[go: up one dir, main page]

WO2015152240A1 - Dispersion de polytétrafluoroéthylène dans un solvant huileux - Google Patents

Dispersion de polytétrafluoroéthylène dans un solvant huileux Download PDF

Info

Publication number
WO2015152240A1
WO2015152240A1 PCT/JP2015/060119 JP2015060119W WO2015152240A1 WO 2015152240 A1 WO2015152240 A1 WO 2015152240A1 JP 2015060119 W JP2015060119 W JP 2015060119W WO 2015152240 A1 WO2015152240 A1 WO 2015152240A1
Authority
WO
WIPO (PCT)
Prior art keywords
dispersion
polytetrafluoroethylene
ether
methyl
solvent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2015/060119
Other languages
English (en)
Japanese (ja)
Inventor
佐藤　厚志
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Pencil Co Ltd
Original Assignee
Mitsubishi Pencil Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2014203287A external-priority patent/JP6430202B2/ja
Priority claimed from JP2014203286A external-priority patent/JP5841648B2/ja
Priority claimed from JP2014203288A external-priority patent/JP6430203B2/ja
Application filed by Mitsubishi Pencil Co Ltd filed Critical Mitsubishi Pencil Co Ltd
Priority to CN201580017851.XA priority Critical patent/CN106164140B/zh
Priority to KR1020167029666A priority patent/KR102387084B1/ko
Publication of WO2015152240A1 publication Critical patent/WO2015152240A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on 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; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on 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; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/18—Homopolymers or copolymers of tetrafluoroethene

Definitions

  • the present invention relates to an oily solvent-based dispersion of polytetrafluoroethylene suitable for addition of a resist material or an epoxy resin material having a fine particle size, a low viscosity, and excellent storage stability.
  • PTFE polytetrafluoroethylene
  • Polytetrafluoroethylene is a material excellent in heat resistance, electrical insulation, low friction characteristics, non-adhesiveness, weather resistance, etc. in addition to the above-mentioned low dielectric constant and low dielectric loss tangent. It is used for electronic devices including insulating materials and substrate materials, sliding materials, automobiles, kitchen utensils and the like. Polytetrafluoroethylene having such properties is used as a micropowder for the purpose of improving product properties by being added to the various resin materials, rubbers, adhesives, lubricants, greases, printing inks, paints, etc. ing.
  • Such polytetrafluoroethylene micropowder is usually obtained by polymerizing tetrafluoroethylene (TFE) monomer in the presence of a stabilizer such as water, a polymerization initiator, a fluorine-containing emulsifier, and paraffin wax by an emulsion polymerization method. After being obtained as an aqueous dispersion containing polytetrafluoroethylene fine particles, it is produced through concentration, aggregation, drying, and the like (see, for example, Patent Document 1).
  • TFE tetrafluoroethylene
  • polytetrafluoroethylene micropowder As a method for adding the polytetrafluoroethylene micropowder to a resin material, for example, in addition to a method of directly mixing, a method of dispersing in water or an oily solvent and mixing as a PTFE dispersion is known. Yes. By adding after dispersing in water or an oily solvent, it can be mixed uniformly.
  • polytetrafluoroethylene micropowder has a strong cohesive force between particles, and in particular, there is a problem that it is difficult to disperse in an oily solvent in a form having a fine particle size, a low viscosity, and excellent storage stability.
  • Patent Document 4 comprises PTFE particles and at least one mono- or polyolefin-based unsaturated oil or oil mixture, and the molecules of the olefin-based unsaturated oil are radicals on the surface of PTFE (primary) particles. There is permanent charge separation between the oil molecules that are covalently / chemically bound by the reaction and then bound to the PTFE particle surface and fine dispersion of the PTFE particles in the oil or oil mixture.
  • a long-term stable oil-PTFE dispersion the process of which is modified PTFE (emulsion) polymer with persistent perfluoro (peroxy) radicals mixed with at least one olefinically unsaturated oil, And the modified PTFE (emulsion) polymer is obtained by a method in which it is subjected to mechanical stress, etc.
  • modified PTFE (emulsion) polymer is obtained by a method in which it is subjected to mechanical stress, etc.
  • a miscellaneous, also not those using PTFE particles generic, the present invention, the technical idea (structures and effects thereof) is one which differs at all.
  • a non-aqueous medium such as a fluoropolymer such as PTFE, an organic solvent having a boiling point of 40 to 250 ° C., and a dispersion stabilizer having a general formula: Rf1- (X) nY
  • Rf1 is a partially fluorinated alkyl group or a fully fluorinated alkyl group having 1 to 12 carbon atoms, n is 0 or 1, and X is —O—, —COO— or —OCO—
  • Y is — (CH 2 ) pH, — (CH 2 ) pOH or — (OR1) q (OR2) rOH
  • p is an integer from 1 to 12
  • q is from 1 to 12
  • R is an integer of 0 to 12
  • R1 and R2 are alkylene groups having 2 to 4 carbon atoms, provided that R1 and R2 are different from each other. At least one selected, and the water content is 1% or more
  • the water content is
  • Patent Document 5 does not have any description or suggestion regarding “polytetrafluoroethylene micropowder having a primary particle diameter of 1 ⁇ m or less”. According to paragraph [0041] of Patent Document 5, “when a powdered fluoropolymer is dispersed, a dispersion liquid that hardly reaggregates can be obtained by dispersing in a size of 5 to 500 ⁇ m”. In the support of Experimental Examples 1 to 12 as examples, “Lublon L-2 (PTFE)” manufactured by Daikin Industries, Ltd. as a fluoropolymer (in the technical data, the average particle size (50 %) 3.5 ⁇ m).
  • PTFE PTFE
  • the present invention manages the amount of water not for mixing but for the stability of the dispersion after preparation of the dispersion, and refers to the mixing in Patent Document 5.
  • Document 5 does not demonstrate the effect of the amount of water in the examples. Therefore, although the said patent document 5 discloses the proximity
  • a method of mixing a powder material such as PTFE micropowder into a resist material for example, as a method for adjusting a resist material for a black matrix, a colored paste mainly containing a pigment was prepared. Thereafter, a method of mixing with a photosensitive resin composition is known (see, for example, Patent Documents 6 and 7). In the same manner as these methods, after PTFE micropowder is dispersed in an oil-based solvent system, a resist is used. Attempts have been made to mix the materials.
  • the PTFE micropowder as in Patent Documents 6 and 7 has a strong cohesion between particles, and it is difficult to uniformly disperse and mix in a resin material such as a resist material with a fine particle size.
  • the resist material is a material that forms a fine pattern by exposure and development. If the particle size of PTFE is large or is not uniformly dispersed, a problem may occur during pattern formation. Therefore, a PTFE dispersion having high dispersibility is required.
  • an epoxy resin material as one of the materials widely used as a substrate or a sealing material for electronic equipment.
  • the relative dielectric constant of the epoxy resin material varies depending on its composition, but is about 2.5-6. It is shown.
  • a material having a low relative dielectric constant and a low dielectric loss tangent polytetrafluoroethylene (PTFE, relative dielectric constant 2.1) having the most excellent characteristics among resin materials is noted as described above. However, it is used by melting and mixing PTFE in various resin materials. (For example, see Patent Document 8)
  • the present invention intends to solve the above-mentioned conventional problems and the present situation, and is a polycrystal suitable for resist material addition, epoxy resin addition, etc., having a fine particle size, low viscosity and excellent storage stability.
  • An object is to provide an oil-based solvent dispersion of tetrafluoroethylene.
  • polytetrafluoroethylene micropowder having a primary particle size of 1 ⁇ m or less is 5 to 70% by mass, and a fluorine-based additive containing at least a fluorine-containing group and a lipophilic group is added to the mass of polytetrafluoroethylene.
  • the oil-based solvent dispersion of polytetrafluoroethylene according to the first invention is characterized in that the water content of the oil-based solvent used in the oil-based solvent-based dispersion is 20000 ppm or less. Is the body.
  • the oily solvent used in the oily solvent dispersion is ⁇ -butyrolactone, acetone, methyl ethyl ketone, hexane, heptane, octane, 2-heptanone, cycloheptanone, cyclohexanone, cyclohexane, methylcyclohexane, ethylcyclohexane, Methyl-n-pentyl ketone, methyl isobutyl ketone, methyl isopentyl ketone, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, ethylene glycol monoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate, Diethylene glycol diethyl ether, propylene glycol monoacetate, dipropylene Recall monoacetate, propylene glycol diacetate,
  • the fourth invention is characterized in that the average particle diameter of the polytetrafluoroethylene micropowder in the oil-based solvent dispersion by laser diffraction / scattering method or dynamic light scattering method is 1 ⁇ m or less. It is an oily solvent-based dispersion of polytetrafluoroethylene according to the third invention.
  • the fifth invention is the oil-based solvent dispersion of polytetrafluoroethylene according to the first to fourth inventions, further comprising a silicone-based antifoaming agent.
  • the sixth invention is characterized in that the oil-based solvent dispersion of polytetrafluoroethylene according to any one of the first to fifth inventions is for adding a resist material or an epoxy resin material. To do.
  • the oil-based solvent dispersion of polytetrafluoroethylene of the present invention has a fine particle size, low viscosity, excellent storage stability, and excellent redispersibility even after long-term storage, especially for resist material addition and epoxy resin addition It can use suitably for. Also, even if it contains a lot of fluorine-based additives, it has excellent antifoaming properties. When added to various resin materials such as resist materials and epoxy resins, rubber, adhesives, lubricants and greases, printing inks and paints, etc. Can be mixed evenly.
  • the oil-based solvent dispersion of polytetrafluoroethylene according to the present invention comprises 5 to 70% by mass of a polytetrafluoroethylene micropowder having a primary particle size of 1 ⁇ m or less, and a fluorine-based additive containing at least a fluorine-containing group and a lipophilic group. Is contained in an amount of 0.1 to 40% by mass with respect to the mass of the polytetrafluoroethylene micropowder.
  • the polytetrafluoroethylene micropowder used in the present invention has a primary particle size of 1 ⁇ m or less.
  • Such polytetrafluoroethylene micropowder is obtained by an emulsion polymerization method, and is generally used, for example, a method described in a fluorine resin handbook (edited by Takaomi Kurokawa, Nikkan Kogyo Shimbun). It can be obtained by a method.
  • the polytetrafluoroethylene micropowder obtained by the emulsion polymerization is agglomerated and dried, and is recovered as a fine powder as secondary particles with a primary particle size aggregated.
  • Various fine powder production methods can be used.
  • the primary particle size of the polytetrafluoroethylene micropowder is 1 ⁇ m in volume-based average particle size (50% volume diameter, median diameter) measured by laser diffraction / scattering method, dynamic light scattering method, image imaging method, etc.
  • the following is necessary for stable dispersion in an oily solvent.
  • the dispersion is made 0.5 ⁇ m or less, more desirably 0.3 ⁇ m or less, whereby a more uniform dispersion is obtained.
  • the primary particle diameter of the polytetrafluoroethylene micropowder exceeds 1 ⁇ m, it is not preferable because it easily settles in an oily solvent and becomes difficult to disperse stably.
  • the lower limit of the average particle diameter is better as it is lower, but 0.05 ⁇ m or more is preferable from the viewpoint of manufacturability and cost.
  • the primary particle diameter of the polytetrafluoroethylene micropowder in the present invention indicates a value obtained by a laser diffraction / scattering method or a dynamic light scattering method in the polymerization stage of the micropowder. In the case of micropowder in powder form, the cohesion between primary particles is strong, and it is difficult to easily measure the primary particle size by laser diffraction / scattering method or dynamic light scattering method. The value obtained by may be indicated.
  • a dynamic light scattering method using FPAR-1000 manufactured by Otsuka Electronics Co., Ltd.
  • FPAR-1000 manufactured by Otsuka Electronics Co., Ltd.
  • a laser diffraction / scattering method using Microtrack manufactured by Nikkiso Co., Ltd.
  • a Macview manufactured by Mountec Co., Ltd.
  • Examples thereof include an image imaging method.
  • the polytetrafluoroethylene micropowder is contained in an amount of 5 to 70% by mass, preferably 10 to 50% by mass, based on the total amount of the dispersion.
  • this content is less than 5% by mass, the amount of the oily solvent is large and the viscosity is extremely lowered, so that the fine particles of the polytetrafluoroethylene micropowder not only easily settle, but also a material such as a resin.
  • problems due to a large amount of the oil-based solvent for example, an unfavorable situation such as time-consuming removal of the solvent may occur.
  • the polytetrafluoroethylene micropowder tends to aggregate together, and it becomes extremely difficult to stably maintain the state of fine particles in a state having fluidity. It is not preferable.
  • the fluorine-based additive in the present invention is required to have at least a fluorine-containing group and a lipophilic group, and is not particularly limited as long as it has at least a fluorine-containing group and a lipophilic group.
  • a hydrophilic group may be contained.
  • a fluorine-based additive having at least a fluorine-containing group and an oleophilic group
  • the surface tension of an oily solvent serving as a dispersion medium is reduced, and the wettability with respect to the surface of polytetrafluoroethylene is improved, so that polytetrafluoroethylene micropowder
  • the fluorine-containing group is adsorbed on the surface of the polytetrafluoroethylene, and the lipophilic group is extended into the oily solvent serving as a dispersion medium.
  • the dispersion stability is further improved.
  • Examples of the fluorine-containing group include a perfluoroalkyl group and a perfluoroalkenyl group.
  • Examples of the lipophilic group include one or more of an alkyl group, a phenyl group, and a siloxane group.
  • Examples of the hydrophilic group include one or more of ethylene oxide, amide group, ketone group, carboxyl group, sulfone group and the like.
  • fluorine-based additive examples include Surflon series (manufactured by AGC Seimi Chemical Co., Ltd.) such as Surflon S-611 containing perfluoroalkyl group, MegaFuck F-555, MegaFuck F-558, MegaFuck A Mega-Fuck series (manufactured by DIC) such as F-563 and a Unidyne series (manufactured by Daikin Industries) such as Unidyne DS-403N can be used.
  • Surflon series manufactured by AGC Seimi Chemical Co., Ltd.
  • Surflon S-611 such as Surflon S-611 containing perfluoroalkyl group
  • MegaFuck F-555 MegaFuck F-558
  • MegaFuck A Mega-Fuck series such as F-563
  • Unidyne series manufactured by Daikin Industries
  • the content of the fluorine-based additive is 0.1 to 40% by mass with respect to the mass of the polytetrafluoroethylene micropowder, preferably 5 to 30% by mass, and more preferably The content is preferably 15 to 25% by mass. If the content is less than 0.1% by mass relative to the mass of polytetrafluoroethylene, the surface of the polytetrafluoroethylene micropowder cannot be sufficiently wetted with an oily solvent, whereas if it exceeds 40% by mass, the surface is dispersed. It is not preferable because the foaming of the body becomes strong and the efficiency of dispersion is lowered, which may cause problems when the dispersion itself is handled and then mixed with a resin material.
  • nonionic, anionic and cationic surfactants and nonionic, anionic and cationic polymeric surfactants can be used, but the present invention is not limited to these. Can do.
  • the oily solvent used in the present invention preferably has a water content by the Karl Fischer method of 20000 ppm or less [0 ⁇ water content ⁇ 20000 ppm].
  • the measurement of water content by the Karl Fischer method is based on JIS K 0068: 2001 and was performed by MCU-610 (manufactured by Kyoto Electronics Industry Co., Ltd.).
  • MCU-610 manufactured by Kyoto Electronics Industry Co., Ltd.
  • the dispersibility of polytetrafluoroethylene micropowder in the oil-based solvent is remarkably inhibited, and the viscosity increases It causes aggregation of particles.
  • the water content in the oily solvent is 20000 ppm or less, it is possible to obtain a polytetrafluoroethylene oily solvent-based dispersion having a fine particle size, low viscosity, and excellent storage stability. .
  • the polytetrafluoroethylene oil-based solvent dispersion of the present invention preferably has a water content by the Karl Fischer method of 20000 ppm or less [0 ⁇ water content ⁇ 20000 ppm].
  • the water contained in the material itself such as polytetrafluoroethylene micropowder and fluorine additives, and also in the manufacturing process in which polytetrafluoroethylene micropowder is dispersed in the oily solvent
  • the polytetrafluoroethylene oil-based solvent dispersion is more excellent in storage stability by reducing the water content of the polytetrafluoroethylene oil-based solvent dispersion to 20000 ppm or less. be able to.
  • a generally used dehydrating method of the oily solvent can be used.
  • molecular sieves or the like can be used.
  • polytetrafluoroethylene can be used in a state in which the amount of water is sufficiently reduced by dehydration by heating or decompression.
  • Any body can be used without particular limitation as long as it can reduce the water content of the body.
  • oily solvent used in the present invention examples include ⁇ -butyrolactone, acetone, methyl ethyl ketone, hexane, heptane, octane, 2-heptanone, cycloheptanone, cyclohexanone, cyclohexane, methylcyclohexane, ethylcyclohexane, methyl-n-pentyl ketone.
  • the above-mentioned oily solvent is used, but it can be used in combination with other oily solvents or other oily solvents, and can be used (various resin materials, rubbers, adhesives). , Lubricant, grease, printing ink, paint, etc.) are selected.
  • the content of the oily solvent used is the balance of the polytetrafluoroethylene micropowder and the fluorine-based additive.
  • the average particle diameter of the polytetrafluoroethylene micropowder in the oily solvent dispersion is 1 ⁇ m or less by the laser diffraction / scattering method or the dynamic light scattering method. Even when polytetrafluoroethylene micropowder having a primary particle size of 1 ⁇ m or less is used, the primary particles are usually aggregated to form micropowder having a particle size of 1 ⁇ m or more as secondary particles.
  • the dispersion is performed using a dispersing machine such as an ultrasonic dispersing machine, a three-roll, a ball mill, a bead mill, or a jet mill.
  • a dispersing machine such as an ultrasonic dispersing machine, a three-roll, a ball mill, a bead mill, or a jet mill.
  • a silicone-based antifoaming agent can be further added to the oil-based solvent dispersion of polytetrafluoroethylene.
  • the polytetrafluoroethylene micropowder is used at a high concentration of 70% by mass or the fluorine-based additive is used at a high concentration of 40% by mass with respect to the mass of the polytetrafluoroethylene micropowder, the foaming of the dispersion
  • Antifoaming agents include silicone emulsion type, self-emulsifying type, oil type, oil compound type, solution type, powder type, solid type, etc., but the most suitable one is selected depending on the combination with the oily solvent used Will be.
  • a hydrophilic or water-soluble silicone-based antifoaming agent in order to exist at the interface between the oily solvent and air rather than the interface between the oily solvent and polytetrafluoroethylene micropowder. Without being limited to these, it can be used.
  • the content of the antifoaming agent varies depending on the content (concentration) of polytetrafluoroethylene micropowder and the like, but is preferably 1% by mass or less as an active ingredient with respect to the total amount of the dispersion.
  • the polytetrafluoroethylene oily solvent-based dispersion of the present invention configured as described above includes a polytetrafluoroethylene micropowder having a primary particle diameter of 1 ⁇ m or less, and a fluorine-based dispersion containing at least a fluorine-containing group and a lipophilic group.
  • a polytetrafluoroethylene micropowder having a primary particle diameter of 1 ⁇ m or less
  • a fluorine-based dispersion containing at least a fluorine-containing group and a lipophilic group By using each specific amount with the additive, the particle size is low, the viscosity is low, and the storage stability is excellent, and the redispersibility is excellent even after long-term storage.
  • the oil-based solvent dispersion of polytetrafluoroethylene of the present invention can be added to a resist material such as a photoresist such as a color filter or a black matrix, or a screen printing resist, and can also be used as a substrate or sealing material for electronic equipment.
  • a resist material such as a photoresist such as a color filter or a black matrix, or a screen printing resist
  • the widely used epoxy resin material it is possible to further lower the dielectric constant and lower the dielectric loss tangent, so that it can be suitably used for resist material addition and epoxy resin material addition it can.
  • Examples 1 to 8 and Comparative Examples 1 to 7 Each polytetrafluoroethylene oil-based solvent dispersion was prepared by the following methods. Moreover, about the oil-based solvent to be used, the oil-based solvent used as a water
  • Example 1 As polytetrafluoroethylene micropowder, a powder having an average particle diameter of 0.12 ⁇ m by laser diffraction / scattering method was used.
  • As the fluorine-based additive Megafac F-558 (fluorine-containing / lipophilic group-containing oligomer, active ingredient 30 wt%) manufactured by DIC Corporation was used after removing the diluent solvent.
  • cyclohexanone was used as the oily solvent.
  • an oil-based solvent dispersion of polytetrafluoroethylene was prepared according to the formulation shown in Table 1 below.
  • the fluorine-based additive was sufficiently stirred and mixed in the oily solvent, and then polytetrafluoroethylene micropowder was added and further stirred and mixed.
  • the polytetrafluoroethylene micropowder mixture obtained as described above was dispersed with zirconia beads having a diameter of 0.3 mm using a horizontal bead mill.
  • the obtained dispersion was subjected to filter filtration in order to remove coarse particles of 1 ⁇ m or more to obtain an oily solvent-based dispersion of polytetrafluoroethylene.
  • Example 2 A dispersion was prepared in the same manner as in Example 1 except that the amounts of polytetrafluoroethylene micropowder and fluorine-based additive were varied, and the diameter of the zirconia beads was 1 mm.
  • Example 3 A dispersion was produced in the same manner as in Example 1 except that the average particle size of the polytetrafluoroethylene micropowder was 0.8 ⁇ m.
  • Example 4 KM-72 (0.05% by mass) made by Shin-Etsu Silicone was added as a silicone-based antifoaming agent after being dispersed in the bead mill, mixed thoroughly and mixed, and then filtered in the same manner as in Example 1. A dispersion was prepared.
  • Example 5 A dispersion was produced in the same manner as in Example 1 except that propylene glycol monomethyl ether acetate (PGMEA) was used as the oily solvent.
  • PGMEA propylene glycol monomethyl ether acetate
  • Example 6 As the fluorine-based additive, the same as in Example 1 except that Megafac F-563 (fluorine-containing / lipophilic group-containing oligomer) manufactured by DIC Corporation was 9% by mass and methyl ethyl ketone was used as the oily solvent. A dispersion was prepared by the method described above.
  • Example 7 A dispersion was produced in the same manner as in Example 1 except that cyclohexanone was used by forcibly adding water as an oily solvent.
  • Example 8 Executed except that Megafac F-555 (fluorinated group / hydrophilic group / lipophilic group-containing oligomer, active ingredient 30 wt%) manufactured by DIC Corporation was used as the fluorosurfactant after removing the diluting solvent. A dispersion was produced in the same manner as in Example 1.
  • Example 1 A dispersion was prepared in the same manner as in Example 1, and then water was forcibly added to obtain a dispersion.
  • Example 2 A dispersion was produced in the same manner as in Example 1 except that the average particle size of the polytetrafluoroethylene micropowder was 1.2 ⁇ m and filtration was not performed after dispersion.
  • Example 3 A dispersion was prepared in the same manner as in Example 1 except that the water that was forcibly added to cyclohexanone and sufficiently stirred was used as the oily solvent.
  • Example 4 Except for the amount of the fluorine-based additive Megafac F-558 being 0.025% by mass (with respect to polytetrafluoroethylene micropowder, less than 0.1% by mass), the same method as in Example 1 was used. A dispersion was prepared.
  • Example 5 Comparative Example 5
  • Example 1 except that 75% by mass of polytetrafluoroethylene micropowder was added, and MegaFac F-563 (fluorine-containing / lipophilic group-containing oligomer) manufactured by DIC Corporation was used as a fluorine-based additive.
  • MegaFac F-563 fluorine-containing / lipophilic group-containing oligomer manufactured by DIC Corporation was used as a fluorine-based additive.
  • Example 6 A dispersion was prepared in the same manner as in Example 1, and then water was forcibly added to obtain a dispersion.
  • Example 7 A dispersion was prepared in the same manner as in Example 1 except that 75% by mass of polytetrafluoroethylene micropowder was added.
  • Examples 1 to 8 within the scope of the present invention were found to have good dispersion fluidity and high storage stability.
  • Example 7 which is within the scope of the present invention, could be redispersed even after storage at 25 ° C. for one month, but Comparative Example 1 and Comparative Examples 3 and 5 having a water content exceeding 20000 ppm were redispersed. Required sufficient agitation.
  • Example 4 containing an antifoaming agent also had good foam breakage.
  • Comparative Examples 1 to 7 outside the scope of the present invention are inferior in fluidity and storage stability. Further, Comparative Examples 5 and 7 could not be dispersed because the polytetrafluoroethylene micropowder was as large as 75% by mass.
  • the oil-based solvent dispersion of polytetrafluoroethylene in the present invention is a substrate composed of various resin materials, for example, resist materials used for color filters and black matrices, epoxy resin materials used for electronic devices, etc. It is uniformly added to each material such as sealant and insulating material, rubber, adhesive, lubricant, grease, printing ink and paint, etc. to improve the electrical characteristics or to give the characteristics possessed by polytetrafluoroethylene Thus, it can be used for the purpose of improving various product characteristics, and can be used for electronic devices, sliding materials, automobiles, kitchen utensils and the like.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une dispersion de polytétrafluoroéthylène (PTFE) dans un solvant huileux, la dispersion présentant un petit diamètre de particule, une faible viscosité et une excellente stabilité au stockage et étant appropriée pour, par exemple, l'addition à des matériaux de type résine photosensible et l'addition à des matériaux de type résine époxy. Un mode de réalisation de cette dispersion de PTFE dans un solvant huileux est une dispersion à base d'un solvant huileux qui contient 5 à 70 % en masse d'une micropoudre de polytétrafluoroéthylène présentant un diamètre de particule primaire de 1 µm ou moins et qui contient en outre un additif fluorochimique contenant au moins un groupe contenant du fluor et un groupe oléophile, en une quantité de 0,1 à 40 % en masse par rapport à la masse de la micropoudre de polytétrafluoroéthylène, et qui présente une teneur totale en eau, telle que mesurée par le procédé de Karl Fischer, de 20.000 ppm ou moins.
PCT/JP2015/060119 2014-04-02 2015-03-31 Dispersion de polytétrafluoroéthylène dans un solvant huileux Ceased WO2015152240A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201580017851.XA CN106164140B (zh) 2014-04-02 2015-03-31 聚四氟乙烯的油性溶剂系分散体
KR1020167029666A KR102387084B1 (ko) 2014-04-02 2015-03-31 폴리테트라플루오로에틸렌의 유성 용제계 분산체

Applications Claiming Priority (12)

Application Number Priority Date Filing Date Title
JP2014076486 2014-04-02
JP2014076487 2014-04-02
JP2014-076487 2014-04-02
JP2014-076486 2014-04-02
JP2014-077351 2014-04-03
JP2014077351 2014-04-03
JP2014203287A JP6430202B2 (ja) 2014-04-02 2014-10-01 レジスト材料添加用のポリテトラフルオロエチレンの油性溶剤系分散体
JP2014203286A JP5841648B2 (ja) 2014-04-02 2014-10-01 ポリテトラフルオロエチレンの油性溶剤系分散体
JP2014-203286 2014-10-01
JP2014203288A JP6430203B2 (ja) 2014-04-03 2014-10-01 エポキシ樹脂材料添加用のポリテトラフルオロエチレンの油性溶剤系分散体
JP2014-203288 2014-10-01
JP2014-203287 2014-10-01

Publications (1)

Publication Number Publication Date
WO2015152240A1 true WO2015152240A1 (fr) 2015-10-08

Family

ID=54240560

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/060119 Ceased WO2015152240A1 (fr) 2014-04-02 2015-03-31 Dispersion de polytétrafluoroéthylène dans un solvant huileux

Country Status (1)

Country Link
WO (1) WO2015152240A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9410105B2 (en) 2012-11-16 2016-08-09 Basf Se Lubricant compositions comprising epoxide compounds
JP2017078102A (ja) * 2015-10-19 2017-04-27 三菱鉛筆株式会社 フッ素系樹脂含有ポリイミド前駆体溶液組成物、それを用いたポリイミド、ポリイミドフィルム、およびそれらの製造方法
KR20170133278A (ko) * 2016-05-25 2017-12-05 미쓰비시 엔피쯔 가부시키가이샤 불소계 수지의 비수계 분산체, 그것을 이용한 불소계 수지 함유 열경화 수지 조성물과 그 경화물, 폴리이미드 전구체 용액 조성물
JP2017222762A (ja) * 2016-06-14 2017-12-21 三菱鉛筆株式会社 フッ素系樹脂の非水系分散体、それを用いたフッ素系樹脂含有熱硬化樹脂組成物とその硬化物
JP2017222761A (ja) * 2016-06-14 2017-12-21 三菱鉛筆株式会社 フッ素系樹脂の非水系分散体、それを用いたフッ素系樹脂含有熱硬化樹脂組成物とその硬化物
JP2018012787A (ja) * 2016-07-21 2018-01-25 三菱鉛筆株式会社 熱硬化樹脂組成物、それを用いた絶縁材料組成物
CN109415571A (zh) * 2016-06-23 2019-03-01 Ａｇｃ株式会社 含有氟树脂粉末的液态组合物的制造方法
CN111492006A (zh) * 2017-12-27 2020-08-04 Ａｇｃ株式会社 分散液、金属层叠板和印刷基板的制造方法
WO2020184725A1 (fr) * 2019-03-13 2020-09-17 東邦化学工業株式会社 Dispersion de résine de polyoléfine et son procédé de production

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62229862A (ja) * 1986-03-28 1987-10-08 Ibiden Co Ltd 封止枠を有する半導体素子搭載用回路基板
JPS6346268A (ja) * 1985-09-19 1988-02-27 ザ　スタンダ−ド　オイル　カンパニ− エポキシフルオロカ−ボン塗料組成物及びその製法
JP2006126246A (ja) * 2004-10-26 2006-05-18 Konica Minolta Business Technologies Inc 画像形成方法及び画像形成装置
JP2008516416A (ja) * 2004-09-17 2008-05-15 エルジー・ケム・リミテッド エッチングレジスト用のインク組成物、これを利用したエッチングレジストパターンの形成方法及び微細溝の形成方法
JP2011225710A (ja) * 2010-04-19 2011-11-10 Daikin Industries Ltd フルオロポリマー非水系分散液
JP2013079326A (ja) * 2011-10-04 2013-05-02 Adeka Corp 樹脂組成物、該組成物を含有するビルドアップ用絶縁体、及び該組成物を用いたプリプレグ
JP2013094777A (ja) * 2011-11-03 2013-05-20 Xerox Corp フルオロプラスチック粉末コーティングを作成するための方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6346268A (ja) * 1985-09-19 1988-02-27 ザ　スタンダ−ド　オイル　カンパニ− エポキシフルオロカ−ボン塗料組成物及びその製法
JPS62229862A (ja) * 1986-03-28 1987-10-08 Ibiden Co Ltd 封止枠を有する半導体素子搭載用回路基板
JP2008516416A (ja) * 2004-09-17 2008-05-15 エルジー・ケム・リミテッド エッチングレジスト用のインク組成物、これを利用したエッチングレジストパターンの形成方法及び微細溝の形成方法
JP2006126246A (ja) * 2004-10-26 2006-05-18 Konica Minolta Business Technologies Inc 画像形成方法及び画像形成装置
JP2011225710A (ja) * 2010-04-19 2011-11-10 Daikin Industries Ltd フルオロポリマー非水系分散液
JP2013079326A (ja) * 2011-10-04 2013-05-02 Adeka Corp 樹脂組成物、該組成物を含有するビルドアップ用絶縁体、及び該組成物を用いたプリプレグ
JP2013094777A (ja) * 2011-11-03 2013-05-20 Xerox Corp フルオロプラスチック粉末コーティングを作成するための方法

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9410105B2 (en) 2012-11-16 2016-08-09 Basf Se Lubricant compositions comprising epoxide compounds
JP2017078102A (ja) * 2015-10-19 2017-04-27 三菱鉛筆株式会社 フッ素系樹脂含有ポリイミド前駆体溶液組成物、それを用いたポリイミド、ポリイミドフィルム、およびそれらの製造方法
JP7093608B2 (ja) 2015-10-19 2022-06-30 三菱鉛筆株式会社 フッ素系樹脂含有ポリイミド前駆体溶液組成物、それを用いたポリイミド、ポリイミドフィルム、およびそれらの製造方法
KR20170133278A (ko) * 2016-05-25 2017-12-05 미쓰비시 엔피쯔 가부시키가이샤 불소계 수지의 비수계 분산체, 그것을 이용한 불소계 수지 함유 열경화 수지 조성물과 그 경화물, 폴리이미드 전구체 용액 조성물
KR102399222B1 (ko) 2016-05-25 2022-05-19 미쓰비시 엔피쯔 가부시키가이샤 불소계 수지의 비수계 분산체, 그것을 이용한 불소계 수지 함유 열경화 수지 조성물과 그 경화물, 폴리이미드 전구체 용액 조성물
JP2017222762A (ja) * 2016-06-14 2017-12-21 三菱鉛筆株式会社 フッ素系樹脂の非水系分散体、それを用いたフッ素系樹脂含有熱硬化樹脂組成物とその硬化物
JP2017222761A (ja) * 2016-06-14 2017-12-21 三菱鉛筆株式会社 フッ素系樹脂の非水系分散体、それを用いたフッ素系樹脂含有熱硬化樹脂組成物とその硬化物
CN109415571A (zh) * 2016-06-23 2019-03-01 Ａｇｃ株式会社 含有氟树脂粉末的液态组合物的制造方法
JP2018012787A (ja) * 2016-07-21 2018-01-25 三菱鉛筆株式会社 熱硬化樹脂組成物、それを用いた絶縁材料組成物
CN111492006A (zh) * 2017-12-27 2020-08-04 Ａｇｃ株式会社 分散液、金属层叠板和印刷基板的制造方法
WO2020184725A1 (fr) * 2019-03-13 2020-09-17 東邦化学工業株式会社 Dispersion de résine de polyoléfine et son procédé de production
JP6761561B1 (ja) * 2019-03-13 2020-09-23 東邦化学工業株式会社 ポリオレフィン樹脂分散液及びその製造方法

Similar Documents

Publication Publication Date Title
KR102387084B1 (ko) 폴리테트라플루오로에틸렌의 유성 용제계 분산체
WO2015152240A1 (fr) Dispersion de polytétrafluoroéthylène dans un solvant huileux
JP5841648B2 (ja) ポリテトラフルオロエチレンの油性溶剤系分散体
JP6430203B2 (ja) エポキシ樹脂材料添加用のポリテトラフルオロエチレンの油性溶剤系分散体
JP6534848B2 (ja) ポリテトラフルオロエチレンの非水系分散体
JP6033939B1 (ja) ポリテトラフルオロエチレンマイクロパウダーの非水系分散体
JP6430202B2 (ja) レジスト材料添加用のポリテトラフルオロエチレンの油性溶剤系分散体
TW201728702A (zh) 平版印刷用印墨
WO2012029929A1 (fr) Procédé pour la production d'organosol de résine fluorée, organosol de résine fluorée, et composition de revêtement
CN109251622B (zh) 一种包含离子液体的水性涂料及其制备方法
CN112142994A (zh) 聚四氟乙烯的非水系分散体
JP6461627B2 (ja) ポリテトラフルオロエチレン含有エポキシ樹脂組成物
KR20160094335A (ko) 폴리테트라플루오로에틸렌 유성 용제계 분산체 및 폴리테트라플루오로에틸렌 함유 에폭시 수지 조성물 및 그 경화물
JP4096031B2 (ja) 界面活性剤
JP6207538B2 (ja) ポリテトラフルオロエチレンの油性溶剤系分散体
JP2022098371A (ja) ポリテトラフルオロエチレンの油性溶剤系分散体
JP2022098372A (ja) ポリテトラフルオロエチレンの非水系分散体
JP5115766B2 (ja) レジスト用洗浄剤
JP2010253406A (ja) 炭素材料用分散剤およびこれを含む組成物並びに分散液
JP6640007B2 (ja) 印刷インキ用ワニス、印刷インキ、及び印刷物
TWI795660B (zh) 水性脫模組合物及其製備方法
CN115991950B (zh) 遮光膜用组合物以及利用其的遮光膜
JP2014070091A (ja) 基材粒子表面にフッ素を含む無機顔料粒子
CN117363091A (zh) 一种防止胶印油墨快速结皮的助剂及其制备方法与应用
JP7207806B2 (ja) 溶剤希釈型フッ素系潤滑剤組成物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15773022

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase
ENP Entry into the national phase

Ref document number: 20167029666

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 15773022

Country of ref document: EP

Kind code of ref document: A1