Liquid composition and substrate with convex portions

Abstract

[Problem] A purpose of the present invention is to provide a liquid composition having appropriate viscosity, suitable for use, for example, as a resist composition, and a base material with protrusions having protrusions with few defects. [Solution] The liquid composition of the present invention has a viscosity of 5000-100,000 mPa∙s and contains a powder of a tetrafluoroethylene polymer having a melting temperature of 160-320°C and a curable aromatic resin having a carboxyl group and an acid value of 150 mg KOH / g or less. Also, the base material with protrusions of the present invention has a base material and protrusions having a predetermined pattern formed from the liquid composition of the present invention, provided on the surface of the base material.

Description

Technical Field

[0001] The present invention relates to a liquid composition having an appropriate viscosity and a substrate with convex portions having few defects.

Background Art

[0002] As a coating agent for forming a molded article having electrical properties such as low dielectric constant and low dielectric tangent, mold release properties, water and oil repellency, chemical resistance, weather resistance, etc. of a tetrafluoroethylene-based polymer, a dispersion liquid containing the powder has been proposed (see Patent Document 1). In recent years, from the viewpoint of improving the electrical properties of insulating portions of electronic components such as printed wiring boards, for example, low dielectric constant and low dielectric tangent properties, studies have been actively conducted on blending the powder of tetrafluoroethylene-based polymers into the materials of electronic components. Patent Document 2 proposes blending the powder of tetrafluoroethylene-based polymers into a resist composition for forming a pattern having an oil retention function.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] Due to the low surface tension of the tetrafluoroethylene-based polymer, its affinity with other components is extremely low. Therefore, in a resist composition (liquid composition) in which the powder is dispersed, an increase in its viscosity and aggregation of the powder become problems. When such a resist composition is used, it is difficult to form a molded article with few defects. As a result of intensive studies, the present inventors have found that the above problems can be solved by selecting a curable aromatic resin as the base polymer and a tetrafluoroethylene-based polymer to be added. An object of the present invention is to provide a liquid composition having an appropriate viscosity and suitable for use as, for example, a resist composition, and a substrate with convex portions having few defects.

Means for Solving the Problems

[0005] The present invention has the following aspects. <1> A liquid composition containing a powder of a tetrafluoroethylene-based polymer having a melting temperature of 160 to 320°C and a curable aromatic resin having a carboxyl group and an acid value of 150 mgKOH / g or less, and having a viscosity of 5000 to 100000 mPa·s. <2> The liquid composition according to <1>, wherein the aromatic resin is a carboxyl group-containing phenol resin. <3> The liquid composition according to <1> or <2>, which does not contain a liquid dispersion medium or contains a liquid dispersion medium at a ratio of 40% by mass or less. <4> The liquid composition according to any one of <1> to <3>, wherein the tetrafluoroethylene-based polymer contains units based on perfluoro(alkyl vinyl ether) and contains 1.5 to 5.0 mol% of units based on perfluoro(alkyl vinyl ether) with respect to all units. <5> The liquid composition according to any one of <1> to <4>, wherein the powder is a powder having an average particle diameter of 0.1 to 10 μm. <6> The liquid composition according to any one of <1> to <5>, wherein the powder is composite particles containing an inorganic substance. <7> The liquid composition according to any one of <1> to <6>, further containing an inorganic filler. <8> The liquid composition according to any one of <1> to <7>, further containing an inorganic filler containing silicon oxide. <9> The liquid composition according to any one of <1> to <8>, wherein the content of the aromatic resin is more than the content of the tetrafluoroethylene-based polymer. <10> The liquid composition according to any one of <1> to <9>, wherein the liquid composition is a negative resist composition. <11> The liquid composition according to any one of <1> to <10>, further containing a curing agent. <12> The liquid composition according to <11>, wherein the curing agent is at least one curing agent selected from the group consisting of amines, imidazoles, phenols, and acid anhydrides. <13> The liquid composition according to <11> or <12>, wherein the curing start temperature of the liquid composition is 120 to 200°C. <14> A substrate with convex portions, comprising a substrate and convex portions provided on the surface of the substrate and having a predetermined pattern formed from the liquid composition according to any one of <1> to <13>. <15> The substrate with convex portions according to <14>, wherein the substrate includes a polymer layer containing a tetrafluoroethylene-based polymer and a metal layer provided on the surface of the polymer layer, and the convex portions are provided on the surface of the metal layer opposite to the polymer layer.

Advantages of the Invention

[0006] Since the liquid composition of the present invention has an appropriate viscosity, it has excellent handleability and can form a molded article with few defects (for example, the convex portions of the substrate with convex portions).

Embodiments for Carrying Out the Invention

[0007] The following terms have the following meanings. "Average particle diameter (D50)" is the volume-based cumulative 50% diameter of an object (powder or inorganic filler) determined by the laser diffraction / scattering method. That is, the particle size distribution of the object is measured by the laser diffraction / scattering method, the cumulative curve is obtained with the total volume of the particle population of the object as 100%, and it is the particle diameter at the point where the cumulative volume becomes 50% on the cumulative curve. "D90" is the volume-based cumulative 90% diameter of the object measured in the same manner. "Melting temperature (melting point)" is the temperature corresponding to the maximum value of the melting peak of the polymer measured by the differential scanning calorimetry (DSC) method. The "glass transition temperature (Tg)" is a value measured by analyzing a polymer using the dynamic viscoelasticity measurement (DMA) method. The "viscosity" is a value obtained by measuring the liquid composition at 25°C under the condition of a rotation speed of 30 rpm using a B-type viscometer. The measurement is repeated three times, and the average value of the three measurement values is used. The "thixotropy ratio" is a value (η1 / η2) calculated by dividing the viscosity η1 obtained by measuring the liquid composition under the condition of a rotation speed of 30 rpm by the viscosity η2 obtained by measuring under the condition of a rotation speed of 60 rpm. The "unit" in a polymer may be an atomic group directly formed from a monomer, or may be an atomic group in which a part of the structure is converted by treating the obtained polymer by a predetermined method. The unit based on monomer A contained in the polymer is also simply referred to as "monomer A unit".

[0008] The liquid composition of the present invention (hereinafter, also referred to as "this composition") contains a powder of a tetrafluoroethylene-based polymer (hereinafter, also referred to as "F polymer") having a melting temperature of 160 to 320°C (hereinafter, also referred to as "F powder") and a curable aromatic resin having a carboxyl group and an acid value of 150 mgKOH / g or less (hereinafter, simply referred to as "aromatic resin"), and has a viscosity of 5000 to 100000 mPa·s. That is, although this composition contains F powder, it has an appropriate viscosity and excellent handleability. Further, the molded article formed from this composition (for example, the convex portion of the base material with a convex portion) has few defects, has a desired complex shape, and can highly exhibit the physical properties of the F polymer. The reason is not necessarily clear, but it is considered as follows.

[0009] The aromatic resin in this composition has a carboxyl group-containing site as a hydrophilic site and an aromatic ring-containing site as a hydrophobic site, and can be said to be a resin with a balanced hydrophilicity and hydrophobicity. Such an aromatic resin easily interacts with the F polymer and is considered to function also as a dispersant for the F powder. Therefore, the F powder is less likely to increase the viscosity of the liquid composition. Also, it is presumed that the F powder is less likely to aggregate, and as a result, the dispersion stability of this composition is enhanced. Also, in order to cure the aromatic resin in such a state, the F powder is firmly held in the matrix of the aromatic resin. Therefore, it is considered that the molded article formed from this composition has the F powder less likely to fall off, the occurrence of defects reduced, and contains the F powder densely and homogeneously and highly has the physical properties based on the F polymer.

[0010] The viscosity of this composition is 5000 to 100000 mPa·s, preferably 5000 to 75000 mPa·s, and more preferably 5500 to 50000 mPa·s. In this case, the handleability of this composition becomes better, and a molded article with fewer defects is more easily obtained. Note that the fact that this composition is liquid means that it is in a liquid, semi-solid or paste state at 25°C, in other words, it is in a state having fluidity at 25°C.

[0011] The D50 of the F powder in this composition is preferably 10 μm or less, more preferably 6 μm or less, and even more preferably 3 μm or less. The D50 of the F powder is preferably 0.1 μm or more, and more preferably 0.5 μm or more. Also, the D90 of the F powder is preferably 10 μm or less, and more preferably 8 μm or less. In the D50 and D90 within this range, the fluidity and dispersibility of the F powder become good, and also, the electrical properties (low dielectric property, low dielectric tangent property, etc.) of the molded article are more likely to be improved. The F powder preferably contains the F polymer as a main component. The content of the F polymer in the F powder is preferably 80% by mass or more, and more preferably 100% by mass.

[0012] The F powder may be composite particles containing an inorganic substance. As the inorganic substance, oxides, nitrides, simple metals, alloys, and carbon are preferable, silicon oxide (silica), metal oxides (beryllium oxide, cerium oxide, alumina, soda alumina, magnesium oxide, zinc oxide, titanium oxide, etc.), boron nitride, or magnesium metasilicate (steatite) are more preferable, silica or boron nitride is even more preferable, and silica is particularly preferable. In this case, the viscosity of this composition becomes sufficiently low, the fluidity increases, and the handleability is more likely to be further improved. Such composite particles preferably have an F polymer as the core and an inorganic substance on the surface of this core. The composite particles can be obtained, for example, by bonding (collision, aggregation, etc.) the powder of the F polymer and the powder of the inorganic substance.

[0013] The F polymer in the present invention is a polymer containing units (TFE units) based on tetrafluoroethylene (TFE). The F polymer is thermally meltable. The melting temperature of the F polymer is 160 to 320°C, preferably 260 to 320°C, and more preferably 285 to 320°C. By using such an F polymer, a dense and excellent adhesion molded product (protrusion) is likely to be formed, and the molded product is also likely to be excellent in water and oil repellency. The glass transition point (Tg) of the F polymer is preferably 75 to 125°C, and more preferably 80 to 100°C. The melt viscosity of the F polymer is preferably 1×10 2 ~1×10 6 Pa·s at 380°C, and more preferably 1×10 3 ~1×10 6 Pa·s.

[0014] Examples of the F polymer include a polymer containing TFE units and units based on ethylene, a polymer containing TFE units and units based on propylene, a polymer (PFA) containing TFE units and units based on perfluoro(alkyl vinyl ether) (PAVE) (PAVE units), a polymer (FEP) containing TFE units and units based on hexafluoropropylene, a polymer containing TFE units and units based on fluoroalkyl ethylene, and a polymer containing TFE units and units based on chlorotrifluoroethylene. PFA or FEP is preferred, and PFA is more preferred. The above polymers may further contain units based on other comonomers. As the PAVE, CF2=CFOCF3, CF2=CFOCF2CF3 or CF2=CFOCF2CF2CF3 (hereinafter also referred to as "PPVE") is preferred, and PPVE is more preferred.

[0015] The F polymer preferably has a polar functional group. In this case, the molded article is likely to have excellent physical properties such as electrical properties and surface smoothness. The polar functional group may be contained in the units contained in the F polymer, or may be contained in the end groups of the F polymer main chain. Examples of the latter F polymer include a polymer having a polar functional group as an end group derived from a polymerization initiator, a chain transfer agent, etc., and a polymer having a polar functional group prepared by plasma treatment or ionization radiation treatment.

[0016] As the polar functional group, a hydroxyl group-containing group, a carbonyl group-containing group, and a phosphono group-containing group are preferred, a hydroxyl group-containing group and a carbonyl group-containing group are more preferred, and a carbonyl group-containing group is even more preferred. As the hydroxyl group-containing group, an alcoholic hydroxyl group-containing group is preferred, and -CF2CH2OH, -C(CF3)2OH, and 1,2-glycol group (-CH(OH)CH2OH) are more preferred. Examples of the carbonyl group-containing group include a carboxyl group, an alkoxycarbonyl group, an amide group, an isocyanate group, a carbamate group (-OC(O)NH2), an acid anhydride residue (-C(O)OC(O)-), an imide residue (-C(O)NHC(O)-, etc.) and a carbonate group (-OC(O)O-), with an acid anhydride residue being more preferred.

[0017] When the F polymer has a polar functional group, the number of polar functional groups in the F polymer is preferably 10 to 5,000 per carbon atom in the main chain, more preferably 100 to 3,000. The number of polar functional groups in the F polymer can be quantified by the composition of the polymer or the method described in International Publication No. 2020 / 145133. 6 As the F polymer, a tetrafluoroethylene-based polymer containing PAVE units and containing 1.5 to 5.0 mol% of PAVE units based on all units is preferred, and a polymer (1) containing PAVE units and having a polar functional group, or a polymer (2) containing PAVE units and containing 2.0 to 5.0 mol% of PAVE units based on all monomer units and having no polar functional group is more preferred. Since these polymers form microspherulites in the molded article, the physical properties of the resulting molded article are likely to be improved.

[0018]

[0019] Polymer (1) preferably contains 90 to 98 mol% of TFE units, 1.5 to 9.97 mol% of PAVE units, and 0.01 to 3 mol% of units based on a monomer having a polar functional group, respectively, based on all units. Moreover, as the monomer having a polar functional group, itaconic anhydride, citraconic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride (hereinafter also referred to as "NAH") are preferred. Specific examples of polymer (1) include the polymers described in International Publication No. 2018 / 16644.

[0020] The polymer (2) is composed only of TFE units and PAVE units, and preferably contains 95.0 to 98.0 mol % of TFE units and 2.0 to 5.0 mol % of PAVE units based on all units. The content of PAVE units in the polymer (2) is preferably 2.1 mol % or more, more preferably 2.2 mol % or more, based on all units. In addition, the polymer (2) having no polar functional group means that the number of carbon atoms constituting the polymer main chain is 1×10 6 This means that the number of polar functional groups per unit of the polymer is less than 500. The number of the polar functional groups is preferably 100 or less, and more preferably less than 50. The lower limit of the number of the polar functional groups is usually 0.

[0021] The polymer (2) may be produced by using a polymerization initiator, a chain transfer agent, or the like that does not generate a polar functional group as a terminal group of the polymer chain, or may be produced by fluorinating a polymer having a polar functional group (e.g., a polymer having a polar functional group derived from a polymerization initiator at the terminal group of the polymer chain). An example of a fluorination treatment method is a method using fluorine gas (see JP 2019-194314 A, etc.). The F powder may contain other polymers other than the F polymer. The other polymers include aromatic polyesters, polyamideimides, polyimides, polyphenylene ethers, polyphenylene oxides, and maleimides.

[0022] The aromatic resin in the composition is preferably a photosensitive resin having a carboxyl group and an alkali-soluble resin. From the viewpoint of improving photocurability and developability, the photosensitive resin preferably has an ethylenically unsaturated double bond in the molecule, and more preferably has a (meth)acryloyloxy group in the molecule. In this specification, the (meth)acryloyloxy group is a term that collectively refers to an acryloyloxy group, a methacryloyloxy group, and both of them. As such an aromatic resin, a carboxyl group-containing phenol resin is preferred, and a carboxyl group-containing phenol resin obtained by reacting epichlorohydrin with phenolic hydroxyl groups to epoxidize a polyfunctional phenol resin (for example, a polyfunctional novolak-type epoxy resin) and then adding a dibasic acid anhydride to the hydroxyl groups present in the side chains after reacting with (meth)acrylic acid is more preferred. Such a carboxyl group-containing phenol resin is preferred because it easily interacts with an F polymer, particularly an F polymer having a polar functional group.

[0023] The acid value of the aromatic resin is 150 mgKOH / g or less, preferably 120 mgKOH / g or less, and more preferably 90 mgKOH / g or less. The acid value of the aromatic resin is preferably 40 mgKOH / g or more, and more preferably 45 mgKOH / g or more. The aromatic resin having such an acid value highly interacts with the F polymer, enhancing the dispersion stability of the F powder in the liquid composition. In addition, such an aromatic resin has good alkali developability and easily obtains a molded article (protrusion) having a desired complex shape. This composition may contain a photopolymerization initiator. Examples of the photopolymerization initiator include alkylphenone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, benzoin-based photopolymerization initiators, benzophenone-based photopolymerization initiators, 2,2'-azobisisobutyronitrile, and benzoyl peroxide.

[0024] This composition preferably further contains a curing agent, and more preferably contains a curing agent capable of undergoing a thermosetting reaction with the aromatic resin. In addition, when the F polymer has a carbonyl-containing group (such as a carboxyl group or an acid anhydride residue), the curing agent may undergo a thermosetting reaction with the F polymer. If this composition contains a curing agent, the hardness of the molded article formed from this composition can be further increased by thermosetting the aromatic resin and / or the F polymer in the molded article. Such a curing agent is preferably at least one selected from the group consisting of amines, imidazoles, phenols, and acid anhydrides. From the viewpoint of enhancing the stability of the present composition and the adhesiveness and electrical properties of the formed molded article, amines or imidazoles are more preferable. The curing agent may be used alone or in combination of two or more. It is preferable to select a curing agent such that the curing start temperature of the present composition is 120 to 200°C. The "curing start temperature" is the temperature indicating the first heat quantity change point when the present composition is heated, as confirmed by differential scanning calorimetry (DSC).

[0025] As the amine, aliphatic polyamines (alkylenediamines, polyalkylenepolyamines, aliphatic polyamines having an aromatic ring, etc.), their adduct compounds, alicyclic polyamines (isophoronediamine, 1,3-bis(aminomethyl)cyclohexane, bis(4-aminocyclohexyl)methane, norbornenediamine, 1,2-diaminocyclohexane, laromin, etc.), or their adduct compounds are preferable. Examples of the former adduct compounds include addition reaction products of aliphatic polyamines and phenyl glycidyl ether, tolyl glycidyl ether, or alkyl glycidyl ether. Examples of the latter adduct compounds include addition reaction products of alicyclic polyamines and n-butyl glycidyl ether or bisphenol A diglycidyl ether. Specific examples of amines include "Fujicure FXR" series (manufactured by Fujikasei Kogyo Co., Ltd.), "Ancamine" series or "Sunmide" series (both manufactured by Air Products Japan Co., Ltd.), jER Cure 113 (manufactured by Mitsubishi Chemical Corporation), Laromin C-260 (manufactured by BASF), etc.

[0026] Examples of the imidazole include 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, an azine compound of imidazole, an isocyanurate of imidazole, a hydroxymethyl form of imidazole, or an adduct compound thereof (such as a reaction product of an epoxy resin and imidazole; Curezol P-0505 (manufactured by Shikoku Kasei Kogyo Co., Ltd.), etc.), and these are preferred.

[0027] Examples of the phenol include hydroquinone, resorcinol, or bisphenol A, and these are preferred. Examples of the acid anhydride include phthalic anhydride, hexahydrophthalic anhydride, methyl nadic anhydride, or benzophenone tetracarboxylic acid, and these are preferred.

[0028] This composition preferably further contains an inorganic filler. In this case, the linear expansion coefficient of the obtained molded article can be decreased. Therefore, even if the molded article is heat-treated, its deformation can be prevented. Such an inorganic filler is preferably a filler containing a nitride or a filler containing an inorganic oxide, more preferably a boron nitride filler, a beryllia filler (a filler of beryllium oxide), a filler containing silicon oxide (such as a silica filler, a wollastonite filler, a talc filler, etc.), or a metal oxide (such as cerium oxide, aluminum oxide, magnesium oxide, zinc oxide, titanium oxide, etc.) filler, and even more preferably a filler containing silicon oxide (particularly, a silica filler). By using a filler containing silicon oxide, the linear expansion coefficient of the obtained molded article can be sufficiently decreased. When the inorganic filler is a silica filler, the content of silica in the inorganic filler is preferably 50% by mass or more, more preferably 75% by mass or more. The content of silica is preferably 100% by mass or less.

[0029] The surface of the inorganic filler is preferably surface-treated with a silane coupling agent, and more preferably surface-treated with 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane or 3-isocyanatopropyltriethoxysilane.

[0030] When the composition contains an inorganic filler surface-treated with a silane coupling agent, the interaction between the F powder and the inorganic filler is likely to increase. In other words, a composite of the F powder and the inorganic filler is likely to be formed, and aggregation of the F powder is likely to be suppressed. As a result, the homogeneity of the molded article formed from the composition is improved, and its various physical properties (electrical physical properties such as low dielectric constant and low dielectric tangent), and its shape stability, particularly the shape stability during convex portion formation, are more likely to be further improved.

[0031] The D50 of the inorganic filler is preferably 25 μm or less, and more preferably 15 μm or less. The D50 of the inorganic filler is preferably 0.1 μm or more. The shape of the inorganic filler may be any of granular, acicular (fibrous), and plate-like. Specific shapes of the inorganic filler include spherical, scaly, layered, flaky, almond-shaped, columnar, cockscomb-shaped, equiaxial, leaf-shaped, mica-shaped, block-shaped, flat-plate-shaped, wedge-shaped, rosette-shaped, mesh-shaped, and prismatic. The inorganic filler may be hollow, or may include a hollow filler and a non-hollow filler.

[0032] Preferable specific examples of the inorganic filler include silica fillers (such as the "Admafine (registered trademark)" series manufactured by Admatechs Co., Ltd.), zinc oxide fillers surface-treated with esters such as propylene glycol dicaprate (such as the "FINEX (registered trademark)" series manufactured by Sakai Chemical Industry Co., Ltd.), spherical fused silica fillers (such as the "SFP (registered trademark)" series manufactured by Denka Co., Ltd.), titanium oxide fillers coated with polyhydric alcohols and inorganic substances (such as the "Typepeek (registered trademark)" series manufactured by Ishihara Sangyo Co., Ltd.), rutile-type titanium oxide fillers surface-treated with alkylsilanes (such as the "JMT (registered trademark)" series manufactured by Teika Co., Ltd.), hollow silica fillers (such as the "E-SPHERES" series manufactured by Pacific Cement Co., Ltd., the "Silanax" series manufactured by Nippon Steel Mining Co., Ltd., the "EcoCosFiller" series manufactured by Emerson and Cuming Co., Ltd., etc.), talc fillers (such as the "SG" series manufactured by Nippon Talc Co., Ltd.), steatite fillers (such as the "BST" series manufactured by Nippon Talc Co., Ltd.), boron nitride fillers (such as the "UHP" series manufactured by Showa Denko K.K., the "Denka Boron Nitride" series (grades "GP", "HGP") manufactured by Denka Co., Ltd., etc.).

[0033] From the viewpoint of improving dispersibility and handleability, the composition may further contain a surfactant. The surfactant is preferably nonionic. The hydrophilic moiety of the surfactant preferably has an oxyalkylene group or an alcoholic hydroxyl group. The hydrophobic moiety of the surfactant 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, and more preferably a silicone-based surfactant. The surfactant may be a glycol-based surfactant. One kind of surfactant may be used, or two or more kinds may be used. When two kinds of surfactants are used, it is preferable to use a silicone-based surfactant and a glycol-based surfactant.

[0034] The composition may further contain other resins. The other resin may be a thermosetting resin or a thermoplastic resin. An aromatic polymer is preferred as the other resin. In this case, the molded article is excellent in UV absorption and tends to be excellent in UV processability. Examples of the other resin include maleimide resins, urethane resins, polyimides, polyamic acids, polyamide-imides, polyphenylene ethers, polyphenylene oxides, liquid crystal polyesters, and fluoropolymers other than F polymers.

[0035] Maleimide resins, polyimides, and polyamic acids are preferred as the other resin. In this case, the molded article formed from the composition tends to be excellent in flexibility and adhesiveness. As the other resin, aromatic maleimide resins, thermoplastic polyimides, and polyamic acids are more preferred.

[0036] In addition, as the fluoropolymer other than the F polymer as the other resin, a tetrafluoroethylene-based polymer having a melting temperature exceeding 320°C is preferred, and non-thermally meltable polytetrafluoroethylene is more preferred. In this case, the molded article formed from the composition tends to be excellent in electrical properties (such as low dielectric constant and low dielectric tangent). Such a fluoropolymer other than the F polymer is preferably contained in the composition as particles. When the fluoropolymer other than the F polymer is contained as particles, the D50 of the particles is preferably 0.1 μm or more, more preferably more than 0.3 μm. Also, the D50 of the F particles is preferably 25 μm or less, more preferably 8 μm or less. When the composition contains F powder and particles of a fluoropolymer other than the F polymer, the proportion of the F powder in the total amount is preferably 25% by mass or more, more preferably more than 50% by mass. That is, the proportion of the fluoropolymer other than the F polymer is preferably 75% by mass or less, more preferably less than 50% by mass.

[0037] In addition to these components, the present composition may also contain additives such as silane coupling agents, dehydrating agents, defoaming agents, plasticizers, weathering agents, antioxidants, heat stabilizers, lubricants, antistatic agents, brightening agents, colorants, conductive agents, mold release agents, surface treatment agents, flame retardants, etc.

[0038] It is preferable that the present composition does not contain a liquid dispersion medium or contains the liquid dispersion medium at a ratio of 40% by mass or less. The ratio of the liquid dispersion medium in the present composition is preferably 25% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less. Also, the lower limit of the ratio (content) of the liquid dispersion medium in the present composition is 0%. Note that the liquid dispersion medium is an inert compound that is liquid at 25°C and does not react with any of the other components contained in the present composition, and has the function of dissolving or dispersing each component. Specific examples of the liquid dispersion medium include water, cellosolve-based solvents, ester-based solvents, propylene glycol-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, and aromatic hydrocarbon-based solvents.

[0039] In the present composition, it is preferable that the content (ratio) of the aromatic resin is more 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 aromatic resin to the content of the F-polymer is preferably 4 to 10, more preferably 5 to 9, and even more preferably 6 to 8. The content of the F-polymer in the present composition is preferably 1 to 30% by mass, and more preferably 10 to 25% by mass. The content of the aromatic resin in the present composition is preferably 20 to 90% by mass, and more preferably 30 to 80% by mass. When the present composition contains a curing agent, its content is preferably 0.01 to 15% by mass, and more preferably 0.1 to 10% by mass. When the present composition contains an inorganic filler, its content is preferably 0.1 to 75% by mass, and more preferably 1 to 60% by mass.

[0040] This composition can be suitably used as a negative resist composition. The resist composition can be applied to the surface of a substrate by coating methods such as screen printing, bar coating, and blade coating. After coating, it is preferable to dry the coating film in order to obtain touch-dry property. The drying conditions are preferably 75 to 95 °C for 40 to 70 minutes. For drying, a hot air circulation drying furnace or a far-infrared drying furnace can be used. From the viewpoint of good developability of the dried film, the thickness of the dried film after drying, that is, the dried coating film, is preferably 10 to 150 μm, more preferably 20 to 60 μm.

[0041] Next, the dried coating 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 light, a metal halide lamp, a black lamp, an electrodeless lamp, etc. can be used. The exposure dose is preferably an integrated light dose of 200 mJ / cm 2 or less. Note that a pattern may be formed on the dried coating film by a laser direct imaging apparatus without using an exposure mask.

[0042] Next, the dried coating film after exposure is developed with a developer. Thereby, unnecessary portions of the dried coating film are removed, and a dried coating film having a predetermined pattern is obtained. The developer can be applied to the dried coating film after exposure by a spray method, a dipping method, etc. As the developer, an alkaline aqueous solution containing an alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium silicate is preferably used, and a dilute alkaline aqueous solution containing the alkali at a concentration of 1.5 mass% or less is more preferably used. According to this composition, since a dilute alkaline aqueous solution can be used as the developer, a dried coating film with less damage and excellent resolution can be obtained.

[0043] As a specific embodiment of the developing solution, a dilute alkaline aqueous solution containing sodium carbonate at a concentration of 0.2 to 2.0% by mass is preferred. In addition, for the dried film after development, it is preferable to perform water washing or acid neutralization in order to remove unnecessary developing solution. Next, the obtained dried film after development is cured (post-cured) by irradiation with active energy rays such as ultraviolet rays. When the liquid composition contains the above-mentioned curing agent, the dried film after development can also be cured by heating. Thereby, a cured film (molded article such as a convex portion) excellent in adhesion and crack resistance can be obtained. In the case of curing by irradiation with ultraviolet rays, the irradiation intensity of ultraviolet rays is preferably 500 to 3000 mJ / cm 2 and more preferably 500 to 2000 mJ / cm 2 On the other hand, in the case of curing by heating, the heating temperature is preferably 200°C or lower, more preferably 180°C or lower, and even more preferably 150°C or lower. The heating temperature is preferably 120°C or higher.

[0044] This composition can also be suitably used as a filling material for filling through holes or recesses in a multilayer printed wiring board. A multilayer printed wiring board has a plurality of circuit patterns laminated via insulating layers. The insulating layer is composed of polyphenylene ether, polyphenylene oxide, cyanate ester, polyimide, fluoropolymer, etc. Further, the circuit pattern is composed of a metal film formed by plating or the like. This multilayer printed wiring board has through holes penetrating in its thickness direction or recesses that are recessed. The through holes or recesses are formed by drilling or laser processing. A conductive film is formed on the inner surface of the through holes or recesses, and predetermined circuit patterns are electrically connected to each other. When such through holes or recesses are filled with this composition and cured, the through holes or recesses can be filled.

[0045] The filling of the through holes or recesses of the present composition can be carried out by screen printing method, roll coating method, die coating method, or vacuum printing method. At this time, it is preferable to fill the through holes or recesses to an extent that the composition protrudes therefrom. When the present composition contains a curing agent, it is preferable to cure the composition filled in the through holes or recesses by heating. The heating conditions of the present composition are preferably heating at 80 to 160 °C for 30 to 180 minutes. From the viewpoint of suppressing outgassing during the curing of the present composition, it is preferable to cure the composition in two stages, namely, a pre-curing stage and a main-curing stage. As the pre-curing conditions, heating at 80 to 110 °C for 30 to 90 minutes is preferable. In this case, since the cured product after pre-curing has a relatively low hardness, unnecessary portions protruding from the through holes or recesses can be easily removed by polishing, etching, etc. The hardness of this cured product can be adjusted by changing the heating time and heating temperature during pre-curing.

[0046] As the main-curing conditions, heating at 130 to 160 °C for 30 to 180 minutes is preferable. By this main-curing, a molded product (filled product) having high adhesion to the insulating layer of a multilayer printed wiring board can be obtained. In addition, since the present composition has a small volume change rate during curing, a decrease in the shape stability of the multilayer printed wiring board can be prevented. The cross-sectional void ratio of the molded product obtained from the present composition is preferably 5% or less, more preferably 3% or less. The lower limit of the cross-sectional void ratio is 0%. Since the present composition has a low content of volatile components, voids are less likely to occur when molding the molded product. At this stage, unnecessary portions protruding from the through holes or recesses of the molded product may be removed and flattened. 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. Note that, prior to the formation of the metal film on the surface of the multilayer printed wiring board, a roughening treatment may be performed with an aqueous potassium permanganate solution or the like, if necessary.

[0047] In addition, the present composition can also be suitably used for producing a dry film. Such a dry film can be produced by applying the present composition on a carrier film and drying it to form a resin film as a dry film. If necessary, a protective film may be laminated on the dry film. The carrier film is a film having a function of supporting the dry film. Examples of such carrier films include polyolefin films, polyester films, polyimide films, polyamideimide films, polytetrafluoroethylene films, polystyrene films, and surface-treated paper substrates. Among them, a polyester film is preferred from the viewpoints of heat resistance, mechanical strength, handleability, etc. The thickness of the carrier film is preferably 10 to 150 μm. In addition, a release treatment may be applied to the surface of the carrier film.

[0048] The protective film is a film adhered to the surface of the dry film opposite to the carrier film of the dry film for the purpose of preventing dust and the like from adhering to the surface of the dry film and improving its handleability. For the protective film, for example, the same films and paper substrates as those mentioned for the above carrier film are used. Among them, a polyolefin film or a polyester film is preferred. The thickness of the protective film is preferably 10 to 150 μm. In addition, a release treatment may be applied to the surface of the protective film.

[0049] A printed wiring board can be manufactured using such a laminated film. First, either the carrier film or the protective film is peeled off from the dry film. When the present composition contains a curing agent, next, after pressing it onto a circuit board on which a circuit pattern has been formed, it is thermally cured. For thermal curing, an oven, a hot press machine, etc. can be used. Then, through holes (via holes) are formed in a predetermined portion of the circuit board by laser processing or drill processing to expose the circuit pattern. Thereby, a printed wiring board is obtained. When unnecessary components (smear) that cannot be completely removed remain on the circuit pattern, it is preferable to perform a desmear treatment. The other of the carrier film and the protective film is peeled off from the dry film at a predetermined stage. For the electrical connection between circuit patterns, a conductive film formed on the inner surface of the through hole, or pillars or posts housed in the through hole can be used.

[0050] The base material with convex portions of the present invention (hereinafter, also referred to as "the present base material with convex portions") has a base material and convex portions provided on the surface of the base material and having a predetermined pattern formed from the present composition. As the base material, a base material I: an active matrix substrate on which a pixel electrode, a switching element, and wiring are formed on a substrate, a base material II: a laminate in which a polymer film and a metal layer are laminated, etc. can be used. In the case of the base material I, the convex portions are provided as a frame on the surface of the active matrix substrate so as to expose, for example, the pixel electrodes. In this case, if an organic EL layer (electron transport layer, light emitting layer, hole transport layer, etc.) and an electrophoretic dispersion liquid containing electrophoretic particles are arranged in the space partitioned by the convex portions, and a counter substrate provided with a common electrode or the like is arranged to face the active matrix substrate, a display device (electronic device) can be manufactured.

[0051] In such a configuration, the convex portions can be given the function of a spacer that defines the distance between the two substrates and a black matrix that prevents crosstalk between adjacent pixels. In addition, the convex portions in the present base material with convex portions are excellent in water and oil repellency and have few defects. Therefore, the ink for forming the organic EL layer or the electrophoretic dispersion liquid hardly adheres to the convex portions, and a display device with excellent display performance can be obtained. Further, since the convex portions are also excellent in electrical characteristics (low dielectric constant property), parasitic capacitance hardly occurs in the display device, and a decrease in switching characteristics can also be prevented.

[0052] In the case of the base material II, the polymer film may be a single-layer film composed only of a polymer layer, or may be a laminated film having a polymer layer as a surface layer and a support layer that supports the surface layer (polymer layer). The support layer can be composed of a heat-resistant resin film, a prepreg which is a precursor of a fiber-reinforced resin plate, a film having a heat-resistant resin layer, or a film having a prepreg layer. The prepreg is a sheet-like substrate obtained by impregnating a fiber base material (such as a tow or a woven fabric) of reinforcing fibers such as glass fibers and carbon fibers with a thermosetting resin or a thermoplastic resin.

[0053] The heat-resistant resin film is a film containing one or more heat-resistant resins. Examples of the heat-resistant resin include polyimide, polyarylate, polysulfone, polyallylsulfone, aromatic polyamide, aromatic polyetheramide, polyphenylene sulfide, polyaryl ether ketone, polyamideimide, liquid crystal polyester, and liquid crystal polyester amide. Polyimide (especially aromatic polyimide), F polymer, and fluororesins other than F polymer are preferred. The polymer layer preferably contains the above heat-resistant resin, more preferably contains an F polymer, and even more preferably contains the above polymer (1) or polymer (2). In such a case, the base material is likely to be excellent in low dielectric tangent. When the polymer layer contains the above polymer (1) or polymer (2), the F polymer in the present composition is also preferably polymer (1) or polymer (2). In such a case, the present convex portion and the base material are likely to be firmly adhered.

[0054] The polymer layer containing an F polymer may be obtained by melt-kneading and extrusion molding the F polymer. In this case, the laminated film is obtained by thermocompression bonding a film containing an F polymer and the support layer. The polymer layer containing an F polymer may be obtained by applying a powder dispersion liquid containing an F polymer powder and a liquid dispersion medium to a base material and heating it. In this case, a single-layer film containing an F polymer can be obtained by peeling the base material. If the film constituting the above support layer is used as the base material and the base material is not peeled, a laminated film can be obtained. The laminated board 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 alloy, stainless steel, nickel, nickel alloy (including Alloy 42), aluminum, aluminum alloy, titanium, titanium alloy, and the like. The metal foil is preferably a copper foil, more preferably a rolled copper foil or an electrolytic copper foil. The ten-point average roughness of the surface of the substrate II is preferably 0.01 to 0.05 μm. In this case, the substrate with the convex portions is likely to be excellent in low transmission loss property. The surface of the substrate II may be surface-treated with a silane coupling agent or may be plasma-treated. In this case, it is easy to obtain the substrate with the convex portions in which the convex portions are firmly adhered to the substrate.

[0055] A preferred embodiment of the laminate as the substrate II includes a prepreg layer / polymer layer containing an F polymer / metal layer. The metal layer may have a predetermined pattern. When the metal layer is a pattern circuit, after applying the present composition to the surface of the metal layer (the surface of the metal layer opposite to the polymer layer of the metal layer), drying, exposure, and development are performed, convex portions having a predetermined pattern are formed on the pattern circuit, and the substrate with the convex portions is obtained. The pattern of the pattern circuit and the pattern of the convex portions may be different. When the substrate is a prepreg layer / polymer layer containing an F polymer / metal layer having a predetermined pattern, the thickness of the polymer layer containing the F polymer is preferably 0.1 to 20 μm, more preferably 1 to 10 μm. In this case, during the pretreatment (such as buff polishing) for forming the convex portions, the polymer layer containing the F polymer is shaved, the prepreg layer and the convex portions are partially in direct contact, and the adhesiveness between the convex portions and the substrate is likely to be improved.

[0056] Alternatively, convex portions may be formed on a metal layer having no pattern, and the metal layer may be etched using these convex portions as a mask to process the circuit to obtain a printed wiring board. For the etching, dry etching or wet etching can be used. The convex portions on the substrate with convex portions have few defects and excellent strength. Therefore, it is possible to prevent the convex portions from being altered or deteriorated during etching, and to accurately process wiring, electrodes, etc. having a complex and fine shape for a metal layer. After processing the metal layer, the convex portions may be removed, or the substrate may be used as a substrate for electronic devices without removing them.

[0057] As described above, the liquid composition and the substrate with convex portions of the present invention have been described, but the present invention is not limited to the configurations of the above-described embodiments. For example, in the configurations of the above-described embodiments, other arbitrary configurations may be added to the liquid composition and the substrate with convex portions of the present invention, or they may be replaced with any configurations that exhibit the same functions.

Examples

[0058] Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. 1. Preparation of Each Component [F Polymer] F Polymer 1: A PFA-based polymer containing 98.0 mol%, 0.1 mol%, and 1.9 mol% of TFE units, NAH units, and PPVE units in this order, and having 1000 carbonyl group-containing groups per 1 × 10 6 main chain carbon atoms (melting temperature: 300 °C) F Polymer 2: A PFA-based polymer containing 97.5 mol% and 2.5 mol% of TFE units and PPVE units in this order, and having 25 carbonyl group-containing groups per 1 × 10 6 main chain carbon atoms (melting temperature: 305 °C) Non-F Polymer 1: Non-thermally fusible polytetrafluoroethylene [Powder] Powder 1: A powder composed of F Polymer 1 with a D50 of 1.9 μm Powder 2: A powder composed of F Polymer 2 with a D50 of 2.0 μm Powder 3: A powder composed of Non-F Polymer 1 with a D50 of 2.0 μm

[0059] [Inorganic Particles] Silica particles 1: Spherical particles made of silica (D50: 0.03 μm) Silica particles 2: Spherical particles made of silica without surface treatment (D50: 0.5 μm) Silica particles 3: Spherical particles made of silica (D50: 0.5 μm) surface-treated with 3-aminopropyltriethoxysilane [Aromatic resin] Aromatic resin 1: A carboxyl group-containing phenolic resin (acid value: 80 mgKOH / g) in which acrylic acid is reacted with an epoxylated multifunctional phenolic resin, and then phthalic anhydride is added to the hydroxyl groups present in the side chains. Aromatic resin 2: A carboxyl group-containing phenolic resin (acid value: 160 mg KOH / g) synthesized in the same manner as aromatic resin 1, except that the amount of phthalic anhydride used was changed. [Liquid dispersion medium] NMP: N-methyl-2-pyrrolidone

[0060] 2. Preparation of Composite Particles First, a mixture of 98 parts by mass of Powder 1 and 2 parts by mass of Silica Particles 1 was prepared. Next, the mixture was put into a powder processing device (hybridization system) that applies stress to the particles by pinching them between the inner wall of the container and the stirring body while stirring the particles with a stirring blade rotating at high speed in a cylindrical container. After that, the particles of Powder 1 and the particles of Silica 1 were suspended in a high-temperature turbulent atmosphere and collided with each other, applying stress between them to perform a composite processing. During the processing, the temperature inside the device was kept below 100°C under a nitrogen atmosphere, and the processing time was 15 minutes. The resulting processed product was a fine powder. Analysis of this powder with an optical microscope revealed that it was composite particle 1 with a core-shell structure, in which F polymer 1 was the core and silica particles 1 were attached to the surface of this core to form a shell. The shape of Composite Particle 1 was spherical, and its D50 was 4 μm.

[0061] 3. Preparation of Liquid Composition (Liquid composition 1) 20 parts by mass of composite particles 1 and 80 parts by mass of aromatic resin 1 were put into a pot together with a varnish (solvent: NMP), and then zirconia balls were put into the pot. Thereafter, the pot was rolled under the conditions of 150 rpm for 1 hour to disperse the composite particles 1, thereby obtaining liquid composition 1. Note that liquid composition 1 had a viscosity of 5500 mPa·s and the content ratio of NMP, which was a liquid dispersion medium, was 40% by mass or less. (Liquid composition 2) Liquid composition 2 was obtained in the same manner as liquid composition 1, except that composite particles 1 were changed to powder 1. Note that the viscosity of liquid composition 2 was 60000 mPa·s. (Liquid composition 3) Liquid composition 3 was prepared in the same manner as liquid composition 1, except that composite particles 1 were changed to powder 2. Note that the viscosity of liquid composition 3 was 70000 mPa·s.

[0062] (Liquid composition 4) Liquid composition 4 was prepared in the same manner as liquid composition 1, except that composite particles 1 were changed to powder 3. Note that liquid composition 4 thickened and aggregated, making it difficult to measure its viscosity, form convex portions, and measure the dielectric constant. (Liquid composition 5) Liquid composition 5 was prepared in the same manner as liquid composition 3, except that aromatic resin 1 was changed to aromatic resin 2. Note that the viscosity of liquid composition 5 exceeded 100000 mPa·s. Also, liquid composition 5 had too high a viscosity, making it difficult to form convex portions and measure the dielectric constant. (Liquid composition 6) Aromatic resin 1 was used as liquid composition 6. Note that the viscosity of liquid composition 6 was 200 mPa·s. (Liquid composition 7) Liquid composition 7 was prepared in the same manner as liquid composition 1, except that composite particles 1 were changed to powder 1 and NMP was used as a liquid dispersion medium for dilution. Note that liquid composition 7 had a viscosity of 20000 mPa·s and the content ratio of the liquid dispersion medium exceeded 40% by mass.

[0063] 4. Evaluation 4-1. Aggregation and dispersibility The aggregation and dispersion states of each liquid composition were visually confirmed and evaluated according to the following criteria. [Evaluation Criteria] ○: No sediment is formed even after standing at 25°C for 3 days. △: Sediment is formed when standing at 25°C for 3 days, but it redisperses when shaken. ×: Sediment is formed when standing at 25°C for 3 days and does not redisperse even when shaken.

[0064] 4-2. Defects in the convex portion First, in a laminate of a film of F-polymer 1 and an electrolytic copper foil (manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., "CF-T49A-DS-HD2"), each liquid composition was applied to the surface of the electrolytic copper foil opposite to the film side to form a coating film on the laminate. This coating film was dried at 80°C for 10 minutes to obtain a dried film. The dried films were prepared in two patterns with film thicknesses of 25 μm and 50 μm. Next, using an exposure mask having openings in a predetermined pattern, ultraviolet rays were irradiated onto the dried film. The integrated light quantity of the ultraviolet rays was 150 mJ / cm 2 as specified. Next, the dried film after ultraviolet irradiation was developed with a 1.0 mass% aqueous sodium carbonate solution to form convex portions. When using Liquid Composition 7, due to the volume reduction during film preparation, multiple applications of the liquid composition and ultraviolet irradiation of the dried film were required to form a film with the desired film thickness. The formed convex portions were confirmed with an optical microscope and evaluated according to the following criteria. [Evaluation Criteria] ○: In both cases of film thicknesses of 50 μm and 25 μm, no powder dropout from the convex portions is confirmed. △: No powder dropout from the convex portions is confirmed when the film thickness is 25 μm, but powder dropout from the convex portions is confirmed when the film thickness is 50 μm. ×: In both cases of film thicknesses of 50 μm and 25 μm, powder dropout from the convex portions is confirmed.

[0065] 4-3. Electrical characteristics First, each liquid composition was applied to an electrolytic copper foil (manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., "CF-T49A-DS-HD2") to form a coating film, and this coating film was dried at 80 °C for 10 minutes to obtain a dried film (thickness: 50 μm). Next, without using an exposure mask, ultraviolet light was irradiated onto the entire dried film. The integrated light amount of the ultraviolet light was 150 mJ / cm 2 as specified. After completely curing the film by heating, the electrolytic copper foil was etched with an aqueous solution of ferric chloride to obtain a sample film. After washing this sample film, it was dried in an oven at 100 °C for 2 hours. After leaving the dried sample film in an environment of 24 °C and 50% RH for 24 hours, the dielectric constant at 10 MHz was measured using an SPDR (split post dielectric resonator) and a network analyzer, and evaluation was performed according to the following criteria. [Evaluation Criteria] ◎: The dielectric constant is 3.0 or less. 〇: The dielectric constant is more than 3.0 and 3.5 or less. △: The dielectric constant is more than 3.5 and 4.0 or less. ×: The dielectric constant is more than 4.0. These results are shown in Table 1 below.

[0066]

Table 1

[0067] (Liquid Composition 8) A liquid composition 8 was obtained in the same manner as liquid composition 1, except that 20 parts by mass of composite particles 1 were changed to 15 parts by mass of powder 1 and 5 parts by mass of powder 3. The viscosity of the liquid composition 8 was 70,000 mPa·s. As a result of evaluating the aggregation and dispersibility of the liquid composition 8, and the defects and electrical characteristics of the convex portions of its molded product in the same manner as above, they were "〇", "〇", and "◎" in order. (Liquid Composition 9) The liquid composition 9 was obtained in the same manner as the liquid composition 1, except that 20 parts by mass of the composite particles 1 were changed to the same amount of powder 1, and further 20 parts by mass of silica particles 2 were added. The liquid composition 9 had a viscosity of 80,000 mPa·s, and the content ratio of NMP, which is the liquid dispersion medium, was lower than that of the liquid composition 1. As a result of evaluating the aggregation / dispersibility, defects on the convex portions, and electrical properties of the liquid composition 9 in the same manner as above, they were "Δ", "Δ", and "◎" in order. (Liquid composition 10) The liquid composition 10 was obtained in the same manner as the liquid composition 1, except that 20 parts by mass of the composite particles 1 were changed to the same amount of powder 1, and further 20 parts by mass of silica particles 3 were added. The liquid composition 10 had a viscosity of 30,000 mPa·s, and the content ratio of NMP, which is the liquid dispersion medium, was lower than that of the liquid composition 1. As a result of evaluating the aggregation / dispersibility, defects on the convex portions, and electrical properties of the liquid composition 10 in the same manner as above, they were "〇", "〇", and "◎" in order. [Industrial Applicability]

[0068] The liquid composition of the present invention is excellent in dispersion stability and handleability, and can be used for manufacturing molded articles (including impregnated articles such as films and prepregs, laminates, etc.) having characteristics based on the physical properties of the F-polymer. The molded article of the present invention is useful as antenna parts, printed circuit boards, aircraft parts, automotive parts, sports equipment, food industry supplies, paints, cosmetics, etc. Specifically, it is useful as wire coating materials (such as aircraft wires), electrical insulating tapes, insulating tapes for oil drilling, materials for printed circuit boards (especially, materials for filling holes in printed circuit boards), separation membranes (precision filtration membranes, ultrafiltration membranes, reverse osmosis membranes, ion exchange membranes, dialysis membranes, gas separation membranes, etc.), electrode binders (for lithium secondary batteries, fuel cells, etc.), copy rolls, furniture, automotive dashboards, covers for home appliances, etc., sliding members (load bearings, sliding shafts, valves, bearings, gears, cams, belt conveyors, belts for food conveyance, etc.), tools (shovels, files, saws, chisels, etc.), boilers, hoppers, pipes, ovens, molds, runners, dies, toilets, container coating materials.

Claims

1. A liquid composition containing 10 to 25% by mass of a powder of a tetrafluoroethylene-based polymer having a melting temperature of 160 to 320°C and having 100 to 3000 carbonyl group-containing groups per 1×10⁶ carbon atoms in the main chain, and 20 to 90% by mass of a curable aromatic resin having a carboxyl group and an acid value of 150 mgKOH / g or less, and having a viscosity of 5000 to 100000 mPa·s.

2. The liquid composition according to claim 1, wherein the aromatic resin is a carboxyl group-containing phenol resin.

3. The liquid composition according to claim 1 or 2, which does not contain a liquid dispersion medium or contains a liquid dispersion medium at a ratio of 40% by mass or less.

4. The liquid composition according to any one of claims 1 to 3, wherein the tetrafluoroethylene-based polymer contains units based on perfluoro(alkyl vinyl ether) and contains 1.5 to 5.0 mol% of units based on perfluoro(alkyl vinyl ether) with respect to all units.

5. The liquid composition according to any one of claims 1 to 4, wherein the powder is a powder having an average particle diameter (D50) which is the volume-based cumulative 50% diameter determined by the laser diffraction / scattering method of 0.1 to 10 μm.

6. The liquid composition according to any one of claims 1 to 5, wherein the powder is a composite particle containing an inorganic substance.

7. The liquid composition according to any one of claims 1 to 6, further containing an inorganic filler.

8. The liquid composition according to any one of claims 1 to 7, further containing an inorganic filler containing silicon oxide.

9. The liquid composition according to any one of claims 1 to 8, wherein the content of the aromatic resin is more than the content of the tetrafluoroethylene-based polymer.

10. The liquid composition according to any one of claims 1 to 9, wherein the liquid composition is a negative-type resist composition.

11. The liquid composition according to any one of claims 1 to 10, further containing a curing agent.

12. The liquid composition according to claim 11, wherein the curing agent is at least one curing agent selected from the group consisting of amines, imidazoles, phenols, and acid anhydrides.

13. The liquid composition according to claim 11 or 12, wherein the curing start temperature of the liquid composition is 120 to 200°C.

14. A substrate with convex portions provided on the surface of the substrate and having a predetermined pattern formed from the liquid composition according to any one of claims 1 to 13.

15. The substrate with convex portions according to claim 14, comprising a polymer layer containing a tetrafluoroethylene-based polymer and a metal layer provided on the surface of the polymer layer, and having the convex portions on the surface of the metal layer opposite to the polymer layer.

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