Liquid composition, and method and system for producing porous reinforced resin molded article

Abstract

To provide a liquid composition having sufficiently high pattern accuracy and uniformity for a porous medium.SOLUTION: A liquid composition for imparting functionality to a porous medium comprises a film-forming agent and functional particles, the composition having a viscosity of 1 Pa s or more and 100 Pa s or less at a shear rate of 0.1 (1 / s), and a viscosity of 1 mPa s or more and 100 mPa s or less at a shear rate of 1,000 (1 / s).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a liquid composition, a method for producing a porous reinforced resin molded product, and a production system. [Background technology]

[0002] BACKGROUND ART Conventionally, a technique is known in which a liquid containing functional particles is patterned onto a porous medium such as a fiber sheet by an inkjet method, thereby imparting a desired function to the porous medium.

[0003] For example, an inkjet recording method has been disclosed in which a pigment textile printing ink composition is ejected from a nozzle of a liquid ejection unit and adhered to a fabric (see, for example, Patent Document 1).

[0004] However, the conventional method has the problem of poor pattern accuracy and uniformity. Summary of the Invention [Problem to be solved by the invention]

[0005] An object of one embodiment of the present invention is to provide a liquid composition that has excellent pattern accuracy and uniformity for a porous medium. [Means for solving the problem]

[0006] A liquid composition according to one embodiment of the present invention, which is a means for solving the above problems, comprises a film-forming agent and functional particles, and has a viscosity of 1 Pa·s or more and 100 Pa·s or less at a shear rate of 0.1 (1 / s) and a viscosity of 1 mPa·s or more and 100 mPa·s or less at a shear rate of 1,000 (1 / s), and is a liquid composition for imparting functionality to a porous medium. [Effects of the Invention]

[0007] According to one embodiment of the present invention, it is possible to provide a liquid composition that exhibits excellent pattern precision and uniformity when applied to a porous medium. [Brief explanation of the drawings]

[0008] [Figure 1] 1 is a flowchart showing a method for producing a porous reinforced resin molded article according to one embodiment of the present invention. [Figure 2] 1 is a schematic diagram of a system for manufacturing a porous reinforced resin molded product according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0009] [Liquid composition] The liquid composition according to one embodiment of the present invention contains a film-forming agent and functional particles, and preferably contains a thickener, and may further contain other components as required. The liquid composition according to one embodiment of the present invention contains a film-forming agent, which allows the liquid composition to form a film in the gaps of a porous medium. The liquid composition according to one embodiment of the present invention is a liquid composition for imparting functionality to a porous medium (hereinafter, sometimes referred to as a "liquid for porous medium"), and the liquid composition contains functional particles, which allows the liquid composition to impart desired functionality to the porous medium.

[0010] <Film-forming agent> The film-forming agent is a material that forms a continuous film on the surface of a porous medium. After the film-forming agent is applied, the dispersion medium evaporates, causing the resin particles to bond or fuse together to form a continuous film. For example, a resin emulsion can be used as the film-forming agent. In a resin emulsion, resin particles are dispersed in water as a dispersant. When the liquid composition contains a film-forming agent, a film can be formed in the gaps of a porous medium such as a fiber sheet.

[0011] The type of film-forming agent is not particularly limited and can be appropriately selected depending on the purpose. Examples include resin emulsions containing at least one of acrylic resin, urethane resin, silicone resin, acrylic-styrene copolymer, acrylic-urethane copolymer, acrylic-silicone copolymer, polyester copolymer, vinyl chloride resin, vinyl acetate resin, etc. as a main component. These may be used alone or in combination of two or more. Among these, vinyl chloride resin, acrylic-silicone copolymer, acrylic-styrene copolymer, and acrylic-urethane copolymer are preferred.

[0012] The film-forming agent may be synthesized appropriately or may be a commercially available product. Examples of commercially available products include Vinyblanc 755 (vinyl chloride resin emulsion, manufactured by Nissin Chemical Industry Co., Ltd.), Vinyblanc 278 (vinyl chloride resin emulsion, manufactured by Nissin Chemical Industry Co., Ltd.), Vinyblanc 690 (vinyl chloride resin emulsion, manufactured by Nissin Chemical Industry Co., Ltd.), Vinyblanc 700 (vinyl chloride resin emulsion, manufactured by Nissin Chemical Industry Co., Ltd.), Vinyblanc 715S (vinyl chloride resin emulsion, manufactured by Nissin Chemical Industry Co., Ltd.), Boncoat SA-6360 (acrylic-silicone resin emulsion, manufactured by DIC Corporation), Boncoat CG-8400 (acrylic-styrene resin emulsion, manufactured by DIC Corporation), Boncoat 5400EF (acrylic-styrene resin emulsion, manufactured by DIC Corporation), and Boncoat CG-5010EF (acrylic-urethane resin emulsion, manufactured by DIC Corporation).

[0013] The average particle size (hydrodynamic diameter (cumulant diameter) measured by dynamic light scattering) of the resin particles contained in the film-forming agent is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 10 nm or more and 500 nm or less. The method for measuring particle size is not particularly limited and can be appropriately selected depending on the purpose. For example, the particle size can be measured using a particle size analyzer FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.).

[0014] The minimum film-forming temperature (MFT) of a film-forming agent is the lowest temperature at which a film is formed. For example, it can be measured according to ASTM D2354. The minimum film-forming temperature of a film-forming agent is not particularly limited and can be selected appropriately depending on the purpose. However, a temperature of 0°C or higher and 100°C or lower is preferable, and a temperature of 20°C or higher and 80°C or lower is more preferable from the viewpoints of excellent pattern precision and uniformity, suppressing film formation when applied, and enabling film formation when heated on a porous medium.

[0015] The content of the film-forming agent is not particularly limited and can be selected appropriately depending on the purpose, but is preferably 0.1% by mass or more and 10.0% by mass or less, and more preferably 1.0% by mass or more and 2.0% by mass or less, relative to the total amount of the liquid composition. When the content is 0.1% by mass or more, a film can be formed in the gaps of the porous medium. When the content is 10.0% by mass or less, the liquid composition has excellent pattern precision and uniformity.

[0016] The glass transition temperature Tg (°C) of the film-forming agent is not particularly limited and can be appropriately selected depending on the purpose, but is preferably -50°C or higher and 90°C or lower.

[0017] <Functional particles> Functional particles are materials that impart desired functionality to porous media. The shape of the functional particles is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include spherical, needle-like, and tabular shapes.

[0018] The type of functional particles is not particularly limited and can be appropriately selected depending on the purpose. Examples include silver, copper, aluminum, titanium, carbon, and pigments. By using silver, copper, aluminum, and the like as functional particles, it is possible to impart conductivity to the porous medium. Furthermore, by using titanium, carbon, pigments, and the like as functional particles, it is possible to impart coloring properties to the porous medium.

[0019] The functional particles may be commercially available products, such as JS-A191 (silver nanoparticle dispersion, manufactured by Novacentrix Inc.) and JS-A211 (aqueous silver nanoink containing a fluorine-based binder polymer, manufactured by Novacentrix Inc.).

[0020] The average particle size of the functional particles is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 10 nm or more and 10,000 nm or less. The particle size can be measured, for example, by the same method as that for the particle size of the film-forming agent.

[0021] The ratio (A / B) of the average particle size (A) of the functional particles to the average particle size (B) of the film-forming agent is not particularly limited and can be selected appropriately depending on the purpose, but is preferably 0.1 or more and 10 or less. When the ratio (A / B) is 0.1 or more, a film can be formed on the gaps in the fiber sheet as a porous medium, and when the ratio (A / B) is 10 or less, a film can be formed with the functional particles appropriately exposed, thereby imparting the desired function.

[0022] The content of the functional particles is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 10.0 to 50.0 mass% and more preferably 30.0 to 40.0 mass% of the total amount of the liquid composition. When the content is 10.0 to 50.0 mass%, it becomes easier to impart desired functions to the porous medium.

[0023] <Thickener> A thickener is used to increase the viscosity of a liquid composition. For example, a thickener is one that increases the viscosity by 100% at 25°C after dissolving 1 g of the thickener in 100 mL of water and leaving it to stand for 60 minutes. When the liquid composition contains a thickener, it can form a film in the gaps of a porous medium.

[0024] The type of thickener is not particularly limited and can be appropriately selected depending on the purpose. Examples include resins, carbon nanotubes, cellulose nanofibers, layered clay minerals, etc. These may be used alone or in combination of two or more. Among these, resins are preferred because of their excellent pattern precision and uniformity.

[0025] The resin is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include polyacrylic resin, polyamide resin, polyurethane resin, etc. Among these, polyamide resin is preferred. Examples of polyamide resins include polyamide, modified polyamide, and fatty acid polyamide.

[0026] Examples of layered clay minerals include bentonite, hectorite, kaolinite, montmorillonite, sericite (sericite), and illite. These may be used alone or in combination of two or more. Among these, bentonite and hectorite are preferred.

[0027] The thickener may be synthesized as appropriate, or a commercially available product may be used. Examples of commercially available products include AQ-633E (modified polyamide, manufactured by Kusumoto Chemicals Co., Ltd.), AQH-800 (modified polyamide, manufactured by Kusumoto Chemicals Co., Ltd.), RHEOBYK-425 (urea-modified polyurethane, manufactured by Big Chemie Japan Co., Ltd.), RHEOBYK-430 (urea-modified polyamide, manufactured by Big Chemie Japan Co., Ltd.), RHEOBYK-431 (urea-modified polyamide, manufactured by Big Chemie Japan Co., Ltd.), and Rheocrysta I- Examples include 2SX (cellulose nanofiber, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), NCD-001 (single-walled carbon nanotube dispersion, manufactured by Kusumoto Chemicals Co., Ltd.), LAPONITE-RD (synthetic hectorite, manufactured by BYK), OPTIGEL-CK (Na-substituted bentonite, manufactured by BYK), AEROSIL200 (hydrophilic fumed silica, manufactured by Nippon Aerosil Co., Ltd.), and PFA-131 (fatty acid amide wax, manufactured by Kusumoto Chemicals Co., Ltd.).

[0028] The content of the thickener is not particularly limited and can be selected appropriately depending on the purpose, but is preferably 0.1% by mass to 10.0% by mass, and more preferably 0.2% by mass to 2.0% by mass, based on the total amount of the liquid composition. A content of 0.1% by mass or more can impart thixotropy to the liquid composition, suppressing the flow of the liquid composition after application to a porous medium and allowing a film to be formed in the gaps of the porous medium. A content of 10.0% by mass or less can provide excellent pattern precision and uniformity of the liquid composition.

[0029] <Other ingredients> The other components are not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include solvents such as organic solvents and water. By including a solvent in the liquid composition, it is possible to prevent the liquid composition from drying out and to prevent poor application caused by clogging of the head nozzles and the like with the liquid composition.

[0030] - Organic solvents - The organic solvent is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include water-soluble organic solvents. Examples of water-soluble organic solvents include polyhydric alcohols, ethers such as polyhydric alcohol alkyl ethers and polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, sulfur-containing compounds, propylene carbonate, and ethylene carbonate.

[0031] Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,3-butanediol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 2 ,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,3-hexanediol, 2,5-hexanediol, 1,5-hexanediol, glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-hexanediol, ethyl-1,2,4-butanetriol, 1,2,3-butanetriol, 2,2,4-trimethyl-1,3-pentanediol, and petriol.

[0032] Examples of polyhydric alcohol alkyl ethers include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and propylene glycol monoethyl ether.

[0033] Examples of polyhydric alcohol aryl ethers include ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.

[0034] Examples of the nitrogen-containing heterocyclic compound include 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, and γ-butyrolactone.

[0035] Examples of amides include formamide, N-methylformamide, N,N-dimethylformamide, 3-methoxy-N,N-dimethylpropionamide, and 3-butoxy-N,N-dimethylpropionamide.

[0036] Examples of amines include monoethanolamine, diethanolamine, and triethylamine.

[0037] Examples of sulfur-containing compounds include dimethyl sulfoxide, sulfolane, and thiodiethanol.

[0038] The boiling point of the organic solvent is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 250° C. or less, since it not only functions as a wetting agent but also provides good drying properties.

[0039] The content of the organic solvent is not particularly limited and can be selected appropriately depending on the purpose. From the viewpoints of the drying property, pattern precision, and uniformity of the liquid composition, the content is preferably 10.0 mass % or more and 60.0 mass % or less, and more preferably 20.0 mass % or more and 60.0 mass % or less, based on the total amount of the liquid composition.

[0040] -water- The water content is not particularly limited and can be selected appropriately depending on the purpose. From the viewpoints of drying properties, pattern precision, and uniformity of the liquid composition, the water content is preferably 10.0% by mass or more and 90.0% by mass or less, and more preferably 20.0% by mass or more and 60.0% by mass or less.

[0041] The viscosity of the liquid composition at a shear rate of 0.1 (1 / s) at 25°C is 1 Pa·s or more and 100 Pa·s or less, and the viscosity at a shear rate of 1,000 (1 / s) at 25°C is 1 mPa·s or more and 100 mPa·s or less. The method for measuring the viscosity of the liquid composition is not particularly limited and can be appropriately selected depending on the purpose. For example, the viscosity can be measured using a rheometer MCR-302 (manufactured by Anton Paar).

[0042] The method for producing the liquid composition is not particularly limited and can be appropriately selected depending on the purpose. For example, the liquid composition can be obtained by adding a thickener, a film-forming agent, and, if necessary, a solvent such as an organic solvent or water, mixing and stirring the mixture at 3,000 rpm for 15 minutes using a homogenizer, and then filtering the mixture using a 10 μm PP membrane filter.

[0043] [Method for manufacturing porous reinforced resin molded products and system for manufacturing porous reinforced resin molded products] A method for producing a porous reinforced resin molding according to one embodiment of the present invention includes an application step of applying a liquid composition onto a porous medium, and a drying step of drying the porous medium, and may further include other steps such as a heating step, a moving step, a spraying step, and a laminating step as necessary. A manufacturing system for porous reinforced resin moldings according to one embodiment of the present invention includes an application device that applies a liquid composition onto a porous medium, and a drying device that dries the porous medium, and may further include other devices such as a heating device, a spraying device, and a laminating device as needed.

[0044] The present invention will now be described in detail with reference to the drawings. 1 is a flowchart showing a method for producing a porous reinforced resin molded article according to one embodiment of the present invention. The method for producing a porous reinforced resin molded article includes an applying step S1 and a drying step S2, which are carried out in this order. 2 is a schematic diagram of a system for manufacturing a porous reinforced resin molded product according to one embodiment of the present invention. The system for manufacturing a porous reinforced resin molded product includes an applying device 100 and a drying device 200. The applying device 100 performs the applying step S1, and the drying device 200 performs the drying step S2.

[0045] <Application process and application device> In the application step S1, a liquid composition is applied onto a porous medium. The application is performed, for example, in a pattern on a predetermined region of the porous medium. By adjusting the region impregnated with the liquid composition in the application step S1, i.e., the pattern arrangement, it is possible to adjust the physical properties of the reinforced porous resin molded product, such as its strength and impact resistance. The applying step can be performed by an applying device.

[0046] The application device is not particularly limited as long as it can impregnate the porous medium with the liquid composition, and can be selected appropriately depending on the purpose. For example, the liquid composition may be ejected onto the porous medium using an inkjet nozzle, or the liquid composition may be applied manually onto the porous medium.

[0047] The pattern arrangement may be such that the liquid composition is impregnated into the porous medium in a regular manner or in an irregular manner. Examples of the pattern arrangement in which the liquid composition is impregnated into the porous medium in a regular manner include stripes and a lattice pattern.

[0048] [Porous media] Porous media are media that contain voids within a solid material, such as fibers, metals, or zeolites. The type of fiber is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include glass fiber, carbon fiber, flax fiber, boron fiber, and aramid fiber. Among these, glass fiber, carbon fiber, and flax fiber are preferred in terms of improving the strength of the porous reinforced resin molded product. These may be used alone or in combination of two or more. The fiber volume fraction of the fibers is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 10% or less. In order to prevent the liquid composition from seeping into the fibers, the surface may be appropriately treated.

[0049] <Drying process and drying equipment> In the drying step S2, the porous medium impregnated with the liquid composition is dried. The drying step can be performed by a drying device.

[0050] The drying device is not particularly limited as long as it can remove the organic solvent and water contained in the liquid composition impregnated into the porous medium, and can be selected appropriately depending on the purpose. Examples of the drying device include a hot air dryer and a vacuum dryer.

[0051] The drying temperature is not particularly limited, but is preferably 50° C. or higher and 300° C. or lower, and more preferably 80° C. or higher and 200° C. or lower. A drying temperature of 80° C. or higher and 200° C. or lower is preferred in terms of achieving both ease of film formation and heat resistance of the resin and fibers.

[0052] <Other processes and other equipment> The other steps are not particularly limited and can be appropriately selected depending on the purpose. Examples include a heating step, a moving step, a spraying step, and a laminating step. The other devices are not particularly limited and can be appropriately selected depending on the purpose. Examples include a heating device, a moving device, a spraying device, and a laminating device.

[0053] -Heating process and heating equipment- In the heating step, the porous medium is heated. The heating step may be performed before or after the application step. The heating step can be performed by a heating device.

[0054] The heating device is not particularly limited and can be appropriately selected depending on the purpose. For example, a silicon rubber heater can be used.

[0055] The heating temperature is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 80° C. or higher and 200° C. or lower. The heating temperature is the surface temperature of the heating device.

[0056] -Transfer process and transfer device- In the transfer step, the porous medium is transferred. The transfer step is a step performed between each step. The transfer step can be performed by a transfer device.

[0057] The moving device is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include a belt conveyor.

[0058] -Spraying process and spraying equipment- In the spreading step, the matrix resin is spread over the porous medium in the areas not impregnated with the liquid composition to obtain a porous reinforced resin composite. The spreading step can be performed by a spreading device.

[0059] In the present invention, the term "porous reinforced resin composite" refers to a porous medium to which a liquid composition and a matrix resin have been applied. The term "porous reinforced resin composite" also refers to a porous reinforced resin composite formed by laminating multiple porous reinforced resin composites. The term "porous reinforced resin molded product" refers to a porous reinforced resin composite molded by heating and pressurizing.

[0060] The spraying device is not particularly limited as long as it can spray the matrix resin onto areas of the porous medium that are not impregnated with the liquid composition, and can be selected appropriately depending on the purpose. The matrix resin may also be sprayed manually.

[0061] [Matrix resin] The type of matrix resin is not particularly limited and can be appropriately selected depending on the purpose. Examples include urethane resin, polyester resin, acrylic resin, vinyl acetate resin, styrene resin, butadiene resin, styrene-butadiene resin, vinyl chloride resin, acrylic-styrene resin, acrylic-silicone resin, polyamide resin, polyimide resin, polyether resin, and polyether ether ketone resin. Among these, polyamide resin is preferred from the viewpoints of heat resistance, chemical resistance, and material cost. These may be used alone or in combination of two or more.

[0062] The melting point of the matrix resin is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 400° C. or lower, more preferably 250° C. or lower. A melting point of 250° C. or lower is preferable because the matrix resin and the liquid composition can be uniformly filled into the porous medium.

[0063] -Lamination process and lamination equipment- In the lamination process, multiple porous reinforced resin composites are laminated. By changing the number of laminated porous reinforced resin composites, a porous reinforced resin composite having a desired thickness can be obtained. The lamination process can be performed using a lamination device.

[0064] The lamination device is not particularly limited as long as it can laminate multiple porous reinforced resin composites, and can be appropriately selected depending on the purpose. According to this embodiment, multiple porous reinforced resin composites are laminated, in which a liquid composition with excellent pattern precision and uniformity is applied to a porous medium, so that a porous reinforced resin composite with a desired thickness and excellent pattern precision and uniformity can be obtained. [Example]

[0065] Examples of the present invention will be described below, but the present invention is not limited to these examples. In the examples, "parts" means "parts by mass" unless otherwise specified.

[0066] Example 1 A container was charged with 7.0 parts by mass of AQ-633E (modified polyamide, manufactured by Kusumoto Chemicals Co., Ltd., active ingredient: 22.5%) as a thickener, 7.0 parts by mass of Vinybran 755 (vinyl chloride, manufactured by Nissin Chemical Industry Co., Ltd., active ingredient: 25%, MFT: 20°C, Tg: 34°C, average particle size: 30 nm) as a film-forming agent, and 86.0 parts by mass of JS-A191 (silver nanoparticle dispersion, manufactured by Novacentrix Inc., active ingredient: 40%, average particle size: 30 nm to 50 nm) as functional particles, and the mixture was mixed and stirred at 3,000 rpm for 15 minutes using a homogenizer (ED-7 Excel Auto Homogenizer, manufactured by Nippon Seiki Co., Ltd.) to obtain a mixture. The resulting mixture was filtered using a 10 μm PP membrane filter to obtain liquid for porous media 1. The composition of liquid for porous media 1 is shown in Table 1.

[0067] Example 2 Liquid for porous media 2 was obtained in the same manner as in Example 1, except that 7.0 parts by mass of AQ-633E used as a thickener in Example 1 was changed to 7.0 parts by mass of AQH-800 (modified polyamide, manufactured by Kusumoto Chemicals Co., Ltd., active ingredient: 10%). The composition of Liquid for porous media 2 is shown in Table 1.

[0068] Example 3 Liquid for porous media 3 was obtained in the same manner as in Example 1, except that 7.0 parts by mass of AQ-633E used as a thickener was changed to 3.0 parts by mass of RHEOBYK-425 (urea-modified polyurethane, manufactured by Big Chemie Japan Co., Ltd., active ingredient: 50%). The composition of Liquid for porous media 3 is shown in Table 1.

[0069] Example 4 Liquid for porous media 4 was obtained in the same manner as in Example 1, except that 7.0 parts by mass of AQ-633E used as a thickener in Example 1 was changed to 10.0 parts by mass of Rheocrysta I-2SX (cellulose nanofiber, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., active ingredient: 2%). The composition of Liquid for porous media 4 is shown in Table 1.

[0070] Example 5 Liquid for porous media 5 was obtained in the same manner as in Example 1, except that 7.0 parts by mass of AQ-633E used as a thickener in Example 1 was changed to 1.0 part by mass of LAPONITE-RD (synthetic hectorite, manufactured by BYK, active ingredient: 100%). The composition of Liquid for porous media 5 is shown in Table 1.

[0071] Example 6 Liquid for porous media 6 was obtained in the same manner as in Example 1, except that 7.0 parts by mass of AQ-633E used as a thickener in Example 1 was changed to 2.0 parts by mass of AEROSIL200 (hydrophilic fumed silica, manufactured by Nippon Aerosil Co., Ltd., active ingredient: 100%). The composition of Liquid for porous media 6 is shown in Table 2.

[0072] Example 7 Liquid 7 for porous media was obtained in the same manner as in Example 1, except that 7.0 parts by mass of Vinyblan 755 used as the film-forming agent was changed to 4.0 parts by mass of Vinyblan 278 (vinyl chloride, manufactured by Nissin Chemical Industry Co., Ltd., active ingredient: 43%, MFT: 50°C, Tg: 30°C). The composition of Liquid 7 for porous media is shown in Table 2.

[0073] Example 8 Liquid for porous media 8 was obtained in the same manner as in Example 1, except that 7.0 parts by mass of Vinybran 755 used as the film-forming agent was changed to 3.0 parts by mass of Vinybran 690 (vinyl chloride, manufactured by Nissin Chemical Industry Co., Ltd., active ingredient: 54%, MFT: 65°C, Tg: 45°C). The composition of Liquid for porous media 8 is shown in Table 2.

[0074] Example 9 Liquid 9 for porous media was obtained in the same manner as in Example 1, except that 7.0 parts by mass of Vinyblan 755 used as the film-forming agent was changed to 5.0 parts by mass of Vinyblan 700 (vinyl chloride, manufactured by Nissin Chemical Industry Co., Ltd., active ingredient: 30%, MFT: 80°C, Tg: 70°C). The composition of Liquid 9 for porous media is shown in Table 2.

[0075] Example 10 Liquid for porous media 10 was obtained in the same manner as in Example 1, except that 7.0 parts by mass of Vinybran 755 used as the film-forming agent was changed to 7.0 parts by mass of Vinybran 715S (vinyl chloride, manufactured by Nissin Chemical Industry Co., Ltd., active ingredient: 24%, MFT: 0°C, Tg: 25°C). The composition of liquid for porous media 10 is shown in Table 2.

[0076] Example 11 Liquid for porous media 11 was obtained in the same manner as in Example 1, except that 7.0 parts by mass of Vinyblan 755 as the film-forming agent was changed to 3.0 parts by mass of Boncoat SA-6360 (acrylic-silicone resin emulsion, manufactured by DIC Corporation, active ingredient: 50%, MFT: 26-32°C, Tg: 21°C, average particle size: 150 nm). The composition of liquid for porous media 11 is shown in Table 3.

[0077] Example 12 Liquid for porous media 12 was obtained in the same manner as in Example 1, except that 7.0 parts by mass of Vinyblan 755 used as the film-forming agent was changed to 3.0 parts by mass of Boncoat CG-8400 (acrylic-styrene resin emulsion, manufactured by DIC Corporation, active ingredient: 50%, MFT: 26-31°C, Tg: 25°C, average particle size: 150nm-200nm). The composition of liquid for porous media 12 is shown in Table 3.

[0078] Example 13 Liquid for porous media 13 was obtained in the same manner as in Example 1, except that 7.0 parts by mass of Vinyblan 755 as the film-forming agent was changed to 3.0 parts by mass of Boncoat 5400EF (acrylic-styrene resin emulsion, manufactured by DIC Corporation, active ingredient: 55%, MFT: 5-10°C, Tg: 6°C, average particle size: 200 nm). The composition of liquid for porous media 13 is shown in Table 3.

[0079] Example 14 Liquid for porous media 14 was obtained in the same manner as in Example 1, except that 7.0 parts by mass of Vinyblan 755 used as the film-forming agent was changed to 3.0 parts by mass of Boncoat CG-5010EF (acrylic-urethane resin emulsion, manufactured by DIC Corporation, active ingredient: 45%, MFT: 20-23°C, Tg: 29°C, average particle size: 100nm-150nm). The composition of Liquid for porous media 14 is shown in Table 3.

[0080] Example 15 Liquid for porous media 15 was obtained in the same manner as in Example 1, except that the amount of JS-A191 used as functional particles was changed from 86.0 parts by mass to 80.0 parts by mass, and 6.0 parts by mass of ethylene glycol was added as a solvent. The composition of Liquid for porous media 15 is shown in Table 3.

[0081] Example 16 Liquid for porous media 16 was obtained in the same manner as in Example 15, except that 6.0 parts by mass of ethylene glycol as the solvent in Example 15 was changed to 6.0 parts by mass of glycerin. The composition of liquid for porous media 16 is shown in Table 3.

[0082] Example 17 Liquid for porous media 17 was obtained in the same manner as in Example 5, except that the amount of LAPONITE-RD (synthetic hectorite, manufactured by BYK, active ingredient: 100%) added as a thickener was changed to 3.0 parts by mass. The composition of Liquid for porous media 17 is shown in Table 3.

[0083] Example 18 Liquid for porous media 18 was obtained in the same manner as in Example 16, except that the amount of glycerin added as a solvent was changed to 10.0 parts by mass. The composition of Liquid for porous media 18 is shown in Table 3.

[0084] (Comparative Example 1) Liquid for porous media 19 was obtained in the same manner as in Example 1, except that Vinyblan 755 as a film-forming agent was not added and the amount of JS-A191 as functional particles was changed from 86.0 parts by mass to 93.0 parts by mass. The composition of Liquid for porous media 19 is shown in Table 4.

[0085] (Comparative Example 2) Liquid for porous media 20 was obtained in the same manner as in Example 1, except that AQ-633E as a thickener was not added and the amount of JS-A191 as functional particles was changed from 86.0 parts by mass to 93.0 parts by mass in Example 1. The composition of liquid for porous media 20 is shown in Table 4.

[0086] (Comparative Example 3) Liquid for porous media 21 was obtained in the same manner as in Example 1, except that AQ-633E as a thickener and Vinybran 755 as a film-forming agent were not added, and the amount of JS-A191 as functional particles was changed from 86.0 parts by mass to 100.0 parts by mass. The composition of liquid for porous media 21 is shown in Table 4.

[0087] Comparative Example 4 Liquid for porous materials 22 was obtained in the same manner as in Example 5, except that the amount of LAPONITE-RD (synthetic hectorite, manufactured by BYK, active ingredient: 100%) added as a thickener was changed to 4.0 parts by mass and Vinybran 755 as a film-forming agent was not added. The composition of liquid for porous materials 22 is shown in Table 4.

[0088] (Comparative Example 5) Liquid for porous media 23 was obtained in the same manner as in Comparative Example 1, except that 12.0 parts by mass of glycerin was added as a solvent. The composition of Liquid for porous media 23 is shown in Table 4.

[0089] [Table 1]

[0090] [Table 2]

[0091] [Table 3]

[0092] [Table 4]

[0093] The liquids for porous medium 1 to 23 in Examples 1 to 18 and Comparative Examples 1 to 5 were evaluated for "viscosity," "stability," "precision," "uniformity," and "conductivity" as follows. The results are shown in Tables 5 and 7.

[0094] <Viscosity> The temperature of each of the obtained porous material liquids was adjusted to 25°C, and the viscosity was measured at shear rates of 0.1 (1 / s) and 1,000 (1 / s) using an Anton Paar MCR-302 rheometer. The results are shown in Tables 5 and 7.

[0095] <Stability> Each porous liquid was loaded into an image forming apparatus equipped with a Ricoh Digital Painting head (nozzle diameter: 60 μm), and droplets were ejected. The ejected droplets were observed for nozzle clogging and ejection disturbance, and the stability was evaluated based on the following evaluation criteria. The results are shown in Tables 5 and 7. [Evaluation criteria] 〇: No missing nozzles and no irregular discharge △: No missing nozzles, but some ejection disturbances, or some missing nozzles, but no ejection disturbances ×: Droplets cannot be ejected from the nozzle

[0096] <Accuracy> Each porous liquid was loaded into an image forming device equipped with a Ricoh Digital Painting head (nozzle hole diameter: 60 μm), and droplets were ejected onto a fiber sheet (Olivest Co., Ltd., basis weight: 30 gsm) as a porous medium heated to 100°C with a silicone rubber heater, with a droplet volume of 10 nl, a droplet density of 100 dpi x 100 dpi, and one overcoat, to print a 40 mm x 40 mm solid image. The printed fiber sheet was dried in a thermostatic oven at 200°C for 1 hour, and then the printed size was measured and the accuracy was evaluated based on the following evaluation criteria. The results are shown in Tables 5 and 7. [Evaluation criteria] ○: The average side of the printed size is 38mm or more and less than 42mm ×: The average side of the printed size is less than 38 mm or more than 42 mm

[0097] <Uniformity> In the same manner as in the evaluation of pattern accuracy, a 40 mm x 40 mm solid image was printed. The printed fiber sheet was dried in a thermostatic oven at 200°C for 1 hour, and then the printed area was observed under a microscope and evaluated for uniformity based on the following criteria. The results are shown in Tables 5 and 7. [Evaluation criteria] ○: Functional particles are attached to the surface of the fibers and in the gaps between the fibers ×: Functional particles are attached only to the surface of the fiber

[0098] <Conductivity> Each porous liquid was loaded into an image forming device equipped with a Ricoh Digital Painting head (nozzle hole diameter: 60 μm), and droplets were ejected onto a fiber sheet (Olivest Co., Ltd., basis weight: 30 gsm) as printing media heated to 100°C with a silicone rubber heater, with a droplet volume of 10 nl, a droplet density of 100 dpi x 100 dpi, and one overcoat, to print a 2 mm x 40 mm line image. The printed fiber sheet was dried in a thermostatic oven at 200°C for 1 hour, and then a tester was connected to the edge of the printed line image to measure the resistance, and the conductivity was evaluated based on the following criteria. The results are shown in Tables 5 and 7. [Evaluation criteria] 〇: Resistance value is less than 0.1Ω △: Resistance is 0.1Ω or more and less than 1Ω ×: Resistance is 1Ω or more

[0099] [Table 5]

[0100] [Table 6]

[0101] [Table 7]

[0102] Examples 1 to 6 are examples in which the type of thickener was changed. Examples 1 to 6 contain a thickener and a film-forming agent, and regardless of the thickener used, the viscosity (viscosity at a shear rate of 0.1 (1 / s) and viscosity at a shear rate of 1,000 (1 / s)) meets the standard values, and are excellent in "stability," "precision," "uniformity," and "conductivity." Examples 7 to 14 are examples in which the type of film-forming agent was changed. Examples 7 to 14 contain a thickener and a film-forming agent, and regardless of the film-forming agent, the viscosity (at a shear rate of 0.1 (1 / s) and at a shear rate of 1,000 (1 / s)) meets the standard values, and are excellent in "stability," "precision," "uniformity," and "conductivity." Furthermore, Examples 7 to 9, 11 to 12, and 14 have film-forming agents with a minimum film-forming temperature (MFT) of 20°C or higher, and are therefore even more excellent in "stability." Examples 15 and 16 are examples in which a solvent was added. Examples 15 and 16 contain a thickener, a film-forming agent, and a solvent, and regardless of the solvent used, the viscosity (viscosity at a shear rate of 0.1 (1 / s) and viscosity at a shear rate of 1,000 (1 / s)) meets the standard values, and are excellent in "stability," "precision," "uniformity," and "conductivity." Comparative Example 1 is a comparative example in which the film-forming agent in Example 1 is not included, and since no film-forming agent is included, the evaluations of "uniformity" and "conductivity" are poor. Comparative Example 2 is a comparative example in which the thickener in Example 1 is not included, and since no thickener is included, the viscosity is low and the evaluations of "precision," "uniformity," and "conductivity" are poor. Comparative Example 3 is a comparative example in which the thickener and film-forming agent in Example 1 are not included. Because no thickener or film-forming agent is included, the viscosity is low and the evaluations of "precision," "uniformity," and "conductivity" are poor. From these findings, it can be seen that the viscosity of the thickener and film-forming agent in the porous liquid according to one embodiment of the present invention (viscosity at a shear rate of 0.1 (1 / s) and viscosity at a shear rate of 1,000 (1 / s)) meets the standard values, and is excellent in "stability," "precision," "uniformity," and "conductivity."

[0103] The embodiments of the present invention are as follows, for example. <1> a film-forming agent and functional particles; A liquid composition for imparting functionality to a porous medium, having a viscosity of 1 Pa·s or more and 100 Pa·s or less at a shear rate of 0.1 (1 / s) and a viscosity of 1 mPa·s or more and 100 mPa·s or less at a shear rate of 1,000 (1 / s). <2> Contains a thickener, The thickener is at least one of a resin, a carbon nanotube, a cellulose nanofiber, and a layered clay mineral. <1> The liquid composition according to claim 1. <3> The thickener is a resin, The resin is at least one of polyamide, modified polyamide, and fatty acid polyamide. <2> The liquid composition according to claim 1. <4> The content of the thickener is 0.1% by mass or more and 10.0% by mass or less with respect to the total amount of the liquid composition. <2> or <3> The liquid composition according to claim 1. <5> the film-forming agent is a resin emulsion containing, as a main component, at least one of an acrylic resin, a urethane resin, a silicone resin, an acrylic-styrene copolymer, an acrylic-urethane copolymer, an acrylic-silicone copolymer, a polyester copolymer, a vinyl chloride resin, and a vinyl acetate resin; <1> from <4> The liquid composition according to any one of the preceding claims. <6> The minimum film-forming temperature of the film-forming agent is 20°C or higher. <1> from <5> The liquid composition according to any one of the preceding claims. <7> The content of the film-forming agent is 0.1% by mass or more and 10.0% by mass or less with respect to the total amount of the liquid composition. <1> from <6> The liquid composition according to any one of the preceding claims. <8> the ratio (A / B) of the average particle size (A) of the functional particles to the average particle size (B) of the film-forming agent is 0.1 or more and 10 or less; <1> from <7> The liquid composition according to any one of the preceding claims. <9> further comprising a solvent; The solvent is at least one of ethylene glycol and glycerin. <1> from <8> The liquid composition according to any one of the preceding claims. <10> For a given area on a porous medium, <1> from <9> an application step of impregnating and applying the liquid composition according to any one of the above items; a drying step of drying the porous medium. <11> The porous medium is a nonwoven fabric made of any one of glass fiber, carbon fiber, and flax fiber. <10> A method for producing the porous reinforced resin molded article according to claim 1. <12> the porous medium is a fibrous sheet; The fiber volume fraction of the fiber sheet is 10% or less. <10> or <11> A method for producing the porous reinforced resin molded article according to claim 1. <13> a heating step of heating the porous medium; <10> from <12> 10. A method for producing the porous reinforced resin molded article according to claim 9. <14> a moving step of moving the porous medium; <10> from <13> 10. A method for producing the porous reinforced resin molded article according to claim 9. <15> For a given area on a porous medium, <1> from <9> an application device that impregnates and applies the liquid composition according to any one of the above items; a drying device for drying the porous medium. [Explanation of symbols]

[0104] 1. Manufacturing system for porous reinforced resin moldings 100 Applicator 200 Drying equipment [Prior art documents] [Patent documents]

[0105] [Patent Document 1] Patent No. 7218571

Claims

1. a film-forming agent and functional particles; A liquid composition for imparting functionality to a porous medium, having a viscosity of 1 Pa·s or more and 100 Pa·s or less at a shear rate of 0.1 (1 / s) and a viscosity of 1 mPa·s or more and 100 mPa·s or less at a shear rate of 1,000 (1 / s).

2. Contains a thickener, The liquid composition according to claim 1 , wherein the thickener is at least one of a resin, a carbon nanotube, a cellulose nanofiber, and a layered clay mineral.

3. The thickener is a resin, The liquid composition according to claim 2 , wherein the resin is at least one of a polyamide, a modified polyamide, and a fatty acid polyamide.

4. The liquid composition according to claim 2 , wherein the content of the thickener is 0.1% by mass or more and 10.0% by mass or less with respect to the total amount of the liquid composition.

5. 3. The liquid composition according to claim 1, wherein the film-forming agent is a resin emulsion containing, as a main component, at least one of an acrylic resin, a urethane resin, a silicone resin, an acrylic-styrene copolymer, an acrylic-urethane copolymer, an acrylic-silicone copolymer, a polyester copolymer, a vinyl chloride resin, and a vinyl acetate resin.

6. The liquid composition according to claim 1 or 2, wherein the minimum film-forming temperature of the film-forming agent is 20°C or higher.

7. The liquid composition according to claim 1 or 2, wherein the content of the film-forming agent is 0.1% by mass or more and 10.0% by mass or less, based on the total amount of the liquid composition.

8. 3. The liquid composition according to claim 1, wherein the ratio (A / B) of the average particle size (A) of the functional particles to the average particle size (B) of the film-forming agent is 0.1 or more and 10 or less.

9. further comprising a solvent; The liquid composition according to claim 1 or 2, wherein the solvent is at least one of ethylene glycol and glycerin.

10. an application step of impregnating and applying the liquid composition according to claim 1 or 2 to a predetermined area on a porous medium; a drying step of drying the porous medium.

11. 11. The method for producing a porous reinforced resin molding according to claim 10, wherein the porous medium is a nonwoven fabric made of any one of glass fiber, carbon fiber, and flax fiber.

12. the porous medium is a fibrous sheet; The method for producing a porous reinforced resin molding according to claim 10, wherein the fiber volume fraction of the fiber sheet is 10% or less.

13. The method for producing a porous reinforced resin molded article according to claim 10, further comprising a heating step of heating the porous medium.

14. The method for producing a porous reinforced resin molded article according to claim 10, further comprising a moving step of moving the porous medium.

15. an application device that impregnates and applies the liquid composition according to claim 1 or 2 to a predetermined area on a porous medium; a drying device for drying the porous medium.

Images