C. and a shear rate of 1 s -1 .
• the total content of the particles and the content of the polar polymer or its precursor is more than 50% by mass, the content of the liquid medium having the polarity is 40% by mass or less, and the content of the particles is The composition of [3], wherein the ratio of the content of the polar polymer or its precursor to the amount is 0.001 or more and less than 0.5.
• the composition of [3] or [4], wherein the polar polymer or its precursor is an imide-based polymer, a precursor of an imide-based polymer, a vinyl-based polymer or a polysaccharide.
• composition according to any one of [1] to [6], wherein the tetrafluoroethylene polymer is a polymer having a carbonyl group-containing group or a hydroxyl group-containing group.
• the tetrafluoroethylene polymer has a fluorine content of 70% by mass or more.
• the tetrafluoroethylene polymer has a melting temperature of 180 to 325 ° C.
• a mixture containing particles derived from a tetrafluoroethylene polymer powder having a specific surface area of 25 m 2 / g or less and a liquid medium is kneaded, and degassing during or after kneading and static after kneading are performed.
• a method for producing a composition wherein the composition according to any one of [1] to [11] is produced by performing at least one of the settings.
• the production method of [12], wherein both the degassing and the standing still are performed.
• a method for producing a dispersion liquid wherein the composition according to any one of [1] to [11] is diluted with a second liquid medium to obtain a dispersion liquid.
• a wet powder comprising a precursor and a liquid medium having at least one polarity selected from the group consisting of amides, ketones and esters.
• a dispersion liquid containing particles derived from a tetrafluoroethylene polymer powder having a small specific surface area and having excellent dispersion stability can be produced.
• the dispersion liquid obtained by such a production method the obtained coating film or molded product has an appearance having excellent surface smoothness.
• the "tetrafluoroethylene-based polymer” is a polymer containing a unit (hereinafter, also referred to as TFE unit) based on tetrafluoroethylene (hereinafter, also referred to as TFE).
• TFE unit a unit based on tetrafluoroethylene
• TFE tetrafluoroethylene
• the "glass transition point (Tg) of the polymer” is a value measured by analyzing the polymer by the dynamic viscoelasticity measurement (DMA) method.
• DMA dynamic viscoelasticity measurement
• the “polymer melting temperature (melting point)” is the temperature corresponding to the maximum value of the melting peak measured by the differential scanning calorimetry (DSC) method.
• D50 is the average particle size of the particles constituting the measurement object such as powder or an inorganic filler, and is the volume-based cumulative 50% diameter of the particles constituting the measurement object obtained by the laser diffraction / scattering method. That is, the particle size distribution of the particles constituting the object to be measured is measured by the laser diffraction / scattering method, the cumulative curve is obtained with the total volume of the object to be measured as 100%, and the cumulative volume is 50% on the cumulative curve. Particle size. “D90” is the cumulative volume particle diameter of the particles constituting the measurement object, and is the volume-based cumulative 90% diameter of the particles obtained in the same manner as in “D50”.
• Viscosity measured by capillary graph is a viscosity measured by using a capillary having a capillary length of 10 mm and a capillary radius of 1 mm, a furnace body diameter of 9.55 mm, and a load cell capacity of 2 tons.
• the "viscosity measured by the B-type viscometer” is a value measured by using a B-type viscometer under the condition of a room temperature (25 ° C.) and a rotation speed of 30 rpm. The measurement is repeated 3 times, and the average value of the measured values for 3 times is used.
• the "tixo ratio" is obtained by measuring the viscosity ⁇ 1 obtained by measuring the viscosity ⁇ 1 at room temperature (25 ° C.) at a rotation speed of 30 rpm using a B-type viscometer under the condition of a rotation speed of 60 rpm. It is a value ( ⁇ 1 / ⁇ 2 ) calculated by dividing by the viscosity ⁇ 2 .
• a "monomer-based unit" in a polymer is an atomic group formed directly from one molecule of a monomer by polymerization, and an atomic group obtained by processing a part of the atomic group into another structure. Means.
• the unit based on the monomer a is also simply referred to as “monomer a unit”.
• the tetrafluoroethylene polymer in the present invention is also referred to as “F polymer”.
• the powder of F polymer having a specific surface area of 25 m 2 / g or less is also referred to as “this powder”.
• the liquid medium having polarity is also referred to as “liquid polar medium”.
• compositions of the present invention contains particles derived from the present powder and a liquid medium, has a solid content concentration of 40% by mass or more, is measured with a B-type viscometer at a temperature of 25 ° C. and a rotation speed of 30 rpm. It is a composition having a viscosity (hereinafter, simply referred to as "viscosity measured by a B-type viscometer") of 8000 to 100,000 mPa ⁇ s.
• the composition of the present invention is referred to as "the present composition (1)”.
• the other one of the compositions of the present invention comprises particles derived from the powder, a polar polymer or precursor thereof, and a liquid polar medium and has a viscosity as measured by a capillograph with a shear rate of 1s -1 (hereinafter, simply "". It is a composition having a viscosity (referred to as viscosity measured by capillograph measurement) of 10,000 to 100,000 Pa ⁇ s.
• the composition of the present invention is referred to as "the present composition (2)”.
• the present composition (1) and the present composition (2) are collectively referred to as "the present composition”.
• the present composition is suitable as an intermediate for obtaining a dispersion liquid in which particles derived from the present powder are dispersed in a liquid medium.
• Such a dispersion can be obtained by diluting the composition with a liquid medium.
• the liquid medium in the composition is also referred to as a "first liquid medium", if necessary, in order to distinguish it from the second liquid medium used for diluting the composition.
• first liquid medium the F polymer, the present powder, the liquid medium, the polar polymer and the precursor thereof related to the present composition.
• the F polymer in the present composition is a polymer containing a unit (hereinafter, also referred to as “TFE unit”) based on tetrafluoroethylene (hereinafter, also referred to as “TFE”).
• TFE unit a unit based on tetrafluoroethylene
• the fluorine content of the F polymer is preferably 70% by mass or more.
• the F polymer having a high fluorine content is excellent in physical properties such as electrical properties of the F polymer, but has a remarkably low affinity with a liquid medium. Therefore, the dispersibility of the particles of the F polymer is further lowered.
• the present composition even in the dispersion liquid of the particles of the F polymer obtained by using the same composition, the physical characteristics of the entire F polymer are not impaired, and a dispersion liquid having excellent dispersibility can be obtained.
• the fluorine content of the F polymer is preferably 76% by mass or less.
• the F polymer may be heat-meltable or non-heat-meltable.
• the heat-meltable polymer means a polymer having a temperature at which the melting flow rate is 1 to 1000 g / 10 minutes under the condition of a load of 49 N.
• the non-thermally meltable polymer means a polymer in which there is no temperature at which the melt flow rate is 1 to 1000 g / 10 minutes under the condition of a load of 49 N.
• the melting temperature of the heat-meltable F polymer is preferably 180 ° C. or higher, more preferably 200 ° C. or higher, and even more preferably 260 ° C. or higher.
• the melting temperature of the F polymer is preferably 325 ° C or lower, more preferably 320 ° C or lower.
• the melting temperature of the F polymer is particularly preferably 180 to 325 ° C.
• the glass transition point of the F polymer is preferably 50 ° C. or higher, more preferably 75 ° C. or higher.
• the glass transition point of the F polymer is preferably 150 ° C. or lower, more preferably 125 ° C. or lower.
• polytetrafluoroethylene hereinafter, also referred to as “PTFE”
• PAVE perfluoro (alkyl vinyl ether)
• PFA unit polymers containing (hereinafter, also referred to as “PFA”) or copolymers containing units based on TFE and hexafluoropropylene (hereinafter, also referred to as “FEP”) are preferable, PFA or FEP is more preferable, and PFA is further preferable.
• FEP polytetrafluoroethylene
• FEP hexafluoropropylene
• CF 2 CFOCF 3
• CF 2 CFOCF 2 CF 3
• CF 2 CFOCF 2 CF 3
• PPVE CFOCF 2 CF 2 CF 3
• the F polymer preferably has a polar functional group.
• the F polymer may have two or more polar functional groups.
• As the polar functional group a carbonyl group-containing group, a hydroxyl group-containing group and a phosphono group-containing group are preferable, and the F polymer has a carbonyl group-containing group or a hydroxyl group-containing group from the viewpoint of easily enhancing physical properties such as dispersibility of the powder. Polymers are more preferred.
• the polar functional group may be contained in the monomer unit in the F polymer, or may be contained in the terminal group of the main chain of the polymer. Examples of the latter aspect include an F polymer having a polar functional group as a terminal group derived from a polymerization initiator, a chain transfer agent, or the like.
• the number of carbonyl group-containing groups in the F polymer is preferably 10 or more and 5000 or less, and 50 or more and 2000 or less per 1 ⁇ 10 6 main chain carbon atoms. More preferred. In this case, the affinity between the F polymer particles and the liquid medium tends to be improved.
• the number of carbonyl group-containing groups in the F polymer can be quantified by the composition of the polymer or the method described in International Publication No. 2020/145133.
• Examples of the carbonyl group-containing group include a carboxyl group, an alkoxycarbonyl group, an amide group, an isocyanate group, a carbamate group (-OC (O) NH 2 ), an acid anhydride residue (-C (O) OC (O)-), and the like.
• An imide residue (-C (O) NHC (O)-etc.) and a carbonate group (-OC (O) O-) are preferable, and an acid anhydride residue is more preferable.
• hydroxyl group-containing group an alcoholic hydroxyl group-containing group is preferable, and —CF 2 CH 2 OH, —C (CF 3 ) 2 OH and 1,2-glycol group (—CH (OH) CH 2 OH) are more preferable.
• Suitable embodiments of the F polymer include a polymer (1) containing TFE and PAVE units and having a carbonyl group-containing group or hydroxyl group, or TFE and PAVE units, with 2 PAVE units for all monomer units.
• examples thereof include the polymer (2) containing up to 5 mol% and having neither a carbonyl group-containing group nor a hydroxyl group-containing group. Since these polymers form microspherulites in the coating film or molded product, the characteristics of the obtained coating film or molded product can be easily improved.
• the polymer (1) a polymer containing a TFE unit, a PAVE unit, and a unit based on a monomer having a hydroxyl group-containing group or a carbonyl group-containing group is preferable.
• the TFE unit is 90 to 99 mol%
• the PAVE unit is 0.5 to 9.97 mol%
• the unit based on the monomer is 0.01 to 3 mol%, based on all the units.
• Polymers containing each are more preferable.
• examples of the monomer having a hydroxyl group-containing group or a carbonyl group-containing group include itaconic anhydride, citraconic anhydride and 5-norbornen-2,3-dicarboxylic acid anhydride (also known as hymic anhydride; hereinafter, "NAH”). Note)) is preferable.
• Specific examples of the polymer (1) include the polymers described in International Publication No. 2018/16644.
• the polymer (2) is preferably composed of only TFE units and PAVE units, and preferably contains 95 to 98 mol% of TFE units and 2 to 5 mol% of PAVE units with respect to all the monomer units.
• the content of PAVE units in the preferred polymer (2) is preferably 2.1 mol% or more, more preferably 2.2 mol% or more, based on all the monomer units.
• the fact that the polymer (2) has neither a carbonyl group-containing group nor a hydroxyl group-containing group means that the carbonyl group possessed by the polymer per 1 ⁇ 10 6 carbon atoms constituting the polymer main chain. It means that the number of containing groups or hydroxyl group-containing groups is less than 500.
• the number of carbonyl group-containing groups or hydroxyl group-containing groups is preferably 100 or less, more preferably less than 50.
• the lower limit of the number of carbonyl group-containing groups or hydroxyl group-containing groups is usually 0.
• the polymer (2) may be produced by using a polymerization initiator, a chain transfer agent, or the like that does not generate a polar functional group as the terminal group of the polymer chain, and the polar functional group derived from the polymerization initiator may be used in the polymer chain.
• a polymer having a polar functional group such as a polymer having a terminal group may be fluorinated to produce the polymer. Examples of the fluorination treatment method include a method using fluorine gas (see JP-A-2019-194314).
• This powder consists of F polymer particles.
• the specific surface area of the powder is preferably 8 m 2 / g or less, more preferably 5 m 2 / g or less, and particularly preferably 3 m 2 / g or less.
• the specific surface area of this powder is preferably 1 m 2 / g or more.
• the D50 of this powder is preferably 20 ⁇ m or less, more preferably 8 ⁇ m or less.
• the D50 of this powder is preferably 0.1 ⁇ m or more, more preferably 0.3 ⁇ m or more, still more preferably 1 ⁇ m or more.
• the D90 of this powder is preferably less than 100 ⁇ m, more preferably 90 ⁇ m or less. If D50 and D90 of the present powder are in such a range, the surface area thereof becomes large, and the dispersibility of the present powder is likely to be further improved.
• the present powder may be a powder composed of particles composed of a mixture of two or more kinds of F polymers, or may be a powder composed of two or more kinds of particles composed of F polymers.
• the latter is a powder composed of particles made of one F polymer and particles made of a different F polymer, and is usually a mixture of a certain F polymer powder and a different F polymer powder (that is, a powder mixture).
• the powder mixture includes a heat-meltable F-polymer powder (such as a heat-meltable F-polymer powder having a carbonyl group-containing group including TFE units and PAVE units) and a non-heat-meltable F-polymer powder (non-heat-melting).
• a mixture of sex PTFE powder and the like) is preferred.
• the ratio of the former particles (particles of the heat-meltable F polymer) to the total amount of the present powder is preferably 50% by mass or less, more preferably 25% by mass or less. ..
• the ratio is preferably 0.1% by mass or more, more preferably 1% by mass or more.
• the D50 of the former particles is preferably 1 to 4 ⁇ m, and the D50 of the latter particles (particles of the non-heat-meltable F polymer) is preferably 0.1 to 1 ⁇ m.
• the particles constituting the powder may contain a polymer, resin or inorganic substance different from the F polymer.
• a polymer, resin or inorganic substance different from the F polymer in this case is insoluble in the liquid medium in the present composition.
• Specific examples of the polymer or resin different from the F polymer include aromatic elastomers such as aromatic polyimides, aromatic maleimides and styrene elastomers, polymers such as aromatic polyamic acids, and cured products of curable resins.
• aromatic elastomers such as aromatic polyimides, aromatic maleimides and styrene elastomers
• polymers such as aromatic polyamic acids
• inorganic substances include silicon oxide (silica), metal oxides (beryllium oxide, cerium oxide, alumina, soda alumina, magnesium oxide, zinc oxide, titanium oxide, etc.), boron nitride, and magnesium metasilicate (steatite). Can be mentioned.
• the powder containing the F polymer and particles containing a polymer or resin or inorganic substance different from the F polymer is composed of, for example, particles composed of a mixture of the F polymer and fine particles of the polymer or resin or inorganic substance different from the F polymer.
• Examples thereof include the present powder composed of the particles having.
• Examples of the latter powder include a powder obtained by colliding and aggregating an F polymer powder with a polymer or resin powder different from the F polymer or a powder made of inorganic fine particles and coalescing them.
• the liquid medium is an inert liquid liquid at 25 ° C. that does not dissolve the F polymer particles (hereinafter, also referred to as “powder particles”) constituting the powder.
• the liquid medium preferably has an affinity with F polymer particles, for example, a liquid polar medium usually has an affinity with F polymer particles having a carbonyl group-containing group or a hydroxyl group-containing group.
• the liquid medium in the present composition may be a low-viscosity one or a high-viscosity one. As the liquid medium in this composition, a low-viscosity liquid medium is preferable.
• the low-viscosity liquid medium means a liquid medium having a viscosity of 10 mPa ⁇ s or less measured by a B-type viscosity meter at 25 ° C.
• the high-viscosity liquid medium means a liquid medium having a viscosity measured by a B-type viscosity meter at 25 ° C.
• the boiling point of the low-viscosity liquid medium is preferably 75 ° C. or higher, more preferably 100 ° C. or higher.
• the boiling point of the low-viscosity liquid medium is preferably 300 ° C. or lower, more preferably 250 ° C. or lower.
• the low-viscosity liquid medium may be a liquid polar medium or a non-polar liquid medium such as a hydrocarbon-based liquid medium.
• the liquid polar medium is a liquid medium having a polar group, and refers to a liquid medium made of an organic compound having a polar group such as an amide group, a carbonyl group or a carbonyloxy group, and a liquid medium made of an inorganic compound having a polarity such as water. ..
• the organic compound having the polar group is preferably an amide, a ketone and an ester, and the inorganic compound having the polarity is preferably water.
• amides which are low-viscosity liquid media, include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylpropanamide, 3-methoxy-N, Examples thereof include N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, N, N-diethylformamide, hexamethylphosphoric triamide and 1,3-dimethyl-2-imidazolidinone.
• ketones that are low-viscosity liquid media include acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, methyl isopentyl ketone, 2-heptanone, cyclopentanone, cyclohexanone, and cycloheptanone.
• acetone methyl ethyl ketone
• methyl isopropyl ketone methyl isobutyl ketone
• methyl n-pentyl ketone methyl isopentyl ketone
• 2-heptanone cyclopentanone
• cyclohexanone cycloheptanone
• esters that are low-viscosity liquid media include methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, and 3-ethoxy.
• examples thereof include ethyl propionate, ⁇ -butyrolactone and ⁇ -valerolactone.
• the low-viscosity liquid medium water, N-methyl-2-pyrrolidone, ⁇ -butyrolactone, cyclohexanone, and cyclopentanone are preferable.
• the boiling point of the high-viscosity liquid medium is preferably 100 ° C. or higher.
• the boiling point of the high-viscosity liquid medium is preferably 350 ° C. or lower, more preferably 300 ° C. or lower.
• glycols such as ethylene glycol, ditylene glycol, triethylene glycol, propylene glycol, dipropylene glycol and tripropylene glycol, and derivatives such as ethers and esters of such glycols are preferable.
• glycol monoalkyl ether As the derivative of such glycol ether, glycol monoalkyl ether, glycol monoaryl ether, glycol monoalkyl ether alkyl ester, glycol monoaryl ether alkyl ester, and glycol dialkyl ether are more preferable, and glycol monoalkyl ether is further preferable.
• the high-viscosity liquid medium include ethylene glycol mono-2-ethylhexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, triethylene glycol monomethyl ether, and tripropylene glycol monobutyl ether. , Propylene Glycol Monophenyl Ether, Diethylene Glycol Monoethyl Ether Acetate, Diethylene Glycol Monobutyl Ether Acetate.
• the present composition (1) may contain a polymer or resin other than the F polymer.
• the fact that the present composition (1) may be contained means that the present powder may be contained in a portion other than the particles constituting the present powder.
• the polymer or resin other than the F polymer in the present composition (1) may be dissolved in a liquid medium, may be contained as particles similar to the inorganic filler without being dissolved, and may swell including the liquid medium. It may be contained as particles.
• the present composition (2) contains a polar polymer which is a polymer other than the F polymer or a resin, or a precursor thereof.
• polymers and resins other than the F polymer that may be contained in the present composition (1) will be described, and then the polar polymer and its precursor contained in the present composition (2) will be described.
• Polymers and resins other than the F polymer are different from the F polymer, and are reactions such as polymers, precursors thereof (meaning low molecular weight compounds and oligomers that can become the polymers by polymerization, cross-linking, etc.), condensation, and the like. It means a combination of two or more kinds of compounds that can be polymerized by the above, and the like.
• a resin called a thermoplastic resin is usually a polymer
• a resin called a curable resin is a combination of a low molecular weight compound, an oligomer, and a low molecular weight compound which are usually reaction-cured to become a polymer.
• an elastomer or rubber depending on the physical characteristics of the polymer, it may be called an elastomer or rubber.
• polymers and resins other than F polymer are collectively referred to as "other resins".
• Other resins include aromatic polyesters, aromatic polyimides, aromatic polyamic acids, aromatic polyamideimides, precursors of aromatic polyamideimides, epoxy resins, maleimide resins, urethane resins, thermoplastic elastomers, polyamideimides, polyphenylene ethers, etc.
• Fluoropolymers other than polyphenylene oxide, liquid crystal polyester, polysaccharides, nylon, acrylic resin, methacrylic resin, butyral, cyanate resin, ABR rubber, cellulose, PVA acrylic methacryl, polyalkylene ether, polyoxyethylene alkyl ether, and F polymer Can be mentioned.
• aromatic polyester aromatic polyimide
• aromatic polyamic acid aromatic polyamideimide
• aromatic polyamideimide precursor of aromatic polyamideimide
• polyphenylene ether epoxy resin
• maleimide resin thermoplastic elastomer
• the aromatic polyimide may be thermoplastic or thermosetting.
• aromatic polyimides include “Neoprim (registered trademark)” series (manufactured by Mitsubishi Gas Chemical Company), “Spixeria (registered trademark)” series (manufactured by Somar), and “Q-PILON (registered trademark)” series ( PI Technology Research Institute), “WINGO” series (Wingo Technology), “Toamide (registered trademark)” series (T & K TOKA), “KPI-MX” series (Kawamura Sangyo), “Yupia (" Registered trademark) -AT “series (manufactured by Ube Kosan Co., Ltd.) can be mentioned.
• Specific examples of the aromatic polyamide-imide and the precursor of the aromatic polyamide-imide include “HPC-1000” and “HPC-2100D” (both manufactured by Showa Denko Materials Co., Ltd.).
• styrene elastomer examples include styrene-butadiene copolymer, hydrogenated-styrene-butadiene copolymer, hydrogenated-styrene-isoprene copolymer, styrene-butadiene-styrene block copolymer, and styrene-isoprene-styrene block copolymer.
• examples thereof include hydrogenated products of styrene-butadiene-styrene block copolymers, and hydrogenated products of styrene-isoprene-styrene block copolymers.
• the urethane resin may be, for example, urethane fine particles containing an acrylic component, or a homopolymer or a copolymer. Specific examples thereof include commercially available dimic beads CM (manufactured by Dainichiseika Kogyo Co., Ltd.), Art Pearl (manufactured by Negami Kogyo Co., Ltd.), and Grand Pearl (manufactured by Aica Kogyo Co., Ltd.).
• CM commercially available dimic beads CM (manufactured by Dainichiseika Kogyo Co., Ltd.), Art Pearl (manufactured by Negami Kogyo Co., Ltd.), and Grand Pearl (manufactured by Aica Kogyo Co., Ltd.).
• Polysaccharides include glycogen, amylose, agarose, amyropectin, cellulose, dextrin, glucan, fructan, xanthan gum, guar gum, casein, arabic gum, gelatin, agaropectin, arabinan, curdlan, carose, carboxymethyl starch, chitin, chitosan, quince.
• Seeds glucomannan, gellan gum, tamarin seed gum, dextrin, nigeran, hyaluronic acid, pustulose, funoran, pectin, porphyran, laminaran, likenan, curdlanan, alginic acid, tragacanth gum, alkathy gum, locust bean gum.
• Acrylic resins and methacrylic resins include polyacrylates, polymethacrylates, ethylene-methylmethacrylate copolymers, ethylene-methylacrylate copolymers, ethylene-ethylacrylate copolymers, ethylene-butylacrylate copolymers, and ethylene-vinyl acetates. Examples include copolymers. Examples of the acrylic resin and the methacrylic resin include the Neocryl series manufactured by Kusumoto Kasei Co., Ltd. as a commercially available product.
• nylon examples include nylon 6, nylon 11, and nylon 12.
• examples of commercially available butyral resins include Sekisui Chemical's Eslek (registered trademark) B series, K (KS) series, SV series, and Kuraray's Mobital (registered trademark) series.
• examples of the bisphenol ester resin include bisphenol A type cyanic acid, bisphenol F type cyanate ester resin, 6F bisphenol A dicyan acid ester resin, bisphenol E type dicyan acid ester resin, tetramethyl bisphenol F dicyan acid ester resin, and bisphenol M dicyan acid. Examples thereof include ester resins, dicyclopentadienbisphenol disyanic acid ester resins, and novolak cyanate resins.
• epoxy resin examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, and glycidylamine type epoxy resin.
• Cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, trimethylol type epoxy resin, halogen Epoxy resin can be mentioned.
• thermoplastic elastomers include TR series (styrene / butadiene thermoplastic elastomer, manufactured by JSR Co., Ltd.), RB series (polybutadiene-based thermoplastic elastomer, manufactured by JSR Co., Ltd.), and JSR EXELINK (olefin-based thermoplastic elastomer, JSR).
• DYNARON (registered trademark) series hydrogenated thermoplastic elastomer, manufactured by JSR Co., Ltd.), Thermolan (registered trademark) (olefin-based thermoplastic elastomer, manufactured by Mitsubishi Chemical Corporation), Epox TPE series (olefin-based heat) Plastic Elastomer, Sumitomo Chemical Co., Ltd.), Septon (Registered Trademark) Series (Hydrogenized styrene Thermoplastic Elastomer, Claret Co., Ltd.), Tough Tech (Registered Trademark) (Hydrogenized Styrene Thermoplastic Elastomer, Asahi Kasei Co., Ltd.) Can be mentioned.
• the fluoropolymer other than the F polymer include polyvinyl fluoride, polyvinylidene fluoride, polychlorotrifluoroethylene and the like.
• the composition (2) contains a polar polymer or a precursor thereof as the other resin.
• the polar polymer in the present composition (2) is a polymer having a polar functional group in the main chain or side chain of the polymer, and the precursor of the polar polymer is a precursor that can be polymerized by heating or the like to become a polar polymer.
• Polar functional groups are usually heteroatoms or atomic groups containing heteroatoms. Heteroatoms include, for example, halogen atoms other than oxygen, sulfur, nitrogen and fluorine.
• a precursor of a polar polymer is such a polar functional group or a precursor having a group that can become such a polar functional group by polymerization.
• Examples of the polymer having a polar functional group in the main chain of the polymer include a polymer having an ether bond, an ester bond, an amide bond, an imide bond, a thioether bond, a sulfide bond or a disulfide bond in the main chain.
• Examples of the polar functional group in the polymer having a polar functional group on the side chain of the polymer include the carbonyl group-containing group, the hydroxyl group-containing group, the thiol group, the sulfide group, the sulfonyl group, the sulfoxyl group, the amino group and the amide group. , A carbonyl group-containing group and a hydroxyl group-containing group are preferable. In this case, the interaction between the F polymer and the polar polymer (or its predecessor) and the liquid medium is likely to be improved, and the above-mentioned mechanism of action is likely to be remarkably developed.
• the molecular weight of the polar polymer and its precursor is preferably 3000 or more, more preferably 5000 or more, and even more preferably 10,000 or more.
• the molecular weight of the polar polymer and its precursor is preferably 50,000 or less, more preferably 30,000 or less.
• the polar polymer and its precursor easily interact with the F polymer and the liquid polar medium, and the present composition (2) tends to have excellent physical properties such as dispersion stability.
• the polar polymer and its precursor are preferably those that are soluble in a liquid polar medium.
• polar polymer examples include ether polymers such as polyacetal, polyalkylene glycol, polyether ketone, polyether ether ketone, and polyether sulfone, ester polymers such as polyalkylene terephthalate and polyalkylene naphthalate, and amide polymers such as nylon and aramid.
• ether polymers such as polyacetal, polyalkylene glycol, polyether ketone, polyether ether ketone, and polyether sulfone
• ester polymers such as polyalkylene terephthalate and polyalkylene naphthalate
• amide polymers such as nylon and aramid.
• Polymers such as polyimide and polyamideimide, sulfide-based polymers such as polythiol, polysulfide, and polydisulfide, sulfonate-based polymers such as polyether sulfone and polyphenyl sulfone, polyvinyl alcohol, polyacrylate, polymethacrylate, polyvinylpyrrolidone, and poly.
• examples thereof include vinyl acetate, carboxyvinyl polymers, polyhalogenated vinyls other than F polymers, vinyl-based polymers such as polyhalogenated vinylidene, polysaccharides and precursors thereof.
• polar polymer a polymer in which the polar functional group is introduced into polyolefin can also be mentioned.
• the polysaccharide include the polysaccharides mentioned as the other resins.
• These polar polymers may be copolymers composed of a plurality of types of monomers.
• an imide-based polymer As the polar polymer and its precursor, an imide-based polymer, a precursor of the imide-based polymer, a vinyl-based polymer and a polysaccharide are preferable.
• Preferred imide-based polymers and precursors thereof include polyimide, polyamide-imide, polyamic acid, and polyamide-imide precursors, with aromatic polyimides, aromatic polyamideimides, aromatic polyamic acids, and aromatic polyamide-imide precursors being more preferred. ..
• imide-based polymers include "Neoprim (registered trademark)” series (manufactured by Mitsubishi Gas Chemical Company), “Spixeria (registered trademark)” series (manufactured by Somar), and “Q-PILON (registered trademark)” series ( PI Technology Research Institute), “WINGO” series (Wingo Technology), “Tombide (registered trademark)” series (T & K TOKA), “KPI-MX” series (Kawamura Sangyo), “Yupia (“ Examples include the “AT” series (manufactured by Ube Kosan Co., Ltd.), “HPC-1000", and “HPC-2100D” (manufactured by Showa Denko Materials Co., Ltd.).
• Preferred vinyl-based polymers include vinyl alcohol-based polymers such as polyvinyl alcohol, vinylpyrrolidone-based polymers such as polyvinylpyrrolidone, acrylic acid-based polymers such as polyacrylic acid, and carboxyvinyl-based polymers such as carboxyvinyl polymer.
• the based polymer is more preferable.
• the vinyl alcohol-based polymer polyvinyl alcohol, polyvinyl acetate, a partially acetylated product of polyvinyl alcohol, a partially acetal product of polyvinyl alcohol, and a copolymer of vinyl alcohol, vinyl butyral, and vinyl acetate are preferable.
• vinyl alcohol polymers include “Eslek (registered trademark) B” series, “Eslek (registered trademark) K (KS)” series, and “Eslek (registered trademark) SV” series (all manufactured by Sekisui Chemical Co., Ltd.). , “Mobital (registered trademark)” series (manufactured by Kuraray).
• acrylic acid-based polymer examples include polyacrylates such as polyacrylic acid, methyl polyacrylate and ethyl polyacrylate, poly- ⁇ -haloacrylate, poly- ⁇ -cyanoacrylate, polyacrylamide, and sodium polyacrylate.
• Preferred polysaccharides include glycogen, amylose, agarose, amylopectin, cellulose, dextrin, glucan, fructan, and chitin among the polysaccharides.
• Carboxymethyl cellulose is preferable as the cellulose.
• the carboxymethyl cellulose may be a carboxymethyl cellulose salt such as sodium carboxymethyl cellulose or ammonium carboxymethyl cellulose.
• the other resins in the present composition are preferably dissolved in a liquid medium or swollen by a liquid medium, particularly polar polymers and
• the precursor is preferably dissolved in a liquid medium.
• the other resin that does not dissolve in the liquid medium is contained in the present composition as particles similar to the particles of the following inorganic filler.
• the particles similar to the particles of the inorganic filler particles made of a cured product of a curable resin are preferable.
• the composition may contain particles of the inorganic filler.
• the inorganic filler is used to improve the physical properties of the coating film or the molded product obtained when the composition or the dispersion obtained by diluting the composition is used for forming various coating films or molded products.
• the type is appropriately selected according to the purpose of the coating film or the molded product.
• the perovskite-type ferroelectric filler and the bismuth layered perovskite-type ferroelectric filler are preferable as the inorganic filler.
• perovskite-type ferroelectric substance examples include barium titanate, lead zirconate titanate, lead titanate, zirconium oxide, and titanium oxide.
• examples of the bismuth layered perovskite type ferroelectric substance include bismuth strontium tantalate, bismuth strontium niobate, and bismuth titanate.
• a low dielectric constant, low dielectric loss tangent or low linear expansion rate inorganic filler is used as the inorganic filler.
• a boron nitride filler a beryllium oxide filler (berilia filler), a silicon oxide filler (silica filler), a wollastonite filler, and a magnesium metasilicate filler (steatite filler) are preferable.
• a metal oxide filler is used as the inorganic filler.
• the metal oxide aluminum oxide, lead oxide, iron oxide, tin oxide, magnesium oxide, titanium oxide, zinc oxide, antimony pentoxide, zirconium oxide, lanthanum oxide, neodium oxide, cerium oxide and niobium oxide are preferable, and aluminum oxide is preferable. Is more preferable.
• a glass fiber filler or a carbon filler may be used as the inorganic filler other than these.
• the carbon filler include carbon fiber (carbon fiber), carbon black, graphene, graphene oxide, fullerene, graphite and graphite oxide.
• carbon fibers include polyacrylonitrile-based carbon fibers, pitch-based carbon fibers, vapor-phase-grown carbon fibers, and carbon nanotubes (single-wall, double-wall, multi-wall, cup-laminated type, etc.).
• the inorganic filler a boron nitride filler, a silica filler and a magnesium metasilicate filler are preferable, and a silica filler is more preferable.
• These fillers may be fired ceramic fillers.
• the shape of the inorganic filler particles (that is, the particles constituting the inorganic filler) is appropriately selected depending on the intended purpose, and may be agglomerate particles or fibrous particles. If a filler composed of agglomerated particles is used, the surface flatness of the coating film or the molded product is improved, the slidability of the surface is improved, and the scratch resistance is likely to be improved. On the other hand, if an inorganic filler composed of fibrous particles is used, a part of the filler particles is exposed on the surface of the coating film or the molded product, and it is easy to improve the wear resistance and scratch resistance of the product surface, for example.
• the average particle size (D50) is preferably 0.02 to 200 ⁇ m.
• the average fiber length thereof is preferably 0.05 to 300 ⁇ m.
• the average fiber diameter of the fibrous inorganic filler is preferably 0.01 to 15 ⁇ m.
• the particles constituting the inorganic filler may have various shapes such as a plate shape, a hollow shape, and a honeycomb shape.
• the inorganic filler is preferably composed of inorganic filler particles surface-treated with a silane coupling agent.
• a silane coupling agent include 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane and 3-. Ixylpropyltriethoxysilane is preferred.
• Suitable specific examples of the inorganic filler are zinc oxide fillers surface-treated with esters such as silica fillers (“Admafine (registered trademark)” series manufactured by Admatex) and propylene glycol dicaprate (Sakai Chemical Industry Co., Ltd.).
• esters such as silica fillers (“Admafine (registered trademark)” series manufactured by Admatex) and propylene glycol dicaprate (Sakai Chemical Industry Co., Ltd.).
• the composition may contain components other than the powder particles, the liquid medium, other resins and the inorganic filler.
• other components include surfactants from the viewpoint of improving dispersion stability and handleability.
• the surfactant is preferably a nonionic surfactant.
• the hydrophilic moiety of the surfactant preferably has an oxyalkylene group or an alcoholic hydroxyl group.
• the oxyalkylene group may be composed of one kind or two or more kinds. In the latter case, the different types of oxyalkylene groups may be randomly arranged or may be arranged in a block shape. As the oxyalkylene group, an oxyethylene group is preferable.
• the hydrophobic moiety of the surfactant preferably has an acetylene group, a polysiloxane group, a perfluoroalkyl group or a perfluoroalkenyl group.
• the surfactant is preferably an acetylene-based surfactant, a silicone-based surfactant or a fluorine-based surfactant, and more preferably a silicone-based surfactant.
• a fluorine-based surfactant a fluorine-based surfactant having a hydroxyl group, particularly an alcoholic hydroxyl group or an oxyalkylene group, and a perfluoroalkyl group or a perfluoroalkenyl group is preferable.
• surfactants include “Futergent” series (manufactured by Neos), “Surflon” series (manufactured by AGC Seimi Chemical), “Megafuck” series (manufactured by DIC), and “Unidyne” series (Daikin Industries).
• the present composition contains a surfactant (however, when the inorganic filler is an inorganic filler previously treated with a surfactant, the surfactant attached to the inorganic filler is excluded), the amount thereof is determined by the present composition.
• the content in the present dispersion is preferably 1 to 15% by mass. In this case, the affinity between the components is increased, and the dispersion stability of the present dispersion is more likely to be improved.
• the present composition also contains a tyxicity-imparting agent, a viscosity modifier, a defoaming agent, a silane coupling agent, a dehydrating agent, a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, a lubricant, and an antistatic agent. It may further contain additives such as agents, whitening agents, colorants, conductive agents, mold release agents, surface treatment agents, flame retardants, and various fillers.
• the composition (1) contains particles derived from F polymer powder and a liquid medium, has a solid content concentration of 40% by mass or more, and has a viscosity measured by a B-type viscometer of 8000 to 100,000 mPa ⁇ s.
• the present composition (1) is a slurry-like, paste-like or gel-like composition, and is preferably a high-viscosity composition called a paste.
• the solid content concentration of the composition (1) is preferably 50% by mass or more.
• the solid content concentration of the composition (1) is preferably 90% by mass or less, more preferably 80% by mass or less.
• the viscosity measured by the B-type viscometer of the present composition (1) is preferably 10,000 mPa ⁇ s or more.
• the viscosity is preferably 80,000 mPa ⁇ s or less, more preferably 40,000 mPa ⁇ s or less, and even more preferably 20,000 mPa ⁇ s or less.
• the liquid medium in the present composition (1) is preferably a low-viscosity liquid medium, and the present composition (1) may contain two or more kinds of liquid media.
• the present composition (1) may contain other components such as the other resin and the inorganic filler.
• the other resin is a resin other than the polar polymer or its precursor
• the other resin is preferably dissolved in a liquid medium, and in that case, the liquid medium in which the other resin is dissolved is other than the liquid polar medium. It may be a liquid medium of.
• the composition (1) preferably has a foam volume ratio of 10% or less.
• the foam volume ratio was measured by measuring the volume ( VN ) of the present composition (1) at standard atmospheric pressure and 20 ° C. and the combined volume ( VV ) of the foam when the pressure was reduced to 0.003 MPa. It is a value obtained by the following formula.
• Foam volume ratio [%] 100 x ( VV - VN) / VN
• the present composition (1) is obtained, for example, by kneading a mixture containing an F polymer powder and a liquid medium, and at least either degassing during or after the kneading or allowing the mixture to stand after the kneading. be able to. If the present composition (1) is prepared by such a method, the foam volume ratio can be within the above range.
• the content of the liquid medium in the composition (1) is preferably 10% by mass or more.
• the content of the liquid medium is preferably 60% by mass or less, more preferably 25% by mass or less.
• the solid content concentration of the present composition (1) can be set within the above range by appropriately setting the amounts of the F polymer and the liquid medium. Even when other resins or inorganic fillers are contained, the solid content concentration in the composition (1) can be set within the above range by appropriately setting the same. Further, by selecting the viscosity of the liquid medium, the viscosity of the present composition (1) can be within the above range.
• the mass ratio of the powder particles to the other resin is such that the mass of the powder particles is 1 and the mass of the other resin is 0.01 to 0.5.
• the ratio is preferable, and the ratio of 0.1 to 0.3 is more preferable.
• the content of the inorganic filler in the solid content is preferably 25% by mass or more, more preferably 50% by mass or more.
• the inorganic filler is preferably 75% by mass or less, more preferably 60% by mass or less.
• the foam volume ratio of the dispersion obtained by diluting the present composition (1) with a second liquid medium can be easily set to the same range as the foam volume ratio of the present composition (1). Therefore, it is possible to reduce the uniformity of the component distribution of the coating film or the molded product obtained from the dispersion liquid and suppress the voids.
• the present composition (2) is a composition containing particles derived from F polymer powder, a polar polymer or a precursor thereof, and a liquid polar medium, and having a viscosity as measured by capillograph of 10,000 to 100,000 Pa ⁇ s.
• the composition (2) is preferably a highly viscous composition, also called a wet powder.
• the composition (2) may further contain other components such as an inorganic filler and a surfactant.
• the ratio of the total mass of the powder particles to the polar polymer in the composition (2) is preferably more than 50% by mass, more preferably 60% by mass or more, with the total mass of the composition (2) being 100% by mass. , 80% by mass or more is more preferable.
• the ratio of the total mass is preferably 99% by mass or less, more preferably 90% by mass or less.
• the mass ratio of the liquid polar medium in the composition (2) is preferably 40% by mass or less, more preferably 20% by mass or less, with the total mass of the composition (2) being 100% by mass.
• the mass ratio is preferably 1% by mass or more, more preferably 5% by mass or more.
• the ratio of the content of the polar polymer to the content of the powder particles in the composition (2) is preferably 0.001 or more and less than 0.5, where the content of the powder particles is 1.
• the ratio is more preferably 0.005 or more, still more preferably 0.01 or more.
• the ratio is more preferably 0.25 or less, still more preferably less than 0.1.
• the viscosity of the composition (2) measured by capillograph is more preferably 15,000 Pa ⁇ s or more.
• the viscosity of the composition (2) is more preferably 50,000 Pa ⁇ s or less, and even more preferably 30,000 Pa ⁇ s or less.
• the state of the present composition (2) having a viscosity as measured by capillograph in such a range is a composition containing the present powder particles wet with a liquid polar medium in which a polar polymer (or a precursor thereof) is sufficiently dissolved, and is in the form of a lump.
• the clay-like composition is also called a wet powder.
• the present powder particles in the present composition (2) are in a state of being dispersed in a small amount of a liquid polar medium in which a polar polymer (or a precursor thereof) is dissolved, or are in a state of being dispersed. It is considered that the powder particles in the composition (2) are in contact with each other and a liquid polar medium in which the polar polymer (or its precursor) is dissolved is present in the particle gaps thereof.
• the composition (2) preferably contains a surfactant.
• particles derived from the powder of the F polymer having a carbonyl group-containing group or a hydroxyl group-containing group having a specific surface area of 25 m 2 / g or less, and a carbonyl group-containing group particles derived from the powder of the F polymer having a carbonyl group-containing group or a hydroxyl group-containing group having a specific surface area of 25 m 2 / g or less, and a carbonyl group-containing group.
• a wet powder containing a polar polymer having a hydroxyl group or a precursor thereof and at least one liquid polar medium selected from the group consisting of amides, ketones and esters can be mentioned.
• the solid content concentration of the composition (2) is preferably more than 50% by mass, more preferably 60% by mass or more.
• the solid content concentration is preferably 99% by mass or less, more preferably 95% by mass or less.
• the composition (2) is excellent in dispersibility with respect to the second liquid medium, and the obtained dispersion is excellent in dispersion stability.
• the solid content in the present composition (2) means the total amount of substances forming the solid content in the coating film or the molded product formed from the present composition (2) or the obtained dispersion liquid.
• the composition (2) contains an F polymer, a polar polymer, and an inorganic filler
• the total content of these components is the solid content in the composition (2).
• the mass ratio of the inorganic filler to the powder particles is preferably 0.5 to 2, more preferably 0.6 to 1.5, and further preferably 0.7 to 1. preferable.
• the content of the powder particles in the solid content is preferably 25% by mass or more, more preferably 30% by mass or more.
• the content of the powder particles is preferably 60% by mass or less, more preferably 50% by mass or less.
• the content of the inorganic filler in the solid content is preferably 10% by mass or more, more preferably 25% by mass or more.
• the content of the inorganic filler is preferably 75% by mass or less, more preferably 60% by mass or less.
• the F polymer is a polymer having low surface tension and rigidity
• the F polymer particles tend to aggregate with each other in a dispersion liquid in which the powder is dispersed in a liquid dispersion medium. Therefore, it has been difficult to obtain a dispersion liquid having excellent processability and dispersion stability.
• foaming becomes intense during the preparation of the dispersion liquid, and the dispersion stability decreases due to aggregation. There was a case. Further, due to the characteristics of this F polymer, it is difficult for this powder to interact with other components in a dispersion liquid containing the powder particles and other components.
• the interaction between the components does not necessarily increase, and agglomeration of F polymer particles occurs, making it difficult to form a dense and uniform dispersion. This tendency was particularly remarkable when the F polymer was mixed with the polar polymer to obtain a uniform dispersion liquid.
• the present composition by using the present composition, wetting of the present powder and interaction between the components can be promoted, and a dispersion liquid without the above-mentioned problems can be obtained.
• the polar polymer interacts with a liquid polar medium having the same polarity, and at least a part thereof is dissolved.
• the degree of freedom of the molecular motion of the polar polymer is increased and the interaction between the polar polymer and the powder particles is promoted. It is considered that this also promotes the interaction between the liquid polar medium in which the polar polymer is dissolved and the powder particles, and makes the powder particles easy to get wet.
• the present composition (2) which is a composition in which the three components are densely and uniformly mixed in a predetermined viscosity range, is formed.
• the dispersion obtained by diluting the composition (2) with a second polar solvent can also be used. It is considered that the dispersion stability has improved.
• the present composition (2) is preferably kneaded with a mixture containing the powder of the F polymer and the liquid polar medium, and is degassed during or after such kneading, as in the present composition (1). It is preferably obtained by performing at least one of standing after kneading.
• the present invention is also a method for producing the present composition, in which a mixture containing the present powder and a liquid medium (hereinafter, also referred to as “the present mixture”) is kneaded, and deaeration and kneading during or after such kneading are performed. It is a method of producing the present composition by performing at least one of the subsequent standing.
• the composition (2) can be produced by this method by using a polar polymer together with the powder and using a liquid polar medium as the liquid medium. Deaeration of the kneaded product during or after kneading promotes efficient removal of gas such as air existing in the particle gaps of the powder and atmospheric gas brought in during the preparation of the composition, and wets the powder particles. Improve sex. Further, the standing of the kneaded product after kneading promotes the penetration of the liquid medium between the powder particles and promotes the wetting of the powder particles. It is preferable to perform both degassing and standing
• each component or a part of the mixture is mixed in the kneader. It may be introduced into the kneader to make the present mixture in a kneader. Further, a part of each component may be introduced into the kneader during the kneading of each component. For example, a liquid medium may be further added to the kneaded product (including the liquid medium) being kneaded. Further, as the polar polymer, it is preferable to use a solution dissolved in a liquid polar medium for forming the present mixture. Further, it is also preferable that the liquid component such as a liquid medium is degassed and used before the formation of the present mixture.
• kneading the present mixture it is preferable to knead the mixture so that the mass of the present mixture does not substantially change, and it is preferable to knead the mixture in a closed system. In other words, it is preferable to knead the mixture so that the liquid components of the present mixture do not evaporate during kneading.
• a kneader equipped with a stirring tank and uniaxial or multiaxial stirring blades. The number of stirring blades is preferably two or more in order to obtain a high kneading action.
• the kneading method may be either a batch method or a continuous method.
• the planetary mixer has a biaxial stirring blade that rotates and revolves with each other, and has a structure in which the kneaded material in the stirring tank is stirred and kneaded. Therefore, there is little dead space in the stirring tank where the stirring blades do not reach.
• the shape of the blade is thick and a high load can be applied, but it can also be used like a normal stirrer in which the stirring blade is rotated in a stirring tank. Therefore, there is little dead space in the stirring tank where the stirring blades do not reach, the load on the blades can be reduced, and the present mixture can be highly kneaded.
• the kneading of the present mixture is preferably carried out while cooling.
• the vaporization of the liquid medium is suppressed, the mixture becomes sticky, and a load is applied to the stirring blades of the kneader, and as a result, the shearing force on the mixture increases.
• a shearing force is likely to be applied to the material between the stirring blades or between the stirring blades and the stirring tank.
• the temperature in the kneading is preferably not less than the boiling point of the liquid medium, and more preferably 30 ° C. or less.
• the temperature in kneading is preferably 0 ° C. or higher, more preferably 10 ° C. or higher.
• the kneading for obtaining the present composition (2) is preferably carried out until the fluctuation range of the viscosity of the kneaded product becomes ⁇ 5% or less when the capillograph is measured at a temperature of 25 ° C. and a shear rate of 1s -1 . ..
• the fluctuation range is more preferably ⁇ 3% or less.
• the fluctuation range of the viscosity can be confirmed by sampling the kneaded product from the kneader every 10 minutes while kneading and measuring the viscosity by capillograph measurement at the upper limit.
• the end point of kneading can be determined by monitoring the current consumption because the load applied to the stirring blade becomes smaller and the current consumption of the kneader decreases as the kneading progresses. Further, the kneading may be controlled by using the value obtained by dividing the load current of the kneader by the shear rate of the kneader as the force and energy given to the kneaded product. Specifically, it is preferable to increase the load current from the start of kneading and gradually decrease it.
• the continuous kneader examples include a twin-screw extrusion kneader and a stone mill type kneader.
• the twin-screw extrusion kneader is, for example, a twin-screw-type continuous kneading device that kneads an object to be kneaded by a shear force between two screws arranged in parallel in close proximity to each other.
• the stone mill type kneader is, for example, a tubular fixed portion having an internal space through which the kneaded material can pass, and a kneaded material which is arranged in the internal space of the fixed portion and passes through the internal space by rotating. It is a kneading machine having a rotating portion that conveys in the direction of the rotation axis while kneading.
• Degassing may be performed during the kneading, after the kneading, or alternately with the kneading a plurality of times. Degassing may be performed continuously or intermittently. Degassing is preferably performed so that the mass of the present mixture does not change substantially.
• the degassing method includes, for example, a method of depressurizing the liquid composition, a method of heating the liquid composition, a method of freezing the liquid composition, a method of irradiating the mixture with ultrasonic waves, and these methods. The combined method can be mentioned.
• a method of putting the present mixture in a depressurized state or a method of putting the present mixture in a heated state is preferable from the viewpoint of simplicity of operation, and a method in which both are combined is more preferable from the viewpoint of degassing efficiency. Further, as described above, it is particularly preferable to carry out the process while cooling.
• the temperature and pressure at the time of degassing are appropriately set according to the present mixture in the liquid composition, and the pressure and temperature at which the present mixture does not boil are selected.
• the pressure is preferably about 0 Pa to 0.01 MPa
• the temperature is preferably 100 ° C. to 250 ° C. lower than the boiling point of the liquid medium in the present mixture.
• the degassing time is not particularly limited, but it is usually 10 minutes to 6 hours because the degassing effect does not change significantly even if the degassing time is too long.
• an operation such as stirring may be performed to prevent bumping.
• the kneaded product is usually allowed to stand after the kneading.
• the kneaded product after kneading is allowed to stand in a container for a certain period of time. It is preferable to allow the kneaded product to stand so that the mass of the kneaded product does not substantially change, and it is preferable to allow the kneaded product to stand in a closed system such as in a closed container.
• the temperature and pressure of the atmosphere in which the kneaded material is allowed to stand are usually about 10 to 30 ° C. and 1 atm, preferably under constant temperature and humidity.
• the powder particles in the kneaded product may be agitated to the extent that they do not coagulate and settle during standing.
• the standing time is preferably 24 hours or more, more preferably 48 hours or more.
• the standing time is preferably 168 hours or less because the effect obtained does not change significantly even if the standing time is too long.
• the viscosity of the kneaded product at the time of standing to obtain the present composition (1) is preferably 40,000 mPa ⁇ s or less, and more preferably 20,000 mPa ⁇ s or less.
• the viscosity is preferably 8000 mPa ⁇ s or more. In this case, the permeation of the liquid medium between the powder particles is further promoted, and the above-mentioned mechanism of action is likely to be enhanced.
• the viscosity of the kneaded product at the time of standing may be adjusted by the temperature thereof or by adding a liquid medium such as a liquid polar medium to the kneaded product.
• either degassing or standing may be performed, but it is preferable to perform both from the viewpoint of the dispersion stability of the dispersion obtained by diluting the composition.
• Examples of performing both are a mode in which the mixture is kneaded, then degassing is continuously or intermittently performed, and then the mixture is allowed to stand without degassing, and the mixture is continuously or intermittently degassed. Kneading while kneading and allowing the obtained kneaded product to stand still, kneading the mixture while continuously or intermittently degassing, and then allowing the obtained kneaded product to stand still, and then further degassing.
• the present mixture is kneaded, and after kneading, the mixture is allowed to stand while being degassed, and then the mixture is allowed to stand without being degassed.
• a mode of degassing continuously or intermittently is mentioned.
• the agglomeration of the powder particles is suppressed, and when the composition and the second liquid medium are mixed. Foaming is suppressed. As a result, the surface smoothness of the obtained coating film or molded product is excellent.
• the present composition is diluted with a second liquid medium and used as a dispersion having a lower viscosity than the present composition.
• the composition can also be used for other purposes.
• the dispersion obtained by diluting the composition with a second liquid medium (hereinafter, also referred to as “the dispersion”) is suitable for applications such as coating agents and paints.
• the second liquid medium is a liquid medium compatible with the first liquid medium, and may be the same liquid medium as the first liquid medium.
• the second liquid medium is a liquid medium that does not dissolve insoluble components such as powder particles and inorganic fillers in the composition by diluting the composition, and is dissolved in the first liquid medium. It is preferably a liquid medium that does not precipitate components.
• the polar polymer swells in the present composition (2).
• a second liquid medium is particularly preferably the same liquid medium as the first liquid medium in the diluted composition.
• the second liquid medium include liquid media that may be used as the first liquid medium, and among them, a liquid medium having a low viscosity is preferable.
• the mixing of the present composition for diluting with the second liquid medium and the second liquid medium is preferably mixed using, for example, a disperser from the viewpoint of the dispersibility and dispersion stability of the obtained dispersion liquid.
• a disperser from the viewpoint of the dispersibility and dispersion stability of the obtained dispersion liquid.
• the disperser using media include an ultrasonic homogenized baint shaker, a ball mill, an attritor, a basket mill, a sand mill, a sand grinder, a dyno mill, a dispermat, an SC mill, a spike mill, and an agitator mill.
• Examples of those that do not use media include an ultrasonic homogenizer, a nanomizer, a resolver, a disper, a high-speed impeller disperser, a rotation / revolution agitator, and a thin-film swirling high-speed mixer.
• a disperser using media is preferable because it has a high dispersive capacity.
• the collision type disperser is a disperser that collides with a liquid medium once pressurized by a high-pressure pump and disperses by the impact force or the like at this time.
• the collision type disperser can be roughly divided into two types depending on the object to be collided. There are a method in which liquid media collide with each other and a method in which the liquid medium collides with an object to collide. Examples of the method of colliding liquid media with each other include nanomizer, Genus PY, ultimateizer, Aqua, microfluidizer and the like. An example of a method of colliding a liquid medium with a collision object is a homogenizer or the like.
• the present composition and the second liquid medium are mixed in the kneader having the stirring tank and the stirring blade used for the kneading.
• the kneader having the stirring tank and the stirring blade used for the kneading.
• examples thereof include a method of mixing the liquid medium of the above, a method of mixing the present composition with the second liquid medium by a different kneading machine, and the like.
• the kneader are the same as those of the batch type and continuous type kneaders.
• this dispersion other resins, inorganic fillers, surfactants and the like may be added as needed.
• the other resin and the inorganic filler may be added separately or together, or a masterbatch in which the other resin and the inorganic filler are mixed in advance. May be prepared and this masterbatch may be added.
• the solid content concentration in the dispersion is preferably 40% by mass or more, more preferably 50% by mass or more. Further, from the viewpoint of dispersibility of the present dispersion, the solid content concentration is preferably 90% by mass or less, more preferably 75% by mass or less.
• the solid content of the present dispersion means the components obtained by removing all the liquid media from the present dispersion, and means the total amount of substances forming the solid components in the coating film or the molded product normally formed from the present dispersion. do.
• the content of the powder particles with respect to the solid content in the dispersion is preferably 20% by mass or more, more preferably 30% by mass or more.
• the content of the powder particles is preferably 70% by mass or less, more preferably 50% by mass or less.
• the viscosity of this dispersion measured by a B-type viscometer is preferably 50 mPa ⁇ s or more, more preferably 75 mPa ⁇ s or more, and even more preferably 100 mPa ⁇ s or more.
• the viscosity is preferably less than 8000 mPa ⁇ s, more preferably 5000 mPa ⁇ s or less, and even more preferably 1000 mPa ⁇ s or less.
• the dispersion having such a viscosity is excellent in coatability.
• the thixotropic ratio of this dispersion is preferably 1 to 10.
• the foam volume ratio in the dispersion is preferably less than 10%, more preferably less than 5%.
• the foam volume ratio is preferably 0% or more. According to this method, a dispersion having excellent physical characteristics can be easily obtained by the above-mentioned mechanism of action.
• a laminate having the base material and the F layer can be produced. ..
• the dispersion may be further allowed to stand before its use.
• Preferable embodiments of the laminate include a metal-clad laminate having a metal foil and an F layer formed on at least one surface thereof, and a multilayer film having a resin film and an F layer formed on at least one surface thereof.
• the metal foil in the metal-clad laminate is preferably a copper foil.
• Such a metal-clad laminate is particularly useful as a printed circuit board material.
• the resin film in the multilayer film is preferably a polyimide film. Such a multilayer film is useful as an electric wire coating material and a printed circuit board material.
• the F layer may be formed on at least one side of the surface of the base material, the F layer may be formed on only one side of the base material, and the F layer is formed on both sides of the base material. You may.
• the surface of the base material may be surface-treated with a silane coupling agent or the like.
• the spray method, roll coat method, spin coat method, gravure coat method, micro gravure coat method, gravure offset method, knife coat method, kiss coat method, bar coat method, die coat method, fountain Mayer bar method. , Slot die coat method, dip coat method can be used.
• the F layer is preferably formed by removing the liquid medium from the dispersion by heating and then firing the polymer by further heating.
• the temperature for removing the liquid medium is preferably as low as possible, preferably 50 to 150 ° C. lower than the boiling point of the liquid medium.
• N-methyl-2-pyrrolidone having a boiling point of about 200 ° C. it is preferable to heat it at 180 ° C. or lower, preferably 100 to 150 ° C. It is preferable to blow air in the step of removing the liquid medium.
• the F layer preferably contains a fired product of the F polymer.
• the F layer is formed through the steps of applying, drying, and firing the present dispersion as described above. These steps may be performed once or twice or more.
• the step of applying the present dispersion liquid to the surface of the base material, removing the liquid medium by heating to form a film is repeated twice, and the film having an increased thickness is heated to form an F polymer. It may be formed by firing. From the viewpoint of easily obtaining a thick F layer having excellent smoothness, the steps of applying and drying the dispersion may be performed twice or more.
• the thickness of the F layer is preferably 0.1 ⁇ m or more, and more preferably 1 ⁇ m or more.
• the upper limit of the thickness is 100 ⁇ m. In this range, the F layer having excellent crack resistance can be easily formed.
• the peel strength between the F layer and the base material layer is preferably 10 N / cm or more, more preferably 15 N / cm or more. The peel strength is preferably 100 N / cm or less. By using this dispersion, such a laminate can be easily formed without impairing the physical properties of the F polymer in the F layer.
• the porosity of the F layer is preferably 5% or less, more preferably 4% or less.
• the porosity is preferably 0.01% or more, more preferably 0.1% or more.
• the porosity is the ratio (%) of the area of the void portion in the cross section of the coating film or the molded product observed using a scanning electron microscope (SEM).
• Materials for the base material include metal substrates (copper, nickel, aluminum, titanium, metal foils such as alloys thereof, etc.), resin films (polyimide, polyarylate, polysulfone, polyallyl sulfone, polyamide, polyetheramide, polyphenylene sulfide, etc.). , Polyallyl ether ketone, polyamideimide, liquid crystal polyester, liquid crystal polyester amide and other films), prepreg (precursor of fiber reinforced resin substrate), ceramics substrate, glass substrate and the like.
• Examples of the shape of the base material include a planar shape, a curved surface shape, and an uneven shape, and may be any of a foil shape, a plate shape, a film shape, and a fibrous shape.
• the ten-point average roughness of the surface of the base material is preferably 0.01 to 0.05 ⁇ m.
• the laminate include a metal-clad laminate having a metal foil and an F layer formed on at least one surface thereof, and a multilayer film having a resin film and an F layer formed on at least one surface thereof.
• the metal foil in the metal-clad laminate is preferably a copper foil.
• Such a metal-clad laminate is particularly useful as a printed circuit board material.
• the resin film in the multilayer film is preferably a polyimide film. Such a multilayer film is useful as an electric wire coating material and a printed circuit board material.
• the printed circuit board includes a flexible printed circuit board and a rigid printed circuit board.
• Another substrate may be laminated on the opposite side of the F layer to the substrate to form a multilayer laminate.
• Lamination can be performed, for example, by thermocompression bonding.
• the structure of the multilayer laminate includes a base material / F layer / another base material / F layer / base material, a metal substrate layer / another base material layer / F layer / another base material layer / metal substrate layer, and the like. Can be mentioned.
• Each layer may further contain a glass cloth or filler.
• Such a laminate is useful as an antenna part, a printed substrate, an aircraft part, an automobile part, a sports tool, a food industry product, a paint, a cosmetic, and the like.
• Insulating tape Insulating tape, insulating tape for oil drilling, material for printed substrate, precision filtration membrane, ultrafiltration membrane, reverse osmosis membrane, ion exchange membrane, dialysis membrane, separation membrane such as gas separation membrane, lithium secondary battery, fuel Electrode binders for batteries, copy rolls, furniture, automobile dash boats, covers for home appliances, load bearings, sliding shafts, valves, bearings, gears, cams, belt conveyors, sliding members such as food transport belts, shovels. It is useful as tools for shavings, cuttings, saws, boilers, hoppers, pipes, ovens, baking molds, chutes, dies, toilet bowls, container covering materials, and mold release films.
• an impregnated woven fabric in which the F polymer is impregnated in the woven fabric can be obtained.
• the impregnated woven fabric can also be said to be a coated woven fabric in which the woven fabric is covered with an F layer.
• the woven fabric is preferably a glass fiber woven fabric, a carbon fiber woven fabric, an aramid fiber woven fabric or a metal fiber woven fabric, and more preferably a glass fiber woven fabric or a carbon fiber woven fabric.
• the woven fabric may be treated with a silane coupling agent from the viewpoint of enhancing the adhesiveness with the F layer.
• the content of the F polymer in the impregnated woven fabric is preferably 30 to 80% by mass.
• Examples of the method of impregnating the woven fabric with the dispersion liquid include a method of immersing the woven fabric in the dispersion liquid and a method of applying the dispersion liquid to the woven fabric.
• the F polymer may be fired.
• the method of firing the F polymer include a method of passing the woven fabric through a ventilation drying oven in an atmosphere of 300 to 400 ° C.
• the drying of the woven fabric and the firing of the polymer may be carried out in one step.
• the woven fabric thus obtained is excellent in characteristics such as high adhesion or adhesiveness between the F layer and the woven fabric, high surface smoothness, and little distortion.
• thermocompression bonding the woven fabric and the metal foil a metal-clad laminate having high peel strength and resistance to warping can be obtained, which can be suitably used as a printed circuit board material.
• the woven fabric impregnated with the dispersion liquid is placed on the surface of the base material by sticking or the like, heated and dried to form an impregnated woven fabric layer containing the F polymer and the woven fabric. May be formed to produce a laminated body in which the base material and the impregnated woven fabric layer are laminated in this order.
• the embodiment is also not particularly limited, and for example, if a woven fabric impregnated with the present dispersion is placed on a part or all of the inner wall surface of a member such as a tank, a pipe, or a container, and the member is heated while rotating.
• An impregnated woven fabric layer can be formed on a part or all of the inner wall surface of the member. This manufacturing method is also useful as a method for lining the inner wall surface of members such as tanks, pipes, and containers.
• this dispersion has excellent dispersion stability and can be efficiently impregnated into a porous or fibrous material.
• porous or fibrous materials include materials other than the above-mentioned woven fabrics, specifically, plate-shaped, columnar or fibrous materials. These materials may be pretreated with a curable resin, a silane coupling agent, or the like, or may be further filled with an inorganic filler, another resin, or the like. In addition, these materials may be twisted together to form a thread, a cable, or a wire. At the time of twisting, an intervening layer made of another polymer such as polyethylene may be arranged.
• the fibrous material examples include high-strength and low-elongation fibers such as carbon fiber, aramid fiber, and silicon carbide fiber.
• a thermosetting resin such as an epoxy resin, an unsaturated polyester resin, or a polyurethane resin is preferable.
• Specific examples of such an embodiment include a composite cable formed by impregnating a cable made by twisting carbon fibers carrying a thermosetting resin with a dispersion liquid and further heating the cable to bake an F polymer.
• Such a composite cable is useful as a cable for large structures, ground anchors, oil excavation, cranes, cableways, elevators, agriculture, forestry and fisheries, and slinging cables.
• the present dispersion having excellent dispersibility and dispersion stability can be obtained.
• aggregation of F polymer particles is suppressed, and foaming during production and use of this dispersion is suppressed.
• the surface smoothness of the obtained coating film or molded product is excellent.
• the present invention is not limited to the configuration of the above-described embodiment.
• the method for producing the present composition and the present dispersion may additionally have any other step in the configuration of the above embodiment, or may be replaced with any step that produces the same action.
• the present composition and the present dispersion may be added to any other composition in the configuration of the above embodiment, or may be replaced with an arbitrary composition exhibiting the same function.
• Powder 12 A powder consisting of a polymer (fluorine content: 76% by mass) having 40 carbonyl group-containing groups per 1 ⁇ 10 6 main chain carbon atoms (D50: 2.4 ⁇ m, consisting of TFE units and PPVE units).
• Varnish 1 Varnish in which thermoplastic aromatic polyimide (PI1) is dissolved in NMP [surfactant]
• Nonionic polymer that is a copolymer and has a fluorine content of 35% by mass [Liquid medium]
• NMP N-methyl-2-pyrrolidone [viscosity]
• the viscosity in Example 1 below refers to the viscosity measured by a B-type viscometer at a temperature of 25 ° C. and a rotation speed of 30 rpm.
• Example 1-1 Production Example of Dispersion Liquid [Example 1-1] Powder 11 (70 parts by mass), PI1 (1.8 parts by mass), and surfactant 1 (3.5 by mass) obtained by mixing powder 11, varnish 1, surfactant 1, and NMP in a planetary mixer. A liquid composition containing (parts by mass) and NMP (30 parts by mass) was added, the liquid composition was kneaded while holding the inside of the planetary mixer under reduced pressure and degassed, and NMP was added to bring the viscosity to 10,000 mPa ⁇ s. A viscosity-adjusted paste-like composition 1 was obtained. After allowing the composition 1 to stand at 25 ° C.
• the NMP is added to the composition 1 in a plurality of times so that the NMP becomes 70 parts by mass as a whole, and the mixture is stirred and mixed. Then, a dispersion liquid 11 having a viscosity of 1000 mPa ⁇ s was obtained.
• Examples 1-2 to 1-6 Except for changing the type of powder, the presence or absence of degassing or standing, and the viscosity adjustment during standing, that is, the presence or absence of additional addition of NMP when producing a paste-like composition, as shown in Table 1.
• the same procedure as in Example 1-1 was carried out to obtain paste-like compositions 2 to 6.
• dispersion liquids 12 to 16 were obtained in the same manner as in Example 1-1.
• the numerical value in parentheses in the "static" column in Table 1 indicates the static time (unit: hr).
• the foam volume ratio of the composition 1, the composition 3, the dispersion liquid 11, and the dispersion liquid 13 is 0% or more and less than 5%, and the composition 2, the composition 4, the composition 6, the dispersion liquid 12, and the dispersion liquid 14
• the foam volume ratio of the dispersion liquid 16 was more than 5% and less than 10%.
• the foam volume ratio of the composition 5 and the dispersion liquid 15 was 10% or more.
• laminated body 1 The dispersion liquid 11 was applied to the surface of a long copper foil having a thickness of 18 ⁇ m using a bar coater to form a wet film. Next, the metal foil on which the wet film was formed was passed through a drying oven at 110 ° C. for 5 minutes and dried by heating to obtain a dry film. Then, the dry membrane was heated at 380 ° C. for 3 minutes in a nitrogen oven. As a result, a laminate 11 having a metal foil and a polymer layer having a thickness of 20 ⁇ m as a molded product containing a melt-fired product of powder 11 and PI1 on the surface thereof was produced.
• Dielectric Dissipation Factor of Laminates For each laminate, the copper foil of the laminate is removed by etching with an aqueous ferric chloride solution to prepare a single polymer layer, and SPDR (split post dielectric) is prepared. By the resonance) method, the dielectric loss tangent of the polymer layer was measured at a measurement frequency of 10 GHz and evaluated according to the following criteria.
• Powder 21 Contains 97.9 mol%, 0.1 mol%, and 2.0 mol% of TFE units, NAH units, and PPVE units in this order, and has 1000 carbonyl groups per 1 ⁇ 10 6 main chain carbon atoms.
• Polar Polymer 1 Aromatic Polyimide (manufactured by Ube Kosan Co., Ltd., "U-Varnish”)
• Polar Polymer 2 Carboxymethyl Cellulose (Nippon Paper Industries, Ltd., "Sunrose MAC Series 200HC”)
• Polar polymer 3 Polyvinyl alcohol (manufactured by Sekisui Chemical Co., Ltd., "Eslek BL-1”)
• Inorganic filler 1 Silica filler surface-treated with an aminosilane coupling agent (D50: 0.2 ⁇ m)
• the viscosity of the composition in Example 2 below refers to the viscosity measured by capillograph at a temperature of 25 ° C. and a shear rate of 1s -1 , and the viscosity of the dispersion liquid is a B-type viscosity at a temperature of 25 ° C. and a rotation speed of 30 rpm. Viscosity measured by a meter.
• Example 2-1 Production Example of Composition
• the varnish (solvent: NMP) of polar polymer 1 and NMP were put into a pot and mixed. Further, a powder mixture of the powder 21 and the inorganic filler 1 was put into a pot and mixed to prepare a mixture. This mixture is kneaded in a planetary mixer and then taken out, and has a composition containing powder 21 (50 parts by mass), inorganic filler 1 (40 parts by mass) and polar polymer 1 (10 parts by mass), and NMP (30 parts by mass). I got the thing 21.
• the composition 21 was lumpy, clay-like, and wet powder. When the capillograph was measured at a temperature of 25 ° C.
• the viscosity of the composition 21 was 18,000 Pa ⁇ s, and even if the composition 21 was further kneaded, the fluctuation range of the viscosity was ⁇ 3%. It was within. NMP was added to the composition 21 in a plurality of times, and the mixture was stirred while degassing at 2000 rpm with a rotating revolution stirrer. Further, NMP was added in a plurality of times and stirred, and 80 parts by mass of NMP as a whole was added to the composition 21 to prepare a dispersion liquid, and a dispersion liquid 21 was obtained. The viscosity of the dispersion 21 was 300 mPa ⁇ s.
• Example 2-2 The composition 22 and the dispersion liquid 22 were obtained in the same manner as in Example 2-1 except that the polar polymer 1 was changed to the polar polymer 2.
• the viscosity of the composition 22 was 20000 Pa ⁇ s, and even when the composition 22 was further kneaded, the fluctuation range of the viscosity was within ⁇ 3%.
• the viscosity of the dispersion 22 was 400 mPa ⁇ s.
• Example 2-3 The composition 23 and the dispersion liquid 23 were obtained in the same manner as in Example 2-1 except that the polar polymer 1 was changed to the polar polymer 3.
• the viscosity of the composition 23 was 21000 Pa ⁇ s, and even when the composition 23 was further kneaded, the fluctuation range of the viscosity was within ⁇ 3%.
• the viscosity of the dispersion liquid 23 was 400 mPa ⁇ s.
• Example 2-4 The composition 24 and the dispersion liquid 24 were obtained in the same manner as in Example 2-1 except that the kneading time was halved.
• the viscosity of the composition 24 was 60,000 Pa ⁇ s, and when the composition 24 was further kneaded, the viscosity fluctuated by more than ⁇ 5%.
• the viscosity of the dispersion liquid 24 was 800 mPa ⁇ s.
• Example 2-5 The composition 25 and the dispersion liquid 25 were obtained in the same manner as in Example 2-1 except that the amount of the powder 21 was changed to 25 parts by mass and the amount of the polar polymer 1 was changed to 5 parts by mass.
• the viscosity of the composition 25 was 8000 Pa ⁇ s.
• the viscosity of the dispersion liquid 25 was 400 mPa ⁇ s.
• Example 2-6 The composition 26 and the dispersion liquid 26 were obtained in the same manner as in Example 2-1 except that the NMP was changed to n-decane.
• the viscosity of the composition 26 was 80,000 Pa ⁇ s, and even when the composition 26 was further kneaded, the fluctuation range of the viscosity was within ⁇ 3%.
• the viscosity of the dispersion liquid 26 was 3000 mPa ⁇ s.
• the dispersion prepared by this method is excellent in dispersibility, dispersion stability, and thixotropic stability, and therefore, the laminate using the dispersion obtained by this method has a uniform component distribution. It was excellent in properties and various physical properties.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Dispersion Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Processes Of Treating Macromolecular Substances (AREA)

Priority Applications (3)

Applications Claiming Priority (4)

Publications (1)

Family

ID=81381475

Family Applications (1)

Country Status (5)

Cited By (1)

Citations (3)

Family Cites Families (3)

• 2021
  • 2021-10-25 CN CN202180072602.6A patent/CN116348534B/zh active Active
  • 2021-10-25 WO PCT/JP2021/039342 patent/WO2022092036A1/ja not_active Ceased
  • 2021-10-25 JP JP2022559131A patent/JPWO2022092036A1/ja active Pending
  • 2021-10-25 KR KR1020237008947A patent/KR20230096971A/ko active Pending
  • 2021-10-26 TW TW110139633A patent/TW202222860A/zh unknown

Patent Citations (3)

Also Published As

Similar Documents

Legal Events