WO2019131809A1

WO2019131809A1 - Dispersion, metal laminate plate, and production method for printed board

Info

Publication number: WO2019131809A1
Application number: PCT/JP2018/047959
Authority: WO
Inventors: 達也寺田; 細田　朋也; 敦美山邊
Original assignee: Ａｇｃ株式会社
Priority date: 2017-12-27
Filing date: 2018-12-26
Publication date: 2019-07-04
Also published as: KR20200103630A; JPWO2019131809A1; TW201934642A; CN111492006A

Abstract

Provided are: a dispersion that has excellent dispersion, excellent dispersion stability, excellent miscibility with varnish, and excellent coating properties; a metal laminate plate; and a production method for a printed board. A dispersion that includes an organic solvent, a powder, and a surfactant, the powder being dispersed in the organic solvent. The powder includes a fluoropolymer that has: a unit that is derived from tetrafluoroethylene; and at least one type of functional group selected from the group that consists of carbonyl-group-containing groups, hydroxyl groups, epoxy groups, and isocyanate groups.

Description

Dispersion liquid, metal laminated board and method of manufacturing printed circuit board

The present invention relates to a method for producing a dispersion, a metal laminate and a printed circuit board.

Fluoropolymers such as polytetrafluoroethylene (PTFE) are excellent in physical properties such as chemical resistance, water and oil repellency, heat resistance, electrical properties and the like, and various uses utilizing such physical properties, powders, films, etc. Various usage forms have been proposed (see Patent Documents 1 to 3).
In recent years, as an insulating material for printed circuit board materials of electronic products, especially for printed circuit boards corresponding to the frequency in the high frequency band, as an insulating material having electrical properties such as low dielectric constant and low dielectric loss tangent and heat resistance to withstand solder reflow , Fluoropolymers have attracted attention.
As such an insulating material, a mixture of PTFE and a varnish containing another insulating resin such as polyimide is applied to the surface of a metal foil and dried to manufacture a metal laminate plate having an insulating resin layer formed thereon, and further, a metal laminate plate Patent Document 4 describes a method of manufacturing a printed circuit board in which a metal foil is etched to form a transmission line. Further, as a PTFE dispersion for forming such a varnish, a dispersion containing a PTFE powder is described in Patent Document 5.

JP 2012-162708 A Unexamined-Japanese-Patent No. 2005-142572 International Publication No. 2016/017801 JP-A-2015-509113 International Publication No. 2016/159102

In the aspect described in Patent Document 4, from the viewpoint of the electrical properties of the resulting printed circuit board, it is required that the other insulating resin and the fluoropolymer are mixed in a good state, but the control thereof is not easy. . For example, when mixing and preparing a varnish containing another insulating resin and a powder of a fluoropolymer, thickening not only makes mixing difficult but also significantly reduces the dispersibility of the fluoropolymer after preparation.
Also in the embodiment described in Patent Document 5, the dispersibility and dispersion stability of the fluoropolymer in the dispersion are not sufficient yet, and the coatability is low. In particular, when the content of the fluoropolymer powder is reduced to improve the dispersibility of the dispersion, not only the coatability thereof is reduced, but also the physical properties of the formed insulating layer are reduced.
An object of the present invention is to provide a dispersion containing a powder of a tetrafluoroethylene-based polymer, which is excellent in mixing properties with different resin materials and the varnish, and is excellent in coatability, dispersibility and dispersion stability.

The present invention has the following aspects.
[1] A dispersion liquid comprising an organic solvent, a powder and a surfactant, wherein the powder is dispersed in the organic solvent, wherein the powder is a unit derived from tetrafluoroethylene, a carbonyl group-containing group, a hydroxy group, an epoxy group, A dispersion, which is a powder comprising a fluoropolymer having at least one functional group selected from the group consisting of isocyanate groups.
[2] The viscosity is 100 to 10000 mPa · s, and the viscosity measured at 30 rpm is divided by the viscosity measured at 60 rpm for a thixo ratio of 1.4 to The dispersion according to [1], which is 2.2.
[3] The dispersion according to [1] or [2], wherein the organic solvent is methyl ethyl ketone, toluene, xylene, cyclohexane or methyl cyclohexane.
[4] The viscosity is 50 to 3000 mPa · s, and the viscosity measured at 30 rpm is divided by the viscosity measured at 60 rpm for a thixo ratio of 1.0 to The dispersion according to [1], which is 1.5.
[5] The dispersion according to [1] or [4], wherein the organic solvent is cyclohexanone, cyclopentanone, N, N-dimethylacetamide or N-methyl-2-pyrrolidone.

[6] The dispersion according to any one of [1] to [5], wherein the powder is a powder having a volume-based cumulative 50% diameter of 0.05 to 4 μm and a volume-based cumulative 90% diameter of 8 μm or less.
[7] The dispersion according to any one of [1] to [6], wherein the fluoropolymer is a fluoropolymer having a ratio of 90 to 99.89 mol% of units derived from tetrafluoroethylene to the total of all units. .
[8] The fluoropolymer according to any one of [1] to [7], which further has a unit derived from at least one monomer selected from the group consisting of perfluoro (alkyl vinyl ether), hexafluoropropylene and fluoroalkylethylene. Dispersion according to any one of the above.
[9] The fluoropolymer is a polymer further having a unit derived from a monomer having at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group and an isocyanate group, [1] The dispersion according to any one of [8].

[10] The dispersion according to any one of [1] to [9], wherein the surfactant has a perfluoroalkyl group or a perfluoroalkenyl group.
[11] The surfactant according to any one of [1] to [10], having a polyoxyethylene group, a polyoxypropylene group, a polyoxytetramethylene group, an amino group, a ketone group, a carboxyl group or a sulfone group. Dispersion as described.
[12] The dispersion according to any one of [1] to [11], wherein the content of the powder is 35 to 70% by mass with respect to the total of the organic solvent, the powder and the surfactant.

[13] A method for producing a metal laminate, comprising forming a resin layer on a metal film using the dispersion according to any one of the above [1] to [12] to obtain a metal film having a resin layer on the surface .
[14] The method for producing a metal laminate plate according to [13], wherein the thickness of the resin layer is 1 to 20 μm.
[15] A method for producing a printed circuit board, wherein a metal laminate is produced by the production method according to [13] or [14], and the metal film is etched to form a patterned circuit.

According to the present invention, a dispersion liquid excellent in different resin materials and their mixing properties with the varnish, coatability, dispersibility and dispersion stability can be obtained, excellent in physical properties such as electrical properties and heat resistance, and high cycle. Provided is a material of a metal laminate for producing a printed circuit board corresponding to a band frequency.

The meanings of the following terms in the present specification are as follows.
The “volume based cumulative 50% diameter of powder” is determined by the laser diffraction / scattering method. That is, the particle size distribution is measured by the laser diffraction / scattering method, and the cumulative curve is obtained with the total volume of the particle group as 100%, and the particle diameter at the point where the cumulative volume is 50% on the cumulative curve. In the present specification, the volume-based cumulative 50% diameter of powder is also referred to as "D50".
The “volume based cumulative 90% diameter of powder” is determined by the laser diffraction / scattering method. That is, the particle size distribution is measured by the laser diffraction / scattering method, and the cumulative curve is obtained with the total volume of the particle group as 100%, and the particle diameter at the point where the cumulative volume is 90% on the cumulative curve. In the present specification, the volume-based cumulative 90% diameter of powder is also referred to as "D90".
The "melting point" is the temperature corresponding to the maximum value of the melting peak of the polymer measured by differential scanning calorimetry (DSC).
The “viscosity of dispersion” is a value measured using a B-type viscometer under conditions of a rotation speed of 30 rpm at room temperature (25 ° C.). Repeat the measurement three times to obtain the average value of the three measurements.
The "thixotropic index of dispersion", is the viscosity eta ₁ of rotational speed is measured under the conditions of 30rpm values rotational speed is calculated by dividing the viscosity eta ₂ as measured under conditions of 60 rpm. Each viscosity measurement is repeated three times, and is taken as the average value of three measurements.
The "dielectric constant" is a dielectric breakdown test device that maintains the temperature in the range of 23 ° C ± 2 ° C and the relative humidity in the range of 50% ± 5% RH by the transformer bridge method according to ASTM D 150. The value obtained at 1 MHz was taken as the relative dielectric constant.
The “surface tension of the organic solvent” is a value measured at 25 ° C. using a surface tension meter.

The dispersion of the present invention is a dispersion comprising an organic solvent, a powder comprising tetrafluoroethylene units and a fluoropolymer having a specific functional group, and a specific surfactant.
The reason why the dispersion of the present invention is excellent in dispersibility, mixing properties with different resin materials and varnishes thereof, and coatability is not necessarily clear, but is considered as follows.
The fluoropolymer in the present invention is a fluoropolymer having a specific functional group (at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group and an isocyanate group), in other words, a polar group It can be said that it is a fluoropolymer having It is considered that the powder containing the fluoropolymer having such a polar group tends to be prone to aggregation in the dispersion due to the interaction between particles also from the physical characteristic that the specific surface area is large. Furthermore, it is considered that this tendency is influenced by the strength of external force (shearing force etc.) applied to the dispersion and the kind of the organic solvent. Thus, while the fluoropolymer having a polar group has unique physical properties (fusion, adhesion, etc.), preparation of the dispersion was not easy.
The dispersion of the present invention contains a surfactant (preferably having a fluorine-containing group and a hydrophilic group), the presence of the surfactant reduces the surface tension of the organic solvent, and the organic solvent and the fluoropolymer It is easy to get wet. It is believed that the fluoropolymer chain on the powder surface and the fluorine-containing group of the specific surfactant, as well as the hydrophilic group of the specific surfactant and the organic solvent form a highly interacted state. As a result, the powder is dispersed in an organic solvent in a stable state, and it is considered that the polar groups of the fluoropolymer itself forming the powder exhibit different resins and their varnishes, and a good mixability and coatability thereof.

The viscosity of the dispersion of the present invention is preferably 100 to 10000 mPa · s, more preferably 130 to 7000 mPa · s, still more preferably 150 to 5000 mPa · s, and particularly preferably 170 to 3000 mPa · s. When the viscosity is 100 mPa · s or more, the dispersion stability of the dispersion is excellent, the resin layer formed from the dispersion is likely to be uniform, and the coatability of the dispersion is excellent. When the viscosity is 10000 mPa · s or less, the dispersion stability of the dispersion is excellent, and the operability (the coatability of the dispersion) at the time of forming the resin layer from the dispersion is excellent.
The viscosity of the dispersion of the present invention is preferably 50 to 3000 mPa · s, more preferably 70 to 1500 mPa · s, still more preferably 80 to 1000 mPa · s, and particularly preferably 100 to 500 mPa · s. In this case, in particular, the dispersion stability of the dispersion is excellent, and the operability when mixing and applying the dispersion and the varnish is excellent.

The thixo ratio of the dispersion of the present invention is preferably 1.4 to 2.2, more preferably 1.45 to 2.10, and still more preferably 1.5 to 2.0. When the thixo ratio is 1.4 or more, the dispersion stability of the dispersion is excellent, the resin layer formed from the dispersion is likely to be uniform, and the coatability is also excellent. When the thixo ratio is 2.2 or less, the dispersibility of the dispersion and the coatability are excellent.
The thixo ratio of the dispersion is also preferably 1.0 to 1.5, more preferably 1.05 to 1.45, still more preferably 1.1 to 1.4, and particularly preferably 1.1 to 1.3. In this case, the mixing properties of the dispersion liquid and the varnish of different resin materials are excellent.
The dispersion of the present invention may contain a thixotropic agent, an inorganic filler, and an antifoaming agent, from the viewpoint of adjusting viscosity and thixotropy. Further, from the above viewpoint, the dispersion liquid of the present invention preferably contains no resin that dissolves in an organic solvent.

The powder in the present invention may contain components other than the fluoropolymer in the present invention as long as the effects of the present invention are not impaired, but preferably the fluoropolymer in the present invention is a main component. 80 mass% or more is preferable, as for content of the fluoropolymer in this invention in a powder, 90 mass% or more is more preferable, and 100 mass% is especially preferable.

The powder D50 is preferably 0.05 to 4 μm, and the D90 is preferably 8 μm or less.
The powder D50 is preferably 0.1 to 3 μm, and particularly preferably 0.2 to 3.0 μm. Within this range, the flowability and the dispersibility of the powder become good, and the coatability of the dispersion liquid and the mixability with the varnish of different resin materials are excellent. Moreover, in the articles (metal laminates, printed circuit boards, etc.) obtained from the dispersion of the present invention, the electrical properties (low dielectric constant, etc.) and heat resistance of the fluoropolymers of the present invention are most easily exhibited. In addition, it is easy to control the thickness of the film obtained from the dispersion of the present invention.
The powder D90 is preferably 6 μm or less, particularly preferably 1.5 to 5 μm. Within this range, the dispersibility of the powder is good, the coatability of the dispersion liquid and the mixing property with the varnish of different resin materials are excellent, and the uniformity of the film obtained from the dispersion liquid tends to be improved.

The loosely packed bulk density of the powder is preferably 0.05 g / mL or more, and particularly preferably 0.08 to 0.5 g / mL.
The densely packed bulk density of the powder is preferably 0.05 g / mL or more, and particularly preferably 0.1 to 0.8 g / mL.
As a method of producing a powder, the methods described in [0065] to [0069] of WO 2016/017801 can be adopted.

The fluoropolymer (hereinafter referred to as "F polymer") in the present invention is a unit derived from tetrafluoroethylene (hereinafter also referred to as "TFE") (hereinafter referred to as "TFE unit"), and a carbonyl group. It has at least one type of functional group selected from the group consisting of containing groups, hydroxy groups, epoxy groups and isocyanate groups.
The "carbonyl group-containing group" means a group containing a carbonyl group. Examples of the carbonyl group-containing group include a carbonate group, a carboxy group, a haloformyl group, an alkoxycarbonyl group (such as a methoxycarbonyl group and an ethoxycarbonyl group), an acid anhydride residue, a fatty acid residue and an amide group. The "acid anhydride residue" means -C (= O) OC (= O)-.

The ratio of TFE units to the total of all units of the F polymer is preferably 90 mol% or more. The upper limit is preferably 99.89 mol or less.
The ratio of the TFE unit to the total of all units of the F polymer is 90 to 99.% from the viewpoints of electrical properties (such as low dielectric constant) of the F polymer, heat resistance, chemical resistance, melt moldability, stress crack resistance, and the like. 89 mol% is preferable, 95 to 99.47 mol% is more preferable, and 96 to 98.95 mol% is particularly preferable.
The functional group is preferably a carbonyl group-containing group from the viewpoint of physical properties of the F polymer (fusion and adhesion, etc.), and more preferably a carbonate group, a carboxy group, a haloformyl group, an alkoxycarbonyl group and an acid anhydride residue. Preferably, a carboxy group and an acid anhydride residue are particularly preferred.

The F polymer may have a unit derived from a monomer having a functional group (hereinafter, also referred to as a “functional monomer”) (hereinafter, also referred to as a “functional unit”), You may have.
The F polymer having a functional group at the main chain terminal can be produced by appropriately selecting the type of polymerization initiator, chain transfer agent, etc. used in the production (for example, in the production, a polymerization initiator having a functional group or a functional group Use a chain transfer agent having a group). The functional group in this case includes an alkoxycarbonyl group, a carbonate group, a carboxy group, a fluoroformyl group, an acid anhydride residue and a hydroxy group.

In addition, the F polymer is produced by subjecting a polymer having TFE units to plasma irradiation, corona irradiation, electron beam irradiation or irradiation, or treating a powder of the polymer with a sodium metal-naphthalene solution. It may be an F polymer. The functional group in this case includes an alkoxycarbonyl group, a carbonyl group, a carboxy group and a hydroxy group.

The F polymer preferably has functional units.
Examples of the functional monomer include monomers having a carbonyl group-containing group, monomers having a hydroxy group, monomers having an epoxy group, and monomers having an isocyanate group, and the physical properties of the F polymer (fusion, adhesion, etc.) Therefore, monomers having a carbonyl group-containing group are preferred.
The monomer having a carbonyl group-containing group includes a monomer having an acid anhydride residue, a monomer having a carboxy group, a monomer having an alkoxycarbonyl group, a monomer having an alkoxycarbonyl group, a monomer having an acid anhydride residue And monomers having a carboxy group are particularly preferred.

Examples of the monomer having an acid anhydride residue include acid anhydrides of unsaturated dicarboxylic acids, and itaconic anhydride (hereinafter also referred to as "IAH") and citraconic anhydride (hereinafter also referred to as "CAH"). 5-norbornene-2,3-dicarboxylic acid anhydride (also referred to as hymic acid anhydride, hereinafter also referred to as "NAH"), and maleic anhydride. From the viewpoint of the physical properties (heat resistance, adhesiveness, etc.) of the F polymer, IAH, CAH and NAH are preferable, and NAH is particularly preferable. When the F polymer has a functional unit, the ratio of the functional unit to the total of all units of the F polymer is obtained from the dispersion which is easy to prepare a dispersion by obtaining a powder having high heat resistance, color and bulk density of the F polymer. From the viewpoint of interlayer adhesion of the resin layer, etc., it is preferably 0.01 to 3 mol%, more preferably 0.03 to 2 mol%, and particularly preferably 0.05 to 1 mol%.

As a monomer having a carboxy group, itaconic acid, citraconic acid, 5-norbornene-2,3-dicarboxylic acid, maleic acid, acrylic acid and methacrylic acid can be mentioned.
As the alkoxycarbonyl group, CF ₂ CCFO (CF ₂ ) ₃ COOCH ₃ , vinyl acetate, vinyl chloroacetate, vinyl butanoate, vinyl pivalate, vinyl benzoate, (polyfluoroalkyl) acrylate, (polyfluoroalkyl) methacrylate Can be mentioned.
Examples of the monomer having a hydroxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl crotonate and allyl alcohol.
Examples of the monomer having an epoxy group include allyl glycidyl ether, 2-methyl allyl glycidyl ether, vinyl glycidyl ether, glycidyl acrylate and glycidyl methacrylate.
Examples of monomers having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 2- (2- (meth) acryloyloxyethoxy) ethyl isocyanate, and 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate. Be

The F polymer is also referred to as perfluoro (alkyl vinyl ether) (hereinafter also referred to as “PAVE”), hexafluoropropylene (hereinafter referred to as “HFP”) from the viewpoint of physical properties (fusing property, processability etc.) of the F polymer. It is preferable to further have a unit derived from at least one monomer selected from the group consisting of fluoroalkylethylene (hereinafter also referred to as “FAE”) and particularly preferable to further have a unit derived from PAVE. When the F polymer has the unit, the ratio of the unit to the total of all units of the F polymer is preferably 0.1 to 9.99 mol%, from the viewpoint of the moldability of the resin layer formed from the dispersion, 1 ~ 9.95 mol% is particularly preferred.

As PAVE, CF ₂ CCFOCF ₃ , CF ₂ (CFO (CF ₂ ) ₂ F, CF ₂ CCFO (CF ₂ ) ₃ F (hereinafter also referred to as “PPVE”), CF ₂ CCFO (CF ₂ ) ₄ F, CF ₂ CCFO (CF ₂ ) ₈ F, etc. are mentioned, and PPVE is preferable.
As the FAE, CH ₂ CHCH (CF ₂ ) ₂ F, CH ₂ CHCH (CF ₂ ) ₃ F, CH ₂ CHCH (CF ₂ ) ₄ F, CH ₂ CFCF (CF ₂ ) ₃ H, CH ₂ = _CF (CF _{2) 4} H can be _{_{mentioned, CH 2 = CH (CF 2}} ) 4 F and _{_{_{CH 2 = CH (CF 2)}}} 2 F are preferred.

The F polymer may further have units derived from other monomers. Such other _{_{_{_{monomers, CH 2 = CH 2, CH}}}} 2 = CHF, CH 2 = CF 2, CHF = CF 2, CF 2 = CFCl, CH 2 = CHCH 3, CH 2 = CFCF 3, CHF = CHCF 3 , CF ₂ CCFOCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ SO ₂ F, CF ₂ CFCFCF ₂ CF ₂ OCF = CF ₂ , perfluoro (2-methylene-4-methyl-1,3-dioxolane), perfluoro ( And 1,3-dimethyl-dioxole).

The F polymer has TFE units, functional units, and units derived from at least one monomer selected from the group consisting of PAVE, HFP and FAE, and the ratio of units to the total of all units is 90 to 90 in this order The F polymer which is 99.89 mol%, 0.01 to 3 mol%, 0.1 to 9.99 mol% is preferred.
The functional unit is preferably a unit derived from NAH, a unit derived from IAH and a unit derived from CAH, particularly preferably a unit derived from NAH.
HFP and PAVE are preferable, PAVE is more preferable, and PPVE is particularly preferable.
Furthermore, the F polymer in this case may have a functional group at the main chain terminus. In addition, the functional group may be further introduced by subjecting the F polymer in this case to plasma irradiation, corona irradiation, electron beam irradiation or radiation, or treating the powder of the polymer with a metal sodium-naphthalene solution.

The proportion of each unit contained in the F polymer can be measured by melt nuclear magnetic resonance (NMR) analysis, fluorine content analysis, infrared absorption spectrum analysis or the like. For example, as described in JP-A-2007-314720, the proportion (mol%) of functional units in all units constituting the F polymer can be measured using a method such as infrared absorption spectrum analysis.

The melting point of the F polymer is preferably 260 to 380 ° C., and particularly preferably 295 to 310 ° C. In this case, the moldability of the resin layer formed from the dispersion is also excellent. In particular, irregularities on the surface of the resin layer due to powder particles can be suppressed.
In addition, the F polymer is a melt-formable fluoropolymer having a temperature at which the melt flow rate is 0.1 to 1000 g / 10 min at a load of 49 N and at a temperature 20 ° C. or more higher than the melting point of the F polymer Is preferred. The "melt flow rate" means a melt mass flow rate (MFR) defined in JIS K 7210: 1999 (ISO 1133: 1997). The MFR is preferably 0.1 to 1000 g / 10 min, and particularly preferably 5 to 20 g / 10 min. In this case, the resin layer formed from the dispersion is excellent not only in surface smoothness and appearance but also in mechanical strength.
The relative dielectric constant of the F polymer is preferably 2.5 or less, more preferably 2.4 or less, and particularly preferably 2.0 to 2.4, from the viewpoint of the electrical properties of the resin layer formed from the dispersion.

The organic solvent in the present invention is a dispersion medium. The organic solvent is an inert component which is liquid at normal temperature (25 ° C.) and is a compound which does not react with the powder. The organic solvent may be a mixture of two or more compatible organic solvents, or may be a mixed solvent of a water-soluble organic solvent and water. As an organic solvent, the organic solvent which does not have a fluorine atom is preferable.
As an organic solvent, alcohol, ether, ester, ketone, glycol ether, cellosolve etc. are mentioned. Specifically, γ-butyrolactone, acetone, methyl ethyl ketone, hexane, heptane, octane, 2-heptanone, cycloheptanone, cyclohexanone, cyclohexane, methylcyclohexane, ethylcyclohexane, methyl n-pentyl ketone, methyl isobutyl ketone, methyl iso Pentyl 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 glycol mono Acetate, propylene glycol Diacetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexyl acetate, ethyl 3-ethoxypropionate, dioxane, methyl lactate, ethyl lactate, methyl acetate, methyl acetate, ethyl acetate, butyl acetate, pyruvate Methyl, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butylphenyl ether, benzene, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene , Toluene, xylene, cymene, mesitylene, methanol, ethanol, iso Propanol, butanol, methyl monoglycidyl ether, ethyl monoglycidyl ether, dimethylformamide, mineral spirits, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and various silicone oils.

The organic solvent in the present invention is preferably a compound having a boiling point lower than that of the other components contained in the dispersion of the present invention, and from the viewpoint of volatilization removability, the boiling point of the organic solvent is preferably 270.degree. Is particularly preferred.
The organic solvent in the present invention is preferably a compound having a boiling point of 70 to 260 ° C. selected from the group consisting of ketones, esters, amides and aromatic hydrocarbons, and aromatic hydrocarbons, chain ketones, cyclic ketones and lactones. Particularly preferred is a compound having a boiling point of 100 to 240 ° C. selected from the group consisting of

The organic solvent in the present invention is preferably an organic solvent having a surface tension of 30 dyn / cm or less in an embodiment in which the viscosity of the dispersion is 100 to 10000 mPa · s and the thixo ratio is 1.4 to 2.2. In this embodiment, in other words, when the external force applied to the dispersion is relatively weak, the viscosity of the dispersion is balanced to form a resin layer formed from the dispersion as a uniform film without unevenness. It can be said that it is an aspect excellent in workability.
The surface tension of the organic solvent in this aspect is more preferably 29 dyn / cm or less, still more preferably 28.5 dyn / cm or less. The upper limit thereof is not particularly limited, and is 1 dyn / cm or more. In this range, the wettability of the organic solvent to the surface of the powder is improved, and not only the powder dispersibility is excellent, but also the thixo ratio of the dispersion can be easily controlled within a predetermined range. It is also excellent in mixing with
Specific examples of such organic solvents include methyl ethyl ketone, toluene, xylene, cyclohexane and methyl cyclohexane.

The organic solvent in the present invention is preferably an organic solvent having a surface tension of more than 30 dyn / cm in an embodiment in which the viscosity of the dispersion is 50 to 3000 mPa · s and the thixo ratio is 1.0 to 1.5. In this embodiment, in other words, when the external force applied to the dispersion is relatively strong, the viscosity of the dispersion is balanced low to improve the mixing property between the dispersion and the different kinds of resin and the varnish, and It can also be said that it is an aspect excellent in coatability which improves the uniform dispersibility of the powder.
The surface tension of the organic solvent in this aspect is more preferably 31 dyn / cm or more, and still more preferably 32 dyn / cm or more. The upper limit thereof is not particularly limited, and is 100 dyn / cm or less. In this range, due to the polarity of the organic solvent, the surfactant is easily adsorbed on the particle surface of the powder, the powder is further easily dispersed in the organic solvent as a single particle, and the thixo ratio of the dispersion liquid is reduced. It is also excellent in the mixing property with the different resin of the liquid and the varnish.
Such organic solvents include cyclohexanone, cyclopentanone, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, preferably cyclopentanone, cyclohexanone and N-methyl-2-pyrrolidone, and cyclopentanone and Cyclohexanone is particularly preferred.

The surfactant in the present invention has a fluorine-containing group and a hydrophilic group.
In the present invention, the interaction between the powder and the organic solvent is likely to be strong under conditions where the external force such as shear applied to the dispersion is weak, and the interaction between the powder and the organic solvent under conditions such that the external force such as shear is applied to the dispersion. Is likely to decline. The surfactant according to the present invention interacts with both the powder and the organic solvent, so that the thixo ratio of the dispersion can be controlled within a predetermined range, and the aggregation of the powder in a stationary state such as storage can be suppressed. It is considered that the dispersion stability of the dispersion is improved.
Further, the surfactant in the present invention is easily adsorbed to the powder surface having a fluorine-containing group and a fluorine atom, and has a hydrophilic group and is easily extended in an organic solvent, so steric hindrance of the hydrophilic group The dispersion stability of the dispersion is improved in order to suppress the aggregation of the powder.

For example, when the powder is directly dispersed in a polar organic solvent such as methyl ethyl ketone, in addition to the interaction between the particles of the powder, the particles of the powder also repel the organic solvent, and the particles of the powder tend to aggregate. Stability tends to decrease. In contrast, the dispersion of the present invention contains a surfactant, which is likely to interact between the particles of the powder. As a result, the interaction between particles of the powder is weakened, the aggregation of the powder is less likely to occur, and the dispersion stability of the dispersion is improved. In addition, the powder is easily dispersed as single particles by the surfactant, aggregation of the powders when wetting the powder in the organic solvent is also suppressed, and the dispersibility of the dispersion in the dispersion is improved. The dispersion of the present invention is excellent in the mixing properties with different resin materials and their varnishes.

As the fluorine-containing group, groups having high hydrophobicity such as perfluoroalkyl group, perfluoroalkenyl group (hexafluoropropylene trimer group etc.) and the like can be mentioned. The carbon number of the fluorine-containing group is preferably 2 or more, and more preferably 4 to 20. -CF (CF ₃ ) C (= C (CF ₃ ) ₂ ) (CF (CF ₃ ) ₂ ) is preferable in that the fluorine-containing group is bulky and excellent in adsorption ability.
The hydrophilic group is a group relatively hydrophilic to a fluorine-containing group, and may be a general hydrophilic group, or a group usually regarded as a hydrophobic group, also containing fluorine. It may be a group relatively hydrophilic to the group. For example, a polyoxypropylene group is relatively hydrophobic to a hydrophilic group, a polyoxyethylene group, and is usually a hydrophobic group, but is relatively hydrophobic to a fluorine-containing group. It is a hydrophilic group in the present invention because
As a hydrophilic group, ethylene oxide (polyoxyethylene group), propylene oxide (polyoxypropylene group), butylene oxide (polyoxybutylene group), polyoxy tetramethylene group, amino group, ketone group, carboxyl group, sulfone group Can be mentioned. The hydrophilic group is preferably a polyoxyalkylene group consisting of an oxyalkylene group having 2 to 4 carbon atoms, and a polyoxyethylene group is particularly preferable.
The surfactant may also be a copolymer of a monomer having a fluorine-containing group and a monomer having a hydrophilic group. As such surfactant, a copolymer of a monomer having a fluorine-containing group and a monomer having a polyoxyalkylene group is particularly preferable.

The weight average molecular weight of the surfactant is preferably 1000 to 150000, more preferably 5000 to 100000, and particularly preferably 5000 to 30000. In this case, the surfactant is more easily adsorbed to the surface of the powder than the organic solvent, and the dispersibility and the dispersion stability of the dispersion are likely to be improved. In addition, the dispersion liquid is excellent in the mixing property with different resin materials, the varnish thereof, and the coatability. The mass average molecular weight of the surfactant is a value measured by gel permeation chromatography (GPC).

The surfactant in the present invention is preferably a nonionic surfactant.
As the surfactant, an optimum compound is appropriately selected depending on the type of organic solvent, and one surfactant may be used alone, or two or more surfactants may be used in combination. In the latter case, a surfactant having at least one fluorine-containing group and a hydrophilic group may be selected, and a surfactant having no fluorine-containing group may be selected as the other surfactant.

Specific examples of the surfactant include perfluoroalkyl group-containing Ftergent M series, Ftergent F 209, Ftergent 222F, Ftergent 208G, Ftergent 218GL, Ftergent 710FL, Ftergent 710FM, Ftergent 710FS, Ftergent 730FL , Futuregent 730 LM (made by Neos), Megafuck F-553, Megafuck F-555, Megafuck F-556, Megafuck F-557, Megafuck F-559, Megafuck F-562, Megafuck F- Examples thereof include Megafuck Series (manufactured by DIC Corporation) such as 565, and Unidyne Series (manufactured by Daikin Industries, Ltd.) such as Unidyne DS-403N. Among them, surfactant 710FL, surfactant 710FM, and surfactant 710FS, which are surfactants having a branched structure and a steric bulk, are preferable.

As a suitable aspect of surfactant in this invention, the main chain consists of a carbon chain derived from an ethylenically unsaturated monomer, and the copolymer which has a fluorine-containing hydrocarbon group and a hydrophilic group in a side chain is mentioned. The fluorine-containing hydrocarbon group is preferably a group having a tertiary carbon atom to which a plurality of (2 or 3) monovalent fluorine-containing hydrocarbon groups are bonded.
Specific examples of such surfactant include a copolymer (1) derived from a compound represented by the following formula (1) and a unit (2) derived from a compound represented by the following formula (2) However, F polymer is excluded.
CH ₂ = CR ¹ C (O) O-X ¹ -OC (-Y ¹ ) (-Z ¹ ) ₂ (1)
_{^{^{CH 2 = CR 2 C (O}}} ) O-X 2 -Q 2 -OH (2)
R ¹ and R ² each independently represent a hydrogen atom or a methyl group.
X ¹ and X ² each independently represent an alkylene group having 1 to 6 carbon atoms which may contain a hetero atom group, and-(CH ₂ ) ₂ -,-(CH ₂ ) ₃ -,-(CH ₂ ) ₂ ) ₄ -,-(CH ₂ ) ₂ NHC (O)-,-(CH ₂ ) ₃ NHC (O)-or -CH ₂ CH (CH ₃ ) NHC (O)-is preferable.
Y ¹ represents a hydrogen atom or a fluorine atom.
Z ¹ represents a fluoroalkyl group having 1 to 10 carbon atoms or a fluoroalkenyl group having 2 to 10 carbon atoms which may contain a hetero atom, and a trifluoromethyl group, a perfluoroalkenyl group having 2 to 10 carbon atoms or It is preferable that it is a C 4-10 fluoroalkyl group containing an etheric oxygen atom. The two Z ¹ may be identical or different.
Q ² represents a polyoxyalkylene group having 4 to 60 carbon atoms, and is preferably a polyoxyethylene group having 4 to 30 carbon atoms or a polyoxypropylene group having 6 to 50 carbon atoms.

The unit (1) is preferably contained in an amount of 20 to 60% by mole or less, and more preferably 20 to 40% by mole, relative to the total units of the copolymer.
The unit (2) is preferably contained in an amount of 40 to 80 mol%, particularly preferably 60 to 80 mol%, based on all units of the copolymer.
The ratio of the content of the unit (2) to the content of the unit (1) in the copolymer is preferably 1 to 5, and particularly preferably 1 to 2.
The copolymer may be composed only of the unit (1) and the unit (2), and may further contain units other than the unit (1) and the unit (2).
The fluorine content of the copolymer is preferably 10 to 45% by weight, particularly preferably 15 to 40% by weight.
The copolymer is preferably nonionic.
The weight average molecular weight of the copolymer is preferably 2,000 to 80,000, and particularly preferably 6,000 to 20,000.

Specific examples of the compound (1) _{_{_{is, 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), CH 2 = C (CH 3) COO (CH 2) 2 NHCOOCH (CH 2 OCH 2 CH 2 (CF ₂ ) ₆ F) ₂ , CH ₂ CC (CH ₃ ) COO (CH ₂ ) ₂ NHCOOCH (CH ₂ OCH ₂ CH ₂ (CF ₂ ) ₄ F) ₂ , CH ₂ CC (CH ₃ ) COO ( CH ₂ ) ₂ NHCOOCH (CH ₂ OCH ₂ (CF ₂ ) ₆ F) ₂ , CH ₂ CC (CH ₃ ) COO (CH ₂ ) ₂ NHCOOCH (CH ₂ OCH ₂ (CF ₂ ) ₄ F) ₂ , CH ₂ = C (C _{_{_{_{3) COO (CH 2) 3}}}} NHCOOCH (CH 2 OCH 2 (CF 2) 6 F) 2, CH 2 = C (CH 3) COO (CH 2) 3 NHCOOCH (CH 2 OCH 2 (CF 2) 4 F) ₂ is mentioned.

Specific examples of the compound (2) _{_{_{_{is, CH 2 = CHCOO (CH 2}}}} CH 2 O) 8 OH, CH 2 = CHCOO (CH 2 CH 2 O) 10 OH, CH 2 = CHCOO (CH 2 CH 2 O) 12 _{_{_{_{OH, CH 2 = C (CH}}}} 3) COO (CH 2 CH (CH 3) O) 8 OH, CH 2 = C (CH 3) COO (CH 2 CH (CH 3) O) 12 OH, CH 2 = C _{_{_{(CH 3) COO (CH 2}}} CH (CH 3) O) 16 OH and the like.

The content of the powder in the dispersion of the present invention is preferably 35 to 70% by mass, preferably 40 to 68% by mass, and more preferably 45 to 65% by mass, based on the total of the organic solvent, the powder and the surfactant. 47 to 60% by mass is more preferable. A dispersion liquid is further excellent in dispersion stability as content of powder is 35 mass% or more, and it becomes easy to control thixo ratio of a dispersion liquid in a predetermined | prescribed range. It becomes easy to control the viscosity of a dispersion liquid to a predetermined | prescribed range as content of powder is 70 mass% or less.

The content of the organic solvent in the dispersion liquid of the present invention is preferably 25 to 60% by mass, more preferably 27 to 55% by mass, and more preferably 30 to 50% by mass, based on the total of the organic solvent, the powder and the surfactant. Particularly preferred. A dispersion liquid is further excellent in coating property as content of an organic solvent is in the said range. When the content of the organic solvent is equal to or less than the upper limit value of the above range, appearance defects of a film or the like produced using the dispersion hardly occur. Such poor appearance often results from the operation of removing the organic solvent.

The content of the surfactant in the dispersion of the present invention is preferably 3.5 to 30% by mass, more preferably 4 to 15% by mass, based on the total of the organic solvent, the powder and the surfactant. -10% by weight is particularly preferred. A dispersion liquid is further excellent in a dispersibility and dispersion stability as content of surfactant is more than the lower limit of the said range. When the content of the surfactant is less than or equal to the upper limit value of the above range, the properties of the powder are less affected by the properties of the surfactant, and the dielectric constant and the dielectric loss tangent of the resin layer containing the powder can be easily lowered.

The ratio of the content of surfactant to the content of powder in the dispersion of the present invention (surfactant / powder) is preferably 1/99 to 30/70, more preferably 3/97 to 20/80, 5 / 95 to 17/83 is particularly preferred. A dispersion liquid is further excellent in dispersibility and dispersion stability as ratio of content of surfactant to content of powder is more than a lower limit of the above-mentioned range. When the ratio of the content of the surfactant to the content of the powder is below the upper limit value of the above range, the characteristics of the powder are less likely to be affected by the characteristics of the surfactant, and the dielectric constant and dielectric tangent of the resin layer containing the powder Makes it easy to lower

The dispersion of the present invention may contain a thixotropic agent as an optional component. As the thixotropic agent, for example, clay minerals such as clay, bentonite and hectorite, polyester emulsion resin, acrylic emulsion resin, polyurethane emulsion resin, emulsion such as blocked isocyanate, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, Hydroxypropyl cellulose, cellulose derivatives of hydroxypropyl methylcellulose, polysaccharides such as xanthan gum and guar gum, metal soap, hydrogenated castor oil, polyamide wax, benzylidene sorbitol, amide wax, linseed oil, modified urea, modified urethane, modified polyether And modified polyesters.

The dispersion of the present invention may contain an inorganic filler. As the inorganic filler, the filler described in [0089] of WO 2016/017801 can be mentioned. When the dispersion contains an inorganic filler, it is easy to lower the dielectric constant and the dielectric loss tangent of the resin layer containing powder.
The dispersion of the present invention may contain an antifoaming agent. As an antifoamer, a silicone type antifoamer and a fluoro silicone type antifoamer are mentioned. As a type of antifoaming agent, an emulsion type, a self emulsification type, an oil type, an oil compound type, a solution type, a powder type, a solid type, etc. are mentioned.

When the dispersion liquid of the present invention contains a thixotropic agent, the content of the thixotropic agent is preferably 0.1 to 20% by mass with respect to the total of the organic solvent, the powder and the surfactant, and 3 to 10 % By weight is particularly preferred. When the content of the thixotropic agent is within the above range, the thixo ratio and viscosity of the dispersion can be easily controlled within a predetermined range.
When the dispersion of the present invention contains an inorganic filler, the content of the inorganic filler is preferably 1 to 300% by mass, particularly preferably 30 to 60% by mass, based on the total of the organic solvent, the powder and the surfactant. In this case, the linear expansion coefficient of the film obtained from the dispersion is low, and the thermal dimensionality and the molding stability of the film are excellent.
When the dispersion of the present invention contains an antifoaming agent, the content of the antifoaming agent varies depending on the content (concentration) of the powder, etc., but the content of the antifoaming agent is an active ingredient relative to the total amount of the dispersion. As 1 mass% or less is preferable.

The method for producing the dispersion liquid of the present invention is not particularly limited, and examples thereof include a method in which an organic solvent, a powder and a surfactant are mixed, stirred and dispersed. As means for mixing and stirring, it is preferable to use a dispersing machine such as a homomixer, a high speed stirrer, an ultrasonic dispersing machine, a homogenizer, a wet ball mill, a bead mill, a wet jet mill and the like.

The dispersion of the present invention is, as described above, excellent in dispersibility, different kinds of resin materials, and the mixing property with the varnish thereof. The dispersion of the present invention is further different in different kinds of resin materials (F polymer, in the present invention It is preferable to mix with a surfactant, a component not corresponding to the component contained in the above-mentioned dispersion liquid of the present invention), or the varnish.
Hereinafter, a solution containing the dispersion liquid of the present invention, another resin material and another resin (hereinafter also referred to as “other resin”) which is soluble in the below-mentioned varnish solvent, and the varnish solvent It is also described as "coating liquid of the present invention". The coating liquid of the present invention is obtained by mixing the dispersion of the present invention and a varnish containing a varnish solvent and another resin. In addition, the dispersion liquid of the present invention and the coating liquid of the present invention are collectively referred to as a powder liquid of the present invention.

The other resin may be a resin that dissolves in the organic solvent in the present invention, or may be a resin that does not dissolve in the organic solvent in the present invention. The latter resin is preferably a resin that dissolves in an organic solvent other than the organic solvent in the present invention (hereinafter also referred to as "varnish solvent").
As an aspect of the coating liquid of this invention, the aspect which mixed the dispersion liquid of this invention, and a varnish solvent and the varnish containing other resin is mentioned.
Examples of the varnish solvent include the same compounds as the organic solvent (hereinafter also referred to as "first organic solvent") in the dispersion liquid of the present invention. The varnish solvent may be the same as or different from the first organic solvent. When the first organic solvent and the varnish solvent are different, the respective organic solvents may be compatible with each other.

When the viscosity of the dispersion of the present invention is 50 to 3000 mPa · s and the thixo ratio is 1.0 to 1.5, and a varnish solvent different from the organic solvent in the present invention is selected, the organic solvent and the varnish solvent in the present invention It is preferable to select the varnish solvent so that the surface tension of the mixed solvent consisting of and is more than 30 dyn / cm. This makes it easy to disperse the powder uniformly in the coating liquid.

The other resin may be a curable resin or a non-curable resin. The other resin may be a heat melting resin or a non-melting resin.
The curable resin is a resin which is cured by the reaction between the reactive groups which it itself has and the reaction with the curing agent. As a curable resin, a polymer, an oligomer, a low molecular weight compound etc. are mentioned. As a reactive group which a curable resin has, a carbonyl group containing group, a hydroxyl group, an amino group, an epoxy group etc. are mentioned. A thermosetting resin is preferable as the curable resin.

As a thermosetting resin, epoxy resin, thermosetting polyimide, polyamic acid which is a polyimide precursor, acrylic resin, phenol resin, polyester resin, polyolefin resin, modified polyphenylene ether resin, polyfunctional cyanate ester resin, polyfunctional maleimide Cyanate ester resins, multifunctional maleimide resins, vinyl ester resins, urea resins, diallyl phthalate resins, melanin resins, guanamine resins, melamine-urea cocondensation resins. Among them, thermosetting polyimides, polyimide precursors, epoxy resins, acrylic resins, bismaleimide resins and polyphenylene ether resins are preferable as thermosetting resins from the viewpoint of being useful for printed board applications, and epoxy resins and polyphenylene ether resins Is particularly 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, dicyclopentadiene epoxy resin, trishydroxyphenylmethane epoxy compound, phenol and phenolic hydroxyl group Epoxides of condensates with aromatic aldehydes, diglycidyl ether of bisphenol, diglycidyl ether of naphthalenediol, phenol Glycidyl ethers, diglycidyl ethers of alcohols, triglycidyl isocyanurate.

As a bismaleimide resin, a resin composition (BT resin) in which a bisphenol A type cyanate ester resin and a bismaleimide compound are used in combination as described in JP-A-7-70315, described in International Publication WO2013 / 008667 Inventions and those described in the background art.
The polyamic acid usually has a reactive group capable of reacting with the adhesive group.
Examples of diamines and polyvalent carboxylic acid dianhydrides that form polyamic acids include [0020] of Japanese Patent No. 5766125, [0019] of Japanese Patent No. 5766125, and [0055] of Japanese Patent Laid-Open No. 2012-145676. , And the like. Among them, aromatic diamines such as 4,4'-diaminodiphenyl ether and 2,2-bis [4- (4-aminophenoxy) phenyl] propane, and pyromellitic dianhydride, 3,3 ', 4,4 Preferred is a combination with an aromatic polyvalent carboxylic acid dianhydride such as '-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic acid dianhydride.

Examples of the heat melting resin include thermoplastic resins such as thermoplastic polyimide, and heat melting cured products of curing resins.
As a thermoplastic resin, polyester resin (polyethylene terephthalate etc.), polyolefin resin (polyethylene etc.), styrene resin (polystyrene etc.), polycarbonate, thermoplastic polyimide (aromatic polyimide etc.), polyarylate, polysulfone, polyallyl Sulfone (polyether sulfone etc.), aromatic polyamide, aromatic polyether amide, polyphenylene sulfide, polyallyl ether ketone, polyamide imide, liquid crystalline polyester, polyphenylene ether etc., thermoplastic polyimide, liquid crystalline polyester and polyphenylene Ether is preferred.
The melting point of the heat-meltable cured product of the heat-meltable resin and the curable resin is preferably 280 ° C. or more. Thereby, in a resin layer such as a film manufactured from a coating liquid, swelling (foaming) due to heat when exposed to an atmosphere corresponding to solder reflow is easily suppressed.

The coating liquid of the present invention may contain a curing agent. As a curing agent, a thermosetting agent (melamine resin, urethane resin, etc.), an epoxy curing agent (novolak type phenol resin, isophthalic acid dihydrazide, etc.), etc. may be mentioned.

The content of the powder in the coating liquid of the present invention is preferably 1 to 80% by mass, and more preferably 10 to 30% by mass, based on the total of the organic solvent, powder, surfactant, other resin and varnish solvent in the present invention. Particularly preferred. The resin layer obtained using a coating liquid as content of powder is more than the lower limit of the said range is excellent in an electrical property. It is easy to disperse | distribute powder uniformly in a coating liquid as content of powder is below the upper limit of the said range, and the resin layer obtained using a coating liquid is excellent in mechanical strength.

The total amount of the organic solvent in the coating liquid of the present invention is preferably 10 to 80% by mass, more preferably 20 to 60% by mass, based on the total of the organic solvent, powder, surfactant, other resin and varnish solvent in the present invention. More preferably, 30 to 50% by mass is particularly preferable. The viscosity of a coating liquid is balanced without becoming high too much that the total amount of an organic solvent is more than the lower limit of the said range, and it is further excellent in coating property. When the total amount of the organic solvent is not more than the upper limit value of the above range, the viscosity of the coating liquid is balanced without becoming too low, the coating property is further excellent, and the appearance defect of the resin layer obtained using the coating liquid It is hard to happen.
The method for producing the coating liquid of the present invention is not particularly limited, and a varnish solvent and another resin are mixed beforehand to prepare a varnish containing another resin, and the varnish and the dispersion liquid of the present invention are mixed. Can be manufactured.

The powder liquid of the present invention can be used, for example, in the production of films, fiber reinforced films, prepregs, and laminates described later.
The powder solution according to the invention can also be used for the production of insulating layers of flat conductors. For example, when producing an insulating layer containing any one of polyamide imide, polyimide, and polyester imide as a main component, dielectric constant of the insulating layer can be obtained by blending the powder liquid of the present invention with the insulating paint containing the resin. Can be reduced. The reduction of the dielectric constant of the insulating layer can be achieved by adding the powder of the present invention to the insulating paint, but from the viewpoint of dispersibility, it is preferable to use the powder liquid of the present invention for the insulating paint. As a specific example of the insulating layer, an insulating film described in JP-A-2013-191356 can be mentioned.

The powder liquid according to the invention can also be used for the production of seamless belts. For example, if a liquid composition containing a liquid containing a polyimide resin and a conductive filler and the powder liquid of the present invention is used, a seamless belt having excellent transportability and cleanability of a recording medium (paper) can be obtained. The seamless belt having excellent transportability and cleanability can be achieved by adding the powder of the present invention to a liquid containing a polyimide resin and a conductive filler, but from the viewpoint of dispersibility, the powder of the present invention is used as the powder of the present invention. It is preferred to use a solution. As a seamless belt, those described in JP-A-2011-240616 can be mentioned.

The present invention also provides a method for producing a film obtained by removing an organic solvent, which is obtained by forming a film using the powder liquid of the present invention. The film forming method is preferably coating on the surface of the carrier, and coating on the carrier forms a film consisting of a powder solution. After the film of the powder liquid is formed, the organic solvent is volatilized by heating the film of the powder liquid or the like, the solid film from which the organic solvent is removed, at least a portion of the liquid medium is removed. A fluid film is formed. Note that removal of the organic solvent is also referred to as "drying".
In the drying, it is preferable to remove 50% by mass or more of the organic solvent contained in the powder solution of the present invention. As the drying method, the methods described in [0091] to [0094] of WO 2018/16644 can be mentioned.

When the membrane provided on the carrier is separated from the carrier, a film is obtained. The membrane can be easily separated from the carrier by using the carrier having a non-adhesive surface as the carrier. Moreover, in this case, it is preferable to apply a surface treatment or the like to reduce adhesion in advance to the carrier. In addition, in the case of a carrier having a highly adhesive surface, the carrier may be removed by means such as dissolving the carrier. For example, in the case of a metal carrier, the carrier can be removed by etching or the like.

The thickness of the film of the present invention is preferably 1 to 1000 μm, except for the fiber reinforced film and the prepreg described later. For printed circuit board applications, the thickness of the film is more preferably 1 to 100 μm, and particularly preferably 1 to 15 μm.
The relative dielectric constant of the film of the present invention is preferably 2.0 to 3.5, and particularly preferably 2.0 to 3.0. When the relative dielectric constant is in the above range, it is excellent in both the electrical properties and the fusion bondability, and is particularly useful as a laminate such as a metal laminate and a printed board.

It is preferable that the film of this invention contains 80 mass% or more of F polymer with respect to the whole quantity of a film. In this case, the thermal expansion change ratio and the thermal contraction change ratio of the film of the present invention are preferably 1.0 to 1.4, and more preferably 1.0 to 1.3, except for the fiber reinforced film and the prepreg described later. The curvature of a laminated body is suppressed as thermal expansion change ratio or heat contraction change ratio is in the said range.
The thermal expansion change ratio and the thermal contraction change ratio are thermal mechanical analysis devices (thermal expansion coefficient or thermal contraction ratio in the longitudinal direction (MD) and continuous direction (TD) during continuous production of the film). Measurement mode: Temperature transition from 30 ° C to 100 ° C using tensile mode, measurement temperature: 30 ° C to 100 ° C, measurement load: 19.6mN, heating rate: 5 ° C / min, measurement atmosphere: nitrogen gas) It can be determined from the respective coefficient of thermal expansion and coefficient of thermal contraction. Specifically, it is determined as the ratio of the maximum value among the respective thermal expansion coefficient and the thermal contraction ratio to the respective minimum value among the thermal expansion coefficient and the thermal contraction ratio.

The present invention can provide a fiber-reinforced film by impregnating the powder liquid of the present invention on a reinforcing fiber base placed on a carrier to form a film, that is, drying and then heating.
The form of the reinforcing fiber base is preferably in the form of a sheet from the viewpoint of the mechanical properties of the fiber reinforcing film, and a cross base obtained by weaving a reinforcing fiber bundle consisting of a plurality of reinforcing fibers, a plurality of reinforcing fibers are drawn in one direction Aligned substrates, substrates on which they are stacked are preferred.
The reinforcing fiber is preferably a continuous long fiber having a length of 10 mm or more. The reinforcing fibers may be divided in the middle.
As the reinforcing fiber, inorganic fiber, metal fiber, organic fiber and the like can be mentioned.
Examples of inorganic fibers include carbon fibers, graphite fibers, glass fibers, silicon carbide fibers, silicon nitride fibers, alumina fibers, silicon carbide fibers, boron fibers and the like.
Examples of metal fibers include aluminum fibers, brass fibers, stainless steel fibers and the like.
Examples of organic fibers include aromatic polyamide fibers, polyaramid fibers, polyparaphenylene benzoxazole (PBO) fibers, polyphenylene sulfide fibers, polyester fibers, acrylic fibers, nylon fibers, polyethylene fibers and the like.

The fiber reinforced film of the present invention can also be used for the production of metal laminates and printed boards.
The thickness of the fiber reinforced film is preferably 1 to 3000 μm. In the case of printed circuit board applications, the thickness of the fiber reinforced film is more preferably 3 to 2000 μm, particularly preferably 6 to 500 μm.
The relative dielectric constant of the fiber reinforced film is preferably 2.0 to 3.5, and particularly preferably 2.0 to 3.0. When the relative dielectric constant is in the above-mentioned range, it is easy to achieve both electrical properties such as printed circuit board application and fusion bonding.

The present invention can also provide a prepreg if the powder liquid of the present invention is impregnated into a reinforcing fiber base disposed on a carrier and dried. The production of the prepreg is the same as the production of the fiber reinforced film except that heating after drying is not performed or is performed without sufficient heating. That is, the prepreg may be said to be a film containing reinforcing fibers and powder not melted (or not sufficiently melted), and optionally containing an uncured curable resin.
In the production of a prepreg, it is preferable to impregnate the coating fluid of the present invention into a reinforcing fiber substrate. The coating liquid in this case preferably contains an uncured curable resin.

In the drying in the production of the prepreg, it is preferable to remove 70% by mass or more of the total amount of the organic solvent contained in the coating liquid of the present invention.
Prepregs can be used as molding materials and can be used in the manufacture of metal laminates and printed circuit boards. In addition, the prepreg of the present invention is also used as a material for manufacturing various materials such as materials of sheet piles, which are required to be durable and lightweight in quay work, aircraft, automobiles, ships, windmills, sports equipment, etc. It can be used.
The specific dielectric constant of the prepreg is preferably 2.0 to 4.0, and particularly preferably 2.0 to 3.5. When the relative dielectric constant is in the above-mentioned range, it is easy to achieve both electrical properties such as printed circuit board application and fusion bonding.

In the method for producing a laminate of the present invention, the resin layer is formed on a substrate using the powder liquid of the present invention, the organic solvent is removed, and a resin layer containing F polymer is provided on the substrate. The manufacturing method of the layered product which it has on the surface of a substrate can also be provided. In other words, the method for producing a laminate of the present invention corresponds to a method for obtaining a laminate having a film and a carrier without separating the carrier and the film in the method for producing a film described above. That is, the substrate corresponds to the carrier, the resin layer corresponds to the film, and the substrate having the resin layer on the surface corresponds to the laminate. The resin layer may be a fiber reinforced film or a prepreg.

It does not specifically limit as a base material, A metal film, a heat resistant resin film, a metal vapor deposition heat resistant resin film etc. are mentioned, A metal film (metal foil) is preferable.
As a metal which comprises a metal film (metal foil), copper, its alloy, stainless steel, its alloy, titanium, its alloy etc. are mentioned. As a metal film (metal foil), copper films (copper foil), such as a rolled copper foil and an electrolytic copper foil, are preferable. A rustproof layer (for example, an oxide film such as chromate) or a heat resistant layer may be provided on the surface of the metal film (metal foil). In addition, in order to improve the adhesion to the resin layer, the surface of the metal film (metal foil) may be treated with a silane coupling agent. The thickness of the metal film (metal foil) is not particularly limited.
As a metal vapor deposition heat resistant resin film, the film which vapor-deposited metal by vapor deposition methods, such as a vacuum vapor deposition method, sputtering method, the ion plating method, is mentioned to single side | surface or both surfaces of the following heat resistant resin film.

The heat resistant resin film is a film containing one or more kinds of heat resistant resins. However, the heat resistant resin film does not contain F polymer. The heat resistant resin film may be a single layer film or a multilayer film. The heat resistant resin means a polymer compound having a melting point of 280 ° C. or more, or a polymer compound having a maximum continuous use temperature of 121 ° C. or more as defined in JIS C 4003: 2010 (IEC 60085: 2007). As the heat resistant resin, for example, polyimide (aromatic polyimide etc.), polyarylate, polysulfone, polyallyl sulfone (polyether sulfone etc.), aromatic polyamide, aromatic polyether amide, polyphenylene sulfide, polyallyl ether Ketone, polyamide imide, liquid crystal polyester and the like can be mentioned.
As a heat resistant resin film, a polyimide film and a liquid-crystal polyester film are preferable. The polyimide film may contain an additive, as needed, insofar as the effects of the present invention are not impaired. The heat resistant resin film may be subjected to surface treatment such as corona discharge treatment or plasma treatment on the surface on which the resin layer is provided. As a heat resistant resin film, a liquid crystalline polyester film is more preferable from the point which is excellent in an electrical property.

In the method for producing a laminate of the present invention, the resin layer may be provided on only one side in the thickness direction of the substrate, or may be provided on both sides. It is preferable to provide a resin layer on both surfaces of a base material in that it is easy to suppress the warp of the laminate and to obtain a metal laminate excellent in electrical reliability. In this case, after applying and drying the powder solution of the present invention on one side of the substrate, it is preferable to apply and dry the powder solution of the present invention on the other side.

The coating liquid of the present invention has an arbitrary thickness such as a thick film resin layer (particularly, a film thickness of 1 μm or more) which is excellent in properties such as surface smoothness because the viscosity and the thixo ratio are within a predetermined range. Suitable for forming.
The thickness of the resin layer of the laminate of the present invention is preferably 0.5 to 30 μm when the filler contained in the resin layer is less than 10% by volume. In the case of printed circuit board use, the thickness of the resin layer is more preferably 0.5 to 25 μm, further preferably 1 to 20 μm, and particularly preferably 3 to 15 μm. In a preferable range, the warpage of the laminate is suppressed. When the filler contained in the resin layer is 10% by volume or more, 0.5 to 3000 μm is preferable. In the case of printed circuit board use, the thickness of the resin layer is more preferably 1 to 1500 μm, particularly preferably 2 to 100 μm.
In the case of a laminate having a resin layer on both sides of the substrate, it is preferable that the composition and thickness of each resin layer be the same in terms of suppression of warpage of the laminate.

25% or less is preferable, 15% or less is more preferable, 10% or less is further more preferable, and the curvature rate of the laminated body of this invention is especially preferable. In this case, in the molding process at the time of processing, the handling property is excellent and the processed product is excellent in dielectric characteristics.
When the powder liquid of the present invention contains an inorganic filler or contains polychlorotrifluoroethylene or the like, warpage of the laminate can be further suppressed.

The relative dielectric constant of the resin layer of the laminate of the present invention is preferably 2.0 to 3.5, and particularly preferably 2.0 to 3.0. It is useful for the use for which the low dielectric constant is calculated | required, such as a printed circuit board use as a relative dielectric constant is below the upper limit of the said range. A laminated body is excellent in an electrical property and fusing property as a dielectric constant is more than the lower limit of the said range. In addition, when a base material consists of nonelectroconductive materials, such as heat resistant resin, the relative dielectric constant of the whole laminated body also has the preferable said range.

The object to be laminated may be laminated on the surface of the resin layer of the laminate of the present invention. In this case, a film or a laminate produced by the production method of the present invention may be applied as a lamination target.
When laminating an object to be laminated on the surface of the resin layer, the substrate surface or the resin layer surface of the object to be laminated is laminated on the exposed surface of the resin layer. When laminating the resin layers, an object of lamination such as a prepreg may be interposed between the resin layer surfaces to be laminated.

When laminating an object to be laminated such as a film or sheet on the surface of the resin layer of the laminate, the resulting laminate has excellent bonding strength and bubbles and the like do not easily remain, so the exposed surface of the resin layer is smoothed. It is preferable to use a high-quality surface. In order to improve the smoothness of the exposed surface of the resin layer, it is preferable to laminate at a temperature at which the film after drying is sufficiently melted, and to press with a heating plate, a heating roll or the like.

Arithmetic mean roughness Ra of the surface of the exposed surface of the resin layer of the laminate is less than the resin layer thickness, and is preferably 2.0 μm or more. Thereby, when laminating | stacking a lamination | stacking target object by heat press etc., the adhesiveness between a resin layer and a lamination | stacking target object is further excellent.
The Ra is less than the resin layer thickness, preferably 2.0 to 30 μm, and most preferably 2.2 to 8 μm. In this case, not only the adhesion between the resin layer and the object to be laminated is excellent, but it is difficult to form through holes in the resin layer. Also, in order to increase the bonding strength, the surface of the resin layer may be subjected to surface treatment such as corona discharge treatment or plasma treatment.

The film and laminate of the present invention can be used for applications of producing a new laminate by laminating with a lamination target in the form of a film or sheet made of a material other than metal. As an object to be laminated, a film or sheet of heat resistant resin, a fiber reinforced resin sheet, a prepreg, etc. may be mentioned.
Examples of the prepreg include those in which a sheet-like reinforcing fiber base material is impregnated with a matrix resin.
The matrix resin may be a thermoplastic resin or a thermosetting resin. The present invention is particularly effective when using a thermoplastic resin having a melting point of 280 ° C. or less or a thermosetting resin having a thermosetting temperature of 280 ° C. or less as a matrix resin from the viewpoint of low temperature bonding.
A commercially available prepreg may be used as the prepreg.
As a commercially available prepreg, the prepreg described in [0133] of WO 2018/16644 can be mentioned.

The temperature at which the film or laminate of the present invention and the prepreg are heat-pressed is preferably equal to or lower than the melting point of the F polymer, and more preferably 120 to 300 ° C. In this case, the film or the laminate and the prepreg can be attached with excellent adhesion while suppressing thermal deterioration of the prepreg.

The film and the laminate obtained by the production method of the present invention can also be used as a coated article such as a capture substrate of an organic EL display described in [0040] to [0044] of WO 2015/182702. The prepreg of the present invention can also be used for FRP and CFRP described in [0046] of WO 2015/182702. The powder liquid of the present invention can also be used as a solvent-based paint described in WO 2015/182702, and can also be used as an insulating paint that constitutes the insulating layer of the insulated wire described in Japanese Patent No. 2686148. .

The present invention can also provide a method for producing a metal laminate in which a film (including a fiber reinforced film and a film of a prepreg) is produced by the method for producing a film of the present invention and a metal layer is provided on the surface of the film. Moreover, in the method for producing a metal laminate of the present invention, a laminate may be produced by the method for producing a laminate of the present invention, and a metal layer may be provided on the surface of the resin layer of the laminate.
As a method of providing a metal layer on one side or both sides of a film or a laminate, for example, a method of laminating a film or a laminate and a metal foil, a method of depositing metal on the surface of a resin layer of a film or a laminate, etc. Be As a lamination method, a thermal lamination etc. are mentioned, for example. As a metal vapor deposition method, a vacuum vapor deposition method, a sputtering method, an ion plating method, etc. may be mentioned.

The layer configuration of the metal laminate includes the film / metal layer of the present invention, the metal layer / film of the present invention / metal layer, the laminate layer of the present invention / metal layer, the metal layer / the laminate of the present invention layer / metal layer And a laminate of However, the layer in the laminate in contact with the metal layer is a resin layer. In addition, "film / metal layer" shows that a film and a metal layer are laminated | stacked in this order, and the other layer structure is also the same.

The metal laminate obtained by the production method of the present invention has a resin layer on one side or both sides of the metal layer. Especially as a metal layer, copper foil is preferable. The resin layer may have reinforcing fibers, and may be a layer of prepreg (that is, a resin layer containing reinforcing fibers and uncured curable resin).
The metal laminate having a copper foil layer may be a metal laminate having a plurality of copper foil layers by laminating a plurality of sheets. When the metal laminated board which has these copper foil layers has a resin layer in the single side | surface or both surfaces, it is preferable to laminate a copper foil layer on the resin layer surface. The metal laminate having a copper foil layer obtained by the method for producing a metal laminate of the present invention and the laminate thereof can be used as a flexible copper-clad laminate or a rigid copper-clad laminate.
Hereinafter, the manufacturing method of the metal laminated board of this invention is further demonstrated by making a metal laminated board which has a copper foil layer into an example.

A metal laminate having a copper foil layer uses a copper foil as a substrate, applies the powder solution of the present invention on one side of the copper foil to form a film thereof, and then removes the organic solvent by heat drying, Subsequently, it is preferably heated to melt the powder and then cooled to produce a metal laminate having a uniform resin layer free of unmelted particles. It may be manufactured by providing a resin layer on both sides of the copper foil.

Film formation from the powder solution of the present invention, heating and drying, and melting of the powder can be carried out under the same conditions as in the film production method. For example, when heating after drying is performed by heating with a heat roll, a metal laminate having a dried unmelted resin layer and a copper foil layer is brought into contact with a heat-resistant roll and transported while being irradiated with far infrared rays. The molten resin layer can be a molten resin layer. The roll transport speed is preferably 4.7 to 0.31 m / min when using a 4.7 m heating furnace, and 4.7 to 4.7 when using a 2.45 m heating furnace. 2.45 m / min is preferable. The heating temperature is preferably 330 to 380 ° C., and more preferably 350 to 370 ° C., where the residence time of the heating furnace is one minute.

15 micrometers or less are preferable, as for the thickness of the resin layer of a metal laminated board, 10 micrometers or less are more preferable, and 8 micrometers or less are especially preferable. The lower limit is not particularly limited, and is 1 μm. The curvature can be suppressed even in the case of the asymmetrical layer constitution of the resin layer / copper foil as it is not more than the upper limit value of the above range. The warp rate of the metal laminate is preferably 25% or less, and particularly preferably 7% or less. It is excellent in the handling property in the formation process at the time of processing into a printed circuit board as a curvature rate is 25% or less, and excellent in the dielectric characteristic as a printed circuit board.

When the powder liquid of the present invention contains a thermosetting resin, a metal laminate having a resin layer containing a cured thermosetting resin and a copper foil layer can be produced. In this case, the powder liquid of the present invention may contain a filler, and a fiber reinforced resin layer may be provided on the copper foil layer using reinforcing fibers. 200 micrometers or less are preferable and, as for the thickness of the resin layer in this case, 100 micrometers or less are more preferable. In this case, the printed circuit board manufactured from the powder liquid of the present invention is excellent in the processability of hole processing, and an electronic circuit excellent in connection reliability can be formed. In addition, if the resin layer contains a filler, warpage can be further suppressed.

In the manufacture of a metal laminate, the annealing process can reduce the linear expansion coefficient in the thickness direction. As a result, it is possible to reduce variations in the electrical characteristics of the substrate due to peeling between the interface of the base material and the resin layer and thickness unevenness in the plane of the metal laminate.
As the annealing conditions, the temperature is preferably 80 to 190 ° C., and particularly preferably 120 to 180 ° C. The treatment time is preferably 10 to 300 minutes, and particularly preferably 30 to 120 minutes. In this case, the linear expansion coefficient can be easily reduced while suppressing the thermal deterioration of the resin layer.
The pressure for annealing is preferably 0.001 to 0.030 MPa, and particularly preferably 0.005 to 0.015 MPa. In this case, it is easy to reduce the linear expansion coefficient of the resin layer while suppressing the compression of the base material.

In the method for producing a metal laminate of the present invention, for example, a resin layer may be provided on one side or both sides of titanium foil to produce a metal laminate having a titanium foil and a resin layer. The thickness of the resin layer is preferably 10 μm or less. By laminating the fiber reinforced composite material on the resin layer side of such a metal laminate, for example, a metal laminate of titanium foil / resin layer / fiber reinforced composite can be obtained. As a fiber reinforced composite material, a carbon fiber reinforced composite material is particularly preferable.

As a layer configuration of a metal laminate having a resin layer and an object to be laminated, a laminate of metal layer / resin layer / object to be laminated / resin layer / metal layer, metal layer / object to be laminated / resin layer / object to be laminated / Laminate of metal layer etc. may be mentioned. The thickness of the resin layer is preferably 0.1 to 300 μm, and particularly preferably 2 to 40 μm. In this case, not only the hole forming processability as the metal laminate is good and the dielectric property is excellent, but the metal layer and the resin layer, and the lamination target object and the resin layer can be stuck with excellent adhesion. 5 N / cm or more is preferable and, as for the adhesiveness (peeling strength) of the film or laminated body manufactured by the manufacturing method of this invention, and a lamination | stacking target object, 7 N / cm or more is especially preferable.

The present invention can also provide a method for producing a printed circuit board in which a metal laminate is produced by the method for producing a metal laminate of the present invention, and a metal layer of the metal laminate is etched to form a patterned circuit. As a manufacturing method of a printed circuit board, the method of etching the metal layer of the metal laminated board obtained by the manufacturing method of this invention, for example, and forming a pattern circuit is mentioned. The method of etching the metal layer is not particularly limited.

In the method of manufacturing a printed circuit board according to the present invention, after the metal layer is etched to form the pattern circuit, the interlayer insulating film may be formed on the pattern circuit, and the pattern circuit may be further formed on the interlayer insulating film. The interlayer insulating film can also be formed by the powder solution of the present invention.
For example, after etching a metal layer of a metal laminate plate of an arbitrary laminated structure to form a patterned circuit, the powder solution of the present invention is applied on the patterned circuit, dried and then heated to form an interlayer insulating film. Then, a metal layer may be provided on the interlayer insulating film by vapor deposition or the like and etched to form a further pattern circuit.
In the manufacture of a printed circuit board, a solder resist may be laminated on a pattern circuit. Specifically, the dispersion liquid and the coating liquid of the present invention may be applied onto a pattern circuit, dried and then heated to form a solder resist.

In the production of a printed circuit board, a coverlay film may be laminated. The coverlay film is typically composed of a base film and an adhesive layer provided on the surface thereof, and the surface on the adhesive layer side is bonded to the printed circuit board. As a cover lay film, the film of the present invention can be used, for example. In addition, an interlayer insulating film using a film obtained by the manufacturing method of the present invention is formed on a pattern circuit formed by etching a metal layer of a metal laminate, and a polyimide film as a coverlay film is formed on the interlayer insulating film. It may be stacked.

The printed circuit board of the present invention is useful as a radar, a network router, a backplane, an electronic device substrate such as a wireless infrastructure, a substrate for various sensors for automobiles, and a substrate for an engine management sensor, which require high frequency characteristics. It is suitable for the application aiming at transmission loss reduction of a millimeter wave band.

Examples of the insulated wire include an insulated wire in which an insulating coating layer having a thickness of 10 to 150 μm is provided on the outer periphery of a flat wire using the powder liquid of the present invention. The dielectric constant of the insulating covering layer is preferably 2.8 or less. Further, the adhesion strength between the insulating coating layer and the metal used in the flat wire is preferably 10 N / cm or more. The insulated wire is suitable as any device of an insulation amplifier, an insulation transformer, an alternator of a car, and a motor of a hybrid car.

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto.
The abbreviations have the following meanings.
TFE: tetrafluoroethylene.
NAH: anhydrous hymic acid.
PPVE: Perfluoro (propyl vinyl ether).
a ₁ : the ratio of the powder to the total of the organic solvent, the powder and the surfactant.
a _2: ratio of the surfactant to the total of the organic solvent and the powder and surfactant.
a ₃ : the ratio of the organic solvent to the total of the organic solvent, the powder and the surfactant.
b ₁ : ratio of the ratio of surfactant to the ratio of powder (a ₂ / a ₁ ).
η ₁ : viscosity measured under the condition of 30 rpm.
η ₂ : Viscosity measured under the condition of 60 rpm.
η ₁ / η ₂ : Thixo ratio.

The materials used are shown below.

<Fluoropolymer>
Polymer 1: A copolymer comprising 97.9 mol%, 0.1 mol%, 2.0 mol% of a unit derived from TFE, a unit derived from NAH and a unit derived from PPVE in this order, having a melting point of 300 ° C. Fluoropolymer.
Polymer 2: A substantially TFE homopolymer containing 99.5 mol% or more of a TFE-derived unit having no functional group (manufactured by Asahi Glass Co., Ltd., L169J).

<Surfactant>
Compound _{_{1: -OCF (CF 3) C}} (= C (CF 3) 2) (CF (CF 3) 2) having a (meth) acrylate and polyoxyethylene group having a group (meth) acrylate copolymer (nonionic Surfactant: Neos Co., Inc., Watergent 710 FL).
Compound _{_{2: -OCF (CF 3) C}} (= C (CF 3) 2) (CF (CF 3) 2) having a (meth) acrylate and polyoxyethylene group having a group (meth) acrylate copolymer (nonionic Surfactant: Neos Co., Ltd., Phaser 710 FM).

<Organic solvent>
MEK: methyl ethyl ketone (surface tension 24 dyn / cm).
Tol: toluene (surface tension 28.5 dyn / cm).
CHN: cyclohexanone (surface tension 34 dyn / cm).
NMP: N-methyl-pyrrolidone (surface tension 41 dyn / cm)
MEK & CHN: A mixed solvent of 70% by mass of MEK and 30% by mass of CHN (surface tension 27 dyn / cm).

<Powder>
Powder X1: a powder of polymer 1 having a D50 of 1.7 μm, a D90 of 3.8 μm, a loosely packed bulk density of 0.269 g / mL and a closely packed bulk density of 0.315 g / mL. The pellet of polymer 1 (particle diameter 1554 μm) is ground twice using a jet mill and further classified using a high efficiency precision air flow classifier.
Powder X2: a powder of polymer 2 having a D50 of 3.0 μm, a D90 of 8.5 μm, a loosely packed bulk density of 0.355 g / mL, a closely packed bulk density of 0.387 g / mL. It is obtained by crushing the pellet of polymer 2.

The analysis conditions are shown below.

Powder D50 and D90
The powder of the polymer was dispersed in water, and measured using a laser diffraction / scattering type particle size distribution measuring apparatus (LA-920 measuring apparatus manufactured by Horiba, Ltd.).

<Viscosity of dispersion>
The temperature was measured with a B-type viscometer (LVDV2T model, manufactured by Brookfield) under the conditions of 25 ° C. and 30 rpm.

<Surface tension of organic solvent>
It was measured with a surface tension meter (DY-200, manufactured by Kyowa Interface Science Co., Ltd.).

<Dispersion stability of dispersion>
The dispersion state of the dispersion after standing for 3 days was visually confirmed and evaluated according to the following criteria.
1: The powder settles and can not be redispersed even if shaken (hard caked).
2: Precipitation of powder is confirmed, but re-dispersion is possible if shaken.
3: A slight sedimentation of powder is confirmed, but it can be redispersed by shaking.

<Coatability of Dispersion>
The dispersion was used to form a film on a copper foil and coated with a wire bar (No. 14 manufactured by Tester Sangyo Co., Ltd.). After coating, the organic solvent was dried and removed at a temperature 5 ° C. lower than the boiling point of the organic solvent to obtain a test piece in which a resin layer was provided on a copper foil. The film thickness of the test piece is about 50 μm when applied uniformly. The test piece after drying the organic solvent is laminated with a resin layer containing powder, and is visually a white layer. However, when there is coating unevenness and the film thickness is thin, the color of the copper foil of the substrate is visible, so that the degree of whiteness is dark and light, and the presence or absence of the coating unevenness can be visually judged. The test piece was visually confirmed, and the coatability was evaluated based on the following criteria.
1: The powder layer on the substrate is coated unevenly, and there is light and shade on the appearance of the powder layer or the color of the substrate is exposed.
2: The powder layer on the substrate was uniformly coated, and there was almost no light and shade on the appearance of the powder layer.

<Film physical properties>
It formed into a film on a copper foil base material using a coating liquid with a wire bar, and was made to dry by oven at 180 ° C for 7 minutes. The dielectric constant of the obtained film was measured, and the film physical properties were evaluated based on the following criteria.
1: The dielectric constant of the film fluctuated from 3.2 which is a reference value.
2: The dielectric constant of the film does not fluctuate from the reference value of 3.2.

Melting point of polymer
Using a differential scanning calorimeter (DSC apparatus) manufactured by Seiko Instruments Inc., record the melting peak when the temperature of the fluorine-containing copolymer is raised at a rate of 10 ° C./min, and the temperature (° C.) corresponding to the maximum value is the melting point did.

[Example 1]
A horizontal ball mill container was filled with 50 g of Compound 1 and 500 g of MEK with respect to 450 g of Powder X1, and a dispersion of Example 1 was obtained using zirconia balls of 15 mm in diameter. The viscosity of the dispersion of Example 1 was η ₁ of 250 mPa · s, η ₂ of 150 mPa · s, and the thixo ratio of 1.7. The dispersion stability and coatability of the dispersion of Example 1 were evaluated. The results are shown in Table 2.

[Examples 2 to 7]
A dispersion was obtained in the same manner as in Example 1 except that the compositional ratio shown in Table 1 was changed. About the obtained dispersion liquid, (eta) ₁ and (eta) ₂ were measured, thixo ratio was calculated, and dispersion stability and coating property were evaluated. The results are shown in Table 2.

[Example 8]
A horizontal ball mill container was filled with 50 g of Compound 2 and 450 g of CHN relative to 500 g of Powder X1, and a dispersion of Example 8 was obtained using zirconia balls of 15 mm in diameter. The viscosity of the dispersion was η ₁ of 150 mPa · s, η ₂ of 130 mPa · s, and the thixo ratio of 1.2. The dispersion stability of the obtained dispersion was "3".
Next, an epoxy resin main agent (DIC, EPICLON HP-7200H-75M, solvent: MEK, solid content: 75% by mass) and a curing agent for epoxy resin (DIC, Inc., Phenolite TD-2090-60M, solvent) : MEK, solid content: 60% by mass) were mixed so that solid content in the main agent: solid content in the curing agent was 26: 9 (mass ratio), to prepare an epoxy varnish containing an epoxy resin. The solid content concentration of the epoxy varnish is 70% by mass. Next, the epoxy varnish and the dispersion liquid were mixed so that solid content: powder in the epoxy varnish was 70:30 (mass ratio). The mixing was stirred for 5 minutes under the condition of 1000 rpm with a stirrer. The viscosity of the obtained powder-containing varnish (coating liquid) was 520 mPa · s. Moreover, the surface tension of the organic solvent in the coating liquid was 28 dyn / cm.
Next, the dielectric constant of the film obtained using a coating liquid was measured, and the film physical property was evaluated.

[Examples 9-14]
A dispersion was obtained in the same manner as in Example 8 except that the compositional ratio shown in Table 3 was changed. For each dispersion, η ₁ and 測定₂ were measured, the thixo ratio was calculated, and the dispersion stability was evaluated.
Next, in the same manner as in Example 8, the respective dispersions and the epoxy varnish were mixed to obtain a powder-containing varnish (coating liquid). Films were produced using each of the coating solutions, and the physical properties of the films were evaluated. The results are shown in Table 4.

[Example 15]
A dispersion is prepared in which powder X1 is uniformly dispersed in CHN, containing 50% by mass, 5% by mass and 45% by mass of powder X1, compound 1 and CHN in this order at 25 ° C., and allowed to stand at 5 ° C. for 7 days did. The dispersion after standing was separated into two layers of a transparent layer and a white layer, and when shaken by hand, it was easily redispersed to form a uniform dispersion. On the other hand, when NMP is used instead of CHN, the dispersion after standing is separated into two layers of a yellow transparent layer and a white layer caused by the compound 1, and it is easy to be shaken again by hand. It did not disperse.

Films, fiber reinforced films, prepregs, metal laminates, printed boards, etc. obtained by the present invention are antenna parts, printed boards, parts for aircraft, parts for automobiles, sports equipment, food industry articles, saws, sliding bearings, etc. It can be used as an article etc.
In addition, Japanese Patent Application Nos. 2017-250952 filed on Dec. 27, 2017 and Japanese Patent Application No. 2018-094782 filed on May 16, 2018, all claims, and abstracts thereof. The contents are incorporated herein by reference and incorporated as disclosure of the specification of the present invention.

Claims

A dispersion comprising an organic solvent, a powder and a surfactant, wherein the powder is dispersed in the organic solvent, wherein the powder is derived from a unit derived from tetrafluoroethylene, a carbonyl group-containing group, a hydroxy group, an epoxy group and an isocyanate group A dispersion comprising a fluoropolymer having at least one functional group selected from the group consisting of
The viscosity is 100 to 10000 mPa · s, and the viscosity measured at 30 rpm is divided by the viscosity measured at 60 rpm for a thixo ratio of 1.4 to 2.2. The dispersion according to claim 1, which is
The dispersion according to claim 1 or 2, wherein the organic solvent is methyl ethyl ketone, toluene, xylene, cyclohexane or methyl cyclohexane.
The viscosity is 50 to 3000 mPa · s, and the viscosity measured under the condition of 30 rpm is divided by the viscosity measured under the condition of 60 rpm and the thixo ratio is 1.0 to 1.5. The dispersion according to claim 1, which is
The dispersion according to claim 1 or 4, wherein the organic solvent is cyclohexanone, cyclopentanone, N, N-dimethylacetamide or N-methyl-2-pyrrolidone.
The dispersion according to any one of claims 1 to 5, wherein the powder is a powder having a 50% volume-based cumulative diameter of 0.05 to 4 μm and a 90% volume-based cumulative diameter of 8 μm or less.
The dispersion according to any one of claims 1 to 6, wherein the fluoropolymer is a fluoropolymer having a ratio of a unit derived from tetrafluoroethylene to a total of all units of 90 to 99.89 mol%.
The polymer according to any one of claims 1 to 7, wherein the fluoropolymer further has a unit derived from at least one monomer selected from the group consisting of perfluoro (alkyl vinyl ether), hexafluoropropylene and fluoroalkylethylene. Dispersion as described in.
9. The polymer according to claim 1, wherein the fluoropolymer further has a unit derived from a monomer having at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group and an isocyanate group. Dispersion according to any one of the preceding claims.
The dispersion according to any one of claims 1 to 9, wherein the surfactant has a perfluoroalkyl group or a perfluoroalkenyl group.
The dispersion according to any one of claims 1 to 10, wherein the surfactant has a polyoxyethylene group, a polyoxypropylene group, a polyoxytetramethylene group, an amino group, a ketone group, a carboxyl group or a sulfone group. liquid.
The dispersion according to any one of claims 1 to 11, wherein the content of the powder is 35 to 70% by mass based on the total of the organic solvent, the powder and the surfactant.
A method for producing a metal laminate, wherein a resin film is formed on a metal film using the dispersion according to any one of claims 1 to 12, to obtain a metal film having a resin layer on the surface.
The method for producing a metal laminate plate according to claim 13, wherein the thickness of the resin layer is 1 to 20 μm.
The manufacturing method of the printed circuit board which manufactures a metal laminated board with the manufacturing method of Claim 13 or 14, etches the said metal film, and forms a pattern circuit.