TW202020025A - Method for producing dispersion - Google Patents

Abstract

Provided is a dispersion that has a high particle dispersion stability even in a high-temperature environment, at a high particle content, etc. The method for producing a dispersion according to the present invention comprises: under elevated pressure, flowing through a channel a liquid composition which has a viscosity of 10000 mPa.s or less and comprises coarse particles of a fluoroolefin polymer having a melt viscosity at 380 DEG C of 1*10<SP>2</SP>-1*10<SP>10</SP> Pa.s, a dispersant having clouding point exceeding 50 DEG C and a liquid dispersion medium; and thus grinding the coarse particles into fine particles having an average particle size smaller than the average particle size of the coarse particles to thereby give a dispersion which comprises the fluorinated dispersant and the fine particles dispersed in the liquid dispersion medium.

Description

Method for manufacturing dispersion

The present invention relates to a method for producing a dispersion in which fine particles of fluoroolefin polymer are dispersed in a liquid dispersion medium.

When a dispersion liquid in which fluoroolefin polymer particles are dispersed in a liquid dispersion medium is applied to the surface of various substrates, it is possible to impart physical properties based on the fluoroolefin polymer to the surface, so it is useful as a coating agent. A known method of producing the dispersion liquid is a method in which a dispersion liquid in which fluoroolefin-based polymer particles are dispersed is supplied to a wet jet milling method (see Patent Documents 1 and 2).

Patent Document 1 discloses a method for producing a dispersion liquid in which a dispersion liquid in which PFA particles having hydroxyl groups are dispersed in water is supplied to a wet jet milling method to granulate the particles. In addition, Patent Document 2 discloses a method in which a dispersion liquid in which PTFE particles and nanocarbon tubes are dispersed in a non-aqueous dispersion medium is supplied to a wet jet milling method to obtain fibrillated nanotubes PTFE captured compound. Prior technical literature Patent Literature

Patent Document 1: Japanese Patent Laid-Open No. 2008-260864 Patent Literature 2: International Publication No. 2017/022229

Problems to be solved by invention Fluoroolefin polymers are inherently low in surface tension and have low interaction with other materials. Therefore, in the liquid composition containing fluoroolefin-based polymer particles, the dispersibility of the particles is unstable. The properties (viscosity, hue, phase, etc.) of the liquid composition are easily changed not only due to internal factors such as the content ratio of each component, but also due to external factors such as temperature and external force. Therefore, if the liquid composition is supplied to the wet jet mill which locally imparts a large number of external factors, the deterioration of the components in the liquid composition or the change in the interaction between the components may occur.

Therefore, even if the fluoroolefin-based polymer particles or the fluoroolefin-based polymer itself is deteriorated and the desired dispersion liquid cannot be obtained. The present inventors specifically learned that in a high-temperature environment or when the particle content is high, a dispersion liquid having excellent dispersion stability of particles cannot be obtained.

Means to solve the problem After careful investigation, the inventors found that if a fluoroolefin polymer having a predetermined melt viscosity is blended with a dispersant, and a liquid composition with a predetermined viscosity is pressurized and circulated through the flow channel, even under a high-temperature environment Or when the particle content is high, a dispersion liquid with excellent dispersion stability of the particles can be obtained. The present invention has the following aspects.

[1] A method for producing a dispersion liquid, in which a liquid composition containing coarse fluoroolefin-based polymer particles, a dispersant, and a liquid dispersion medium and having a viscosity of 10000 mPa.s or less is circulated under pressure in a flow channel to grind the coarse particles into A fine particle having an average particle diameter smaller than that of the coarse particle, to obtain a dispersion liquid containing the dispersant and the fine particle dispersed in the liquid dispersion medium; wherein the fluoroolefin polymer is melted at 380°C The viscosity is 1×10 ² ~1×10 ¹⁰ Pa.s, and the cloud point of the dispersant exceeds 50℃. [2] The production method according to [1], wherein the melting temperature of the fluoroolefin-based polymer is 200° C. or higher. [3] The production method according to [1] or [2], wherein the dispersant is a fluorine-based dispersant. [4] The production method according to [3], wherein the fluorine-based dispersant is at least one selected from the group consisting of fluorinated monoalcohols, fluorinated polyols, fluorinated polysiloxanes, and fluorinated polyethers 1 compound. [5] The production method according to [3] or [4], wherein the fluorine content of the fluorine-based dispersant is 10 to 50% by mass.

[6] The production method according to any one of [1] to [5], wherein the dispersant is at least one compound selected from the group consisting of fluorinated monoalcohols and fluorinated polyols, and It is a compound with a hydroxyl value of 10~100mgKOH/g. [7] The production method according to any one of claims [1] to [6], wherein the dispersant is a fluorinated monoalcohol and the liquid dispersion medium is an aqueous dispersion medium. [8] The production method according to any one of [1] to [6], wherein the dispersant is a fluorinated polyol, and the liquid dispersion medium is a non-aqueous dispersion medium. [9] The production method according to any one of [1] to [8], wherein the average particle diameter of the fine particles is 1 μm or less. [10] The manufacturing method according to any one of [1] to [9], wherein the average particle diameter of the coarse particles is greater than 1 μm and less than 10 μm.

[11] The production method according to any one of [1] to [10], wherein the liquid composition contains 1 part by mass or more of the dispersant relative to 100 parts by mass of the coarse particles. [12] The production method according to any one of [1] to [11], wherein the liquid composition contains 1 to 50% by mass of the coarse particles. [13] The production method according to any one of [1] to [12], which circulates the liquid composition through the flow path. [14] The manufacturing method as described in any one of [1] to [13], which is based on the condition that the value of the product of the flow rate and the circulation time divided by the total amount of the liquid composition will exceed 10, so that The liquid composition circulates through the flow channel. [15] The production method according to any one of [1] to [14], wherein the average particle diameter of the fine particles is 0.5 μm or less, and the volume-based cumulative 90% particle diameter of the fine particles is 2 μm or less.

Effect of invention According to the present invention, a dispersion liquid having excellent dispersion stability of particles even in a high-temperature environment or when the particle content is high can be obtained.

The following terms have the following meanings. "Average particle diameter (D50)" is the cumulative 50% diameter length of the volumetric basis of particles determined by the laser diffraction method. That is, the particle size distribution is measured by the laser diffraction scattering method, and after the cumulative curve is obtained by making the total volume of the particle group 100%, the particle size at the point where the cumulative volume is 50% on the cumulative curve. "D90 of particles" is the cumulative 90% diameter length of the volume basis of particles determined in the same manner as D50 above. "The melt viscosity of the polymer" is based on ASTM D 1238, using a flow tester and a 2Φ-8L mold, the polymer sample (2g) that has been pre-heated at the measured temperature for 5 minutes under a load of 0.7MPa The value measured at the measurement temperature. "Melting temperature of polymer (melting point)" is the temperature corresponding to the maximum value of the melting peak measured by differential scanning calorimetry (DSC). "Viscosity of liquid composition" is a value measured using a B-type viscometer at room temperature (25°C) at a rotation speed of 30 rpm. Repeat the measurement three times and take the average of the three measurements. The "unit" of a polymer may be an atomic group formed directly from a monomer by polymerization, or may be an atomic group in which a part of the structure is converted by processing a polymer obtained by polymerization in a predetermined method.

The manufacturing method of the present invention relates to a method for preparing a dispersion liquid, which is a mixture of coarse particles, a dispersant and a liquid dispersion medium belonging to a fluoroolefin-based polymer (hereinafter also referred to as "F polymer") and a viscosity of 10000 mPa The liquid composition below .s flows through the flow channel under pressure (hereinafter also referred to as "for wet jet milling method"), pulverizing coarse particles into fine particles with a smaller average particle size, and by the action of a dispersant The fine particles are dispersed in a liquid dispersion medium to obtain a dispersion liquid, wherein the melt viscosity of the fluoroolefin polymer at 380°C is 1×10 ² to 1×10 ¹⁰ Pa.s, and the cloud point of the dispersant exceeds 50 ℃. The dispersion liquid prepared by the production method of the present invention is excellent in dispersion stability of fine particles and excellent in compatibility with other materials even in a high-temperature environment or when the content of fine particles is high. Although the reason is not very clear, but we speculate as follows.

The smashing of the particles in the wet jet milling method is believed to occur when the particles hit the channel wall or the particles collide with each other in the channel. The present inventors found that the thermal energy at the time of impact causes the F polymer to be deteriorated in or near the flow channel, and the physical properties (dispersion stability, viscosity, etc.) of the resulting dispersion liquid are easily reduced. Another point is that if the viscosity of the liquid composition supplied to the wet jet milling method, the melt viscosity of the F polymer contained therein, and the cloud point of the dispersant contained therein are adjusted, the particle state of the F polymer will be affected Highly stabilized, the decrease in the physical properties is suppressed, and a dispersion liquid with excellent dispersibility can be obtained.

The F polymer in the present invention is a polymer containing a unit mainly composed of fluoroolefin, and may be a homopolymer or a copolymer. The F polymer is preferably a homopolymer composed of units mainly composed of tetrafluoroethylene (hereinafter also referred to as "TFE units"); polymers containing units mainly composed of difluoroethylene (VDF); or, A copolymer containing a TFE unit and a unit mainly composed of at least one comonomer described below, the at least one comonomer system is selected from units mainly composed of perfluoro (alkyl vinyl ether) (hereinafter also expressed) "PAVE unit"), a unit mainly composed of hexafluoropropylene (hereinafter also referred to as "HFP unit") and a unit mainly composed of halothane (hereinafter also referred to as "FAE unit").

Here, a homopolymer composed of TFE units also encompasses polymers containing units other than extremely small amounts of TFE units. In the aforementioned polymer, the ratio of TFE units to the total units contained in the polymer is preferably 99.9 mol% or more. For example, if the dispersion liquid obtained by the present invention is used to form an insulating resin layer of a printed wiring board for transmitting high-frequency signals, the transmission characteristics of the printed wiring board can be improved. From the viewpoint of excellent electrical characteristics (relative permittivity, dielectric loss tangent) and heat resistance, the F polymer is preferably a copolymer of TFE units and PAVE units (hereinafter also referred to as "PFA") or TFE units and A copolymer of HFP units (hereinafter also referred to as "FEP"), and PFA is preferred.

The F polymer is preferably a polymer having at least one functional group selected from the group consisting of carbonyl group-containing groups, hydroxyl groups, epoxy groups, oxetanyl groups, amine groups, nitrile groups, and isocyanate groups Thing. As long as the F polymer has the above-mentioned functional group, when the insulating resin layer of the printed wiring board is formed from the dispersion liquid obtained by the present invention, for example, the adhesion of the insulating resin layer to the metal wiring (metal foil) of the printed wiring board will be good. In addition, the functional group can also be introduced into the F polymer by plasma treatment or the like. The functional group may be contained in the unit constituting the F polymer, or may be contained in the terminal group of the main chain of the polymer. Examples of the latter polymer include a polymer having a functional group and derived from a terminal group such as a polymerization initiator or a chain transfer agent.

The F polymer is preferably a polymer containing units having functional groups and TFE units. The polymer preferably further contains other units. When the insulating resin layer of the printed wiring board is formed from the dispersion liquid obtained in the present invention, from the viewpoint of further improving the adhesion between the insulating resin layer and the metal wiring in the printed wiring board, the functional group is preferably a carbonyl group-containing group. Examples of the carbonyl group-containing group include carbonate groups, carboxyl groups, haloformamide groups, alkoxycarbonyl groups, acid anhydride residues, and fatty acid residues, preferably carboxyl groups or acid anhydride residues. The monomer having a carbonyl group-containing group is preferably a cyclic monomer having an acid anhydride residue or a monomer having a carboxyl group, and preferably a cyclic monomer having an acid anhydride residue, and itaconic anhydride, citraconic anhydride , 5-norcamene-2,3-dicarboxylic anhydride (alias: Nadic anhydride; also referred to as "NAH" below) or maleic anhydride is particularly preferred.

Units with functional groups and units other than TFE units are preferably HFP units, PAVE units or FAE units. PAVE can be exemplified by CF ₂ =CFOCF ₃ , CF ₂ =CFOCF ₂ CF ₃ , CF ₂ =CFOCF ₂ CF ₂ CF ₃ (hereinafter also referred to as “PPVE”), CF ₂ = CFOCF ₂ CF ₂ CF ₂ CF ₃ , CF ₂ =CFO(CF ₂ ) ₈ F, and PPVE is suitable. FAE can be exemplified by CH ₂ =CH(CF ₂ ) ₂ F, CH ₂ =CH(CF ₂ ) ₃ F, CH ₂ =CH(CF ₂ ) ₄ F, CH ₂ =CF(CF ₂ ) ₃ H, CH ₂ =CF(CF ₂ ) ₄ H, preferably CH ₂ =CH(CF ₂ ) ₄ F or CH ₂ =CH(CF ₂ ) ₂ F.

The F polymer is preferably a polymer containing units having functional groups, TFE units, and PAVE units or HFP units. Specific examples of the polymer include those described in International Publication No. 2018/16644. At this time, relative to the total units contained in the F polymer, the proportions of TFE units, PAVE units, and units with functional groups should be in the order of 90 to 99 mol%, 0.5 to 9.97 mol%, and 0.01 to 3 mol ear%.

The melt viscosity of the F polymer in the present invention at 380°C is 1×10 ² to 1×10 ¹⁰ Pa.s, and preferably 1×10 ³ to 1×10 ⁹ Pa.s, 1×10 ⁴ to 1 ×10 ⁸ Pa.s is particularly preferred. If it is a coarse particle of the melt viscosity F polymer, it can be pulverized into fine particles without fibrillation. The coarse particles in the present invention may contain components other than the F polymer, but the F polymer is preferably the main component. The amount of the F polymer contained in the coarse particles (the fine particles after micronization are also substantially the same) is preferably 80% by mass or more, preferably 100% by mass.

The melting temperature of the F polymer is preferably above 200°C, and preferably 250 to 380°C, more preferably 300 to 350°C. At this time, when the liquid composition is supplied to the wet jet milling method, it is possible to prevent a situation in which coarse particles are melted and adhered to each other due to heat generation when the liquid composition circulates in the flow path. Moreover, if it is the coarse particle of the said F polymer, even if it heats, high hardness can be maintained, Therefore It can be made into fine particles well, and the desired fine particle can be obtained. In particular, if the melting temperature is 380°C or lower, fibrillation of fine particles is unlikely to occur. Therefore, if the melting temperature of the F polymer is within the above range, the fine particles of the coarse particles can be promoted, and the fibrillation of the fine particles can be easily suppressed.

The D50 of coarse particles should be smaller than the diameter of the flow channel, and more preferably greater than 1µm and less than 10µm, more preferably greater than 2µm and less than 8µm, and more preferably greater than 3µm and less than 6µm. If the D50 of coarse particles is within the above range, it can smoothly circulate in the flow channel without clogging, and fine particles with a target particle diameter can be produced. The D90 of coarse particles should be smaller than the diameter of the flow channel, and it is preferably below 15µm, more preferably below 13µm, and even more preferably below 11µm. If the D90 of coarse particles is within the above range, the flow path will be more difficult to block. As a method for producing the above-mentioned coarse particles, the method described in International Publication No. 2016/017801 [0065] to [0069] can be used. In addition, as the coarse particles, commercially available desired particles can also be used.

The dispersant of the present invention is a compound that has a function of interacting on the surface of F polymer particles to stably disperse fine particles in a liquid dispersion medium and has a cloud point. Here, the cloud point of the dispersant is the temperature at which its effect will disappear or be extremely reduced due to molecular motion accompanying the temperature rise. The function of the dispersant should preferably be a function caused by interfacial activity. That is, the dispersant of the present invention is preferably a surfactant. The cloud point at this time is the temperature at which the dispersant cannot dissolve or form microcells in the liquid dispersion medium used in the liquid composition and appears cloudy. The cloud point of the dispersant is greater than 50°C, and is preferably 60°C or higher, and preferably 70°C or higher. The cloud point of the dispersant is preferably 100°C or lower, and preferably 90°C or lower. If a dispersant with a cloud point in the above range is used, it is not only easy to prepare the liquid composition of the desired viscosity, but also easily suppress the F polymer caused by heat generation when the liquid composition is supplied to the wet jet mill Spoiled.

The dispersant in the present invention is preferably a fluorine-based dispersant. Fluorine-based dispersants are compounds that have the following functions: chemical and/or physical adsorption is performed on the surface of the fine particles of the F polymer, so that the fine particles are stably dispersed in the liquid dispersion medium. If the dispersant is a fluorine-based dispersant, both the F polymer and the molecules of the liquid dispersion medium are easy to increase the affinity, and it is easy to enhance the interaction between the components in the wet jet milling method, so that the coarse particles can be efficiently carried out Change. In addition, the interaction between the surface of the formed fine particles and the fluorine-based dispersant is also easily improved. As a result, by the action of the fluorine-based dispersant, it is easy to obtain a dispersion liquid in which fine particles are more highly dispersed in the liquid dispersion medium.

The fluorine-based dispersant is preferably a compound (surfactant) having a hydrophobic portion and a hydrophilic portion containing a fluorine atom, and is selected from the group consisting of fluorinated monoalcohol, fluorinated polyol, fluorinated polysiloxane and fluorinated polyether At least one compound in the group is preferred. The fluorine content of the fluorine-based dispersant is preferably 10 to 50% by mass, preferably 10 to 45% by mass, and more preferably 15 to 40% by mass. Within the above range, a dispersion liquid containing fine particles having a smaller particle size and having excellent dispersion stability is easily obtained. The above-mentioned fluorine-based dispersant is preferably the aforementioned one compound having a fluorine content of 10 to 50% by mass. In addition, suitable aspects of the fluorine-based dispersant can be exemplified by at least one compound selected from the group consisting of fluorinated monoalcohols and fluorinated polyols, and more suitable aspects can be exemplified by A compound of at least one compound in the group consisting of fluorinated monoalcohol and fluorinated polyol and having a hydroxyl value of 10 to 100 mgKOH/g, a more suitable aspect may be the aforementioned one compound and having a hydroxyl value of 10 ~100mgKOH/g compound. The fluorine-based dispersant may be polymer-like or non-polymer-like. The fluorine-based dispersant is preferably nonionic.

These fluorine-based dispersants have excellent affinity with both F polymer and liquid dispersion media. In the case of an aqueous dispersion medium, the fluorine-based dispersant is preferably fluorinated monoalcohol; in the case of a non-aqueous dispersion medium, the fluorine-based dispersant is preferably a fluorinated polyol. In addition, if the melting temperature of the F polymer is within the above range, or the F polymer has the above functional group, the affinity with the fluorine-based dispersant is further improved.

In addition, the fluorinated monoalcohol is a non-polymeric fluorine-containing compound (surfactant) that is different from the F polymer and the liquid dispersion medium and has one hydroxyl group. Furthermore, the fluorinated polyol is a polymer-like fluorine-containing compound (surfactant) that is different from the F polymer and the liquid dispersion medium and has two or more hydroxyl groups and fluorine atoms. In addition, a part of the hydroxyl group of the fluorinated polyol can be modified by chemical modification. Examples of the fluorinated polyol include a polymer polyol having a main chain composed of a carbon chain derived from an ethylenically unsaturated monomer, and a fluorine-containing hydrocarbon group and a hydroxyl group as side chains branched from the main chain. Here, the fluorine-containing hydrocarbon group is preferably a group having a third-order carbon atom bonded through a plurality (2 or 3) of monovalent fluorine-containing hydrocarbon groups.

The fluorinated unit alcohol should have a fluorine content of 10 to 50% by mass and a hydroxyl value of 40 to 100 mgKOH/g. The fluorinated unit alcohol is preferably a compound represented by the following formula (a). Formula (a) R ^a -(OQ ^a ) _ma -OH The symbol in the formula has the following meaning. R ^a represents a polyfluoroalkyl group or ^a polyfluoroalkyl group containing an etheric oxygen atom, and is preferably -CH ₂ (CF ₂ ) ₄ F, -CH ₂ (CF ₂ ) ₆ F, -CH ₂ CH ₂ (CF ₂ ) ₄ F, -CH ₂ CH ₂ (CF ₂ ) ₆ F, -CH ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₃ , -CH ₂ CF (CF ₃ ) CF ₂ OCF ₂ CF ₂ CF ₃ , -CH ₂ CF(CF ₃ )OCF ₂ CF(CF ₃ )OCF ₃ , or -CH ₂ CF ₂ CHFO(CF ₂ ) ₃ OCF ₃ . Q ^a represents an alkylene group having 1 to 4 carbon atoms, and is preferably vinyl (-CH ₂ CH ₂ -) or propenyl (-CH ₂ CH(CH ₃ )-). Q ^a may be composed of one kind of base, or two or more kinds of bases. When composed of two or more groups, the arrangement of the groups may be random or block. ma represents an integer of 4~20, and preferably 4~10. The hydroxyl group of the fluorinated monoalcohol is preferably a secondary hydroxyl group or a tertiary hydroxyl group, and a secondary hydroxyl group is particularly preferred.

Specific examples of the fluorinated monoalcohol include F(CF ₂ ) ₆ CH ₂ (OCH ₂ CH ₂ ) ₇ OCH ₂ CH(CH ₃ )OH, F(CF ₂ ) ₆ CH ₂ (OCH ₂ CH ₂ ) ₁₂ OCH ₂ CH(CH ₃ )OH, F(CF ₂ ) ₆ CH ₂ CH ₂ (OCH ₂ CH ₂ ) ₇ OCH ₂ CH(CH ₃ )OH, F(CF ₂ ) ₆ CH ₂ CH ₂ (OCH ₂ CH ₂ ) ₁₂ OCH ₂ CH(CH ₃ )OH, F(CF ₂ ) ₄ CH ₂ CH ₂ (OCH ₂ CH ₂ ) ₇ OCH ₂ CH(CH ₃ )OH. The fluorinated monoalcohol may be a commercially available product ("Fluowet N083", "Fluowet N050", etc. manufactured by Archroma).

The fluorinated polyol should have a fluorine content of 10 to 45% by mass and a hydroxyl value of 10 to 35 mgKOH/g. The fluorinated polyol is preferably a copolymer of a compound represented by formula (f) described later and a monomer represented by formula (d).

The fluorinated polyol is preferably a copolymer containing the following units: (meth)acrylate having a polyfluoroalkyl group or polyfluoroalkenyl group (hereinafter also referred to as "fluorine-containing (meth)acrylate") as the main body Unit; and, a unit mainly composed of a (meth)acrylate having a polyoxyalkylene unit alcohol group (hereinafter also referred to as "hydroxyl-containing (meth)acrylate"). In addition, (meth)acrylate is a general term for acrylate derivatives in which the α-position hydrogen atom of acrylate, methacrylate, and acrylate is substituted with other atoms or atomic groups.

The fluorine-containing (meth)acrylate is preferably a compound represented by the following formula (f). The symbol in the formula (f) CH ₂ =CR ^f C(O)OX ^f -Z ^f has the following meaning. R ^f represents a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group or a trifluoromethyl group. X ^f represents an alkylene group, an oxyalkylene group, or an alkylamide group. Z ^f represents a perfluoroalkyl group or a perfluoroalkenyl group. On the other hand, the hydroxyl group-containing (meth)acrylate is preferably a compound represented by the following formula (d). Formula (d) CH ₂ =CR ^d C(O)OX ^d1 -X ^d2 -OH The symbol in the formula has the following meaning. ^Rd represents a hydrogen atom or a methyl group. X ^d1 represents an alkylene group. X ^d2 represents oxyalkylene.

Specific examples of fluorine-containing (meth)acrylates include CH ₂ =CHCOO(CH ₂ ) ₂ (CF ₂ ) ₄ F, CH ₂ =C(CH ₃ )COO(CH ₂ ) ₂ (CF ₂ ) ₄ F , CH ₂ = CHCOO(CH ₂ ) ₂ (CF ₂ ) ₆ F, CH ₂ = C(CH ₃ ) COO(CH ₂ ) ₂ (CF ₂ ) ₆ F, CH ₂ = CHCOO(CH ₂ ) ₄ OCF(CF ₃ )(C(CF(CF ₃ ) ₂ )(=C(CF ₃ ) ₂ ), CH ₂ =CHCOO(CH ₂ ) ₄ OC(CF ₃ )(=C(CF(CF ₃ ) ₂ )(CF( CF ₃ ) ₂ ).

Specific examples of hydroxyl-containing (meth)acrylates include CH ₂ =CHCOO(CH ₂ ) ₂ (OCH ₂ CH ₂ ) ₁₀ OH, CH ₂ =CHCOO(CH ₂ ) ₄ (OCH ₂ CH ₂ ) ₁₀ OH, CH ₂ =C(CH ₃ )COO(CH ₂ ) ₂ (OCH ₂ CH ₂ ) ₁₀ OH, CH ₂ =C(CH ₃ )COO(CH ₂ ) ₄ (OCH ₂ CH ₂ ) ₁₀ OH, CH ₂ =CHCOO (CH ₂ ) ₂ (OCH ₂ CH(CH ₃ )) ₁₀ OH, CH ₂ =C(CH ₃ )COO(CH ₂ ) ₂ (OCH ₂ CH(CH ₃ )) ₁₀ OH.

Relative to the total units contained in the fluorinated polyol, the ratio of the unit mainly composed of fluorine-containing (meth)acrylate is preferably 20 to 60 mol%. Relative to the total units contained in the fluorinated polyol, the ratio of units containing hydroxyl (meth)acrylate as the main unit is preferably 40 to 80 mole %. The ratio of the amount of units containing hydroxy-containing (meth)acrylate as the main unit to the amount of units containing fluoro-containing (meth)acrylate as the main unit is preferably 1-5, and 1-2 good.

The fluorinated polyol may contain only units containing fluorine-containing (meth)acrylate as the main unit and units containing hydroxyl-containing (meth)acrylate as the main unit, or may contain other units. The fluorine content of the fluorinated polyol is preferably 10 to 45% by mass, and preferably 15 to 40% by mass. The fluorinated polyol is preferably nonionic. In addition, the weight average molecular weight of the fluorinated polyol is preferably 2,000 to 80,000, and preferably 6,000 to 20,000.

The fluorinated polysiloxane can be exemplified by a polyorganosiloxane containing a C-F bond in a part of the side chain. As for the fluorinated polyether, for example, a compound in which a part of hydrogen atoms of the polyoxyalkylene alkyl ether is substituted with a fluorine atom can be mentioned. In addition, fluorinated polyethers also cover the unit alcohols of the aforementioned compounds.

烷等)、酯(乳酸乙酯、乙酸乙酯等)、酮(甲基乙基酮、甲基異丙基酮、環戊酮、環己酮等)、二醇醚(乙二醇單異丙基醚等)、賽璐蘇(甲賽璐蘇、乙賽璐蘇等)。液態分散介質可單獨使用該等化合物中之1種亦可將2種以上併用。 液態分散介質可為水性分散介質、亦可為非水性分散介質，若從將液態組成物之黏度調整成所欲範圍的觀點來看，以非水性分散介質為佳。The liquid dispersion medium of the present invention is a dispersion medium in which particles of F polymer (coarse particles and fine particles) are dispersed. The liquid dispersion medium is a non-reactive compound that is liquid at 25°C and does not react with the F polymer. Specifically, the liquid dispersion medium is preferably a compound whose boiling point is lower than the boiling point of the components other than the liquid dispersion medium contained in the dispersion liquid and can be removed by heating. The liquid dispersion medium can be exemplified by water, alcohol (methanol, ethanol, isopropanol, etc.), nitrogen-containing compounds (N,N-dimethylformamide, N,N-dimethylacetamide, N- Methyl-2-pyrrolidone, etc.), sulfur compounds (dimethyl sulfoxide, etc.), ether (diethyl ether, di

Alkanes, etc.), esters (ethyl lactate, ethyl acetate, etc.), ketones (methyl ethyl ketone, methyl isopropyl ketone, cyclopentanone, cyclohexanone, etc.), glycol ethers (ethylene glycol monoiso Propyl ether, etc.), celluloid (A cellulose, B cellulose, etc.). The liquid dispersion medium may be used alone or in combination of two or more. The liquid dispersion medium may be an aqueous dispersion medium or a non-aqueous dispersion medium. From the viewpoint of adjusting the viscosity of the liquid composition to a desired range, a non-aqueous dispersion medium is preferable.

Non-aqueous dispersion media are preferably nitrogen-containing compounds, sulfur-containing compounds, ethers, esters, ketones, glycol ethers, etc. At this time, the liquid dispersion medium is preferably an organic dispersion medium with a low specific heat at 20°C. If this liquid dispersion medium is used, the heat dissipation effect of the liquid composition when the wet jet milling method is applied is high, and it is possible to prevent the adhesion of fine particles obtained by micronization. In addition, it is possible to prevent the microparticles from being deformed or fibrillated. In addition, the specific value of specific heat is preferably 3J/(g‧K) or less, and preferably 2.8J/(g‧K) or less, and more preferably 1.8 to 2.5J/(g‧K).

In addition, the boiling point of the liquid dispersion medium is preferably 80 to 275°C, and preferably 125 to 250°C. Examples of the liquid dispersion medium satisfying the above conditions include N-methyl-2-pyrrolidone (boiling point: 202°C), dimethylacetamide (boiling point: 165°C), cyclohexanone (boiling point: 155°C), N,N-dimethylformamide, (boiling point: 153°C), methyl ethyl ketone (specific heat: 2.1J/(g‧K), boiling point: 80°C).

The liquid composition of the present invention may contain other components as long as the effects of the present invention are not impaired. Other ingredients can be dissolved in the liquid composition or not. Other ingredients include resins (non-curable resins, curable resins, etc.), thixotropy-imparting agents, defoamers, inorganic fillers, reactive alkoxysilanes, dehydrating agents, plasticizers, weathering agents, antioxidants, Heat stabilizer, lubricant, antistatic agent, whitening agent, colorant, conductive agent, release agent, surface treatment agent, viscosity regulator, flame retardant. Examples of non-curable resins include hot-melt resins and non-melt resins. Examples of the hot-melt resin are thermoplastic polyimide. Examples of the non-melting resin include cured products of curable resins. Examples of the curable resin include polymers having reactive groups, oligomers having reactive groups, low molecular compounds, and low molecular compounds having reactive groups. Examples of reactive groups include carbonyl group-containing groups, hydroxyl groups, amine groups, and epoxy groups.

Examples of the curable resin include epoxy resin, thermosetting polyimide, polyamic acid as a precursor of polyimide, acrylic resin, phenol resin, polyester resin, polyolefin resin, modified polyphenylene ether Resin, multifunctional cyanate resin, multifunctional maleimide-cyanate resin, multifunctional maleimide resin, vinyl ester resin, urea resin, diallyl phthalate resin, melamine resin , Guanamine resin, melamine-urea co-condensation resin. Among them, from the viewpoint of using the dispersion prepared by the present invention for printed wiring boards, the curable resin is preferably a thermosetting polyimide, a polyimide precursor, an epoxy resin, an acrylic resin, Bismaleimide resin or polyphenylene ether resin, and epoxy resin or polyphenylene ether resin are preferred.

Specific examples of the epoxy resin include naphthalene type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alicyclic Epoxy resin, aliphatic chain epoxy resin, cresol novolac epoxy resin, phenol novolac epoxy resin, alkylphenol novolac epoxy resin, aralkyl epoxy resin, biphenol epoxy resin Resins, dicyclopentadiene-type epoxy resins, para-hydroxytoluene-type epoxy compounds, epoxides of condensates of phenols and aromatic aldehydes with phenolic hydroxyl groups, diglycidyl etherate of bisphenol, Diglycidyl etherate of naphthalene glycol, phenolic glycidyl etherate, alcoholic diglycidyl etherate, and triglycidyl tripolyisocyanate.

The bismaleimide resin may be a resin composition (BT resin) formed by using a bisphenol A type cyanate resin and a bismaleimide compound as described in Japanese Patent Laid-Open No. 7-70315, or The resin composition described in International Publication No. 2013/008667 and the resin composition described in the background of the invention. Examples of diamines and polycarboxylic acid dianhydrides that form polyamides include Japanese Patent Publication No. 5766125 [0020], Japanese Patent Publication No. 5766125 [0019], and Japanese Patent Publication No. 2012-145676. [0055] The compounds described in [0057]. Among them, aromatic diamines such as 4, 4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, and pyromellic dianhydride, A combination of aromatic polycarboxylic acid dianhydrides such as 3, 3', 4, 4'-biphenyltetracarboxylic dianhydride and 3, 3', 4, 4'-diphenyl ketonetetracarboxylic dianhydride is suitable.

Examples of the hot-melt resin include thermoplastic resins such as thermoplastic polyimide, and hot-melt cured products of curable resins. Examples of thermoplastic resins include polyester resins, polyolefin resins, styrene resins, polycarbonates, thermoplastic polyimides, polyarylates, polysaccharides, polyaryls, aromatic polyamides, aromatic polyetheramides Amine, polyphenylene sulfide, polyaryl ether ketone, polyamidoamide, liquid crystal polyester, polyphenylene ether, and preferably thermoplastic polyimide, liquid crystal polyester or polyphenylene ether.

The viscosity of the liquid composition in the present invention can be adjusted to 10000 mPa·s or less depending on the type and/or blending amount of each component, whether other components are blended, and the temperature of the liquid composition. On the other hand, if a liquid composition with a viscosity greater than 10000 mPa‧s is supplied to the wet jet milling method, the fine particles will easily fibrillate. In the present invention, the viscosity of the liquid composition is adjusted to 10000 mPa·s or less, so that the components in the liquid composition can be brought into high contact with each other, and fibrillation can be prevented while promoting the fine particles of coarse particles. In addition, the fine particles obtained by micronization have many dispersants attached (adsorbed) on their surfaces, so they are stably dispersed in the dispersion medium. The viscosity of the liquid composition is preferably 5000 mPa‧s or less, and preferably 1000 mPa‧s or less. If the viscosity of the liquid composition is below the above upper limit, the above effects will be further enhanced. The viscosity of the liquid composition is preferably 1 mPa‧s or more, and preferably 5 mPa‧s or more, more preferably 10 mPa‧s or more, and particularly preferably 20 mPa‧s or more. As long as the viscosity of the liquid composition is above the above lower limit, even if the wet jet milling method is applied, the components in the liquid composition are likely to be in high contact with each other, and the productivity is excellent. Therefore, the coarse particles can be sufficiently finely divided, the interaction of the dispersant on the surface of the fine particles can be improved, and the fine particles can be stably dispersed in the liquid dispersion medium.

The treatment (dispersion treatment) of mixing the components may include ultrasonic treatment, stirring treatment, and shaking treatment. From the viewpoint of allowing the coarse particles to be sufficiently dispersed in the liquid composition and suppressing aggregation, ultrasonic treatment or stirring treatment is suitable. In addition, two or more of the above treatments may be used in combination. From the viewpoint of promoting the dispersion of coarse particles, the treatment temperature is preferably 35 to 60°C. The stirring speed in the stirring process is preferably 100 to 1000 rpm. By stirring at this stirring speed, the coarse particles can be uniformly dispersed into the liquid composition, and at the same time, the fibrillation of the coarse particles can be easily suppressed. The flow form of the liquid composition in the stirring process may be any of swirl flow, ascending flow, up-down circulation flow, and radial flow. However, from the viewpoint of promoting the redispersion of the settling components in the liquid composition, the flow form is preferably upflow or up-down circulation flow. In addition, in the stirring process, a baffle may be provided in the stirring tank to control the flow form, and the installation position and/or installation angle of the stirring device may also be adjusted to make the flow form eccentric.

The amount of coarse particles contained in the liquid composition is preferably 1 to 50% by mass, preferably 5 to 45% by mass, and more preferably 10 to 40% by mass. The amount of the dispersant contained in the liquid composition is preferably 1 part by mass or more relative to 100 parts by weight of the coarse particles, preferably 5-50 parts by mass, more preferably 10-40 parts by mass. Setting the amount of each component within the above range makes it easy to adjust the viscosity of the liquid composition within the desired range. In addition, the average particle size of the fine particles in the finally obtained dispersion liquid can be optimized, and at the same time, the dispersion stability of the fine particles in the dispersion liquid can be improved.

In the wet jet milling method, the liquid composition is forced to flow through a flow path (orifice) with a small pore diameter. At this time, a high shear force can be applied to the liquid composition, and at the same time, the components in the liquid composition are highly in contact with each other, so the coarse particles will be finely divided by contact with each other to generate fine particles. In particular, in the present invention, the viscosity of the liquid composition is adjusted to the above range, so the shear force applied to the coarse particles is high, and the coarse particles can be made into fine particles smoothly and efficiently. In addition, since the dispersant is highly in contact with the fine particles, the dispersant will adhere to the surface of the fine particles through their interaction. As a result, a dispersion liquid in which fine particles have been stably dispersed in a liquid dispersion medium can be obtained.

Examples of devices that can implement the wet jet milling method include Nano Jet Pul manufactured by Changguang Company and ultra-high pressure wet micronization device manufactured by Yoshida Industrial Co., Ltd. The pressurizing pressure of the wet jet milling method is preferably 50 to 200 MPa, and preferably 100 to 170 MPa. By pressurizing the liquid composition under the pressure, the fine particles of coarse particles can be further promoted. The diameter of the flow channel can be appropriately set according to the viscosity of the liquid composition and the particle size of the coarse particles of the F polymer, and it should be 200 µm or less, preferably 180 µm or less, and more preferably 50 to 150 µm. If the above-mentioned viscosity liquid composition flows through such a fine-diameter flow channel, the fine particles of coarse particles and the dispersion stability of fine particles can be further improved.

The D50 of the obtained fine particles is preferably 1 µm or less, preferably 0.05 to 0.8 µm, more preferably 0.1 to 0.6 µm, and particularly preferably 0.15 to 0.4 µm. The fine particles of D50 have good fluidity and dispersibility. For example, when forming an insulating resin layer of a printed wiring board, it is most likely to exhibit the electrical properties (low dielectric constant, etc.) and heat resistance of the F polymer. Moreover, the D90 of the fine particles is preferably 3 µm or less, and preferably 2.5 µm or less, and more preferably 2 µm or less. The fine particles of D90 have good fluidity and dispersibility. For example, when forming an insulating resin layer of a printed wiring board, it is most likely to exhibit the electrical characteristics (low dielectric constant, etc.) and heat resistance of the F polymer.

Specific forms of D50 and D90 of the obtained fine particles can be exemplified by those in which D50 is 0.5 μm or less and D90 is 2 μm or less. In addition, other specific aspects may be those in which D50 is 0.05 to 1 µm and D90 is 1.1 to 3 µm, while more suitable aspects may be those in which D50 is 0.05 to 0.5 µm and D90 is 1.1 to 2 µm. The density of loose body of fine particles should be 0.08~0.5g/mL. The density of the compact packing body of fine particles should be 0.1~0.8g/mL.

The liquid composition that has been supplied to the wet jet milling method can be used directly as a dispersion liquid, or the liquid composition after the wet jet milling method can be used again as a dispersion liquid after being supplied to the wet jet milling method. That is, the liquid composition can be circulated in the flow channel. If the liquid composition is repeatedly supplied to the wet jet milling method, it is easy to obtain the desired fine particles of D50. In the latter case, the liquid composition supplied to the wet jet milling method should be forcedly cooled. If the cooled liquid composition is supplied to the wet jet milling method again, it will prevent the F polymer from being deteriorated or deteriorated, and at the same time, the fibrillation of the fine particles will not easily occur. If the above specific heat liquid dispersion medium is used, the effect will be more apparent.

The temperature of the liquid composition after the wet jet milling method is preferably 75°C or lower, and preferably 50°C or lower. If it is the temperature, the viscosity change of the liquid composition due to the deterioration or deterioration of the F polymer or the aggregation of fine particles are unlikely to occur. To reduce the temperature of the liquid composition supplied to the wet jet milling method, there are methods for lowering the temperature of the reservoir before passing through the nozzle of the prescribed flow path and methods for lowering the temperature of the piping after passing through the nozzle, but both methods are suitable. use.

In the case of repeatedly supplying the liquid composition to the wet jet milling method, the number of times is not particularly limited, but it is preferably 10 to 70 times, preferably 20 to 60 times, and more preferably 30 to 50 times. If the number of times is too low, the effect of repeatedly supplying the liquid composition to the wet jet milling method may not be sufficiently obtained due to the flow channel diameter, pressurizing pressure, and the like. On the other hand, even if the number of times is increased more than necessary, the effect of micronization of the corresponding coarse particles and the effect of improving the dispersion stability of the fine particles may not be obtained.

When circulating the liquid composition in the flow channel, if the total amount of the liquid composition, the flow rate of the flow channel, and the circulation time are sequentially set to V, v, and t, the value of v × t/V (between v and t The value obtained by dividing the product by V; hereinafter referred to as "pass number" should be adjusted to greater than 10. The number of passes is preferably 12 or more, especially 20 or more. From the viewpoint of productivity of the dispersion, the upper limit of the number of passes is preferably 100 or less, and preferably 50 or less. In addition, in terms of the amount of liquid composition, device capacity, and manufacturing time, the total amount of liquid composition is determined by the total volume (unit: L) of the liquid composition for manufacturing, and the flow rate of the flow channel is determined by the flow channel The flow rate of the outlet (unit: L/hr) is determined, and the cycle time is determined by the operating time (unit: hr) of the manufacturing device.

In the present invention, since the F polymer with a predetermined melt viscosity is selected, the liquid composition contains a dispersant, and its viscosity has been adjusted within a predetermined range, the deterioration of the F polymer can be suppressed by the above-mentioned cycle procedure, and at the same time Efficiently crush its coarse particles into tiny particles. The effect is particularly obvious when the liquid dispersion medium is an aqueous dispersion medium and the dispersant is a fluorinated monoalcohol, or when the liquid dispersion medium is a non-aqueous dispersion medium and the dispersant is a fluorinated polyol.

In the dispersion obtained by the circulation procedure, the D50 and D90 of the fine particles are preferably D50 of 1 µm or less and D90 of less than 2 µm, and D50 of 0.50 µm or less and D90 of 2.0 µm or less. At this time, D50 is usually 0.05 µm or more and D90 is 1.1 µm or more. According to the present invention, it is possible to easily produce a dispersion liquid containing the fine polymer particle of the narrow particle size distribution.

The dispersion liquid obtained by the present invention is a dispersion liquid in which fine particles of the F polymer are dispersed in a liquid dispersion medium and have excellent dispersion stability and compatibility with other materials in a high-temperature environment. If the dispersion liquid obtained by the present invention is coated on the surface of various substrates, it is used as a coating agent and the like that can form a dense smooth layer of F-containing polymer on the surface. For example, if the dispersion liquid obtained by the present invention is used, a resin-coated metal foil having an insulating resin layer used in a printed wiring board for high-frequency signal transmission can be easily produced. That is, if the dispersion liquid obtained by the present invention is applied to the surface of a metal foil and heated, a resin-coated metal foil having an insulating resin layer on the surface of the metal foil can be produced. The insulating resin layer may be formed on at least one surface of the metal foil. When forming the insulating resin layer on both sides of the metal foil, it is suitable to apply the dispersion liquid on one side of the metal foil and then apply the dispersion liquid on the other side. In addition, when heating, the dispersion liquid on both sides can be fired together, or the dispersion liquid on each side can be fired one by one.

Examples of the material of the metal foil include copper, copper alloy, stainless steel, nickel, nickel alloy (including 42 alloy), aluminum, aluminum alloy, titanium, and titanium alloy. Examples of the metal foil include rolled copper foil and electrolytic copper foil. A rust preventive layer (oxide film such as chromate, etc.), a heat-resistant layer, etc. may also be formed on the surface of the metal foil. The ten-point average roughness of the metal foil surface should be 0.01~1.5µm. The thickness of the metal foil may be any thickness that can function in the application of the metal foil with resin. The surface of the metal foil can be treated with a silane coupling agent, the entire surface of the metal foil can be treated with a silane coupling agent, or a part of the surface of the metal foil can be treated with a silane coupling agent.

The metal foil with resin has a warpage rate of 7% or less. At this time, the processability of the metal foil with resin and the physical properties of the processed product (transport characteristics of the printed board, etc.) are excellent. The dimensional change rate of the metal foil with resin is preferably ± 0.2% or less. In this case, it is easy to process the metal foil with resin into a printed circuit board and further multilayer it. The water contact angle of the surface of the insulating resin layer is preferably 70 to 100°. At this time, the insulating resin layer has excellent adhesiveness, and the physical properties of the processed product (electrical characteristics of the printed board, etc.) are excellent. The thickness of the insulating resin layer should be 1~50µm. Within this range, it is easy to strike a balance between the electrical characteristics and the warpage rate of printed boards made of resin-attached metal foil. When the metal foil with resin has insulating resin layers on both sides of the metal foil, each insulating resin layer may be made the same. The relative dielectric constant of the insulating resin layer should be 2.0 to 3.5. In this case, the metal foil with resin can be suitably used for a printed circuit board or the like that requires a low dielectric constant. The Ra of the surface of the insulating resin layer should be 2.2~8µm. Within this range, it is easy to strike a balance between the adhesion and processability of the metal foil with resin.

The coating method may be any method that can form a wet film composed of a powder dispersion on the surface of the metal foil after coating, and examples thereof include spray coating, roll coating, spin coating, gravure coating, and microgravure. Coating method, gravure lithography method, blade coating method, contact coating method, bar coating method, die coating method, fountain winding bar method, slit die coating method, etc.

The heating after coating the dispersion is preferably performed in a low temperature region to distill off the liquid dispersion medium. The temperature in the low temperature area should be above 80°C and below 180°C. In this case, it is easy to form a resin-attached metal foil excellent in adhesion without impairing the physical properties of the metal foil and the insulating resin layer. The heating method in the low-temperature region includes, for example, a method using an oven, a method using a ventilating drying furnace, a method irradiating heat rays such as infrared rays, etc. The heating environment in the low-temperature region can be in either state under normal pressure or under reduced pressure. In addition, the environment in the low temperature region may be any of an oxidizing gas environment (oxygen, etc.), a reducing gas environment (hydrogen, etc.), and an inert gas environment (helium, neon, argon, nitrogen, etc.).

The heating after coating the dispersion liquid is more preferably performed at a temperature (high temperature range) at which the F polymer is fired. As a result, the fine particles of the F polymer are densely deposited and fused, so that it is easy to form an insulating resin layer having excellent surface properties. The heating method in the high temperature region may be the same as the heating method in the low temperature region. In order to improve the smoothness of the surface of the insulating resin layer, pressure may also be applied using a heating plate, heating roller, or the like. Regarding the heating method, from the viewpoint of being capable of firing in a short time and having a far-infrared furnace smaller, a method of irradiating far-infrared rays is suitable. The heating method can also combine infrared heating and hot air heating. The heating environment in the high temperature area can adopt the same conditions as the heating in the low temperature area. The temperature in the high-temperature area should be below 250℃~400℃. The time for maintaining in the high temperature area should be 30 seconds to 5 minutes.

In order to control the expansion of the metal foil with resin, or to further improve the adhesion of the insulating resin layer, annealing treatment, corona discharge treatment, atmospheric pressure plasma treatment, vacuum plasma treatment, UV ozone treatment, etc. Surface treatment such as excimer treatment, chemical etching, silane coupling agent treatment. The temperature, pressure and time during annealing treatment should be 120~180℃, 0.005~0.015MPa and 30~120 minutes in order. Plasma irradiation devices in plasma treatment include high-frequency induction method, capacitive coupling electrode method, corona discharge electrode-plasma spray method, parallel plate type, remote plasma type, atmospheric piezoelectric plasma type, ICP type high Density plasma type. The gas used for plasma treatment can be exemplified by oxygen, nitrogen, rare gas (argon, etc.), hydrogen, ammonia, and rare gas or nitrogen is suitable. Specific examples of the gas used in plasma treatment include: argon; mixed gas of hydrogen and nitrogen; mixed gas of hydrogen, nitrogen, and argon. The plasma treatment environment is preferably an environment with a rare gas or nitrogen volume fraction of 100% by volume. Plasma treatment in this gas environment makes it easy to adjust the Ra of the surface of the insulating resin layer to 2 µm or less to form fine irregularities on the surface of the insulating resin layer.

The metal foil with resin can also be a substrate on the surface area of the insulating resin layer. Examples of the substrate include a heat-resistant resin film, a prepreg as a precursor of a fiber-reinforced resin sheet, a laminate having a heat-resistant resin film layer, and a laminate having a prepreg layer. The prepreg system impregnates a thermosetting resin or thermoplastic resin into a substrate (fibre bundle, woven fabric, etc.) of reinforcing fibers (glass fibers, carbon fibers, etc.) to form a sheet substrate. The lamination method may be, for example, a method of hot-pressing a metal foil with resin and a substrate. When the substrate is a prepreg, the pressing temperature is preferably below the melting temperature of the F polymer. When the substrate is a heat-resistant resin film, the pressing temperature is preferably 310 to 400°C. From the viewpoint of suppressing the mixing of bubbles into the interfaces of the substrate, the insulating resin layer, and the metal foil and suppressing the deterioration caused by oxidation, hot pressing is preferably performed under a reduced-pressure gas environment, and is preferably performed under a vacuum of 20 kPa or less. In addition, the hot pressing is preferably performed in a state where the insulating resin layer has been softened, that is, in a state where it has a certain degree of fluidity and adhesion in a reduced-pressure gas environment to reach the above-mentioned vacuum degree. The pressure of hot pressing should be 0.2~10MPa.

The metal foil with resin and its laminate as described above can be used as a flexible copper-clad laminate or a rigid copper-clad laminate to manufacture a printed wiring board. For example, a printed wiring board can be manufactured from a metal foil with resin by using the following method: a method of processing the metal foil with resin into a predetermined pattern of metal wiring by etching; the metal foil with resin is plated (Semi-additive method (SAP), modified semi-additive method (MSAP method), etc.) A method of processing into metal wiring. When manufacturing a printed wiring board, after forming a metal wiring (conductor circuit), an interlayer insulating film may be formed on the metal wiring, and then a metal wiring may be further formed on the interlayer insulating film. The interlayer insulating film can be formed by the above-described dispersion liquid, for example. When manufacturing printed wiring boards, solder resist can also be deposited on the metal wiring. When manufacturing a printed wiring board, a cover film may be laminated on the metal wiring board. The solder resist and the cover film can be formed by the above dispersion liquid.

The method for producing the dispersion liquid of the present invention has been described above, but the present invention should not be limited to the configuration of the foregoing embodiment. For example, in the method for producing a dispersion liquid of the present invention, other arbitrary steps may be added in terms of the configuration in the above-mentioned embodiment, or it may be replaced with any step that produces the same effect.

Examples The following examples are given to specifically illustrate the present invention, but the present invention is not limited thereto. 1. Prepare the ingredients 1-1. Coarse particles of F polymer

(Coarse Particle A) It is obtained by the procedure described in International Publication No. 2016/017801, and it contains TFE units containing 98.0 mol%, 0.1 mol% and 1.9 mol% in sequence, units with NAH as the main unit and PPVE is the powder (D50: 2.6µm, D90: 7.1µm) of the polymer of the main unit (melting temperature: 300℃, 380℃ melt viscosity: 3×10 ⁵ Pa‧s). (Coarse particles B) A polymer containing 98.0 mol% and 2.0 mol% of TFE units and PPVE-based units in sequence (melting temperature: 305°C, 380°C melt viscosity: 3×10 ⁵ Pa‧s ) Powder (D50: 3.5µm, D90: 9.2µm). (Coarse particles C) The liquid dispersion medium obtained by removing FEP DISPERSION 120-JRB (manufactured by Mitsui DuPont Fluorine Chemical Co., Ltd.) is a TFE unit containing 88.0 mol% and 12.0 mol% in sequence, and is mainly composed of HFP Powder (D50: 0.4µm, D90: 1.2µm) of polymer of the unit (melting temperature: 270°C, melt viscosity at 380°C: 2×10 ⁵ Pa‧s) (Coarse particles D) PTFE powder (manufactured by Kitamura Corporation, KTL-500F) is a polymer containing 100.0 mol% of TFE units (melting temperature: 327°C, melting viscosity at 380°C: 1×10 ⁹ Pa‧s) Powder (D50: 0.7µm, D90: 1.0µm). (Coarse particles E) PTFE powder (manufactured by Kitamura Corporation, KTL-1N) is a polymer containing 100.0 mol% of TFE units (melting temperature: 327℃, 380℃ melting viscosity: 1×10 ¹¹ Pa‧s) The powder (D50: 2.8µm, D90: 4.2µm).

In addition, the physical properties of each polymer and powder can be measured in the following manner. >melt viscosity> The melt viscosity is measured under the following conditions to change the complex viscosity (unit: Pa‧s). Device: dynamic viscoelasticity measuring device (manufactured by ANTON PAAR, MCR302) Measuring method: parallel plate Φ25mm Measuring temperature: 380℃ Shear frequency: 0.05Hz >Melting temperature> A melting scanning calorimeter (manufactured by Seiko Instruments Inc., DSC-7020) was used to record the melting peak when the polymer was heated at a rate of 10°C/minute, and the temperature (°C) corresponding to the maximum value was used as the melting temperature. >D50 and D90 of powder> After dispersing the powder in water, measurement was carried out using a laser diffraction scattering type particle size distribution measuring device (Horiba Manufacturing Co., Ltd., LA-920 measuring instrument).

1-2. Dispersant (Fluorine-based Dispersant 1) Non-ionic fluorinated polyol, such that CH ₂ =CHCOO(CH ₂ ) ₄ OCF(CF ₃ )(C(CF(CF ₃ ) ₂ )(= C(CF ₃ ) ₂ ) and CH ₂ =CHCOO(CH ₂ ) ₄ (OCH ₂ CH ₂ ) ₁₀ OH copolymer obtained by polymerization at a molar ratio of 1:1 (weight average molecular weight: about 10,000, cloud point : 62°C). (Fluorine-based dispersant 2) CH ₂ ＝C(CH ₃ )COO(CH ₂ ) ₂ (CF ₂ ) ₆ H homopolymer. (Fluorine-based dispersant 3) Non-ionic fluorination Unit alcohol F(CF ₂ ) ₆ CH ₂ (OCH ₂ CH ₂ ) ₇ OCH ₂ CH(CH ₃ OH, cloud point: 60°C). (Non-fluorine-based dispersant 1) A dispersant that does not contain fluorine atoms and has a hydroxyl group and polyoxyethylidene (cloud point: 48°C). 1-3. The liquid dispersion medium is prepared with N-methyl-2-pyrrolidone (hereinafter also referred to as "NMP") and methyl ethyl ketone (hereinafter also referred to as "MEK").

2. Evaluation 2-1. Differences in effect caused by different types of F polymers (example 1) After 75 parts by mass of NMP, 10 parts by mass of fluorine-based dispersant 1 and 15 parts by mass of coarse particles A were put into the tank, zirconia balls were put into the tank. Then, the can body was rotated at 150 rpm × 1 hour to obtain a liquid composition A in which coarse particles A were dispersed and had a viscosity of 200 mPa‧s. Next, the liquid composition A was supplied to the wet jet milling method under the following conditions to make the coarse particles A finely divided to obtain a dispersion liquid in which the fine particles were dispersed and the viscosity was 300 mPa‧s.

>Wet spray conditions> Device 　　　　　　: JN100 (manufactured by Changguang Company) Nozzle (flow channel) diameter length: 100µm Pressurized pressure: 150MPa Number of passes 　　　　: 30 times Reservoir temperature 　　　: 15℃ Temperature after passing through the nozzle: 50℃ Viscosity of liquid composition: 200mPa‧s In the wet jet milling method, the cold shock is caused to cool the liquid reservoir through the cooling sleeve, so that the temperature of the liquid composition (reservoir temperature) in the liquid reservoir is 15°C. In addition, after passing through the nozzle, the temperature of the liquid composition after passing through the nozzle (temperature after passing through the nozzle) was set to 50°C by winding the guide through which the cold shock flowed through the metal pipe. In addition, these temperatures are measured by the metal piping part after the contact thermocouple touches the reservoir and passes through the nozzle.

(Example 2~7) Except for mixing the components with the composition shown in Table 1, liquid compositions B to G were prepared in the same manner as in Example 1, and each was subjected to a jet milling method to obtain a dispersion. In addition, the viscosity of the liquid composition B~G is 20~1000mPa‧s. In addition, the dispersion obtained in Example 6 will increase the viscosity to about 1500 mPa‧s.

[Table 1]

>D50 and D90 of tiny particles> D50 and D90 of the fine particles contained in each dispersion liquid were calculated using a laser diffraction scattering type particle size distribution measuring device (made by HORIBA, Inc., LA-920 measuring instrument). >Agglutination after storage> The dispersion liquid obtained in each example was placed in a plastic bottle and allowed to stand at 40°C for 1 month. Thereafter, the stirring blade was inserted into the dispersion in the plastic bottle and stirred at 500 rpm for 30 minutes. The stirred dispersion liquid was applied to an A4-size substrate with a #14 bar coater and dried. Calculate the number of aggregates above 500µm present on the dried coating film visually, and evaluate according to the following criteria.

[Evaluation criteria] ◎(Best): 1 or less ○(good)　: more than 1 and less than 5 △(possible)　: more than 5 and less than 10 × (bad): more than 10 The evaluation results are shown in Table 2.

[Table 2]

2-2. The difference in effect caused by the different viscosity of the liquid composition (Examples 8 and 9 (comparative example)) The liquid compositions H and I were prepared in the same manner as in Example 1 except that the components were mixed in the composition shown in Table 3 below, and were separately supplied to a jet mill method to obtain a dispersion.

[table 3]

For the dispersion liquids obtained in each example, D50 and D90 of the fine particles were obtained, and the aggregation of the fine particles after storage was evaluated. The results are shown in Table 4.

[Table 4]

2-3. Differences in effects caused by different conditions in the wet jet milling method (Example 10~12) A dispersion liquid was obtained in the same manner as in Example 1, except that the pressurizing pressure was changed to the following Table 5 in the wet jet milling method. (Examples 13, 14) A dispersion liquid was obtained in the same manner as in Example 1 except that the nozzle diameter length was changed to the following Table 5 in the wet jet milling method. (Example 15, 16) A dispersion liquid was obtained in the same manner as in Example 1, except that the reservoir temperature and the temperature after passing through the nozzle were changed to those shown in Table 5 below in the wet jet milling method. In addition, the temperature increase after passing through the nozzle in Example 15 is the result of omitting the cooling of the reservoir. On the other hand, the temperature increase after passing through the nozzle in Example 16 is the result of increasing the pressurizing pressure in the wet jet milling method and omitting the cooling of the metal piping. (Example 17, 18) A dispersion liquid was obtained in the same manner as in Example 1 above except that the number of passes was changed to the following Table 5 in the wet jet milling method.

For the dispersions obtained in each example, D50 and D90 of the fine particles were measured and the aggregation of the fine particles after storage was evaluated. The results are shown in Table 5.

[table 5]

As shown in Table 5, it can be confirmed that when the various conditions in the wet jet milling method are changed, the viscosity of the dispersion liquid, the particle size of the fine particles, and the degree of aggregation of the fine particles change.

2-4. Differences in effects caused by different types of dispersants (Example 19 (comparative example)) A non-fluorine-based dispersant 1 was used instead of the fluorine-based dispersant 1, and water was used instead of NMP. A dispersion liquid was prepared in the same manner as in Example 1, except that the agglomerated state after storage was "×". (Example 20 (Comparative example)) A dispersion liquid was obtained in the same manner as in Example 1, except that no fluorine-based dispersant was added and 10 parts by mass of MEK was added, but the aggregation state after storage was "×". (Example 21) After putting 67 parts by mass of water, 3 parts by mass of fluorine-based dispersant 3 and 30 parts by mass of coarse particles A into the tank, zirconia balls were put into the tank. Then, the can body was rotated at 150 rpm × 1 hour to obtain a liquid composition H in which coarse particles A were dispersed and had a viscosity of 15 mPa‧s. Except that the liquid composition H was used, wet jet milling (30 passes) was performed in the same manner as in Example 1 to obtain a dispersion liquid in which fine particles of coarse particles A had been dispersed into fine particles and had a viscosity of 300 mPa‧s. The fine particles have a D50 of 0.3µm and D90 of 1.5µm. The aggregation state of the dispersion after storage is "◎". (Example 22) Except that the number of passes of the liquid composition H was set to 10, the wet jet mill was supplied under the same conditions as in Example 1, to obtain dispersion of fine particles in which coarse particles A were dispersed into fine particles and a viscosity of 200 mPa‧s liquid. The D50 of fine particles is 0.6µm and D90 is 2.3µm. The aggregation state of the dispersion after storage is "△".

As shown in the above examples, if a liquid composition with a predetermined viscosity containing a dispersant with a predetermined cloud point is supplied to the wet jet milling method, a dispersion liquid in which fine particles of F polymer are stably dispersed can be obtained. In addition, using at least one of fluorinated polysiloxane and fluorinated polyether instead of fluorinated polyol as a dispersant to adjust the viscosity of the liquid composition to a predetermined range will also show the same tendency as the above examples the result of. Industrial availability

The dispersion prepared by the present invention can easily form an F polymer layer having excellent adhesion and crack resistance, and is suitable for manufacturing a resin-coated copper foil or a metal laminate for printed wiring boards. In addition, the aforementioned dispersion liquid can be used to produce molded products such as films, infiltrate (prepreg, etc.), and is suitable for requiring mold release properties, electrical properties, water and oil repellency, chemical resistance, weather resistance, heat resistance, slip resistance, Molded products for applications such as wear resistance. The molded product made from the aforementioned dispersion can be used as antenna parts, printed circuit boards, aircraft parts, automotive parts, sports equipment, food industry supplies, paints, cosmetics, etc., and can be used specifically as an insulating layer for power modules , Wire coating materials (aircraft wires, etc.), electrical insulating tapes, insulating tapes for petroleum exploration, printed circuit board materials, electrode adhesives (for lithium secondary batteries, fuel cells, etc.), replication rollers, furniture , Automobile instrument panel, housing of household appliances, sliding members (bearing bearings, sliding shafts, valves, bearings, gears, cams, belt conveyors, food conveyor belts, etc.), tools (shovel, file, cone, saw, etc.), boiler , Funnel, tube, oven, baking mold, chute, mold, toilet, container coating material. In addition, the specification and patent application of Japanese Patent Application No. 2018-166187 filed on September 5, 2018 and Japanese Patent Application No. 2018-240870 filed on December 25, 2018 are cited here. The entire contents of the scope and abstract are incorporated as the disclosure of the specification of the present invention.

Claims (15)

A method for manufacturing a dispersion liquid, in which a liquid composition containing coarse fluoroolefin-based polymer particles, a dispersant, and a liquid dispersion medium and having a viscosity of 10000 mPa.s or less is circulated under pressure to crush the coarse particles into an average particle size Fine particles having a smaller particle size than the coarse particles to obtain a dispersion containing the dispersant and the fine particles dispersed in the liquid dispersion medium; wherein the melt viscosity of the fluoroolefin polymer at 380°C is 1 ×10 ² ~1×10 ¹⁰ Pa.s, the cloud point of this dispersant exceeds 50℃. The manufacturing method according to claim 1, wherein the melting temperature of the fluoroolefin-based polymer is 200°C or higher. The manufacturing method according to claim 1 or 2, wherein the aforementioned dispersant is a fluorine-based dispersant. The manufacturing method according to claim 3, wherein the fluorine-based dispersant is at least one compound selected from the group consisting of fluorinated monoalcohol, fluorinated polyol, fluorinated polysiloxane, and fluorinated polyether. The manufacturing method according to claim 3 or 4, wherein the fluorine content of the aforementioned fluorine-based dispersant is 10 to 50% by mass. The manufacturing method according to any one of claims 1 to 5, wherein the dispersant is at least one compound selected from the group consisting of fluorinated monoalcohols and fluorinated polyols, and has a hydroxyl value of 10 to 100 mgKOH /g of compound. The manufacturing method according to any one of claims 1 to 6, wherein the aforementioned dispersant is a fluorinated monoalcohol, and the aforementioned liquid dispersion medium is an aqueous dispersion medium. The manufacturing method according to any one of claims 1 to 6, wherein the aforementioned dispersant is a fluorinated polyol, and the aforementioned liquid dispersion medium is a non-aqueous dispersion medium. The manufacturing method according to any one of claims 1 to 8, wherein the average particle diameter of the aforementioned fine particles is 1 µm or less. The manufacturing method according to any one of claims 1 to 9, wherein the average particle diameter of the aforementioned coarse particles is greater than 1 µm and less than 10 µm. The manufacturing method according to any one of claims 1 to 10, wherein the liquid composition contains 1 part by mass or more of the dispersant relative to 100 parts by mass of the coarse particles. The manufacturing method according to any one of claims 1 to 11, wherein the liquid composition contains 1 to 50% by mass of the coarse particles. The manufacturing method according to any one of claims 1 to 12, which circulates the liquid composition through the flow path. The manufacturing method according to any one of claims 1 to 13, which circulates the aforementioned liquid composition under the condition that the value of the product of the flow channel flow rate and the circulation time divided by the total amount of the liquid composition will exceed 10 In the aforementioned flow path. The manufacturing method according to any one of claims 1 to 14, wherein the average particle diameter of the fine particles is 0.5 μm or less, and the volume-based cumulative 90% particle diameter of the fine particles is 2 μm or less.