WO2019098202A1 - Resin powder production method, resin powder, and laminate production method - Google Patents

Abstract

Provided are: a resin powder production method with which it is possible to efficiently produce a resin powder with a narrow particle size distribution; a resin powder capable of forming a thin resin layer in which surface irregularities are suppressed; and a method for producing a laminate having a thin resin layer formed from said resin powder. This resin powder production method comprises: subjecting a material resin body including a hot-melt fluoropolymer having a D50 of 10 µm or greater to primary pulverization by performing a mechanical pulverization treatment at least once until the D50 is from 1 to 300 µm; then performing secondary pulverization with a jet mill; and performing classification if necessary, to obtain a resin powder having a D50 of from 0.01 to 3 µm. The D90 of the obtained resin powder is preferably from 2.5 to 4 µm.

Description

Method of producing resin powder, resin powder and method of producing laminate

The present invention is a method for producing a resin powder wherein a raw resin body containing a heat-meltable fluoropolymer is primarily crushed and then secondarily crushed by a jet mill, a powder of the above resin having a narrow particle size distribution, and such resin powder The present invention relates to a method for producing a laminate having a thin resin layer.

For a printed wiring board for transmission of high frequency signals, an insulating material having a small dielectric constant and a dielectric loss tangent is used for the purpose of enhancing the transmission characteristics. A fluorine resin is known as such an insulating material. In addition, a metal having a printed wiring board having good transmission characteristics, a substrate, a resin layer including a resin powder (resin particle aggregate) mainly composed of a fluorocarbon resin and being in contact with the substrate, and a metal layer contacting the resin layer A method has been proposed in which a metal layer is processed into a patterned circuit and manufactured from a laminate (see Patent Document 1).

In recent years, in order to further miniaturize electronic devices, printed wiring boards tend to be further thinned. In order to make the printed wiring board thinner, it is also necessary to make the resin layer thinner.
At this time, if the resin powder contains coarse particles having a relatively large particle size (that is, if the particle size distribution of the resin powder is too wide), the shape of the coarse particles is reflected as the resin layer is thinned. Asperities are easily formed. When the unevenness is formed on the surface of the resin layer, the adhesion between the resin layer and the pattern circuit (metal layer) is reduced. In addition, since the pattern circuit becomes long due to the unevenness, the transmission characteristics may be deteriorated.

International Publication No. 2016/017801

In the resin powder obtained by grinding and classifying the raw resin body of the heat-meltable fluoropolymer, in order to reduce the amount of coarse particles contained in the resin powder, the grinding conditions and the classification conditions may be strict. However, if these conditions are tightened, the amount of raw resin material that can be crushed at one time can not but be reduced. In addition, the resin particles may be easily fibrillated, or the amount of resin powder to be removed in classification may be increased. For this reason, the production efficiency of resin powder falls and it is industrially disadvantageous.

The present invention relates to a method for producing a resin powder capable of efficiently producing a resin powder having a narrow particle size distribution, a resin powder capable of suppressing surface unevenness and forming a thin resin layer, and a thin resin layer formed from such resin powder. It aims at provision of the manufacturing method of the layered product which has.

The present invention has the following aspects.
<1> Volume based cumulative 50% diameter 10 μm or more, a raw resin body containing a heat-meltable fluoropolymer, at least one mechanical grinding treatment until the volume based cumulative 50% diameter becomes 1 to 300 μm primary After pulverizing, secondary pulverizing with a jet mill, and classification as necessary, to obtain a resin powder having a 50% diameter by volume cumulative 0.01% to 3 μm.
<2> The method according to <1>, wherein the volume-based cumulative 90% diameter of the produced resin powder is 2.5 to 4 μm.
<3> The manufacturing method of <1> or <2>, wherein the primary grinding treatment is treatment including grinding with a jet mill.

<4> Any one of <1> to <3>, wherein the heat-meltable fluoropolymer has 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. Production method.
<5> The method for producing <4>, wherein the heat-meltable fluoropolymer is a fluoropolymer including a unit having the functional group and a unit based on tetrafluoroethylene.
<6> The method for producing <4> or <5>, wherein at least one of the carbonyl group-containing group and the hydroxy group is a functional group introduced by plasma treatment or corona treatment on the heat-meltable fluoropolymer .
<7> The method according to any one of <1> to <6>, wherein the melting point of the heat-meltable fluoropolymer is 260 to 320 ° C.

<8> A resin powder comprising a heat-melting fluorine polymer, having a volume-based cumulative 50% diameter of 0.01 to 3 μm, and a volume-based cumulative 90% diameter of 2.5 to 4 μm.
The resin powder of <8> whose full width at half maximum in the particle size distribution curve of <9> said resin powder is 2.5 micrometers or less.
When <10> 100 g of the resin powder is dispersed in 100 g of water to prepare a dispersion, the resin powder of <8> or <9>, wherein the viscosity of the dispersion is 50 to 400 mPa · s.
<11> 100 g of the resin powder is dispersed in 100 g of water to prepare a dispersion, and when the dispersion is passed through a 200-mesh sieve according to JIS Z 8801-1: 2006, it remains on the sieve. Resin powder according to any one of <8> to <10>, wherein the amount of residue is 3 g or less.
<12> The resin powder according to any one of <8> to <11>, wherein the fluidity of the resin powder is 20 to 80 sec / 50 g.

<13> Any one of <8> to <12>, wherein the heat-meltable fluoropolymer has 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. Resin powder.
<14> The resin powder according to any one of <8> to <13>, wherein the melting point of the heat-meltable fluoropolymer is 260 to 320 ° C.
A method of producing a laminate comprising a <15> flat base and a resin layer provided on the base and formed from the resin powder according to any one of claims 8 to 14, ,
The manufacturing method of the laminated body which supplies the liquid composition containing the said resin powder and a liquid medium on the said base material, and it heats, and obtains the said resin layer.

According to the present invention, resin powder having a narrow particle size distribution can be efficiently produced. Moreover, according to the resin powder of this invention, the unevenness | corrugation of the surface is suppressed and a thin resin layer can be formed.
The laminate having such a resin layer is thin, surface unevenness is suppressed, and when used as a printed wiring board, the adhesion between the pattern circuit and the resin layer is high and the transmission characteristics are excellent.

It is a schematic diagram which shows the change of the particle size and shape of resin powder in a grinding process.

The definitions of the following terms in the present specification and claims are as follows.
“Hot melt polymer” means a polymer having a MFR of 0.01 to 1000 g / 10 min under a load of 49 N at a temperature 20 ° C. or more higher than the melting point of the polymer.
"Polymer melting point" means the temperature corresponding to the maximum of the melting peak of the polymer as measured by differential scanning calorimetry (DSC).
“MFR of polymer” is a melt mass flow rate defined in JIS K 7210-1: 2014 (corresponding international standard ISO 1133-1: 2011).
“Viscosity” 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.
For the "volume based cumulative 50% diameter (D50)" of resin powder, measure the particle size distribution of resin powder by laser diffraction and scattering method, determine the cumulative curve with the total volume of resin powder as 100%, and find the cumulative curve on that curve It is the particle diameter of the point where the cumulative volume is 50%.
For the "volume based cumulative 90% diameter (D90)" of resin powder, measure the particle size distribution of resin powder by laser diffraction / scattering method, determine the cumulative curve with the total volume of resin powder as 100%, and find the cumulative curve on that curve It is the particle diameter of the point where the cumulative volume is 90%.
The “full width at half maximum” is the width of the peak at half the height of the peak (maximum value) in the particle size distribution curve of the resin powder.
The "fluidity" of the resin powder is a value measured according to the "flowability test method of metal powder" defined in JIS Z 2502: 2012.
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).
The “unit based on a monomer” is a generic name of an atomic group formed directly by polymerization of one monomer molecule and an atomic group obtained by chemical conversion of a part of the atomic group. In the present specification, units based on monomers are also referred to simply as "units".
"(Meth) acrylate" is a generic term for acrylate and methacrylate. The same applies to “(meth) acrylic acid” and “(meth) acryloyl”.

The resin powder of the present invention (hereinafter, also referred to as “resin powder X”) is an aggregate of resin particles containing a heat-fusible fluoropolymer (hereinafter, also referred to as “F polymer”).
The resin particles constituting the resin powder X may contain components other than the F polymer as needed, as long as the effects of the present invention are not impaired.
80 mass% or more is preferable, as for the quantity of F polymer contained in resin powder X, 85 mass% or more is more preferable, 90 mass% or more is further more preferable, and 100 mass% is especially preferable. By using the resin powder X containing the F polymer in such an amount, the transmission characteristics of the resin layer are further improved. F polymers may be used in combination of two or more.
Other components include polymers other than F polymers, inorganic fillers having a low dielectric constant and dielectric loss tangent, and rubber.
As the other polymer, a compound which does not impair the electric reliability of the resin layer is preferable, and a fluorine polymer other than the F polymer (non-heat-meltable fluorine polymer such as polytetrafluoroethylene), aromatic polyester, polyamide imide, thermoplasticity Polyimide, polyphenylene ether, polyphenylene oxide can be mentioned.

The D50 of the resin powder X is 0.01 to 3 μm, preferably 0.1 to 3 μm, more preferably 0.5 to 2.7 μm, and still more preferably 0.8 to 2.5 μm. When D50 of the resin powder X is equal to or more than the above lower limit, aggregation is difficult when the resin powder is dispersed in a liquid medium, and the dispersibility of the resin powder in the liquid composition and in the resin layer is excellent. If D50 of the resin powder X is equal to or less than the above upper limit, the resin layer (hereinafter, also simply referred to as “resin layer”) formed from the resin powder can be thinned, and the surface smoothness can be enhanced. Moreover, the filling rate to the resin layer of resin powder can be made high, and the characteristic (transmission characteristic etc.) of a resin layer improves.

The D90 of the resin powder X is 2.5 to 4 μm, preferably 2.7 to 3.9 μm, and more preferably 2.9 to 3.9 μm. When D90 of the resin powder X is equal to or more than the above lower limit, aggregation is more difficult when the resin powder is dispersed in a liquid medium, and the dispersibility of the resin powder in the liquid composition and in the resin layer is more excellent. If D90 of the resin powder X is equal to or less than the above upper limit, that is, as long as resin particles having a relatively large particle diameter (hereinafter, also referred to as "coarse particles") are not included, the irregularities on the surface of the resin layer are suppressed.

The full width at half maximum in the particle size distribution curve of the resin powder X is preferably 0.5 to 3.5 μm, and more preferably 1 to 2.5 μm. Since the resin powder X has a small variation in particle diameter, the irregularities on the surface of the resin layer are more suitably suppressed. In addition, the resin layer tends to be compact and the characteristics thereof tend to be uniform. It can be said that resin powder X having a small variation in particle diameter suppresses deformation (elongation) and filitling of resin particles, and the physical properties of resin powder (such as dispersibility in a liquid medium) and the physical properties of resin layer It is easier to improve.

The resin particles that constitute the resin powder X are not deformed (elongated) or fibrillated from the viewpoint of enhancing the moldability and characteristics of the resin layer, and it is preferable that the degree of circularity be as high as possible (see FIG. 1).
The degree of circularity of the resin particles directly observes the shape of the resin particles, the viscosity of the dispersion in which the resin powder is dispersed, and the amount of residue remaining on the sieve when the dispersion is passed through a sieve And the fluidity of resin powder can be used as an index.
That is, in the case of resin particles having a high degree of circularity (hereinafter also referred to as “circular particles”), the viscosity of the dispersion tends to be low, while resin particles having a low degree of circularity (hereinafter referred to as “differently shaped particles”). In the case of), the viscosity of the dispersion tends to be high. Further, in the case of circular particles, it is difficult for the circular particles to aggregate in the dispersion liquid and the amount of residue on the sieve tends to be small, while in the case of the irregularly shaped particles, the irregularly shaped particles are easily aggregated in the dispersion , The amount of residue on the sieve tends to be large. Similarly, the flowability of circular particles tends to be low, while the flowability of irregularly shaped particles tends to be high.

Specifically, when 100 g of resin powder X is dispersed in 100 g of water to prepare a dispersion, the viscosity of the dispersion is preferably 50 to 400 mPa · s, and more preferably 100 to 200 mPa · s.
Moreover, when 100 g of resin powder X is dispersed in 100 g of water to prepare a dispersion, and the dispersion is passed through a 200-mesh sieve according to JIS Z 8801-1: 2006, the residue remaining on the sieve The amount of is preferably 3 g or less, more preferably 1.5 g or less.
The fluidity of the resin powder X is preferably 20 to 80 sec / 50 g, and more preferably 30 to 60 sec / 50 g.
If the viscosity of the dispersion, the amount of residue on the sieve, and the fluidity of the resin powder X fall within the above ranges, it can be determined that the degree of circularity of the resin particles is sufficiently high. In the preparation of the dispersion, when the water dispersibility of the resin powder is low, the dispersion may be prepared using the surfactant described in WO 2016/017801.

As the F polymer, tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer, polyvinylidene fluoride, polychlorotrifluoroethylene, ethylene-chlorotrifluoroethylene Copolymers, polymers into which at least one functional group (hereinafter also referred to as “adhesive group”) selected from the group consisting of carbonyl group-containing groups, hydroxy groups, epoxy groups and isocyanate groups are added thereto, modified polytetra Fluoroethylene is mentioned. In addition, if it shows heat melting property, polytetrafluoroethylene can also be used as F polymer.

As modified polytetrafluoroethylene, (i) a copolymer of tetrafluoroethylene (hereinafter also referred to as “TFE”) and a trace amount of CH ₂ CHCH (CF ₂ ) ₄ F, (ii) above-mentioned (i) Copolymer of a copolymer and a monomer having a very small amount of adhesive group (hereinafter also referred to as "adhesive monomer"), (iii) Copolymer of TFE and a very small amount of adhesive monomer, (iv) plasma treatment The polytetrafluoroethylene with which the adhesive group was introduce | transduced by etc., (v) The copolymer of said (i) with which the adhesive group was introduce | transduced by plasma processing etc. is mentioned.
In the case of using a non-heat melting fluorine polymer (polytetrafluoroethylene or the like not exhibiting heat melting property) instead of the F polymer, the raw material particles are crushed by mechanical grinding in the method for producing a resin powder described later In addition, since the raw resin body containing the non-heat-meltable fluoropolymer fibrillates, it becomes difficult to obtain the resin powder X of the target shape and particle size.

The melting point of the F polymer is preferably 260 to 320 ° C., more preferably 280 to 320 ° C., still more preferably 295 to 315 ° C., and particularly preferably 295 to 310 ° C. If the melting point of the F polymer is at least the above lower limit value, the heat resistance of the resin is enhanced. When the melting point of the F polymer is equal to or less than the above upper limit value, the heat melting property of the F polymer is improved.
The melting point of the F polymer can be adjusted by the type and ratio of units constituting the F polymer, the molecular weight of the F polymer, and the like. For example, the melting point of the F polymer tends to increase as the proportion of units based on TFE (hereinafter also referred to as “TFE units”) increases.

The MFR at a temperature 20 ° C. or more higher than the melting point of the F polymer is preferably 0.01 to 1000 g / 10 min, more preferably 0.05 to 1000 g / 10 min, and still more preferably 0.1 to 1000 g / 10 min. 0.5 to 100 g / 10 min is more preferable, 1 to 30 g / 10 min is particularly preferable, and 5 to 20 g / 10 min is most preferable. When the MFR is at least the above lower limit, the heat melting property of the F polymer is further improved, and the smoothness and the appearance of the surface of the resin layer become good. If MFR is below the said upper limit, the mechanical strength of a resin layer will increase.
MFR is a measure of the molecular weight of the F polymer, and indicates that the molecular weight is small when the MFR is large, and the molecular weight is large when the MFR is small. MFR of F polymer can be adjusted with the manufacturing conditions of F polymer. For example, shortening the polymerization time during the polymerization of monomers tends to increase the MFR of the F polymer.
2.5 or less is preferable and, as for the dielectric constant of F polymer, 2.4 or less is more preferable. As the relative dielectric constant of the F polymer is lower, the transmission characteristics of the resin layer are further improved. The lower limit value of the relative dielectric constant is usually 2.0. The relative permittivity of the F polymer can be adjusted by the proportion of TFE units.

The F polymer preferably has an adhesive group from the viewpoint of enhancing the adhesion between the resin layer and the other layer, or the dispersibility of the resin powder when dispersed in another resin.
As a method of introducing an adhesive group into the F polymer, (i) a method of copolymerizing a fluorine-containing monomer and an adhesive monomer, (ii) a surface treatment agent (a solution containing a complex of sodium metal and naphthalene) in the F polymer (Iii) plasma treatment or corona treatment of the F polymer.

As the F polymer having an adhesive group, a fluorine-containing copolymer having a unit having an adhesive group (hereinafter, also referred to as "adhesive unit") and a TFE unit (hereinafter, referred to as "copolymer A"), carbonyl Examples include F polymers in which at least one of the group-containing group and the hydroxy group is introduced by plasma treatment or corona treatment, and F polymers in which the adhesive group is introduced by the action of a polymerization initiator or a chain transfer agent. As the F polymer having an adhesive group, copolymer A is preferable from the viewpoint of excellent adhesion between the resin layer and the other layers. Copolymer A may contain other units besides adhesive units and TFE units.

The adhesive group is preferably a carbonyl group-containing group from the viewpoint of excellent mechanical crushability of the copolymer A and adhesion between the resin layer and the metal layer (metal foil).
As the carbonyl group-containing group, a hydrocarbon group having a carbonyl group between carbon atoms, a carbonate group, a carboxy group, a haloformyl group, an alkoxycarbonyl group, an acid anhydride residue (-C (O) -OC (O) -), Polyfluoroalkoxycarbonyl group, fatty acid residue.
As the carbonyl group-containing group, the above-mentioned hydrocarbon group, carbonate group, carboxy group, haloformyl group, alkoxycarbonyl group and acid anhydride are preferable because mechanical grindability of the copolymer A and adhesion between the resin layer and the metal layer are further excellent. At least one selected from the group consisting of substance residues is preferable, and at least one of a carboxy group and an acid anhydride residue is more preferable.
The above-mentioned hydrocarbon group includes, for example, an alkylene group having 2 to 8 carbon atoms. The carbon number of the alkylene group does not include the number of carbons constituting the carbonyl group.
The haloformyl group includes —C (= O) —F and —C (= O) Cl.
The alkoxy group in the alkoxycarbonyl group includes a methoxy group or an ethoxy group.
The number of adhesive groups possessed by the adhesive monomer may be one or two or more. When having two or more adhesive groups, the two or more adhesive groups may be the same as or different from each other.

Examples of the adhesive monomer include a monomer having a carbonyl group-containing group, a monomer having a hydroxy group, a monomer having an epoxy group, and a monomer having an isocyanate group. The adhesive monomer is preferably a monomer having a carbonyl group-containing group, from the viewpoint of excellent mechanical crushability of the copolymer A and adhesion between the resin layer and the metal layer.
As a monomer having a carbonyl group-containing group, a cyclic monomer having an acid anhydride residue, a monomer having a carboxy group, a vinyl ester, (meth) acrylate, CF ₂ = CFOR ^f1 CO ₂ X ¹ (where R ^f1 is It is a C1-C10 perfluoroalkylene group, or a C2-C10 perfluoroalkylene group which has an ether oxygen atom between carbon atoms, and X ¹ is a hydrogen atom or a C1-C3 alkyl group. Is mentioned.

As a cyclic monomer having an acid anhydride residue, unsaturated dicarboxylic acid anhydride (hereinafter, also referred to as "IAH"), citraconic anhydride (hereinafter, also referred to as "CAH"), 5-norbornene. And -2,3-dicarboxylic acid anhydride (another name: hymic acid anhydride, hereinafter also referred to as "NAH"), maleic anhydride and the like.
Examples of monomers having a carboxy group include unsaturated dicarboxylic acids (itaconic acid, citraconic acid, 5-norbornene-2,3-dicarboxylic acid, maleic acid, etc.) and unsaturated monocarboxylic acids (acrylic acid, methacrylic acid, etc.). Be
Examples of vinyl esters include vinyl acetate, vinyl chloroacetate, vinyl butanoate, vinyl pivalate, vinyl benzoate and vinyl crotonate.
Examples of (meth) acrylates include (polyfluoroalkyl) acrylates and (polyfluoroalkyl) methacrylates.

The monomer having a carbonyl group-containing group is preferably a cyclic monomer having an acid anhydride residue, more preferably IAH, CAH or NAH, from the viewpoint of excellent thermal stability of the resin and further improving the adhesion of the resin layer. . The use of IAH, CAH or NAH facilitates the preparation of a copolymer A having an acid anhydride residue. As the monomer having a carbonyl group-containing group, NAH is particularly preferable in that the adhesiveness of the layer formed from the resin powder is likely to be enhanced.

Examples of the monomer having a hydroxy group include vinyl esters having a hydroxy group, vinyl ethers having a hydroxy group, allyl ethers having a hydroxy group, (meth) acrylates having a hydroxy group, hydroxyethyl crotonate and allyl alcohol.
Examples of the monomer having an epoxy group include unsaturated glycidyl ether (allyl glycidyl ether, 2-methyl allyl glycidyl ether, vinyl glycidyl ether, etc.) and unsaturated glycidyl ester (glycidyl (meth) acrylate, etc.).
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 adhesive monomer may be used in combination of two or more.

As other units other than the adhesive unit and TFE unit, a unit based on perfluoro (alkyl vinyl ether) (hereinafter also referred to as “PAVE”) (hereinafter also referred to as “PAVE unit”), hexafluoropropylene (hereinafter referred to as Units based on “HFP” (hereinafter also referred to as “HFP units”), adhesive monomers, TFE, units based on PAVE and other monomers other than HFP can be mentioned.

As PAVE, CF ₂ CCFOCF ₃ , CF ₂ CFCFOCF ₂ CF ₃ , CF ₂ CCFOCF ₂ CF ₂ CF ₃ (hereinafter also referred to as “PPVE”), CF ₂ CCFOCF ₂ CF ₂ CF ₂ CF ₃ , CF ₂ CCFO (CF ₂ ) ₈ F may be mentioned, with PPVE being preferred.
PAVE may be used alone or in combination of two or more.

As other monomers, adhesive monomers, fluorine-containing monomers excluding TFE, PAVE and HFP (hereinafter referred to as "other fluorine-containing monomers"), fluorine-free monomers excluding adhesive monomers (hereinafter, "others" And “fluorine-free monomer”.
Other fluorine-containing monomers include vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, CF ₂ CCFOR ^{f 3} SO ₂ X ³ (however, R ^f3 is a C 1-10 perfluoroalkylene group) Or a C 2-10 perfluoroalkylene group having an etheric oxygen atom between carbon atoms, and X ³ is a halogen atom or a hydroxy group), CF ₂ CFCF (CF ₂ ) _p OCFCFCF ₂ (Where p is 1 or 2), CH ₂ = CX ⁴ (CF ₂ ) _q X ⁵ (where X ⁴ is a hydrogen atom or a fluorine atom, q is an integer of 2 to 10, and X is ⁵ is a hydrogen atom or a fluorine atom), and perfluoro (2-methylene-4-methyl-1,3-dioxolane). The other fluorine-containing monomer may be used in combination of two or more.
CH ₂ = The ^{_{CX 4 (CF 2) q X}} 5, CH 2 = CH (CF 2) 2 F, CH 2 = CH (CF 2) 3 F, CH 2 = CH (CF 2) 4 F, CH 2 CFCF (CF ₂ ) ₃ H, CH ₂ CFCF (CF ₂ ) ₄ H, CH ₂ CHCH (CF ₂ ) ₄ F, and CH ₂ CHCH (CF ₂ ) ₂ F are preferable.

Other fluorine-free monomers include ethylene and propylene, with ethylene being preferred. Other fluorine-free monomers may be used in combination of two or more.
As other monomers, other fluorine-containing monomers and other fluorine-free monomers may be used in combination.

The copolymer A may have an adhesive group as an end group bonded to the end of the main chain. As the adhesive group as a terminal group, an alkoxycarbonyl group, a carbonate group, a carboxy group, a fluoroformyl group, an acid anhydride residue and a hydroxy group are preferable. Such an adhesive group can be introduced by appropriately selecting a radical polymerization initiator, a chain transfer agent and the like used at the production of the copolymer A.

The copolymer A is preferably a copolymer A1 having an adhesive unit, TFE units and PAVE units, a copolymer A2 having an adhesive unit, TFE units and HFP units, from the viewpoint of enhancing the heat resistance of the resin, and the copolymer A1 is more preferable. preferable.
The copolymer A1 may optionally have at least one of HFP units and other units. That is, the copolymer A1 may be a copolymer having adhesive units, TFE units and PAVE units, or may be a copolymer having adhesive units, TFE units, PAVE units and HFP units, and adhesive units, TFE units and PAVE units And other units, or copolymers having adhesive units, TFE units, PAVE units, HFP units and other units.

As the copolymer A1, a copolymer having a unit based on a monomer having a carbonyl group-containing group, a TFE unit and a PAVE unit is preferable from the viewpoint of further enhancing the mechanical grindability of the copolymer A1 and the adhesion between the resin layer and the metal layer. More preferred are copolymers having units based on cyclic monomers having an acid anhydride residue, TFE units and PAVE units.
Preferred specific examples of the copolymer A1 include copolymers having TFE units, PPVE units and NAH units, copolymers having TFE units, PPVE units and IAH units, and copolymers having TFE units, PPVE units and CAH units. .

The proportion of adhesive units in the copolymer A1 is preferably 0.01 to 3 mol%, and more preferably 0.05 to 1 mol%, of the total units constituting the copolymer A1. In this case, it is easy to balance the adhesiveness of the resin layer, the heat resistance of the resin, and the color.
The proportion of TFE units in the copolymer A1 is preferably 90 to 99.89 mol%, more preferably 96 to 98.95 mol%, of the total units constituting the copolymer A1. In this case, it is easy to balance the electrical properties (such as low dielectric constant), heat resistance, chemical resistance, etc. of the resin layer with the heat melting property, stress crack resistance, etc. of the copolymer A1.
The proportion of PAVE units in the copolymer A1 is preferably 0.1 to 9.99 mol%, more preferably 1 to 9.95 mol%, of the total units constituting the copolymer A1. In this case, it is easy to adjust the heat melting property of the copolymer A1.
90 mol% or more is preferable and, as for the sum total of the adhesive unit, TFE unit, and PAVE unit in copolymer A1, 98 mol% or more is more preferable. The upper limit is 100 mol%.

The copolymer A2 may optionally have at least one of PAVE units and other monomer units. That is, the copolymer A2 may be a copolymer having adhesive units, TFE units and HFP units, or a copolymer having adhesive units, TFE units, HFP units and PAVE units, and the adhesive units, TFE units and HFP units And other monomer units, and copolymers having adhesive units, TFE units, HFP units, PAVE units and other units.

As the copolymer A2, a copolymer having units based on a monomer having a carbonyl group-containing group, TFE units and HFP units is preferable from the viewpoint of further enhancing the mechanical grindability of the copolymer A2 and the adhesion between the resin layer and the metal layer. More preferred are copolymers having units based on cyclic monomers having acid anhydride residues, TFE units and HFP units.
Preferred specific examples of the copolymer A2 include copolymers having TFE units, HFP units and NAH units, copolymers having TFE units, HFP units and IAH units, and copolymers having TFE units, HFP units and CAH units. .

The proportion of adhesive units in the copolymer A2 is preferably 0.01 to 3 mol%, more preferably 0.05 to 1.5 mol%, of the total units constituting the copolymer A2. In this case, it is easy to balance the adhesiveness of the resin layer, the heat resistance of the resin, and the color.
The proportion of TFE units in the copolymer A2 is preferably 90 to 99.89 mol%, more preferably 92 to 96 mol%, of the total units constituting the copolymer A2. In this case, it is easy to balance the electrical properties (such as low dielectric constant), heat resistance, chemical resistance, etc. of the resin layer with the heat melting property, stress crack resistance, etc. of the copolymer A2.
The proportion of HFP units in the copolymer A2 is preferably 0.1 to 9.99 mol%, more preferably 2 to 8 mol%, of the total units constituting the copolymer A2. When the proportion of HFP units is within the above range, the heat melting property of the copolymer A2 is further enhanced.
90 mol% or more is preferable and, as for the ratio in the sum total of the adhesive unit, TFE unit, and HFP unit in copolymer A2, 98 mol% or more is more preferable. The upper limit is 100 mol%.
The proportion of each unit in the copolymer A is determined by NMR analysis such as melt nuclear magnetic resonance (NMR) analysis, fluorine content analysis, infrared absorption spectrum analysis. For example, as described in JP-A-2007-314720, the proportion (mol%) of adhesive units in all the units constituting the copolymer A can be determined using a method such as infrared absorption spectrum analysis.

As a method of producing the copolymer A, (i) a method of polymerizing an adhesive monomer and TFE, and optionally PAVE, FEP, and other monomers, (ii) a functional group capable of generating an adhesive group by thermal decomposition A method of heating a fluorine-containing copolymer having units and TFE units to thermally decompose a functional group to form an adhesive group (for example, a carboxy group), (iii) a fluorine-containing copolymer having a TFE unit, an adhesive monomer The method of graft-polymerizing is mentioned and the method of said (i) is preferable.

The polymerization method (bulk polymerization method, solution polymerization method, suspension polymerization method, emulsion polymerization method, etc.) is not particularly limited, and can be appropriately set. In addition, the amount and type of the solvent, the polymerization initiator, and the chain transfer agent used in the polymerization can be appropriately set.
The polymerization conditions (temperature, pressure, time, etc.) can also be set appropriately depending on the type of monomer used.

In the method for producing a resin powder of the present invention, a raw resin body having a D50 of 10 μm or more is subjected to primary grinding until at least one mechanical grinding treatment until D50 becomes 1 to 300 μm, and then secondary grinding is performed using a jet mill. This is a method of obtaining a resin powder having a D50 of 0.01 to 3 μm by classification as necessary. The resin particles constituting the resin powder (hereinafter also referred to as "resin powder Y") obtained by the production method of the present invention are hereinafter also referred to as "microparticles".
The resin powder X can be produced by the production method of the present invention. That is, a resin powder having D50 of 0.01 to 3 μm and D90 of 2.5 to 4 μm can be produced by the production method of the present invention.

The raw resin body may be a powder composed of raw resin particles having a large particle diameter, and is a non-powder-like resin body aggregate such as an aggregate of pellet-like resin particles or an aggregate of massive resin bodies It is also good. As a raw material resin body, the powder comprised from the resin particle with a large particle diameter is preferable, and, below, this raw material resin body is also described as "raw material powder."
Hereinafter, the production method of the present invention will be described by taking the case of using a raw material powder as a raw material resin body as an example. When using another raw material resin body, it is preferable to make a raw material resin body into raw material powder at the beginning of primary grinding, and to carry out primary grinding succeedingly.

FIG. 1 is a schematic view showing changes in the particle size and shape of resin particles in the grinding process.
As shown in FIG. 1, the raw material powder is usually composed of an aggregate (so-called secondary particles) in which primary particles of F polymer are collected. The raw material powder is ground (crushed) by primary grinding to become a resin powder of D50 smaller than the D50 of the raw material powder. Hereinafter, the resin powder obtained by this primary pulverization is also referred to as "crushed powder". Even in this state, most of the particles constituting the crushed powder are composed of aggregates of primary particles. Furthermore, when the crushed powder is subjected to secondary grinding, it is ground to a resin powder of D50 smaller than the D50 of the crushed powder. Most of the microparticles constituting the obtained resin powder are primary particles.
In addition, in FIG. 1, the particle | grains which comprise raw material powder are described as "raw material particle | grains", and the particle | grains which comprise crushing powder are described as "crushed particle | grains."

According to the production method of the present invention, the raw material powder is ground by the two-step grinding of the primary grinding and the second grinding. In other words, after positively obtaining crushed powder composed of relatively large particles, the crushed powder is further crushed into resin powder. For this reason, the grinding conditions in each grinding step can be set to relatively mild conditions. As a result, it is possible to prevent or suppress the deformation and fibrillation of the particles constituting the crushed powder. Moreover, since the opportunity which powder constituent particles collide will increase in this way, it can grind | pulverize efficiently, without leaving a coarse particle, and the resin powder comprised from the microparticles with a uniform particle size can be obtained. It will be.
Furthermore, since each grinding process can be performed under mild grinding conditions, it is not necessary to reduce the amount of resin powder that can be processed at one time in each grinding process. As described above, although the pulverizing process is performed in two steps, the amount of resin powder which can be treated at one time in each process can be sufficiently secured, so that the production efficiency and the yield of the desired resin powder as a whole are high.

On the other hand, when the raw material powder is ground by grinding in only one step (primary grinding), the grinding conditions are severe because it is necessary to grind the raw material powder to the target powder in one treatment. It must be a condition. For this reason, the pressure and temperature applied to the raw material powder tend to be high, and as shown in FIG. 1, resin particles (deformed particles) which are deformed (extended) or fibrillated are easily generated. In addition, since irregular shaped particles having a relatively large particle diameter are also easily formed, it is difficult to obtain a resin powder having a uniform particle diameter.
Furthermore, since the grinding conditions are severe conditions, the amount of raw material powder that can be processed at one time must be reduced, and it can hardly be said that the production efficiency of the resin powder as a whole is high.

When D50 of the resin powder at the end of the secondary pulverization is 0.01 to 3 μm and D90 is 2.5 to 4 μm, this resin powder may be used as the resin powder X.
If necessary, the resin powder at the end of the secondary pulverization may be classified to adjust D50 to 0.01 to 3 μm and D90 to 2.5 to 4 μm to obtain resin powder X.
According to the method for producing resin powder Y of the present invention described in detail below, it is easy to obtain resin powder X having D50 of 0.01 to 3 μm and D90 of 2.5 to 4 μm at the time of completion of secondary grinding .

The D50 of the raw material powder is 10 μm or more, preferably 100 to 10000 μm, and more preferably 100 to 5000 μm. When D50 of the raw material powder is equal to or more than the above lower limit value, the handleability of the raw material powder is improved. If D50 of the raw material powder is equal to or less than the above upper limit value, the load on the raw material powder in the mechanical grinding process is small.

In the production method of the present invention, first, the raw material powder is subjected to primary grinding by at least one mechanical grinding treatment until D50 reaches 1 to 300 μm to obtain crushed powder.
The D50 of the crushed powder is 1 to 300 μm, preferably 2 to 100 μm, and more preferably 3 to 50 μm. When the D50 of the crushed powder is equal to or more than the above lower limit, the handleability of the crushed powder is improved, and the grindability in the jet mill in the secondary grinding is improved. If D50 of the crushed powder is equal to or less than the above upper limit value, resin powder with sufficiently small D90 can be obtained in high yield.

The crushed powder D90 is preferably 10 to 300 μm, and more preferably 30 to 100 μm. When D90 of the crushed powder is equal to or more than the above lower limit, the handleability of the crushed powder becomes better, and the crushability in the jet mill in the secondary crushing is further improved. If D90 of the crushed powder is less than or equal to the above upper limit value, resin powder with sufficiently small D90 can be obtained in a higher yield.
The number of times of mechanical grinding treatment may be the number of times to obtain the intended crushed powder of D50. From the viewpoint of resin powder productivity, the number of times of mechanical pulverizing treatment is preferably small, and particularly preferably once.

The mechanical grinding process in the primary grinding is a process of grinding the raw material powder using a grinder capable of applying at least one of shear force and crushing force sufficient to break (break) the raw material powder. It is.
As a grinder, a jet mill, a hammer mill, a pin mill, a bead mill, a turbo mill is mentioned, a jet mill, a bead mill, a pin mill is preferable, and a jet mill is particularly preferable. According to these methods, it is easy to obtain the intended crushed powder of D50 with a small number of mechanical grinding processes, and thus the production efficiency of the finally obtained resin powder Y is further improved.

As a jet mill, particles collide with each other in a crushing zone formed by a collision type in which particles or particles and a collision object (target) are collided and crushed, and a plurality of crushing nozzles disposed in a circulating air flow A swirling air flow type and a loop type which grind | pulverize, a fluidized bed type and a supersonic speed type which grind | pulverize by collision and friction of particles in a fluidized bed, etc. are mentioned.
The impact type, swirl flow type, loop type and fluidized bed type jet mills are described in detail in “Advanced Grinding Technology and Application”, edited by Nippon Powder Industrial Technology Association, “LNG Co., Ltd.”, page 162.
As a collision type jet mill, a fluid such as compressed air is discharged from a nozzle, and a crusher for colliding particles to collide in high speed turbulence formed in the jet mill, resin particles are transported by high speed air flow, And crushers that collide with and collide with an impactor.

Commercial products of jet mill include cross jet mill (made by Kurimoto Iron Works Co., Ltd.); jet o mill, AO jet mill, sanitary AOM, cojet, single track jet mill, super STJ mill (all are Seishin Enterprise Co., Ltd.) Current jet mill (Nisshin Engineering Co., Ltd.); Ulmax (Nissan Engineering Co., Ltd.) supersonic jet crusher PJM, supersonic jet crusher CPY, supersonic jet crusher LJ-3, Supersonic jet crusher type I (all manufactured by Nippon Pneumatic Mfg. Co., Ltd.); counter jet mill, micro jet T type, spiral jet mill, micron jet MJQ (all manufactured by Hosokawa Micron Corporation); fluidized bed jet mill (Nippon Coke Industrial Co., Ltd.) Made in Japan; Nano Grinding Mill (Tokujuko) Tokorosha, Ltd.) and the like.
As a jet mill, a single track jet mill is preferable from the viewpoint of excellent productivity of resin powder.

The grinding pressure in the jet mill is preferably 0.5 to 2 MPa, and more preferably 0.6 to 0.9 MPa. If the grinding pressure is equal to or higher than the above lower limit value, it is easy to obtain the intended crushed powder of D50 with a small number of mechanical grinding processes. If the crushing pressure is equal to or less than the above upper limit value, the crushability of the raw material powder is excellent.

The treatment rate in the jet mill is preferably 5 to 80 kg / hr, more preferably 8 to 50 kg / hr. If the processing speed is equal to or more than the above lower limit value, the productivity of crushed powder is improved. When the processing speed is equal to or less than the above upper limit value, mixing of coarse particles contained in the resin powder at the end of the secondary pulverization is reduced.

In the production method of the present invention, next, the crushed powder is subjected to secondary grinding by a jet mill until D50 becomes 0.01 to 3 μm, and classified as necessary to obtain a resin powder Y.
D50 of the resin powder Y obtained by the production method of the present invention is 0.01 to 3 μm, preferably 0.1 to 3 μm, more preferably 0.5 to 2.7 μm, and 0.8 to 2.5 μm. More preferable. If D50 of the resin powder Y is equal to or more than the above lower limit, aggregation is difficult when the resin powder is dispersed in a liquid medium, and the dispersibility of the resin powder in the liquid composition and in the resin layer is excellent. If D50 of the resin powder Y is equal to or less than the above upper limit, D90 also tends to be sufficiently small.

The D90 of the resin powder Y is preferably 2.5 to 4 μm, and more preferably 2.7 to 3.9 μm. That is, the resin powder Y is preferably a resin powder X. If D90 of the resin powder Y is equal to or more than the above lower limit, aggregation is difficult when the resin powder is dispersed in a liquid medium, and the dispersibility of the resin powder in the liquid composition and in the resin layer is more excellent. If D90 of the resin powder Y is equal to or less than the upper limit value, classification of the resin powder can be omitted, so that the yield of the resin powder is increased.

As a jet mill, the jet mill similar to the above-mentioned is mentioned, A preferable form is also the same.
The grinding pressure in the jet mill is preferably 0.5 to 2 MPa, and more preferably 0.6 to 0.9 MPa. If the grinding pressure is equal to or higher than the above lower limit value, it is easy to accurately obtain the target resin powder Y of D50. If the crushing pressure is equal to or less than the above upper limit value, the crushability of the crushed particles is excellent.

The treatment rate in the jet mill is preferably 5 to 80 kg / hr, more preferably 8 to 50 kg / hr. If the processing speed is equal to or more than the above lower limit value, the productivity of the resin powder Y is further improved. If the processing speed is equal to or less than the above upper limit value, mixing of coarse particles contained in the resin powder (resin powder at the time of completion of the secondary pulverization) is further reduced.

When the target resin powder Y of D50 and D90 is obtained at the end of the secondary pulverization, the resin powder Y can be used as the resin powder X as it is without classification.
On the other hand, when D50 is out of the target value at the end of the secondary pulverization, the resin powder after the secondary pulverization is classified to obtain resin powder Y. Furthermore, in the case of producing the resin powder X, when D50 and D90 are out of the target value at the end of the second grinding, or D50 is the target value, but D90 is out of the target value. If so, the resin powder after completion of the secondary pulverization is classified to obtain resin powder X.
According to the production method of the present invention, the yield of the target resin powder Y and resin powder X can be increased even when classification needs to be performed after completion of secondary grinding. When classifying resin powder after completion of secondary pulverization, the yield of resin powder Y and resin powder X with respect to resin powder after completion of secondary pulverization is preferably 80% by mass or more, more preferably 90% by mass or more, and 95% by mass The above is particularly preferable.

In the production method of the present invention, classification may be performed before secondary grinding. For example, in the case of performing mechanical grinding treatment several times in primary grinding, crushed particles may be classified between two mechanical grinding treatments, and between primary grinding and secondary grinding, The crushed particles may be classified.
Classification is a process of removing at least one of resin particles having a too large particle diameter and resin particles having a too small particle diameter in a resin powder.
The classification method includes sieving and air classification, and air classification is preferable in terms of operability or classification accuracy. As a classifier used for air classification, a precision air flow classifier is preferable in terms of productivity or classification accuracy.
For classification, secondary grinding and classification may be performed continuously by using a jet mill equipped with a classifier or the like.

The resin powder (i.e., resin powder X) of the present invention is useful as a raw material for various molded articles.
When using the powder X, a resin composition containing a resin powder X and a resin for dispersing powder particles (hereinafter, also referred to as “dispersion resin”) may be prepared.
Examples of the dispersing resin include thermoplastic resins other than F polymers, thermosetting resins, and photosensitive resins. As a dispersing resin, a non-fluororesin is preferable.

As a thermoplastic resin, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyarylate, polycaprolactone, phenoxy resin, polysulfone, polyether sulfone, polyether ketone, polyether ether ketone, polyether ether ketone, polyether imide, semi aromatic Polyamide, polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 610, polyphenylene oxide, polyphenylene sulfide, polytetrafluoroethylene, acrylonitrile-styrene-butadiene copolymer, polymethyl methacrylate, polypropylene, polyethylene, polybutadiene, butadiene- Styrene copolymer, ethylene-propylene copolymer, ethylene-propylene-diene rubber , Styrene - butadiene block copolymer, butadiene - acrylonitrile copolymer, acrylic rubber, styrene - maleic anhydride copolymer, styrene - phenylmaleimide copolymer, aromatic polyesters, polyamideimide, thermoplastic polyimide. The thermoplastic resin may be used in combination of two or more.

The melting point of the thermoplastic resin is preferably 280 ° C. or more. When the melting point of the thermoplastic resin is 280 ° C. or more, when the resin layer composed of the resin composition is exposed to the atmosphere corresponding to the solder reflow, it is possible to suppress swelling (foaming) due to heat.
Examples of the thermosetting resin include polyimide, epoxy resin, acrylic resin, phenol resin, polyester resin, bismaleimide resin, polyolefin, polyphenylene ether, and fluorine resin. The thermosetting resin may be used alone or in combination of two or more.
As a thermosetting resin, a polyimide, an epoxy resin, an acrylic resin, bismaleimide resin, and a polyphenylene ether are preferable, and at least 1 sort (s) chosen from the group which consists of a polyimide and an epoxy resin is more preferable. The resin composition containing a thermosetting resin is suitably used for a printed wiring board.
As photosensitive resin, resin used for a resist material etc., specifically an acrylic resin is mentioned. Further, as the photosensitive resin, thermosetting resin to which photosensitivity is imparted can also be used. As a specific example of this photosensitive resin, the thermosetting resin which has the (meth) acryloyl group etc. which were introduce | transduced by making (meth) acrylic acid etc. react with a reactive group (epoxy group etc.) is mentioned.

The resin composition may contain other components other than the dispersing resin and the resin powder, as needed, as long as the effects of the present invention are not impaired.
Other components include liquid media, inorganic fillers having a low dielectric constant and dielectric loss tangent, surfactants, and antifoaming agents.
The resin powder X or the resin composition may be a liquid composition containing a liquid medium.

As the liquid medium, water, alcohol (methanol, ethanol etc.), nitrogen-containing compounds (N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone etc.), sulfur-containing compounds (dimethyl sulfoxide etc.) ), Ethers (diethyl ether, dioxane etc.), esters (ethyl lactate, ethyl acetate etc.), ketones (methyl ethyl ketone, methyl isopropyl ketone etc.), glycol ethers (ethylene glycol monoisopropyl ether etc.), cellosolve (methyl cellosolve, ethyl cellosolve etc.) Can be mentioned. The liquid medium may be used alone or in combination of two or more. The liquid medium preferably does not react with the F polymer and the dispersing resin, or has poor reactivity.

The amount of the resin powder X contained in the resin composition is preferably 5 to 500 parts by mass, and more preferably 20 to 300 parts by mass with respect to 100 parts by mass of the dispersing resin. In this case, the electrical properties of the resin composition and the mechanical strength of the resin layer are enhanced.
When the resin powder X or the resin composition is used as a liquid composition, the total amount of solids contained in the liquid composition is preferably 80 to 30% by mass, and more preferably 65 to 45% by mass. In this case, the coatability of the liquid composition when forming the resin layer is good.
When the liquid composition contains a surfactant, the amount of the surfactant contained in the liquid composition is preferably 1 to 30 parts by mass, more preferably 5 to 10 parts by mass with respect to 100 parts by mass of the resin powder X . In this case, the dispersibility of the resin powder X in the liquid composition and the characteristics (such as transmission characteristics) of the resin layer can be easily balanced.
When the liquid composition contains an antifoaming agent, the amount of the antifoaming agent contained in the liquid composition is preferably 1% by mass or less.
When the resin composition contains an inorganic filler, the amount of the inorganic filler contained in the resin composition is preferably 0.1 to 100 parts by mass, and 0.1 to 60 parts by mass with respect to 100 parts by mass of the dispersing resin. Is more preferred.

As a method for producing a resin composition according to the present invention, (i) a method of mixing a thermoplastic resin which is a dispersing resin and a resin powder X and melt kneading it, (ii) a thermosetting resin which is a dispersing resin The method of disperse | distributing resin powder X to the varnish containing, (iii) The method of mixing the varnish containing the thermosetting resin which is resin for dispersion | distribution, and the dispersion liquid containing resin powder X is mentioned.

As a use of the resin composition containing resin powder X or powder X, the resin layer in the laminated body mentioned later is mentioned. Other applications include interlayer insulating films, solder resists, and base films of coverlay films.
As described above, the resin composition containing the resin powder X or the powder X contains a resin powder having a D90 of 2.5 to 4 μm, that is, a resin powder having a small amount of coarse particles. For this reason, the resin layer in which the unevenness | corrugation on the surface was suppressed can be formed. Further, the resin composition containing the resin powder X or the powder X contains a resin powder having a D50 of 0.01 to 3 μm, that is, a resin powder having a sufficiently small average particle diameter. Therefore, a thin resin layer can be formed. Furthermore, if the F polymer has an adhesive group while the resin powder has a particle size in the above range, the dispersibility of the resin powder in the dispersing resin will be better.

The present invention is also a method for producing a laminate having a flat substrate and a resin layer provided on the substrate and formed from the resin powder X, the resin powder X and a liquid medium. The liquid composition is supplied onto a flat substrate and heated to obtain a resin layer formed of the above resin powder on a substrate.
The laminate has a flat substrate and a resin layer provided on at least one surface of the substrate. That is, the laminate may have a structure in which the resin layer is laminated only on one side of the base, or a structure in which the resin layer is laminated on both sides of the base.
The latter laminate is preferable from the viewpoint of suppressing the warpage of the laminate or in terms of obtaining a double-sided metal laminate excellent in electrical reliability. In this case, the composition and thickness of the two resin layers may be the same or different. From the viewpoint of suppressing the warpage of the laminate, the compositions and thicknesses of the two resin layers are preferably the same.

The resin layer is composed of the resin composition in the present invention. For this reason, the effects as described above are exhibited.
The thickness of the resin layer is preferably 0.5 to 300 μm, more preferably 3 to 200 μm, and still more preferably 10 to 150 μm, from the viewpoint of thickness reduction and balance of electrical characteristics when the laminate is used for a printed wiring board preferable.

The relative dielectric constant of the resin layer is preferably 2 to 3.5, and more preferably 2 to 3. In this case, the laminate can be suitably used for a printed wiring board or the like for which a low dielectric constant is required, and both of the electrical properties and adhesiveness of the resin layer are excellent.

Examples of the substrate include a heat resistant resin film, a fiber reinforced resin plate, a laminated film having a heat resistant resin film layer, and a laminated film having a fiber reinforced resin layer. When using a laminated body as a board | substrate of a flexible printed wiring board, as a base material, a heat resistant resin film is preferable.

The heat resistant resin film is a film containing one or more heat resistant resins, and may be a single layer film or a multilayer film.
As the heat resistant resin, 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 can be mentioned.
As a heat resistant resin film, a polyimide film is preferable. The polyimide film is a film composed of polyimide. A polyimide film may contain other components other than a polyimide as needed in the range which does not impair the effect of this invention.

When the laminate is used for a printed wiring board, the thickness of the heat resistant resin film is preferably 0.5 to 100 μm, more preferably 1 to 50 μm, from the viewpoint of the balance between thinning and mechanical strength. 25 μm is more preferred.
The heat resistant resin film can be manufactured by a method of forming a heat resistant resin or a resin composition containing a heat resistant resin into a film by a known forming method (cast method, extrusion method, inflation method, etc.). The heat resistant resin film may be a commercially available product.
The surface of the heat resistant resin film may be subjected to surface treatment. The surface treatment method includes corona discharge treatment and plasma treatment.

The laminate in the present invention can also be used as a metal laminate having a metal layer as a substrate. In this case, the metal laminate may further have a substrate provided on the surface of the resin layer opposite to the metal layer.
That is, examples of the layer configuration of the metal laminate include metal layer / resin layer, metal layer / resin layer / metal layer, substrate / resin layer / metal layer, metal layer / resin layer / substrate / resin layer / metal layer . Here, “metal layer / resin layer” indicates a configuration in which a metal layer and a resin layer are laminated in this order, and the other layer configurations are the same.

Examples of the metal constituting the metal layer include copper, copper alloy, stainless steel, nickel, nickel alloy (including 42 alloy), aluminum, and aluminum alloy.
As a metal layer, the layer which consists of metal foil, and a metal vapor deposition film are mentioned.
As metal foil, rolled copper foil and electrolytic copper foil are mentioned. On the surface of the metal foil, an anticorrosive layer (oxide film such as chromate etc.), a heat resistant layer etc. may be formed. Further, in order to improve the adhesion to the resin layer, the surface of the metal foil may be treated with a coupling agent or the like.
The thickness of the metal layer may be a size that can exhibit a sufficient function in the application of the metal laminate.

The laminated body (metal laminated board) applies the liquid composition which is a resin composition to the surface of a substrate (metal foil), removes the liquid medium by drying, and hardens the resin for dispersion as needed. (Ii) a method of pressure bonding a resin layer (resin film) and a substrate (metal foil) by a heat press method, etc. (iii) a vacuum evaporation method, a sputtering method, an ion plating method on the surface of the resin layer And the like, and the method of vapor-depositing a metal is mentioned.

Furthermore, the metal laminate can also be used as a printed wiring board by processing the metal layer into a pattern circuit (a shape having a predetermined pattern) by etching.
In such a printed wiring board, the unevenness of the interface between the pattern circuit and the resin layer can be suppressed. As a result, while being excellent in the adhesiveness of a pattern circuit and a resin layer, it is excellent in a transmission characteristic.
In the printed wiring board, the interlayer insulating film and the pattern circuit may be stacked in this order on the pattern circuit. The interlayer insulating film may be formed using the resin composition of the present invention.
In the printed wiring board, a solder resist may be laminated on the pattern circuit. The solder resist may be formed using the resin composition of the present invention.

A coverlay film may be laminated on the surface of the printed wiring board. The coverlay film is composed of a base film and an adhesive layer formed on the surface of the base film. The base film of the coverlay film may be formed using the resin composition of the present invention.
In the printed wiring board, an interlayer insulating film (adhesive layer) using the resin composition of the present invention and a polyimide film as a coverlay film may be laminated in this order on a patterned circuit.

As mentioned above, although the manufacturing method of the resin powder of this invention, the resin powder, and the manufacturing method of a laminated body were demonstrated, this invention is not limited to the structure of embodiment mentioned above.
For example, the resin powder of the present invention may be added with any other configuration in the configuration of the embodiment described above, or may be replaced with any configuration that exhibits the same function.
Moreover, the method for producing a resin powder and the method for producing a laminate according to the present invention may additionally have another optional step in the configuration of the above embodiment, and any step and substitution which produce the same action It may be done.

EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.
1. Preparation of Raw Material Powder A raw material powder consisting of F polymer was manufactured using NAH, TFE and PPVE according to the procedure described in paragraph [0123] of WO 2016/017801.
The proportions (mol%) of NAH units, TFE units and PPVE units contained in the F polymer were 0.1, 97.9 and 2.0 in this order. The melting point of the F polymer was 300 ° C., the MFR was 17.6 g / 10 min, and the D50 of the raw material powder was 1554 μm.

The proportion of each unit contained in the F polymer, the melting point of the F polymer, the relative dielectric constant and the MFR, and the D50 of the raw material powder were measured as follows.
The melting point was measured using a differential scanning calorimeter (DSC-7020) manufactured by Seiko Instruments Inc. The temperature rising rate of the F polymer was 10 ° C./min.
MFR measures mass (g) of F polymer flowing out from a nozzle of 2 mm in diameter and 8 mm in length for 10 minutes (unit time) under a load of 372 ° C. and 49 N using Melt Indexer manufactured by Techno Seven Co., Ltd. I asked for it.
The D50 of the raw material powder was determined by the following procedure.
From the top, in order: 2.000 mesh sieve (2.400 mm mesh), 1.410 mesh sieve (1.705 mm mesh), 1.000 mesh sieve (1.205 mm mesh mesh), 0.710 mesh sieve (mesh mesh) An opening 0.855 mm), a 0.500 mesh sieve (opening 0.605 mm), a 0.250 mesh sieve (opening 0.375 mm), a 0.149 mesh sieve (opening 0.100 mm) and a tray were overlaid.
The raw material powder was put on the top sieve and sieved by a shaker for 30 minutes. The mass of the raw material powder remaining on each sieve was measured, and the accumulated mass of the passing mass with respect to each opening value was represented on a graph, and the particle size at which the accumulated mass of the passing mass was 50% was obtained as D50 of the raw material powder.
The relative dielectric constant is a dielectric breakdown test in a test environment in which the temperature is maintained within a range of 23 ° C. ± 2 ° C. and the relative humidity is maintained within a range of 50% ± 5% RH according to the transformer bridge method in accordance with ASTM D 150. It was determined at 1 MHz using a device (YSY-243-100 RHO, manufactured by Yamayo Test Instruments Co., Ltd.) to determine the relative dielectric constant of the polymer.

2. Production of resin powder (Example 1)
First, using a jet mill (single track jet mill STJ-400 type, manufactured by Seishin Enterprise Co., Ltd.), the raw material powder was primarily crushed under the conditions shown in Table 1 to obtain a crushed powder (a1).
Next, the crushed powder (a1) was again charged into a jet mill, and secondary grinding was performed under the conditions shown in Table 1 to obtain a resin powder (b1).
Next, fine particles Y1 were classified under the conditions shown in Table 1 using a high-efficiency precision air flow classifier (Crusher N-5 manufactured by Seishin Enterprise Co., Ltd.) to obtain a resin powder (c1).

(Comparative example 1)
A resin powder (c'1) was obtained in the same manner as Example 1, except that the secondary grinding was omitted and only the primary grinding (one-stage grinding) was performed.

(Example 2)
First, using the same jet mill as in Example 1, the raw material powder was subjected to primary grinding under the conditions shown in Table 1 to obtain crushed powder (a2).
Next, the crushed powder (a2) was again charged into a jet mill, and secondary grinding was performed under the conditions shown in Table 1 to obtain a resin powder (b2).
Next, using the same classifier as in Example 1, resin powder (b2) was classified under the conditions shown in Table 1 to obtain resin powder (c2).

(Example 3)
First, the raw material powder was cooled to -196 ° C with liquid nitrogen.
Next, using a hammer mill (manufactured by Hosokawa Micron and Liquid Gas, Lynex Rex Mill LX-0), the raw material particles are primarily pulverized at -160 ° C under the conditions shown in Table 2 to obtain crushed powder (a3) Obtained.
Next, using the same jet mill as in Example 1, the crushed powder (a3) was subjected to secondary grinding under the conditions shown in Table 2 to obtain a resin powder (b3).

(Example 4)
First, raw material particles were primarily crushed under the conditions shown in Table 2 using a pin mill (pin mill M-4 type, manufactured by Seishin Enterprise Co., Ltd.) to obtain crushed powder (a4).
Next, using the same jet mill as in Example 1, the crushed powder (a4) was subjected to secondary grinding under the conditions shown in Table 2 to obtain a resin powder (b4).

(Comparative example 2)
A resin powder (b'3) was obtained in the same manner as in Example 3, except that secondary grinding was omitted, and grinding was performed twice using a hammer mill in primary grinding.
(Comparative example 3)
A resin powder (b'4) was obtained in the same manner as in Example 4 except that secondary grinding was omitted, and grinding was performed twice using a pin mill in primary grinding.

(Example 5)
In primary crushing, the crushed powder (a3) obtained by crushing using a hammer mill is further crushed using the same pin mill as in Example 4 to obtain crushed powder (a5); In the same manner as in 3, a resin powder (b5) was obtained.
(Comparative example 4)
A resin powder (c'6) was obtained in the same manner as in Comparative Example 1 except that the conditions of the jet mill were changed as shown in Table 3 in the primary pulverization.

3. Preparation of Single-sided Copper-clad Laminate As shown in Tables 1 to 3, a single-sided copper-clad laminate was prepared as follows using a predetermined resin powder.
First, 300 g of resin powder, 30 g of a nonionic surfactant (manufactured by Neos Co., Ltd., Phasegent 710 FL), and 330 g of N-methyl-2-pyrrolidone were charged into a horizontal ball mill pot, and then 15 mm in diameter of zirconia. The balls were filled and dispersed to obtain a dispersion.

Next, a thermosetting modified polyimide varnish (manufactured by PI Research, solvent: N-methyl pyrrolidone, solid content: 15% by mass) and a dispersion liquid are prepared by mass ratio of the thermosetting modified polyimide and the fine particles. The mixture was mixed to obtain a mixed solution of 20: 20.
The mixed solution is applied to the surface of a copper foil with a thickness of 12 μm, dried at 150 ° C. for 10 minutes in a nitrogen atmosphere, heated at 260 ° C. for 10 minutes and cooled to 25 ° C. to have a resin layer with a thickness of 5 μm. A single-sided copper clad laminate was obtained.

4. Measurement and evaluation 4-1. Measurement of D50 and D90 of particles The particles were dispersed in water using a laser diffraction / scattering particle size distribution measuring device (LA-920 measuring device manufactured by Horiba, Ltd.), the particle size distribution was measured, and D50 and D90 were calculated. .
4-2. Measurement of full width at half maximum The full width at half maximum was determined from the particle size distribution curve obtained above.

4-3. Evaluation of smoothness of resin layer The surface of the resin layer of each of the produced single-sided copper clad laminates was visually observed, and the smoothness of the resin layer was evaluated according to the following criteria.
1: Unevenness is formed on the surface by streaks and coarse particles, and there is no gloss.
2: Slight surface roughening due to coarse particles is observed, but it is glossy.
3: The surface is flat and glossy.

4-3. Evaluation of peel strength of single-sided copper-clad laminates A single-sided copper-clad laminate cut out in a rectangular shape (length 100 mm, width 10 mm) is fixed at 50 mm from one end in the length direction, with a tensile speed of 50 mm / min. The peeling strength of the copper foil and the resin layer was evaluated by setting the maximum load to be the peeling strength (N / cm) applied when peeling 90 ° to the single-sided copper clad laminate from one end in the longitudinal direction.
1: Peeling strength is less than 5 N / cm.
2: Peeling strength is 5 N / cm or more and 10 N / cm or less.
3: Peeling strength is more than 10 N / cm.

In addition to the above results, the yield from the raw material powder of the resin powder finally obtained is also shown in Tables 1 to 3.

In Examples 1 to 5, the resin powder with few coarse particles is dispersed in the resin layer of the single-sided copper clad laminate without aggregation. Therefore, the surface of the resin layer is smooth, and as a result, a glossy surface is formed.
In Comparative Examples 1 to 4, the resin layer of the single-sided copper-clad laminate contains resin powder with a large number of coarse particles. As a result, reflecting the shape of the coarse particles, irregularities are generated on the surface of the resin layer, and the gloss is also lost. When the surface of the resin layer has many irregularities as described above, the adhesion to other layers in the printed wiring board may be reduced, or the pattern circuit may be elongated to conform to the irregularities, resulting in a decrease in transmission characteristics.
Therefore, it is preferable that the amount of coarse particles be small and the particle diameter be uniform so that the resin powder can be monodispersed in the resin layer. In order to produce such a resin powder, it is understood that it is necessary to grind raw material particles by two or more mechanical grinding processes, and to use at least the final mechanical grinding process as a jet mill.

5. Study on Shape of Particles Constituting Resin Powder 5-1. Measurement of Viscosity of Dispersion The following procedure was carried out using resin powder (c1) (Example 1), resin powder (c'1) (comparative example 1) and resin powder (c'6) (comparative example 4) The dispersion was prepared and its viscosity was measured.
First, 100 g of resin powder was dispersed in 100 g of water to prepare a dispersion.
Next, the viscosity of the obtained dispersion was measured using a Brookfield viscometer under conditions of a rotation speed of 30 rpm at room temperature (25 ° C.). The value of viscosity was determined by repeating measurement three times and taking the average value of three measurements.

As a result, the viscosity of the dispersion in which the resin powder (c1) is dispersed is 150 mPa · s, and the viscosity of the dispersion in which the resin powder (c′1) is dispersed is 405 mPa · s. The viscosity of the dispersion in which c'6) was dispersed was 500 mPa · s.
Thus, the viscosity of the dispersion in which the resin powder (c'6) was dispersed was clearly higher than the viscosity of the other dispersions. This is a result indicating that the particles contained in the resin powder (c'6) are irregularly shaped particles.

5-2. Evaluation of cohesiveness of resin powder Using resin powder (c1) (example 1), resin powder (c'1) (comparative example 1) and resin powder (c'6) (comparative example 5), as shown below The dispersion was prepared and its viscosity was measured.
First, 100 g of resin powder was dispersed in 100 g of water to prepare a dispersion.
Next, the obtained dispersion was passed through a 200-mesh sieve according to JIS Z 8801-1: 2006 to recover the residue remaining on the sieve, and the mass of the residue after drying was measured.

As a result, in the case of the resin powder (c1), the amount of the residue is 1.3 g, and in the case of the resin powder (c'1), the amount of the residue is 2.1 g, and the resin powder (c ') In the case of 6), the amount of residue was 4.2 g.
Thus, the amount of residue in the case of resin powder (c'6) was clearly greater than the amount of residue of other resin powders. This is a result indicating that the particles contained in the resin powder (c'6) are irregularly shaped particles.

5-3. Measurement of Fluidity of Resin Powder The fluidity of resin powder (c1) (Example 1), resin powder (c'1) (Comparative example 1) and resin powder (c'6) (Comparative example 4) It measured based on "the fluidity | liquidity test method of metal powder" prescribed in JIS Z 2502: 2012.
As a result, the fluidity of the resin powder (c1) is 40 sec / 50 g, the fluidity of the resin powder (c'1) is 81 sec / 50 g, and the fluidity of the resin powder (c'6) is 100 sec. It was / 50 g.
Thus, the flow rate of the resin powder (c'6) was clearly higher than the flow rates of the other resin powders. This is also a result indicating that the particles contained in the resin powder (c'6) are irregularly shaped particles.

The resin powder of the present invention is useful for improving the transmission characteristics of a printed wiring board by using the resin powder in contact with a pattern circuit in the printed wiring board. Moreover, the resin composition in the present invention can be used for the production of a resin layer provided in a film, an impregnated material (prepreg etc.), etc., and the releasability, electrical properties, water and oil repellency, chemical resistance, weather resistance, heat resistance It can also be used for the production of molded articles for applications where slipperiness, abrasion resistance and the like are required. The resin layer composed of such a resin composition is useful as an antenna component, a printed circuit board, a component for an aircraft, a component for an automobile, a sports equipment, a food industry article, a paint, a cosmetic, etc. Insulating layer, wire covering material (electric wire for aircraft etc.), electrical insulating tape, insulating tape for oil drilling, material for printed circuit board, electrode binder (for lithium secondary battery, for fuel cell etc.), copy roll, furniture , Car dashboards, covers for household appliances, sliding members (load bearings, sliding shafts, valves, bearings, gears, cams, belt conveyors, food conveying belts, etc.), tools (shoes, files, cuttings, saws, etc.). ), Boilers, hoppers, pipes, ovens, baking molds, chutes, dies, toilet bowls, container coatings.
The entire contents of the specification, claims, abstract and drawings of Japanese Patent Application No. 2017-221274 filed on Nov. 16, 2017 are incorporated herein by reference and incorporated as disclosure of the specification of the present invention. It is a thing.

Claims (15)

1. A primary resin body containing a heat-meltable fluoropolymer having a volume-based cumulative 50% diameter of 10 μm or more after primary grinding to a volume-based cumulative 50% diameter of 1 to 300 μm by at least one mechanical grinding treatment A method for producing a resin powder comprising: secondary pulverizing with a jet mill; and classification as necessary to obtain a resin powder having a volume-based cumulative 50% diameter of 0.01 to 3 μm.
2. The manufacturing method according to claim 1, wherein a volume-based cumulative 90% diameter of the produced resin powder is 2.5 to 4 μm.
3. The manufacturing method according to claim 1, wherein the primary grinding process is a process including grinding by a jet mill.
4. The preparation according to any one of claims 1 to 3, wherein the heat-meltable fluoropolymer has 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. Method.
5. 5. The method according to claim 4, wherein the heat-meltable fluoropolymer is a fluoropolymer comprising a unit having the functional group and a unit based on tetrafluoroethylene.
6. The method according to claim 4 or 5, wherein at least one of the carbonyl group-containing group and the hydroxy group is a functional group introduced by plasma treatment or corona treatment on the heat-meltable fluoropolymer.
7. The method according to any one of claims 1 to 6, wherein the melting point of the heat-meltable fluoropolymer is 260 to 320 属 C.
8. A resin powder comprising a heat-meltable fluoropolymer, having a volume-based cumulative 50% diameter of 0.01 to 3 μm, and a volume-based cumulative 90% diameter of 2.5 to 4 μm.
9. The resin powder according to claim 8, wherein the full width at half maximum in the particle size distribution curve of the resin powder is 2.5 μm or less.
10. The resin powder according to claim 8 or 9, wherein when 100 g of the resin powder is dispersed in 100 g of water to prepare a dispersion, the viscosity of the dispersion is 50 to 400 mPa · s.
11. 100 g of the resin powder is dispersed in 100 g of water to prepare a dispersion, and when the dispersion is passed through a 200 mesh sieve according to JIS Z 8801-1: 2006, the residue remaining on the sieve The resin powder according to any one of claims 8 to 10, wherein the amount is 3 g or less.
12. The resin powder according to any one of claims 8 to 11, wherein the fluidity of the resin powder is 20 to 80 sec / 50 g.
13. The resin according to any one of claims 8 to 12, wherein the heat-meltable fluoropolymer has 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. powder.
14. The resin powder according to any one of claims 8 to 13, wherein the melting point of the heat-meltable fluoropolymer is 260 to 320 属 C.
15. A method for producing a laminate comprising a flat base material and a resin layer provided on the base material and formed from the resin powder according to any one of claims 8 to 14,
    The manufacturing method of the laminated body which supplies the liquid composition containing the said resin powder and a liquid medium on the said base material, and it heats, and obtains the said resin layer.

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