CN116761845A - Liquid composition, method for producing same, and member with protruding portion - Google Patents

Liquid composition, method for producing same, and member with protruding portion Download PDF

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Publication number
CN116761845A
CN116761845A CN202280010736.XA CN202280010736A CN116761845A CN 116761845 A CN116761845 A CN 116761845A CN 202280010736 A CN202280010736 A CN 202280010736A CN 116761845 A CN116761845 A CN 116761845A
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meth
acrylate
liquid
liquid composition
polymer
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光永敦美
长谷川刚
关满
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AGC Inc
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Asahi Glass Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
    • C08F259/08—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C08L101/08—Carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/10—Epoxy resins modified by unsaturated compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Provided are a liquid composition containing tetrafluoroethylene polymer powder, which is suitable as a resist composition and has excellent dispersion stability and operability, a method for producing the liquid composition, and a member with protrusions having protrusions with a predetermined pattern formed from the liquid composition. The liquid composition comprises: a powder of a tetrafluoroethylene polymer having a carbonyl group or a hydroxyl group, at least 1 liquid (meth) acrylate having a viscosity of less than 10000 mPa.s selected from the group consisting of multifunctional (meth) acrylates and mono (meth) acrylates having a hydroxyl group or an oxyalkylene group, and a (meth) acrylic acid-modified carboxyl group-containing aromatic resin.

Description

Liquid composition, method for producing same, and member with protruding portion
Technical Field
The present invention relates to a liquid composition containing tetrafluoroethylene polymer powder, a method for producing the same, and a convex-portion-equipped substrate having a convex portion with few defects.
Background
Tetrafluoroethylene polymers such as Polytetrafluoroethylene (PTFE) are excellent in physical properties such as electrical properties, water and oil repellency, chemical resistance, and heat resistance, and are used for various industrial applications such as printed boards. As a coating agent for imparting the above physical properties to the surface of a substrate, a liquid composition containing tetrafluoroethylene polymer powder is known.
In recent years, from the viewpoint of improving the electrical characteristics (low dielectric constant, low dielectric loss tangent) of an insulating part of an electronic component such as a printed circuit board, the blending of tetrafluoroethylene polymer powder into a material of the insulating part has been actively discussed.
Patent document 1 proposes blending tetrafluoroethylene polymer powder into a resist composition for forming an electronic component.
Patent document 2 proposes blending tetrafluoroethylene polymer powder into a thermosetting resin composition for forming a permanent protective film of a printed circuit board, such as a solder resist layer, an interlayer insulating layer, and a cover layer of a flexible printed circuit board.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication No. 2019-090923
Patent document 2: japanese patent laid-open publication No. 2019-167426
Disclosure of Invention
Technical problem to be solved by the invention
The tetrafluoroethylene polymer has low surface tension, is not easy to interact with other components, and has obviously low dispersion stability. Therefore, in preparing a liquid composition in which the powder thereof is dispersed, a large amount of solvent (dispersion medium) is often used from the viewpoint of suppressing the increase in viscosity and aggregation of the powder. In addition, from the viewpoint of imparting various physical properties to a molded article formed from the liquid composition, it is often necessary to additionally blend various additives into the liquid composition, and the present inventors have found that there is a problem that the liquid properties and the molded article thereof are deteriorated in uniformity and compactness of the distribution of components, and it is difficult to develop the physical properties of the tetrafluoroethylene polymer. Further, it has been found that when a molded article having a fine or complex shape such as a substrate with a convex portion is formed from such a liquid composition, problems such as a limited thickness of the molded article that can be formed by one-time coating and a limited material and shape of the substrate to be coated are also prominent.
The present inventors have conducted intensive studies and have found that a liquid composition excellent in dispersion stability and handleability can be obtained by selecting a tetrafluoroethylene polymer to be blended and selecting a base polymer without using a large amount of a dispersion medium. Further, it has been found that such a liquid composition is suitable for forming not only a molded article excellent in low dielectric loss tangent, low linear expansibility and the like but also a molded article having a fine or complex shape or a molded article of a micrometer order or less.
The purpose of the present invention is to provide a liquid composition containing tetrafluoroethylene polymer powder, which is suitable as a resist composition and has excellent dispersion stability and operability, a method for producing the liquid composition, and a member with protrusions having protrusions with a predetermined pattern formed from the liquid composition.
Means for solving the technical problems
The present invention has the following aspects.
[1] A liquid composition comprising: a powder of a tetrafluoroethylene polymer having a carbonyl group or a hydroxyl group, at least 1 liquid (meth) acrylate having a viscosity of less than 10000 mPa.s selected from the group consisting of multifunctional (meth) acrylates and mono (meth) acrylates having a hydroxyl group or an oxyalkylene group, and a (meth) acrylic acid-modified carboxyl group-containing aromatic resin.
[2] The liquid composition according to [1], wherein the liquid composition does not contain any other liquid component than the liquid (meth) acrylate, or contains the other liquid component at a ratio of 30 mass% or less.
[3] The liquid composition according to [1] or [2], wherein the liquid (meth) acrylate is at least 1 multifunctional (meth) acrylate selected from the group consisting of glycol (meth) acrylate, alkylene glycol (meth) acrylate, glycerol (meth) acrylate, trimethylolpropane (meth) acrylate, ditrimethylolpropane (meth) acrylate, pentaerythritol (meth) acrylate, dipentaerythritol (meth) acrylate, erythritol (meth) acrylate and dipentaerythritol (meth) acrylate.
[4] The liquid composition according to any one of [1] to [3], wherein the tetrafluoroethylene polymer is a tetrafluoroethylene polymer having a fluorine atom content of 70 mass% or more.
[5] The liquid composition according to any one of [1] to [4], wherein the average particle diameter (cumulative 50% diameter on a volume basis) of the powder is 0.1 to 25. Mu.m.
[6]Such as [1]]～[5]The liquid composition according to any one of the above, wherein the powder has a specific surface area of 1 to 25m 2 /g。
[7] The liquid composition according to any one of [1] to [6], further comprising an inorganic filler.
[8] The liquid composition according to any one of [1] to [7], further comprising an epoxy compound.
[9] The liquid composition according to any one of [1] to [8], further comprising a curing agent.
[10] The liquid composition according to any one of [1] to [9], which is used for a negative resist composition.
[11] A process for producing a liquid composition, wherein a powder of a tetrafluoroethylene polymer having a carbonyl group or a hydroxyl group is mixed with at least 1 liquid (meth) acrylate having a viscosity of less than 10000 mPa.s selected from the group consisting of a polyfunctional (meth) acrylate and a mono (meth) acrylate having a hydroxyl group or an oxyalkylene group to obtain a mixture, and the mixture is mixed with a varnish of a (meth) acrylic acid-modified carboxyl-containing aromatic resin to obtain a liquid composition comprising the tetrafluoroethylene polymer and the liquid (meth) acrylate and the (meth) acrylic acid-modified carboxyl-containing aromatic resin.
[12] A process for producing a liquid composition, wherein a powder of a tetrafluoroethylene polymer having a carbonyl group or a hydroxyl group, at least 1 liquid (meth) acrylate having a viscosity of less than 10000 mPa.s selected from a polyfunctional (meth) acrylate and a mono (meth) acrylate having a hydroxyl group or an oxyalkylene group, and a (meth) acrylic acid-modified carboxyl-containing aromatic resin are mixed to obtain a mixture, and the mixture is mixed with a varnish of a (meth) acrylic acid-modified carboxyl-containing aromatic resin to obtain a liquid composition comprising the tetrafluoroethylene polymer and the liquid (meth) acrylate and the (meth) acrylic acid-modified carboxyl-containing aromatic resin.
[13] A substrate with protrusions comprising a substrate and protrusions having a predetermined pattern formed from the liquid composition according to any one of [1] to [11] provided on the surface of the substrate.
[14] The substrate with protrusions according to [13], wherein the height of the protrusions is 500 μm or less.
[15] The substrate with a convex portion according to [13] or [14], wherein the substrate comprises a polymer layer containing a tetrafluoroethylene polymer and a metal layer provided on a surface of the polymer layer, and the convex portion is provided on a surface of the metal layer opposite to the polymer layer.
Effects of the invention
According to the present invention, a liquid composition containing tetrafluoroethylene polymer powder excellent in dispersion stability and handleability can be provided. The liquid composition of the present invention is excellent in physical properties such as electrical properties and can form a molded article (convex portion) having few defects, and therefore, can be used as, for example, a solder resist composition or a constituent material of a printed circuit board.
Detailed Description
The following terms have the following meanings.
The "average particle diameter (D50)" is a cumulative 50% diameter based on the volume of the object (powder and filler) obtained by the laser diffraction/scattering method. That is, the particle size distribution was measured by a laser diffraction/scattering method, and a cumulative curve was obtained with the total volume of the object group being 100%, and the particle diameter at the point on the cumulative curve where the cumulative volume reached 50%.
The D50 of the object was obtained by dispersing the object in water and analyzing the dispersion by a laser diffraction/scattering method using a laser diffraction/scattering particle size distribution measuring apparatus (LA-920 measuring apparatus manufactured by horiba Seisakusho Co., ltd.).
The "specific surface area" is a value calculated by measuring the powder by a BET multipoint method by gas adsorption (constant volume method), and is obtained by using NOVA 4200e (manufactured by Kang Da instruments (Quantachrome Instruments)).
"melting temperature" refers to the temperature corresponding to the maximum value of the melting peak of a polymer measured by Differential Scanning Calorimetry (DSC).
"viscosity" refers to the viscosity measured with a type B viscometer at 25℃and 30 rpm. The measurement was repeated 3 times, and the average of the 3 measured values was taken.
"Unit" in a polymer refers to an atomic group formed from the polymerization of a monomer based on the monomer. The unit may be a unit directly formed by polymerization reaction, or may be a unit in which a part of the unit is converted into another structure by treating a polymer. Hereinafter, the unit based on the monomer a is also simply referred to as "monomer a unit".
"(meth) acrylate" is a generic term for acrylate, methacrylate, and both. "(meth) acrylic" is a generic term for acrylic acid, methacrylic acid, and both. "(meth) acryloyloxy" is a generic term for acryloyloxy, methacryloyloxy, and both.
The liquid composition of the present invention (hereinafter also referred to as "the present composition") is a liquid composition suitable for a negative resist composition comprising a powder (hereinafter also referred to as "F powder") comprising a tetrafluoroethylene polymer having a carbonyl group or a hydroxyl group (hereinafter also referred to as "F polymer"), and at least one liquid (meth) acrylate having a viscosity of less than 10000mpa·s (hereinafter also referred to as "liquid (meth) acrylate") selected from the group consisting of a multifunctional (meth) acrylate and a mono (meth) acrylate having a hydroxyl group or an oxyalkylene group, and a (meth) acrylic acid-modified carboxyl group-containing aromatic resin (hereinafter also referred to as "modified aromatic resin").
The production method of the present invention (hereinafter also referred to as "present method 1") is a method of mixing F powder with a liquid (meth) acrylate to obtain a mixture, and mixing the mixture with a varnish of a modified aromatic resin to obtain a liquid composition containing F powder, liquid (meth) acrylate and modified aromatic resin.
Another production method of the present invention (hereinafter also referred to as "present method 2") is a method of mixing an F powder and a liquid (meth) acrylate with a modified aromatic resin to obtain a mixture, and then mixing the mixture with a varnish of the modified aromatic resin to obtain a liquid composition containing the F powder and the liquid (meth) acrylate with the modified aromatic resin.
The composition contains F powder, but is excellent in liquid properties (viscosity, thixotropic ratio, etc.), and excellent in miscibility with other various additives, dispersion stability, and handleability. Further, the molded article (e.g., convex portion) formed from the composition has few defects, has a desired complex shape, and can highly exhibit the physical properties of the F polymer. The cause and the mechanism of action thereof are not clear, but are presumed as follows, for example.
The F polymer having carbonyl group-containing or hydroxyl group-containing has higher surface energy and excellent affinity with other materials than other tetrafluoroethylene-based polymers such as polytetrafluoroethylene. Therefore, the F powder not only is excellent in dispersibility itself, but also tends to be stable by interacting with the modified aromatic resin. In addition, the liquid (meth) acrylate contained in the present composition is highly compatible with both the F powder and the modified aromatic resin, and not only functions as a dispersion medium, but also promotes the dispersion stability of the F powder and the high compatibility of the modified aromatic resin due to the action of the surfactant thereof. Therefore, the F powder is less likely to aggregate, and as a result, it is presumed that the dispersion stability of the present composition is improved.
In the present method, a composition using a mixture of F powder and a liquid (meth) acrylate is employed, and the liquid (meth) acrylate effectively covers the surface of the F powder in advance and also contributes to the function of the F powder itself as a dispersion medium having the F powder as a dispersoid. Since the F powder in a state where dispersion stability is improved is mixed with the varnish of the modified aromatic resin, it is considered that a composition having excellent dispersion stability and handleability can be obtained by the present method.
Further, since the present composition is cured in this state, the F powder is firmly held in the matrix of the modified aromatic resin and the liquid (meth) acrylate, and shrinkage accompanying curing is suppressed. Therefore, it is considered that the F powder of the molded article formed from the composition is less likely to fall off, the occurrence of defects is reduced, the F powder is densely and homogeneously contained, the molded article has high physical properties based on the F polymer,
the F polymer of the present invention is a polymer having carbonyl group-containing or hydroxyl group-containing units (TFE units) based on Tetrafluoroethylene (TFE). The F polymer may be hot-melt or non-hot-melt, preferably hot-melt. The hot melt property means a polymer exhibiting melt fluidity, and the polymer has a melt flow rate of 0.1 to 1000g/10 minutes at a temperature 20 ℃ or higher than the melting temperature of the polymer under a load of 49N.
When the F polymer is hot-melt, the melting temperature is preferably 200 to 320℃and more preferably 260 to 320 ℃. The limitation of the molecular motion of such hot-melt F polymers having a single molecular level is alleviated in a high degree of freedom conformation, making the effect of the present invention highly apparent.
The fluorine atom content in the F polymer is preferably 70 mass% or more, more preferably 70 to 76 mass%. The F polymer having a high fluorine content has a tendency to have particularly low affinity for other components and to be easily aggregated, but according to the present invention, a composition excellent in dispersion stability and handleability can be obtained even when the F polymer is used.
The glass transition temperature of the F polymer is preferably 75 to 125℃and more preferably 80 to 100 ℃.
Examples of the F polymer include: polymers containing TFE units and units based on ethylene (ETFE), polymers containing TFE units and units based on perfluoro (alkyl vinyl ether) (PAVE units) (PFA), polymers containing TFE units and units based on Hexafluoropropylene (HF)P) of units of the polymer (FEP). ETFE, PFA and FEP may each also contain other units. As PAVE, CF is preferred 2 ＝CFOCF 3 、CF 2 ＝CFOCF 2 CF 3 And CF (compact F) 2 ＝CFOCF 2 CF 2 CF 3 (PPVE), more preferably PPVE.
The F polymer is preferably PFA or FEP, more preferably PFA.
The F polymer is also a polymer having carbonyl-containing groups or hydroxyl-containing groups. In this case, the microsphere crystals are easily formed at the level of the molecular aggregate, the wettability of the F powder is improved, and the above-described effects of the present invention are easily exhibited to a high degree. In this case, the dispersion stability of the composition tends to be high, and the physical properties such as adhesion to a substrate, electrical characteristics, and surface balance of the resulting convex-portion-equipped member tend to be high.
The carbonyl-containing groups or hydroxyl-containing groups may be contained in units in the F polymer or in terminal groups of the F polymer backbone. The latter method may be exemplified by a polymer F having a carbonyl group or a hydroxyl group as a terminal group derived from a polymerization initiator, a chain transfer agent, or the like, and a polymer F having a carbonyl group or a hydroxyl group obtained by subjecting a polymer F to plasma treatment or ionization line treatment.
The carbonyl-containing group is a carbonyl (> C (O)) containing group, preferably a carboxyl group, an alkoxycarbonyl group, an amide group, an isocyanate group, a carbamate group (-OC (O) NH) 2 ) An acid anhydride residue (-C (O) OC (O) -), an imide residue (-C (O) NHC (O) -, etc.), or a carbonate group (-OC (O) O-), more preferably an acid anhydride residue.
The hydroxyl-containing group is preferably an alcoholic hydroxyl-containing group, more preferably-CF 2 CH 2 OH、-C(CF 3 ) 2 OH and 1, 2-ethanediol (-CH (OH) CH) 2 OH)。
The F polymer is preferably a polymer having a carbonyl group and containing TFE units and PAVE units, more preferably a polymer having TFE units, PAVE units and units based on a monomer having a carbonyl group, and even more preferably a polymer containing these units in this order at a content of 90 to 99 mol%, 0.5 to 9.97 mol%, and 0.01 to 3 mol% relative to the total units. The presence of carbonyl group-containing groups is preferable from the viewpoint of further improving the affinity and adhesion of the F polymer.
In the case where the F polymer contains carbonyl-containing groups, the number of carbonyl-containing groups in the F polymer is 1X 10 per unit 6 The number of main chain carbons is preferably 10 to 5000, more preferably 100 to 3000, and still more preferably 800 to 1500. The number of carbonyl groups in the F polymer can be quantified by the method described in International publication No. 2020/145133.
Further, the monomer having a carbonyl group is preferably itaconic anhydride, citraconic anhydride or 5-norbornene-2, 3-dicarboxylic anhydride (hereinafter also referred to as "NAH"). Specific examples of the polymer include those described in International publication No. 2018/16644.
In the present invention, the D50 of the F powder is preferably 0.1 to 25. Mu.m. The D50 of the F powder is preferably 20 μm or less, more preferably 10 μm or less, and still more preferably 8 μm or less. The D50 of the F powder is preferably 0.01 μm or more, more preferably 0.1 μm or more, and still more preferably 0.3 μm or more. When D50 is within this range, the fluidity and dispersibility of the F powder tend to be good.
From the viewpoint of dispersion stability, the specific surface area of the F powder is preferably 1 to 25m 2 Preferably 1 to 8m 2 Preferably 1 to 3m 2 /g。
The amount of F may be 1 or 2 or more.
The F powder may further contain a resin other than the F polymer or an inorganic filler, but the F polymer is preferably used as a main component. The content of the F polymer in the F powder is preferably 80 mass% or more, more preferably 100 mass%.
Examples of the resin include heat-resistant resins such as aromatic polyesters, polyamideimides, (thermoplastic) polyimides, polyphenylene oxides, polyphenylene ethers, and maleimides. Examples of the inorganic filler include silicon oxide (silica), metal oxide (beryllium oxide, cerium oxide, aluminum oxide, basic aluminum oxide, magnesium oxide, zinc oxide, titanium oxide, etc.), boron nitride, and magnesium metasilicate (steatite). At least a portion of the surface of the inorganic filler may be surface-treated.
The F powder containing a resin or an inorganic filler other than the F polymer may have a core-shell structure in which the F polymer is a core and the resin or the inorganic filler other than the F polymer is present on the core, or may have a core-shell structure in which the F polymer is a shell and the resin or the inorganic filler other than the F polymer is present in the shell. The F powder is obtained by, for example, combining (collision, agglomeration, etc.) a powder of the F polymer with a powder of a resin other than the F polymer or an inorganic filler.
The liquid (meth) acrylate in the present composition is at least 1 compound selected from polyfunctional (meth) acrylates and mono (meth) acrylates having a hydroxyl group or an oxyalkylene group, which are liquid at 25 ℃. If the liquid (meth) acrylate is the former (meth) acrylate, the photo-curability is improved particularly when the present composition is used as a resist composition, and a cured product having properties such as acid resistance and heat resistance can be obtained.
The viscosity of the liquid (meth) acrylate is less than 10000 mPas, preferably 1000 mPas or less, and more preferably 300 mPas or less. The viscosity is preferably 1 mPas or more, more preferably 5 mPas or more.
The molecular weight of the liquid (meth) acrylate is not particularly limited, but is preferably 60 to 2000, more preferably 100 to 1000.
The boiling point of the liquid (meth) acrylate is preferably 100℃or higher. The boiling point is preferably 400 ℃ or lower, more preferably 300 ℃ or lower. In this case, when the polymer layer is formed from the present composition (preferably the present composition as a resist composition), liquid (meth) acrylate is less likely to remain in the polymer layer, and physical properties (electrical insulating properties and the like) of the polymer layer are likely to be improved. In addition, the surface smoothness of the polymer layer is easily further improved.
Specific examples of the liquid (meth) acrylate include the following compounds.
Mono (meth) acrylates having a hydroxyl group or an oxyalkylene group, such as 2-hydroxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, diethylene glycol mono (meth) acrylate, and glycerin mono (meth) acrylate;
diol (meth) acrylates such as 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone-modified dicyclopentanyl di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, allylated dicyclohexyl di (meth) acrylate;
Alkylene glycol (meth) acrylates such as diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, neopentyl glycol di (meth) adipate, and polyethylene glycol di (meth) acrylate;
glycerol di (meth) acrylate, glycerol tri (meth) acrylate, ethoxylated glycerol tri (meth) acrylate, propoxylated glycerol (1 PO/OH) tri (meth) acrylate, and the like;
trimethylolpropane (meth) acrylates such as trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane di (meth) acrylate, and propylene oxide modified trimethylolpropane tri (meth) acrylate;
di (trimethylol) propane (meth) acrylate such as di (trimethylol) propane di (meth) acrylate, di (trimethylol) propane tri (meth) acrylate, and di (trimethylol) propane tetra (meth) acrylate;
pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and other pentaerythritol (meth) acrylate;
dipentaerythritol (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol propionate-modified tripentaerythritol tri (meth) acrylate, dipentaerythritol caprolactone-modified dipentaerythritol hexa (meth) acrylate, and the like;
Erythritol di (meth) acrylate, erythritol tri (meth) acrylate, erythritol tetra (meth) acrylate, and the like (meth) acrylate; di (meth) acrylate such as di (meth) acrylate, and di (meth) acrylate such as di (meth) acrylate; ethylene oxide modified di (meth) phosphate acrylates, tri (acryloxyethyl) isocyanurates, isocyanurate di (meth) acrylates, urethane (meth) acrylates.
The liquid (meth) acrylic acid ester may be used alone or in combination of 1 or 2 or more. When 2 or more types of the (meth) acrylic acid esters are used in combination, it is preferable that the (meth) acrylic acid esters in different liquid forms are compatible with each other.
The liquid (meth) acrylate is preferably at least 1 multifunctional (meth) acrylate selected from the group consisting of glycol (meth) acrylate, alkylene glycol (meth) acrylate, glycerol (meth) acrylate, trimethylolpropane (meth) acrylate, ditrimethylolpropane (meth) acrylate, pentaerythritol (meth) acrylate, dipentaerythritol (meth) acrylate, erythritol (meth) acrylate and dipentaerythritol (meth) acrylate.
Liquid (meth) acrylic acid esters are also commercially available, and for example, < NK ester > series such as "A-DPH" (dipentaerythritol polyacrylate, 7500 mPas (25 ℃)), "A-9550" (dipentaerythritol polyacrylate, 6500 mPas (25 ℃)) and the like, which are manufactured by Xinzhou Kogyo Co., ltd.
From the viewpoint of the shape of a molded article, particularly, suppression of shrinkage, when the molded article is formed from the present composition, the present composition does not contain other liquid components than the liquid (meth) acrylate, or in the case of containing such other liquid components, the ratio thereof is preferably 30 mass% or less. The proportion of the other liquid component in the present composition is preferably 25% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less. The lower limit of the ratio (content) of other liquid components in the present composition is 0%.
The other liquid component is a liquid component which is liquid at 25 ℃, does not react with any other constituent component of the present composition, and has a viscosity of 10000mpa·s or less. Specifically, the liquid polymer other than the liquid (meth) acrylate or the liquid dispersion medium having an effect of dissolving or dispersing each component is used. Specific examples of the liquid dispersion medium include water, cellosolve solvents, ester solvents, propylene glycol solvents, ketone solvents, alcohol solvents, amide solvents, and aromatic hydrocarbon solvents.
The modified aromatic resin in the present composition has a carboxyl group and an ethylenically unsaturated double bond derived from a (meth) acryloyloxy group in the molecule. The modified aromatic resin is a photosensitive resin having good photocurability and developability, and is an alkali-soluble resin, and thus can be suitably used in a negative resist composition.
The modified aromatic resin is preferably a carboxyl group-containing phenol resin, more preferably a multifunctional phenol resin (for example, a multifunctional novolac type epoxy resin) obtained by reacting epichlorohydrin with a phenolic hydroxyl group, and a carboxyl group-containing phenol resin obtained by reacting (meth) acrylic acid with the same and adding an organic polybasic acid anhydride to a hydroxyl group present in a side chain. Examples of the organic polybasic acid anhydride include phthalic anhydride, maleic anhydride, succinic anhydride, itaconic anhydride, tetrahydrophthalic anhydride and hexahydrophthalic anhydride.
Such carboxyl group-containing phenolic resins are preferred because of their ease of interaction with F polymers (particularly F polymers having polar functional groups).
The acid value of the modified aromatic resin is preferably 150mgKOH/g or less. The acid value is more preferably 120mgKOH/g or less, and still more preferably 90mgKOH/g or less. The acid value is preferably 40mgKOH/g or more, more preferably 45mgKOH/g or more. The modified aromatic resin having such an acid value highly interacts with the F polymer, and the dispersion stability of the F powder in the present composition is improved.
In addition, such a modified aromatic resin is excellent in alkali developability, and a molded article (convex portion) having a desired complex shape can be easily obtained.
The content of the F polymer in the present composition is preferably 1 to 30% by mass, more preferably 5 to 20% by mass.
The content of the modified aromatic resin in the present composition is preferably 10 to 60% by mass, more preferably 25 to 50% by mass.
In the present composition, the content (ratio) of the modified aromatic resin is preferably larger than the content (ratio) of the F polymer. In this case, the handleability, photocurability and developability of the present composition are further improved. Specifically, the mass ratio of the content of the modified aromatic resin to the content of the F polymer is preferably 1 to 10, more preferably 1 to 5.
The total content of the F powder and the modified aromatic resin in the present composition is preferably 50 mass% or more, more preferably 60 mass% or more. The total content is preferably 90 mass% or less.
The ratio of the mass of the liquid (meth) acrylate to the mass of the F powder in the present composition is preferably 0.1 to 100, more preferably 0.5 to 50.
Inorganic fillers may also be included in the present compositions.
Examples of the inorganic filler include fillers composed of oxides, nitrides, metal monomers, alloys and carbon, preferably silicates (silica (silicon dioxide), wollastonite, talc, mica), metal oxides (beryllium oxide, cerium oxide, aluminum oxide, basic aluminum oxide, magnesium oxide, zinc oxide, titanium oxide and the like), boron nitride and magnesium metasilicate (steatite) fillers, more preferably fillers of inorganic oxides containing at least one element selected from aluminum, magnesium, silicon, titanium and zinc, still more preferably fillers of silica, titanium oxide, zinc oxide, steatite and boron nitride, and particularly preferably fillers of silica. The inorganic filler may be ceramic. The inorganic filler may be used in an amount of 1 or 2 or more kinds. When 2 or more inorganic fillers are used in combination, 2 kinds of fillers of silica may be used in combination, or a filler of silica and a filler of metal oxide may be used in combination.
The use of the silica filler can sufficiently reduce the linear expansion coefficient of the molded article (cured article) obtained from the present composition.
When the inorganic filler is a silica filler, the content of silica in the inorganic filler is preferably 50 mass% or more, more preferably 75 mass% or more. The content of silica is preferably 100 mass% or less.
At least a portion of the surface of the inorganic filler is preferably surface-treated. The surface treatment agent used for the surface treatment is preferably a silane coupling agent, and more preferably 3-aminopropyl triethoxysilane, vinyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-glycidoxypropyl methyldiethoxysilane, 3-methacryloxypropyl triethoxysilane, or 3-isocyanatopropyl triethoxysilane.
The D50 of the inorganic filler is preferably 25 μm or less, more preferably 15 μm or less. The inorganic filler D50 is preferably 0.1 μm or more.
The shape of the inorganic filler may be any of a granular shape, a needle shape (fibrous shape), and a plate shape. Specific shapes of the inorganic filler may be exemplified by: spherical, scaly, lamellar, leaf-like, almond-like, columnar, cockscomb-like, equiaxed, leaf-like, mica-like, block-like, flat-plate-like, wedge-like, flower-like, mesh-like, prismatic. The inorganic filler may be hollow, or may contain a hollow filler and a non-hollow filler.
Preferable specific examples of the inorganic filler include: silica filler (admafin (registered trademark) series, etc. made by ya Dou Ma corporation), zinc oxide surface-treated with an ester such as propylene glycol dicaprate (FINEX (registered trademark) series, etc. made by sakean chemical industry corporation), spherical fused silica (SFP (registered trademark) series, etc. made by electrochemical corporation), titanium oxide surface-treated with a polyhydric alcohol and an inorganic substance (TIPAQUE (registered trademark) series, etc. made by stoneware corporation (Dan Yuan corporation), rutile titanium oxide surface-treated with an alkylsilane (JMT (registered trademark) series, etc. made by imperial corporation) hollow silica filler (E-SPHERES (registered trademark) series manufactured by pacific cement corporation, "SiliNax" series manufactured by heliite corporation, "Eccospheres" series manufactured by emma conming corporation, etc.), talc filler (SG "series manufactured by japan talc corporation, etc.), steatite filler (BST" series manufactured by japan talc corporation, etc.), boron nitride filler (UHP "series manufactured by sho electrician corporation, etc.), electrochemical boron nitride (Denka Boron Nitride) series (" GP "," HGP "grade, etc.).
When the present composition contains an inorganic filler, the content thereof is preferably 0.1 to 75% by mass, more preferably 1 to 60% by mass. When the inorganic filler is contained in this range, the linear expansion coefficient of the obtained molded article (cured article) can be reduced. Therefore, even if the molded article is heat-treated, deformation thereof can be prevented.
The present composition may further comprise an epoxy compound. If the present composition contains an epoxy compound, the crosslinking density of a cured product obtained by curing the present composition tends to be increased, and the properties such as mechanical strength, heat resistance, moisture resistance, chemical resistance, adhesion, flexibility, and hardness tend to be improved.
Examples of the epoxy compound include epoxy compounds having 2 or more epoxy groups in 1 molecule, such as ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, resorcinol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycidyl phthalate, tetrahydrodiglycidyl phthalate, diglycidyl hexahydrophthalate, diglycidyl p-hydroxybenzoate, diglycidyl dimer acid ester, tetraglycidyl diaminodiphenylmethane, triglycidyl para-aminophenol, triglycidyl tris (2, 3-epoxypropyl) isocyanurate, triglycidyl tris (2-hydroxyethyl) isocyanurate, and triglycidyl isocyanurate having a triazine ring;
Novolac type epoxy resins (biphenyl novolac type epoxy resins, phenol novolac type epoxy resins, orthocresol novolac type epoxy resins, para-t-butylphenol novolac type and the like), bisphenol a type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, bisphenol S type epoxy resins, naphthalene type epoxy resins, triphenol type epoxy resins, t-butylcatechol type epoxy resins, aminophenol type epoxy resins, biphenyl aralkyl type epoxy resins, phenylalkyl type epoxy resins, dicyclopentadiene type epoxy resins, adamantane type epoxy resins, alicyclic epoxy resins having cyclohexene oxy groups, tricyclo decyl alkoxy groups, cyclopentenoxy groups and the like, and the like. These epoxy resins may be in any of solid (solid at 40 ℃), semi-solid (solid at 20 ℃ and liquid at 40 ℃) or liquid (liquid at 20 ℃).
These epoxy compounds may be used singly or in combination of 1 kind or 2 or more kinds.
In the case where the present composition contains an epoxy compound, the content thereof is preferably 1 to 40 parts by mass per 100 parts by mass of the modified aromatic resin (solid content) in order to reliably obtain a cured product having sufficient mechanical strength.
When the present composition contains a semi-solid epoxy resin as the epoxy compound, the cured product obtained by curing the present composition (preferably, a negative resist composition) tends to have an increased glass transition temperature (Tg), a decreased linear expansion coefficient, and a favorable crack resistance. On the other hand, when the epoxy resin is contained in a solid state, the cured product tends to have a high glass transition temperature and excellent heat resistance, and when the epoxy resin is contained in a liquid state, the dry film tends to have excellent flexibility.
The present composition may further comprise a curing agent. Examples of the curing agent include a photopolymerization initiator (sensitizer) and a curing agent capable of undergoing a thermal curing reaction with the modified aromatic resin. In the case where the F polymer has carbonyl-containing groups (carboxyl groups, anhydride residues, etc.), the curing agent may also undergo a thermal curing reaction with the F polymer. If the present composition contains a curing agent, the hardness of a molded article formed from the present composition can be further improved.
Examples of the photopolymerization initiator include an alkylbenzene ketone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, a benzoin photopolymerization initiator, a benzophenone photopolymerization initiator, 2' -azobisisobutyronitrile, and benzoyl peroxide.
As the curing agent capable of undergoing a thermal curing reaction with the modified aromatic resin, at least 1 selected from the group consisting of an amine, an imidazole, a phenol, an acid anhydride, a compound having a phenolic hydroxyl group, a compound having a cyanate group, and a compound having a maleimide group is preferable. From the viewpoint of improving the stability of the present composition and the adhesiveness and electrical characteristics of a molded article (cured article) formed from the present composition, amine or imidazole is more preferable. The curing agent may be used alone or in combination of 1 or 2 or more. When 2 or more types of the compound are used, any 1 of the compounds may serve as a curing agent, and the other compounds may serve as curing accelerators.
Examples of the amine include: aliphatic polyamines (alkylene diamine, polyalkylene polyamine, aliphatic polyamine having an aromatic ring, etc.), addition compounds thereof (reactant with phenyl glycidyl ether, triglycidyl ether or alkyl glycidyl ether, etc.), alicyclic polyamines (isophorone diamine, 1, 3-bis (aminomethyl) cyclohexane, bis (4-aminocyclohexyl) methane, norbornene diamine, 1, 2-diaminocyclohexane, laromin, etc.), or addition compounds thereof (reactant with n-butyl glycidyl ether or bisphenol a diglycidyl ether, etc.).
As the imidazole, 2-methylimidazole, 4-methyl-2-ethylimidazole, 2-phenylimidazole, 4-methyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, azine compounds of imidazole, isocyanurates of imidazole, imidazole methylol, or addition compounds of these (reactants of epoxy resin and imidazole, etc.) are preferable.
As phenols, preference is given to hydroquinone, resorcinol or bisphenol A. As the acid anhydride, phthalic anhydride, hexahydrophthalic anhydride, methylnadic anhydride or benzophenone tetracarboxylic acid is preferable.
Examples of the compound having a phenolic hydroxyl group include: phenol novolac resins, alkylphenol novolac resins, bisphenol a novolac resins, dicyclopentadiene type novolac resins, xylok type novolac resins, terpene modified novolac resins, cresol/naphthol resins, polyvinyl phenols, phenol/naphthol resins, phenol resins containing an α -naphthol skeleton, cresol novolac resins containing a triazine skeleton, biphenyl aralkyl type novolac resins, xylok type novolac resins, and the like.
Examples of the compound having a cyanate group include: phenol novolac type cyanate resin, alkylphenol novolac type cyanate resin, dicyclopentadiene type cyanate resin, bisphenol a type cyanate resin, bisphenol F type cyanate resin, bisphenol S type cyanate resin. In addition, a part of the prepolymer may be triazinized.
Examples of the compound having a maleimide group include: 4,4 '-bismaleimide diphenylmethane, bismaleimide phenylmethane, m-phenylene bismaleimide, 3' -dimethyl-5, 5 '-dimethyl-4, 4' -bismaleimide phenylmethane, 4-methyl-1, 3-phenylene bismaleimide, (1, 6-bismaleimide-2, 4-trimethyl) hexane, oligomers thereof, and diamine condensates having maleimide skeleton.
When the composition contains a curing agent, the content thereof is preferably 0.01 to 15% by mass, more preferably 0.1 to 10% by mass.
The curing agent is preferably selected such that the cure initiation temperature of the present composition is 120 to 200 ℃. The "curing initiation temperature" is a temperature which shows an initial change point when the resulting composition is heated, as confirmed by Differential Scanning Calorimetry (DSC) measurement.
From the viewpoint of improving dispersibility and handleability, the present composition may further contain a surfactant as a dispersant.
The surfactant is preferably nonionic.
The hydrophilic part of the surfactant preferably has an oxyalkylene group or an alcoholic hydroxyl group, and the hydrophobic part preferably has an acetylene group, a polysiloxane group, a perfluoroalkyl group or a perfluoroalkenyl group. In other words, the surfactant is preferably an acetylene-based surfactant, a silicone-based surfactant, or a fluorine-based surfactant.
The present composition may also comprise other resins. The other resin may be a thermosetting resin or a thermoplastic resin.
Examples of the other resin include maleimide resins, polyurethane resins, polyimides, polyamic acids, polyamideimides, and polyvinyl acetal resins having no aromatic property.
As the other resin, maleimide resin, polyimide and polyamic acid are preferable. In this case, the molded article formed from the composition tends to have good flexibility and adhesion.
In addition to these components, the present composition may further contain additives such as silane coupling agents, dehydrating agents, antifoaming agents, plasticizers, weather-resistant agents, antioxidants, heat stabilizers, lubricants, antistatic agents, whitening agents, colorants, conductive agents, mold release agents, surface treatment agents, flame retardants, and the like.
The solvent constituting the varnish of the modified aromatic resin in the present method 1 or 2 may be, for example, N-methyl-2-pyrrolidone, cyclohexanone, toluene, or the like. The content of the modified aromatic resin in the varnish of the modified aromatic resin is preferably in the range of 20 to 90 mass%.
In the present method 1, the F powder is mixed with a liquid (meth) acrylate to obtain a mixture, and the mixture is mixed with a varnish of a modified aromatic resin to obtain a liquid composition containing the F polymer, the liquid (meth) acrylate and the modified aromatic resin. In the method 1, the mixture may be mixed with the varnish of the modified aromatic resin, the mixture may be mixed into the varnish one by one, or the varnish may be mixed into the mixture one by one.
In the present method 2, an F powder, a liquid (meth) acrylate and a modified aromatic resin are mixed to obtain a mixture, and the mixture is mixed with a varnish of a modified aromatic resin to obtain a liquid composition containing an F polymer, a liquid (meth) acrylate and a modified aromatic resin. In the method 2, the mixture obtained in advance may be mixed with the varnish of the modified aromatic resin, the mixture may be mixed with the varnish of the modified aromatic resin one by one, or the varnish of the modified aromatic resin may be mixed with the varnish of the modified aromatic resin one by one.
The modified aromatic resin and the modified aromatic resin constituting the varnish of the modified aromatic resin which are mixed in advance in the method 2 may be different types of resins or the same type of resins, and the same type of resins is preferably used.
The present composition is preferably produced by the present method 1 or the present method 2.
The mixing method may be either a batch type or a continuous type, and examples thereof include: for example, stirring by a stirring device having blades (stirring wings) such as propeller blades, turbine blades, paddle blades, and shell blades, a henschel mixer, a pressure kneader, a banbury mixer, or a planetary mixer; mixing by a ball mill, a pulverizer, a basket mill, a sand mill, a DINO mill (a bead mill using a pulverizing medium such as glass beads or zirconia beads), a DISPERMAT disperser, an SC mill, a nail pulverizer, a stirrer mill, or a dispersing machine using a medium such as a stirring mill; high pressure homogenizers such as microfluidizers (mizers), nano-dispersion machines (nano-dispersion machines), ultimaizer dispersion machines (nano-dispersion machines), ultrasonic homogenizers (ultrasonic homogenizers), dissolvers (nano-dispersion machines), dispersion machines (dispersion machines), high-speed impeller dispersion machines (dispersion machines), etc. which are mixed by a dispersion machine without using a medium. Preferably a henschel mixer, a pressure kneader, a banbury mixer, or a planetary mixer, more preferably a planetary mixer. The planetary mixer has 2-axis stirring blades rotating and revolving with each other, and has a structure for stirring and kneading the mixture in the stirring tank. Therefore, the dead space for stirring the blade in the stirring tank is small, the load of the blade can be reduced, and the content can be highly mixed.
The mixing may be performed using a biaxial extrusion kneader or a stone mortar type kneader. The twin-screw extrusion kneader is, for example, a twin-screw continuous kneader that kneads by using a shearing force between two screws arranged adjacently in parallel. The stone mortar mixer is a mixer having a cylindrical fixed part having an inner space through which a mixture can pass, and a rotating part disposed in the inner space of the fixed part and configured to convey the mixture passing through the inner space in a rotation axis direction while continuously kneading the mixture by rotation.
The present composition may be stirred by a stirrer having a cylindrical stirring tank and a rotating portion having a cylindrical portion with a plurality of holes formed therein and rotating inside the inner wall surface of the stirring tank while being expanded into a thin film cylindrical shape by centrifugal force generated by the rotation of the rotating portion.
Mixing can also be carried out using a three-roll mill. The three-roll mill is a mill provided with three rotating rolls including a low-speed roll (feed roll), a medium-speed roll (intermediate roll), and a high-speed roll (finishing roll), and also provided with a mechanism for compressing and shearing a mixture to be mixed through a gap between the low-speed roll and the medium-speed roll, and transferring the mixture to the high-speed roll through a gap between the low-speed roll and the medium-speed roll, and scraping the mixture by a doctor blade. The rotational speed of the three rotating rollers is preferably 3 times the speed of the low speed roller with respect to the speed of the low speed roller, and 9 times the speed of the high speed roller.
In addition, the mixing method in the present method may be a combination of a plurality of the above-described mixing methods.
In the present method 1 or the present method 2, if any additional components such as an inorganic filler, an epoxy compound, a curing agent, a dispersant, and other liquid components are further mixed, they may be mixed at any stage.
The mixing method may be the same as the above mixing method.
The preferable content ranges of the F polymer, the liquid (meth) acrylate and the modified aromatic resin in the liquid composition obtained by the present method 1 or the present method 2 are the same as the content of the F polymer in the present composition. In the present method 2, the content of the modified aromatic resin is the total amount of the modified aromatic resin and the modified aromatic resin constituting the varnish of the modified aromatic resin which are mixed in advance.
The present composition is suitable for use as a negative resist composition.
The resist composition may be applied to the surface of the substrate by a coating method such as screen printing, bar coating, or blade coating.
After the coating, the coating film is preferably dried in order to obtain touch dryness. The drying conditions are preferably from 40 to 70 minutes at 75 to 95 ℃.
The drying can be performed by using a hot air circulation type drying furnace or a far infrared ray drying furnace.
The thickness of the dried coating film (dried coating film) is preferably 10 to 150 μm, more preferably 20 to 60 μm, from the viewpoint of good developability of the dried coating film.
Next, the dry film is irradiated with exposure light using an exposure mask having a predetermined exposure pattern (opening).
As the exposure light source, a halogen lamp, a high-pressure mercury lamp, a laser, a metal halide lamp, a black light lamp, an electrodeless lamp, or the like can be used. The pattern may be formed on the dry film by a laser direct imaging device without using an exposure mask.
Subsequently, the dried film after exposure is developed with a developer. Thereby, unnecessary portions of the dried film are removed, and a dried film having a predetermined pattern is obtained.
The developer may be applied to the dried film after exposure by spraying, dipping, or the like.
The developer preferably uses an aqueous alkali solution containing an alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, etc.
By using the present composition, a dried film having less damage and excellent resolution can be obtained because a dilute aqueous alkali can be used as a developer. In order to remove unnecessary developer, the dried film after development is preferably washed with water or neutralized with an acid.
Then, the obtained developed dry film is cured (post-cured) by irradiation with active energy rays such as ultraviolet rays. In the case where the present composition contains the above-mentioned curing agent, the dried film after development can be cured by heating. Thus, a cured film (molded article such as a convex portion) excellent in adhesion and crack resistance can be obtained.
The composition is also suitable for use as a filler for filling through holes or recesses in a multilayer printed circuit board.
The multilayer printed circuit board has a plurality of circuit patterns laminated via insulating layers. The insulating layer is composed of polyphenyl ether, polyphenylene ether, cyanate ester, polyimide, fluorine-containing polymer and the like. The circuit pattern is formed of a metal film formed by electroplating or the like.
The multilayer printed circuit board has a through hole or a recessed portion penetrating in the thickness direction thereof. The through-hole or the recess is formed by drilling and laser processing. Conductive films are formed on the inner surfaces of the through holes or the concave portions, and predetermined circuit patterns are electrically connected to each other.
The through-hole or the recess can be filled with the present composition and cured.
The filling of the through-holes or recesses with the present composition can be performed by screen printing, roll coating, die coating, or vacuum printing. In this case, the present composition is preferably filled to such an extent that the composition is exposed from the through-hole or the recess.
When the present composition contains a curing agent, the present composition filled in the through-hole or the recess is preferably cured by heating.
The heating conditions of the present composition are preferably from 80 to 160℃for from 30 to 180 minutes. In addition, from the viewpoint of suppressing exhaust gas at the time of curing the present composition, it is preferable to cure the present composition in two stages, a pre-curing stage and a main curing stage. As the conditions for the pre-curing, it is preferable to use the curing at 80 to 110℃for 30 to 90 minutes. As the conditions for the primary curing, it is preferable that the temperature is 130 to 160℃for 30 to 180 minutes. The composition has a small rate of change of volume upon curing, and thus can prevent the decrease in shape stability of a multilayer printed wiring board.
In addition, in the pre-curing stage or curing stage of the present composition, unnecessary portions exposed from the through-holes or recesses of the molded article may be removed and planarized. Thereafter, a metal film may be formed on the surface of the multilayer printed wiring board by plating or the like, and patterned into a predetermined pattern to form a circuit pattern. Here, before the metal film is formed on the surface of the multilayer printed wiring board, roughening treatment with an aqueous potassium permanganate solution or the like may be performed as needed.
In addition, the present compositions are also suitable for making dry films.
The dry film can be produced by applying the composition to a carrier film and drying the film to form a resin film as a dried film. The dry film may be laminated with a protective film as needed.
The carrier film is a film having a function of supporting the dry film. Examples of the carrier film include: polyolefin films, polyester films, polyimide films, polyamideimide films, polytetrafluoroethylene films, polystyrene films, surface-treated paper substrates. Among them, polyester films are preferable from the viewpoints of heat resistance, mechanical strength, handleability, and the like.
The surface of the carrier film may be subjected to a mold release treatment.
The protective film is a film that is attached to the opposite side of the dry film from the carrier film for the purpose of preventing dust and the like from adhering to the surface of the dry film and improving the operability thereof.
The protective film may be, for example, the same film or paper substrate as exemplified for the carrier film, and is preferably a polyolefin film or a polyester film. The surface of the protective film may be subjected to a mold release treatment.
As a method for manufacturing a printed wiring board from a laminate film having a dry film, a carrier film, and a protective film, the following method can be exemplified.
First, either one of the carrier film and the protective film is peeled from the dry film. When the composition contains a curing agent or a curing accelerator, the composition is then pressure-bonded to a circuit board on which a circuit pattern is formed, and then thermally cured. The heat curing may use an oven, a hot press, or the like. Then, a through hole (via hole) is formed at a predetermined portion of the circuit board by laser processing or drilling processing, so that the circuit pattern is exposed. Thereby, a printed circuit board is obtained. In addition, in the case where unnecessary components (stains) remain after the circuit pattern is not completely removed, it is preferable to perform the desmear treatment.
The other of the carrier film and the protective film is peeled from the dry film at a predetermined stage. In addition, in terms of electrical connection between the circuit patterns, a conductive film formed on the inner surface of the through-hole, a stud or a pillar accommodated in the through-hole may be used.
The substrate with protrusions (hereinafter also referred to as "substrate with protrusions") of the present invention comprises a substrate and protrusions provided on the surface of the substrate and having a predetermined pattern formed from the present composition. The convex portion can be produced by the above-described method using the present composition as a negative resist composition.
The convex part of the substrate with the convex part is not easy to collapse even if the height is low, and a high-precision pattern with few defects can be formed. The height of the protruding portion is preferably 500 μm or less, more preferably less than 100 μm. The height of the protruding portion is preferably 1 μm or more, more preferably 10 μm or more.
As the substrate, substrate I: an active matrix substrate having pixel electrodes, switching elements, and wirings formed on the substrate, a base material II: laminate laminated with polymer film and metal layer, etc.
In the case of the base material I, the convex portion is provided as a frame on the surface of the active matrix substrate so as to expose the pixel electrode, for example. In this case, if an organic EL layer (electron transport layer, light emitting layer, hole transport layer, or the like) or an electrophoretic dispersion liquid containing electrophoretic particles is disposed in a space defined by the convex portions, and a counter substrate including a common electrode or the like is disposed to face the active matrix substrate, a display device (electronic device) can be manufactured.
In this configuration, the convex portion can function as a spacer defining the distance between the two substrates and as a black matrix preventing crosstalk between the unit pixels.
Further, since the convex portion of the convex portion-containing substrate is excellent in water and oil repellency and has few defects, the ink or electrophoretic dispersion liquid forming the organic EL layer is less likely to adhere to the convex portion, and a display device excellent in display performance can be obtained. Further, since the convex portion is excellent in electrical characteristics (low dielectric constant), parasitic capacitance is not easily generated in the display device, and degradation of switching characteristics can be prevented.
In the case of the base material II, the polymer film may be a single-layer film composed of only a polymer layer, or may be a laminated film having a polymer layer as a surface layer and a support layer supporting the surface layer (polymer layer).
The support layer may be composed of a heat-resistant resin film, a prepreg which is a precursor of a fiber-reinforced resin sheet, a film having a heat-resistant resin layer, or a film having a prepreg layer.
The prepreg is a sheet-like substrate in which a fiber base material (short hemp, woven fabric, etc.) of reinforcing fibers (glass fibers, carbon fibers, etc.) is impregnated with a thermosetting resin or a thermoplastic resin.
The heat-resistant resin film is a film containing 1 or more heat-resistant resins. Examples of the heat-resistant resin include: polyimide, polyarylate, polysulfone, polyarylsulfone, aromatic polyamide, aromatic polyether amide, polyphenylene sulfide, polyaryletherketone, polyamideimide, liquid crystalline polyester, and liquid crystalline polyester amide, and polyimide (particularly aromatic polyimide), F polymer, and fluororesin other than F polymer are preferable.
The polymer layer preferably contains the above heat-resistant resin, more preferably contains an F polymer. In this case, the low dielectric loss tangent of the base material tends to be high, and the convex portion and the base material tend to be firmly bonded.
The polymer layer containing the F polymer can be obtained by melt-kneading the F polymer and extrusion-molding the F polymer. In this case, the laminated film can be obtained by thermocompression bonding a film containing an F polymer and a support layer.
The polymer layer containing the F polymer can also be obtained by applying a dispersion liquid containing the F powder and a liquid dispersion medium to a substrate and heating the same. In this case, a single-layer film containing the F polymer can be obtained by peeling the substrate, and a laminated film can be obtained by using the film constituting the support layer as the substrate and peeling the substrate.
The laminate as the base material II can be produced by thermocompression bonding a polymer film and a metal foil.
Examples of the material of the metal foil include: copper, copper alloys, stainless steel, nickel alloys (including 42 alloys as well), aluminum alloys, titanium alloys, and the like.
The metal foil is preferably a copper foil, more preferably a rolled copper foil or an electrolytic copper foil.
The preferable form of the laminate of the substrate II may be a form of a prepreg layer/a polymer layer containing an F polymer/a metal layer. The metal layer may have a prescribed pattern. Further, the present convex portion may be formed on the metal layer without the pattern, and the metal layer may be etched using the convex portion as a mask and processed into a circuit to obtain a printed wiring board.
The present composition, the method for producing the present composition, and the substrate with projections have been described above, but the present invention is not limited to the configuration of the above embodiment.
For example, the present composition may be added to the structure of the above embodiment, or may be replaced with any structure that exhibits the same function. The method for producing the present composition may be added to the structure of the above embodiment, or may be replaced with any process that produces the same effect.
Examples
The present invention will be specifically described below by way of examples, but the present invention is not limited thereto.
1. Details of the ingredients
[ F powder ]
F powder 1: from a mixture containing 97.9 mol% TFE units, 0.1 mol% NAH units and 2.0 mol% PPVE units, per 1X 10 6 Powder of F Polymer 1 having 1000 carbonyl groups in the carbon atoms of the main chain (melting temperature: 300 ℃ C.) (D50: 2.1 μm, specific surface area: 2.5m 2 /g)
[ varnish of modified aromatic resin ]
Varnish 1: a varnish (solvent: toluene) comprising an acrylic-modified carboxyl-containing phenolic resin (modified aromatic resin 1, acid value: 80 mgKOH/g) obtained by reacting acrylic acid with an epoxidized multifunctional phenolic resin and adding phthalic anhydride to the hydroxyl group
[ liquid (meth) acrylate ]
Acrylic ester 1: triethylene glycol diacrylate (viscosity: 9 mPa. S)
[ inorganic filler ]
Inorganic filler 1: aluminum hydroxide filler
[ epoxy Compound ]
Epoxy compound 1: biphenyl type epoxy resin
[ curing agent ]
Curing agent 1: melamine
2. Preparation example of liquid composition
Examples 1 to 1
The F powder 1 and the acrylic acid ester 1 were put into a planetary mixer to be kneaded, to obtain a mixture 1 containing the F powder 1 (40 parts by mass) and the acrylic acid ester 1 (20 parts by mass).
Then, the varnish 1 was added to the mixture 1 in multiple portions and kneaded with a planetary mixer to obtain a liquid composition 1A containing F powder 1 (40 parts by mass), modified aromatic resin 1 (20 parts by mass), acrylate 1 (20 parts by mass) and toluene. The proportion of toluene in the liquid composition 1A was adjusted to less than 10 mass%.
Next, the liquid composition 1A, varnish 1, inorganic filler 1, epoxy compound 1, and curing agent 1 were charged into a planetary mixer and mixed to obtain a liquid composition 1B containing F powder 1 (40 parts by mass), modified aromatic resin 1 (80 parts by mass), acrylate 1 (20 parts by mass), inorganic filler 1 (5 parts by mass), epoxy compound 1 (15 parts by mass), and curing agent 1 (2 parts by mass). The proportion of toluene in the liquid composition 1B was adjusted to less than 10 mass%. Liquid composition 1B had excellent dispersibility even after 30 days of storage at 25 ℃ and no aggregates were observed.
Examples 1 to 2
Liquid composition 2A containing F powder 1 (40 parts by mass), modified aromatic resin 1 (20 parts by mass), methyl methacrylate (20 parts by mass) and toluene was obtained in the same manner as liquid composition 1A of production example 1-1, except that acrylic acid ester 1 was changed to methyl methacrylate.
Next, the liquid composition 2A, varnish 1, inorganic filler 1, epoxy compound 1, and curing agent 1 were put into a planetary mixer and mixed to obtain a liquid composition 2B containing F powder 1 (40 parts by mass), modified aromatic resin 1 (80 parts by mass), methyl methacrylate (20 parts by mass), inorganic filler 1 (5 parts by mass), epoxy compound 1 (15 parts by mass), and curing agent 1 (2 parts by mass). The proportion of toluene in the liquid composition 2B was adjusted to less than 10 mass%. Liquid composition 2B separated into two layers after 30 days of storage at 25 ℃ and redispersed was also difficult.
3. Example of production of substrate with protruding portion
[ example 2-1]
A film of the liquid composition 1B was applied to the surface of the laminate of the film of the F polymer 1 and the electrolytic copper foil (CF-T49A-DS-HD 2, manufactured by Fufield Metal foil Co., ltd.) on the opposite side of the film of the electrolytic copper foil, and a coating film was formed on the laminate. The coating film was dried at 80℃for 10 minutes to give a layer (thickness: 50 μm) formed from the liquid composition 1B.
Next, the layer side was irradiated with ultraviolet rays (cumulative light amount: 150 mJ/cm) using an exposure mask having an opening portion of a predetermined pattern 2 ). Subsequently, the layer irradiated with ultraviolet light was developed with 1.0 mass% aqueous sodium carbonate solution to form projections.
As a result of confirming the convex portion with an optical microscope, no particles or fillers were confirmed to fall off from the convex portion. The pencil hardness of the protruding portion was 4H, which was the same as that of the protruding portion formed only of varnish 1.
The film in which the layer after ultraviolet irradiation was recovered alone was measured for its electrical characteristics at 10MHz using SPDR (separation column dielectric resonator) and a network analyzer, and as a result, the film had a dielectric constant of 3 or less and a dielectric loss tangent of 0.05 or less, and exhibited excellent electrical characteristics.
[ examples 2-2]
A layer formed of the liquid composition 2B was formed on the laminate by applying the liquid composition 2B to the surface of the laminate of the film of the F polymer 1 and the electrolytic copper foil in the same manner as in examples 1 to 3, except that the liquid composition 1B was changed to the liquid composition 2B. The layer was exposed to light in the same manner as in examples 1 to 3 to attempt to form projections, but it was confirmed that particles and fillers were detached from the projections, and projections having good shapes could not be formed.
Industrial applicability
The liquid composition of the present invention is excellent in dispersion stability and handleability. Since a molded article excellent in physical properties such as electrical characteristics can be formed from such a liquid composition, the liquid composition can be used as a material for, for example, a solder resist composition, a film, a fiber reinforced film, a prepreg, or a metal laminate (metal foil with resin).

Claims (15)

1. A liquid composition comprising: a powder of a tetrafluoroethylene polymer having a carbonyl group or a hydroxyl group, at least 1 liquid (meth) acrylate having a viscosity of less than 10000 mPa.s selected from the group consisting of multifunctional (meth) acrylates and mono (meth) acrylates having a hydroxyl group or an oxyalkylene group, and a (meth) acrylic acid-modified carboxyl group-containing aromatic resin.
2. The liquid composition according to claim 1, wherein the liquid composition contains no other liquid component than the liquid (meth) acrylate or contains the other liquid component at a ratio of 30 mass% or less.
3. The liquid composition according to claim 1 or 2, wherein the liquid (meth) acrylate is at least 1 multifunctional (meth) acrylate selected from the group consisting of glycol (meth) acrylate, alkylene glycol (meth) acrylate, glycerol (meth) acrylate, trimethylolpropane (meth) acrylate, ditrimethylolpropane (meth) acrylate, pentaerythritol (meth) acrylate, dipentaerythritol (meth) acrylate, erythritol (meth) acrylate and dipentaerythritol (meth) acrylate.
4. The liquid composition according to any one of claims 1 to 3, wherein the tetrafluoroethylene polymer is a tetrafluoroethylene polymer having a fluorine atom content of 70 mass% or more.
5. The liquid composition according to claim 1 to 4, wherein the average particle diameter of the powder, i.e., the cumulative 50% by volume diameter, is 0.1 to 25. Mu.m.
6. The liquid composition according to any one of claims 1 to 5, wherein the powder has a specific surface area of 1 to 25m 2 /g。
7. The liquid composition according to any one of claims 1 to 6, further comprising an inorganic filler.
8. The liquid composition according to any one of claims 1 to 7, further comprising an epoxy compound.
9. The liquid composition according to any one of claims 1 to 8, further comprising a curing agent.
10. The liquid composition according to any one of claims 1 to 9, which is used for a negative resist composition.
11. A process for producing a liquid composition, wherein a powder of a tetrafluoroethylene polymer having a carbonyl group or a hydroxyl group is mixed with at least 1 liquid (meth) acrylate having a viscosity of less than 10000 mPa.s selected from the group consisting of a polyfunctional (meth) acrylate and a mono (meth) acrylate having a hydroxyl group or an oxyalkylene group to obtain a mixture, and the mixture is mixed with a varnish of a (meth) acrylic acid-modified carboxyl-containing aromatic resin to obtain a liquid composition comprising the tetrafluoroethylene polymer and the liquid (meth) acrylate and the (meth) acrylic acid-modified carboxyl-containing aromatic resin.
12. A process for producing a liquid composition, wherein a powder of a tetrafluoroethylene polymer having a carbonyl group or a hydroxyl group, at least 1 liquid (meth) acrylate having a viscosity of less than 10000 mPa.s selected from a polyfunctional (meth) acrylate and a mono (meth) acrylate having a hydroxyl group or an oxyalkylene group, and a (meth) acrylic acid-modified carboxyl-containing aromatic resin are mixed to obtain a mixture, and the mixture is mixed with a varnish of a (meth) acrylic acid-modified carboxyl-containing aromatic resin to obtain a liquid composition comprising the tetrafluoroethylene polymer and the liquid (meth) acrylate and the (meth) acrylic acid-modified carboxyl-containing aromatic resin.
13. A substrate with protrusions comprising a substrate and protrusions having a predetermined pattern, which are provided on the surface of the substrate and formed from the liquid composition according to any one of claims 1 to 11.
14. The substrate with protrusions according to claim 13, wherein the height of the protrusions is 500 μm or less.
15. The substrate with a convex portion according to claim 13 or 14, wherein the substrate comprises a polymer layer containing a tetrafluoroethylene polymer and a metal layer provided on a surface of the polymer layer, and the convex portion is provided on a surface of the metal layer opposite to the polymer layer.
CN202280010736.XA 2021-02-12 2022-02-09 Liquid composition, method for producing same, and member with protruding portion Pending CN116761845A (en)

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