Pultruded body and method for producing pultruded body

Abstract

The objective of the present invention is to provide: a thin pultruded body which has excellent endothermic properties, fire resistance and mass productivity despite being thin; and a method for producing the pultruded body. The present invention relates to a pultruded body obtained by impregnating a base material composed of fibers with a matrix resin composition and pultruding the base material impregnated with the matrix resin composition. The matrix resin composition contains: at least one selected from inorganic acids, hydroxide compounds, and hydrated compounds; a thermosetting resin; and a polymerization initiator. The content ratio of the base material in the pultruded body is 10 mass% to 35 mass% (inclusive).

Description

Drawn molded body and method for manufacturing drawn molded body

[0001] The present invention relates to a drawn molded body and a method for manufacturing a drawn molded body.

[0002] Conventionally, metal materials and concrete materials have been widely used for the structural frameworks (columns, beams, floors, walls, etc.) of buildings.

[0003] Recently, from the perspective of SDGs and the like, a shift to organic materials such as wood materials in the structural frameworks of buildings has been attracting attention.

[0004] However, organic materials have properties such that they are likely to burn, deform, or have a decrease in strength when exposed to high temperatures. Therefore, fire resistance is required against fires that occur during disasters.

[0005] For example, if an organic material is used for the structural framework of a building, when a fire occurs, the heat causes the organic material to burn or deform, and the strength significantly decreases, and there is a risk that the building will collapse.

[0006] In response to such problems, for example, in Patent Document 1, by using a laminate of a gypsum board, a panel heat insulating material (such as phenolic foam), and a non-combustible material (such as a calcium silicate board) for a wood material, the fire resistance of the organic material is improved.

[0007] Japanese Unexamined Patent Application Publication No. 2019 - 150389

[0008] However, in Patent Document 1, the specifically disclosed laminate uses inorganic non-combustible materials such as gypsum boards and calcium silicate boards, and in order to ensure fire resistance, it is necessary to increase the thickness of the entire laminate. Also, increasing the thickness of the entire laminate will compress the space such as the living space and increase the weight.

[0009] Therefore, the problem to be solved by the present invention is to provide a drawn molded body that is thin and excellent in heat absorption, fire resistance, and mass productivity (continuous productivity, formability) even when thin, and a method for manufacturing the drawn molded body.

[0010] Therefore, the present inventors diligently studied to solve the above problems and found that by using an pultruded molded article composed of a substrate impregnated with a specific matrix resin composition, and by keeping the content ratio of the substrate in the pultruded molded article low, it is possible to keep the thickness thin, and even with a thin thickness, an pultruded molded article with excellent heat absorption and fire resistance, as well as excellent mass productivity (continuous productivity, moldability), can be obtained, thus completing the present invention.

[0011] In other words, the present invention relates to an extruded molded article obtained by impregnating a substrate made of fibers with a matrix resin composition and extruding the substrate impregnated with the matrix resin composition, wherein the matrix resin composition comprises one or more selected from inorganic acids, hydroxide compounds and hydrated compounds, a thermosetting resin and a polymerization initiator, and the content ratio of the substrate in the extruded molded article is 10% by mass or more and 35% by mass or less.

[0012] In the pultruded article of the present invention, it is preferable that the inorganic acid contains boric acid.

[0013] In the pultruded article of the present invention, it is preferable that the thermosetting resin comprises an unsaturated polyester resin and / or a vinyl ester resin, and an unsaturated monomer.

[0014] In the pultruded article of the present invention, it is preferable that the polymerization initiator contains an organic peroxide.

[0015] The present invention relates to a method for manufacturing an extruded molded article, comprising: (1) a substrate supply step of supplying a substrate composed of the fibers; (2) an impregnation step of impregnating the substrate with the matrix resin composition; (3) a heat molding step of drawing the substrate impregnated with the matrix resin composition into a heated mold and heat molding it; (4) an extrusion step of drawing the substrate from the mold after heat molding; and (5) a cutting step of cutting the substrate after heat molding.

[0016] The present invention is useful because it can reduce the thickness of an extruded molded article by keeping the proportion of the substrate in the extruded molded article, which is composed of a substrate impregnated with a specific matrix resin composition, low, and even when the thickness is thin, it can provide an extruded molded article with excellent heat absorption, fire resistance, and mass productivity, as well as a method for manufacturing the extruded molded article. Furthermore, by reducing the thickness, it is also possible to reduce the weight.

[0017] This is a schematic diagram showing a manufacturing apparatus for pultruded molded articles according to Embodiment 1. This is a schematic diagram showing a base material (a laminated structure consisting of roving and nonwoven fabric) used in pultruded molded articles. This is a schematic diagram showing a manufacturing apparatus for pultruded molded articles according to Embodiment 1. This is a schematic diagram showing a base material (a laminated structure consisting of nonwoven fabric) used in pultruded molded articles.

[0018] 1, 21, A: Linear substrate (roving) made of fibers 2, 31, B: Planar substrate (glass nonwoven fabric) made of fibers 10: Guide roll 20: Linear substrate supply unit 30: Planar substrate supply unit 40: Resin impregnation unit 41: Matrix resin composition 42: Container 43: Impregnation roll 50: Heat molding unit 51: Mold 52: Hot plate 60: Tensioning unit 61: Tensioning machine 62: Belt 63: Drive unit 70: Cutting unit 71: Cutting machine 81: Pulled molded body 100, 200: Manufacturing equipment

[0019] The following describes embodiments for carrying out the present invention.

[0020] [Matrix Resin Composition] The pultruded article of the present invention is characterized in that the matrix resin composition comprises one or more selected from inorganic acids, hydroxide compounds, and hydrated compounds (collectively referred to as "endothermic compounds" below), a thermosetting resin, and a polymerization initiator.

[0021] (Endothermic Compound) The extruded molded article of the present invention is characterized in that the matrix resin composition contains one or more (endothermic compounds) selected from inorganic acids, hydroxide compounds, and hydrated compounds. The endothermic compound is a component that imparts endothermic properties and fire resistance.

[0022] Examples of the inorganic acid include boric acid, phosphoric acid, sulfuric acid, sulfurous acid, nitric acid, silicic acid, and carbonic acid. Examples of the boric acid include boric acid, metaboric acid, orthoboric acid, diboric acid, tetraboric acid, octaboric acid, and one or more of these can be used. From the viewpoint of endothermic properties and fire resistance, the content of the boric acid is preferably 80% by mass or more of the total inorganic acid, more preferably 90% by mass or more, even more preferably 95% by mass or more, and particularly preferably 100% by mass. In other words, it is particularly preferable that the inorganic acid contains only boric acid.

[0023] Examples of the hydroxide compounds include lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, aluminum hydroxide, titanium hydroxide, vanadium hydroxide, manganese hydroxide, iron hydroxide, nickel hydroxide, copper hydroxide, zinc hydroxide, zirconium hydroxide, and tin hydroxide, and one or more of these can be used. In the present invention, from the viewpoint of endothermic properties, it is preferable to use magnesium hydroxide, aluminum hydroxide, etc., and it is more preferable to use aluminum hydroxide. From the viewpoint of endothermic properties and fire resistance, the content of aluminum hydroxide is preferably 80% by mass or more of the total hydroxide compound, more preferably 90% by mass or more, even more preferably 95% by mass or more, and particularly preferably 100% by mass. In other words, it is particularly preferable that the hydroxide compound contains only aluminum hydroxide.

[0024] As the hydrated compound, one or more can be selected from, for example, hydrates of inorganic acids such as boric acid, sulfuric acid, sulfurous acid, phosphoric acid, nitric acid, silicic acid, oxalic acid, and carbonic acid, or metal salt hydrates of inorganic acids; metal salt hydrates of organic acids such as benzoic acid, phthalic acid, maleic acid, succinic acid, salicylic acid, citric acid, acetic acid, oxalic acid, and sulfonic acid; and hydrates of metal chloride salts, metal bromide salts, metal iodide salts, metal hydroxide salts, etc. As the metal, one or more can be selected from sodium, aluminum, calcium, zinc, manganese, lanthanum, titanium, zirconium, iron, cobalt, nickel, magnesium, and copper.

[0025] As the endothermic compound, it is preferable to use one or more selected from boric acid, boric acid hydrate and / or metal salt hydrate of boric acid, sulfuric acid hydrate and / or metal salt hydrate of sulfuric acid, sulfurous acid hydrate and / or metal salt hydrate of sulfurous acid, phosphoric acid hydrate and / or metal salt hydrate of phosphoric acid, nitric acid hydrate and / or metal salt hydrate of nitric acid, metal chloride salt hydrate, and metal hydroxide salt hydrate, and it is more preferable to use boric acid, boric acid hydrate and / or metal salt hydrate of boric acid.

[0026] Examples of the boric acid hydrates include boric acid, metaboric acid, orthoboric acid, diboric acid, tetraboric acid, octaboric acid, and other boric acid hydrates, and one or more of these can be used. Examples of the metal salt hydrates of boric acid include hydrates of metal salts of boric acid such as lithium salt, potassium salt, sodium salt, rubidium salt, cesium salt, magnesium salt, calcium salt, barium salt, zinc salt, aluminum salt, cobalt salt, and zirconium salt, and one or more of these can be used.

[0027] More specifically, as the boric acid hydrate and / or the metal salt hydrate of boric acid, for example, boric acid monohydrate, boric acid dihydrate, boric acid trihydrate, lithium borate decahydrate, lithium metaborate dihydrate, lithium metaborate octahydrate, lithium tetraborate trihydrate, lithium tetraborate pentahydrate, lithium tetraborate dilithium trihydrate, lithium perborate monohydrate, potassium borate dihydrate, potassium borate tetrahydrate, potassium metaborate 1.5hydrate, potassium perborate monohydrate, potassium tetraborate tetrahydrate, potassium tetraborate octahydrate, potassium tetraborate decahydrate, potassium tetraborate dipotassium tetrahydrate, potassium tetraborate 5 One or more of the following can be used: potassium tetrahydrate, sodium tetraborate pentahydrate, sodium tetraborate decahydrate, disodium octaborate tetrahydrate, sodium perborate monohydrate, sodium perborate tetrahydrate, rubidium borate decahydrate, cesium borate decahydrate, magnesium borate decahydrate, magnesium metaborate octahydrate, calcium borate hexahydrate, calcium borate decahydrate, calcium tetraborate tetrahydrate, zinc borate 3.5hydrate, zinc borate hexahydrate, barium borate decahydrate, barium metaborate monohydrate, barium metaborate dihydrate, etc.

[0028] Among the boric acid hydrates and / or metal salt hydrates of boric acid, boric acid monohydrate and sodium tetraborate hydrate are preferred from the viewpoint of endothermic properties and fire resistance, and one or more selected from boric acid monohydrate, sodium tetraborate pentahydrate, and sodium tetraborate decahydrate are more preferred.

[0029] As the sulfuric acid hydrate and / or metal salt hydrate of sulfuric acid, one or more selected from the following can be used: ammonium aluminum sulfate dodecahydrate, sodium aluminum sulfate dodecahydrate, aluminum sulfate heptahydrate, aluminum sulfate 18hydrate, aluminum sulfate hexahydrate, aluminum sulfate decahydrate, aluminum sulfate hexahydrate, potassium aluminum sulfate dodecahydrate, iron sulfate heptahydrate, iron sulfate nonahydrate, potassium iron sulfate dodecahydrate, magnesium sulfate heptahydrate, sodium sulfate decahydrate, nickel sulfate hexahydrate, zinc sulfate heptahydrate, beryllium sulfate tetrahydrate, zirconium sulfate tetrahydrate, etc.

[0030] As the sulfurous acid hydrate and / or metal salt hydrate of sulfurous acid, one or more selected from, for example, zinc sulfite dihydrate, sodium sulfite heptahydrate, etc., can be used.

[0031] As the hydrate of phosphoric acid and / or the metal salt hydrate of phosphoric acid, one or more selected from aluminum phosphate dihydrate, cobalt phosphate octahydrate, magnesium phosphate octahydrate, magnesium ammonium phosphate hexahydrate, magnesium hydrogen phosphate trihydrate, magnesium hydrogen phosphate heptahydrate, zinc phosphate tetrahydrate, zinc dihydrogen phosphate dihydrate, etc., can be used.

[0032] As the hydrate of nitric acid and / or the metal salt hydrate of nitric acid, one or more selected from, for example, aluminum nitrate notahydrate, zinc nitrate hexahydrate, calcium nitrate tetrahydrate, cobalt nitrate hexahydrate, bismuth nitrate pentahydrate, zirconium nitrate pentahydrate, cerium nitrate hexahydrate, iron nitrate hexahydrate, iron nitrate notahydrate, nickel nitrate hexahydrate, magnesium nitrate hexahydrate, etc., can be used.

[0033] As the hydrate of the metal chloride salt, one or more selected from, for example, cobalt chloride hexahydrate, aluminum chloride hexahydrate, iron chloride tetrahydrate, manganese chloride tetrahydrate, calcium chloride dihydrate, etc., can be used.

[0034] As the hydrate of the metal hydroxide salt, one or more selected from aluminum hydroxide monohydrate, aluminum hydroxide trihydrate, magnesium hydroxide monohydrate, calcium hydroxide monohydrate, barium hydroxide monohydrate, zirconium hydroxide monohydrate, etc., can be used.

[0035] (Thermosetting resin) The pultruded article of the present invention is characterized in that the matrix resin composition contains a thermosetting resin. The thermosetting resin is a component that contributes to mass production.

[0036] Examples of the thermosetting resin include polyester resin, unsaturated polyester resin, vinyl ester resin, vinyl acetate resin, alkyd resin, epoxy resin, benzoxazine resin, acrylic resin, acrylic silicone resin, urethane resin, silicone resin, phenolic resin, urea resin, polyimide resin, melamine resin, polycarbonate resin, fluororesin, acrylic vinyl acetate resin, acrylic urethane resin, acrylic epoxy resin, and ethylene vinyl acetate resin. Furthermore, these resins may be made from biomass raw materials or modified with biomass raw materials. In addition to the resin components, monomer components such as unsaturated monomers may be used. Among these, from the viewpoint of heat resistance and moldability, it is preferable that the thermosetting resin contains unsaturated polyester resin and / or vinyl ester resin, and unsaturated monomers, and more preferably unsaturated polyester resin and unsaturated monomers. The mixing ratio of the unsaturated polyester and / or vinyl ester to the unsaturated monomer is preferably 10 to 200 parts by mass of the unsaturated monomer, and more preferably 20 to 180 parts by mass, per 100 parts by mass of the unsaturated polyester and / or vinyl ester. By mixing the unsaturated polyester and / or vinyl ester and the unsaturated monomer within this range and mixing in an initiator, etc., an unsaturated polyester resin and / or vinyl ester resin having excellent heat resistance, and an extruded molded article using the unsaturated polyester resin and / or vinyl ester resin can be obtained.

[0037] (Unsaturated polyester resin) Examples of the unsaturated polyester resin include those produced by the esterification reaction of a polyhydric alcohol and a polybasic acid.

[0038] Examples of the aforementioned polyhydric alcohols include alkylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and neopentyl glycol, as well as trimethylolethane, trimethylolpropane, glycerin, pentaerythritol, 1,6-hexanediol, ester glycol, 1,4-cyclohexanedimethanol, and 1,3-butanediol, which can be used individually or in combination of two or more.

[0039] Examples of the aforementioned polybasic acids include unsaturated polybasic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, and citraconic acid. Phthalic acid (orthophthalic acid), isophthalic acid, terephthalic acid, phthalic anhydride, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, cyclohexanedicarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, trimellitic acid, pyromellitic acid, etc., can also be used in combination, and one or more of these can be used.

[0040] (Vinyl ester resin) Examples of the vinyl ester resin include bisphenol A type vinyl ester resin, novolac type vinyl ester resin, bromination type vinyl ester resin, and special modified vinyl ester resin, and one or more of these can be used. Among these, bisphenol A type vinyl ester resin is particularly preferred from the viewpoint of stable supply and cost.

[0041] (Unsaturated Monomers) Examples of the unsaturated monomers include (meth)acrylic acid ester monomers such as methyl (meth)acrylate, aromatic monomers such as styrene, methylstyrene, and divinylbenzene, and one or more of these can be used. Among these, styrene and methyl methacrylate are particularly preferred from the viewpoint of curability.

[0042] (Polymerization initiator) The drawn molded body of the present invention is characterized in that the matrix resin composition contains a polymerization initiator. The polymerization initiator is a component that contributes to the curing of the thermosetting resin.

[0043] Examples of the polymerization initiator include organic peroxides such as hydroperoxide, dialkyl peroxide, dialkyl ketone peroxide, diacyl peroxide, ketone peroxide, peroxy ester (such as tert-butyl peroxy pivalate), peroxy ketal, and peroxy dicarbonate, and azo compounds such as azobisisobutyronitrile, azobiscarboxamide, and 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile. One or more of these can be used. Among them, from the viewpoints of stable supply and cost, the organic peroxide is preferable.

[0044] (Other components) Other components can be blended in the matrix resin composition as long as the properties of the present invention are not impaired. For example, fillers, flame retardants, foaming agents, foam stabilizers, viscosity modifiers, curing accelerators, initiators, metal hydrates, colorants, dyes, film-forming aids, leveling agents, wetting agents, plasticizers, antifreeze agents, pH adjusters, preservatives, fungicides, algicides, antibacterial agents, dispersants, surfactants, adsorbents, fibers, carbonizing agents, solvents, internal mold release agents, etc. can be mentioned.

[0045] The mixing amount of the heat-absorbing compound is preferably 50 parts by mass or more and 150 parts by mass or less, more preferably 60 parts by mass or more and 140 parts by mass or less, and still more preferably 70 parts by mass or more and 130 parts by mass or less, from the viewpoints of heat absorption, fire resistance, and moldability, with respect to 100 parts by mass of the thermosetting resin. Also, the mixing amount of the hydrated compound is preferably 50 parts by mass or more and 150 parts by mass or less, more preferably 60 parts by mass or more and 140 parts by mass or less, and still more preferably 70 parts by mass or more and 130 parts by mass or less, from the viewpoints of heat absorption, fire resistance, and moldability, with respect to 100 parts by mass of the thermosetting resin.

[0046] The mixing amount of the polymerization initiator is preferably 0.1 to 3.0 parts by mass, more preferably 0.3 to 2.0 parts by mass, from the viewpoint of moldability, based on 100 parts by mass of the thermosetting resin.

[0047] [Pulled molded body] The pulled molded body of the present invention is characterized in that it is obtained by impregnating a base material composed of fibers with a matrix resin composition and then pull-forming the base material impregnated with the matrix resin composition. By impregnating the base material with the matrix resin composition, the obtained pulled molded body is excellent in heat absorption, fire resistance, and mass productivity, and is useful.

[0048] (Fiber) The fiber is composed of at least one selected from the group consisting of glass, carbon, and basalt. The fiber is preferably composed of glass, which is excellent in processability. Hereinafter, the fiber composed of glass is called glass fiber, the fiber composed of carbon is called carbon fiber, and the fiber composed of basalt is called basalt fiber.

[0049] (Base material) The base material is characterized in that it is composed of the fiber. In the present invention, since the base material is composed of the fiber, the fiber and the matrix resin composition are integrated to exhibit necessary physical properties (heat absorption, fire resistance, etc.), or the moldability (mass productivity, dimensional stability, etc.) after the fiber and the resin are cured in the mold is excellent and useful. Examples of the base material include a linear base material (roving, etc.) formed by linearly aggregating the fibers, or a planar base material (woven fabric, non-woven fabric, etc.) formed by forming the fibers into a planar shape.

[0050] The linear base material composed of the glass fiber or the basalt fiber is a linear base material in which the single fiber (monofilament) is aggregated so as to be 100 to 9600 g / 1000 m. The diameter of the linear base material is preferably 10 to 30 μm, more preferably 10 to 25 μm. A sizing agent (binder) may be used to aggregate a plurality of single fibers in the linear base material.

[0051] The linear substrate made of carbon fibers is a linear substrate formed by aligning and bundling 1,000 to 60,000 single fibers. The diameter of the linear substrate is 4 to 15 μm. A binder may also be used with the linear substrate made of carbon fibers. An example of a commercially available linear substrate made of carbon fibers is STS40-24K (thread diameter 7 μm) manufactured by Teijin Corporation.

[0052] Furthermore, it is preferable that the planar substrate is composed of at least one selected from the group consisting of woven fabrics, nonwoven fabrics, and unidirectional fiber sheets formed by weaving the aforementioned fibers.

[0053] The aforementioned textiles include those woven with satin weave, plain weave, and twill weave.

[0054] Examples of the nonwoven fabrics include continuous strand mats (CSM), chopped strand mats (CM), stitch mats, and paper.

[0055] Examples of the aforementioned unidirectional fiber sheet include those in which multiple fibers are aligned in one direction.

[0056] The content of the base material in the pultruded molded body is 10% by mass or more and 35% by mass or less, preferably 10% by mass or more and 30% by mass or less, more preferably 11% by mass or more and 25% by mass or less, and even more preferably 12% by mass or more and 20% by mass or less. Within this range, the pultruded molded body can be made thinner while ensuring heat absorption and fire resistance, and mass production (pultrudeability) can be achieved, which is useful. Furthermore, within the above range, physical properties such as rigidity can also be ensured.

[0057] Furthermore, in addition to the base material composed of the fibers and the matrix resin composition, the pultruded molded article of the present invention may also use metal sheets such as aluminum sheets, to the extent that it does not impair the effects of the present invention. When such metal sheets are used, they can be laminated on the surface or back surface of the pultruded molded article.

[0058] [Method for Manufacturing an Extruded Molded Article] The method for manufacturing an extruded molded article of the present invention preferably includes: (1) a substrate supply step of supplying a substrate composed of the fibers; (2) an impregnation step of impregnating the substrate with the matrix resin composition; (3) a heat molding step of drawing the substrate impregnated with the matrix resin composition into a heated mold and heat molding it; (4) an extrusion step of drawing the substrate from the mold after heat molding; and (5) a cutting step of cutting the substrate after heat molding. The extruded molded article obtained by the manufacturing method including steps (1) to (5) is excellent in heat absorption, fire resistance, and mass productivity, and is useful. In the manufacturing method including steps (1) to (5), an endothermic compound can be contained in the substrate composed of fibers, and is therefore excellent in heat absorption, fire resistance, and mass productivity, and is useful.

[0059] In the present invention, linear substrates and / or planar substrates can be used as substrates composed of fibers. In particular, planar substrates can be impregnated with more endothermic compounds, contributing to heat absorption and fire resistance, and are more efficient in mass production, making them useful. Furthermore, by using multiple substrates, endothermic compounds can be impregnated not only within the substrates but also between the multiple substrates. When using multiple substrates, the total number of substrates is preferably 2 to 30, more preferably 2 to 10, and more preferably 3 to 8. The content ratio (mass ratio) of the linear substrate composed of fibers and the planar substrate composed of fibers is preferably 0:100 to 40:60, and more preferably 3:97 to 30:70.

[0060] Furthermore, since the pultruded molded article is required to have heat-absorbing and fire-resistant properties, it is preferable that it contains a larger amount of heat-absorbing compounds. However, if the base material is composed only of linear base materials (such as roving), the fibers in the fibrous base material are arranged regularly, which may make it difficult to incorporate a large amount of heat-absorbing compounds between the fibers. In contrast, by using a planar base material (such as woven fabric or nonwoven fabric) as the fibrous base material, it becomes possible to mold the pultruded molded article while incorporating a certain amount or more of heat-absorbing compounds in the planar base material, which is useful.

[0061] Specific examples of methods for manufacturing an extruded molded article of the present invention include the following: Prepare a matrix resin composition. The matrix resin composition is obtained by adding a predetermined amount of a thermosetting resin or the like to a container and stirring. Next, a substrate made of fibers (linear substrate and / or planar substrate) is supplied (substrate supply step), the matrix resin composition is impregnated into the substrate (impregnation step), the substrate impregnated with the matrix resin composition is drawn into a mold having the shape of a rectangular parallelepiped and heat-molded (heat molding step). After that, the substrate is drawn out of the mold (drawing step), cooled, and then the drawn substrate is cut (cutting step) to obtain an extruded molded article.

[0062] The heating conditions in the heat forming process can be adjusted according to the desired size of the pultruded molded body and the material used. From the viewpoint of resin hardening, the heating temperature in the heat forming process is preferably 60°C or higher, more preferably 75°C or higher, and even more preferably 90°C or higher. From the viewpoint of inorganic acid water retention, it is preferably 180°C or lower, more preferably 150°C or lower, and even more preferably 130°C or lower. From the viewpoint of resin hardening, the time in the heat forming process is preferably 1 minute or more, more preferably 2 minutes or more, and even more preferably 3 minutes or more. From the viewpoint of molding cost, it is preferably 15 minutes or less, more preferably 10 minutes or less, and even more preferably 6 minutes or less. In addition, known heating methods such as infrared heating, planar heater heating, high-frequency heating, and microwave heating can be used for heat forming, and it can be carried out in one stage or multiple stages.

[0063] The cross-sectional shape of the pultruded molded body may be a polygon (triangle, square, rectangle, etc.), a circle, or other shape. The cross-sectional shape is not limited to these, and any shape can be selected depending on the application. Here, the cross-sectional shape of the pultruded molded body refers to the shape of the plane perpendicular to the longitudinal direction of the pultruded molded body.

[0064] The method for manufacturing an extruded molded article according to the present invention will be described in more detail below, based on embodiments.

[0065] (Embodiment) The manufacturing apparatus 100 used in the manufacturing method of the drawn molded article according to the embodiment will be described below with reference to Figure 1. Upstream and downstream refer to the upstream and downstream directions in the conveying direction, and up and down refer to the up and down directions in the manufacturing apparatus 100.

[0066] The manufacturing apparatus 100 includes a linear substrate supply unit 20, a planar substrate supply unit 30, a resin impregnation unit 40, a heat molding unit 50, a tensioning unit 60, and a cutting unit 70.

[0067] The linear substrate supply unit 20 is equipped with linear substrates 21 wound on a bobbin (not shown). The planar substrate supply unit 30 is equipped with planar substrates 31 wound on a bobbin (not shown). The linear substrates 1 and planar substrates 2 become the base materials that constitute the pultruded molded body 81. The number of linear substrates 1 placed in the linear substrate supply unit 20 varies depending on the shape of the pultruded molded body 81, but is between 10 and 2000. When the tensioning machine 61, which will be described later, is activated, the linear substrates 1 and planar substrates 2 are pulled downstream. The linear substrates 1 and planar substrates 2 move to the resin impregnation unit 40 via guide rolls.

[0068] The resin-impregnated section 40 comprises a container 42 filled with a matrix resin composition 41, and an impregnation roll 43 for impregnating the linear substrate 1 and the planar substrate 2 with the matrix resin composition 41. At least a portion of the impregnation roll 43 is immersed in the matrix resin composition 41. The matrix resin composition 41 is, for example, the matrix resin composition of the embodiment.

[0069] The linear substrate 1 and the planar substrate 2 pass through the matrix resin composition 41 via the impregnation roll 43. The linear substrate 1 and the planar substrate 2 that have left the matrix resin composition 41 move to the heat molding section 50 via the guide roll 10.

[0070] The heat molding section 50 includes a mold 51 in which a predetermined shape is formed, and heating plates 52 installed on the upper and lower surfaces of the mold 51. The mold 51 is heated by the heating plates 52. The temperature of the heated mold 51 is, for example, 60°C to 180°C.

[0071] The linear substrate 1 and the planar substrate 2 are integrated by guide rolls in front of the mold 51 and then drawn into the mold 51. When the linear substrate 1 and the planar substrate 2 enter the heated mold 51, the matrix resin composition 41 hardens and an extruded molded body 81 is formed along the mold of the mold 51. The formed extruded molded body 81 is drawn out of the mold 51 by a tensile machine 61.

[0072] The tensioning section 60 is equipped with a tensioning machine 61. The tensioning machine 61 includes a belt 62 for pulling out the pultruded molded body 81 and a drive unit 63 for rotating the belt 62 in the direction of the arrow in Figure 1. In Figure 1, the belt 62 is sandwiching the pultruded molded body 81. When the drive unit 63 is activated, the belt 62 rotates in conjunction. As a result, the pultruded molded body 81 moves so as to be pushed downstream. The pushed-out pultruded molded body 81 moves to the cutting section 70.

[0073] The rotational speed of the belt 62 and the drive unit 63 is adjusted by the curing speed of the matrix resin composition 41.

[0074] The cutting section 70 is equipped with a cutting machine 71. The rotational speed of the belt 62 and the movement of the cutting machine 71 are linked. Depending on the application, the pultruded molded body 81 is cut to a predetermined length by the cutting machine 71.

[0075] Furthermore, the manufacturing apparatus 200 used in the separate manufacturing method for the pultruded molded product according to the embodiment will be described with reference to Figure 3. Upstream and downstream refer to the upstream and downstream directions in the conveying direction, and up and down refer to the up and down directions in the manufacturing apparatus 200.

[0076] The manufacturing apparatus 200 includes a planar substrate supply section 30, a resin impregnation section 40, a heat molding section 50, a tensioning section 60, and a cutting section 70.

[0077] The planar substrate supply unit 30 includes a planar substrate 31 wound on a bobbin (not shown). When the tensioning machine 61, which will be described later, is activated, the planar substrate 2 is pulled downstream. The planar substrate 2 moves to the resin impregnation unit 40 via guide rolls.

[0078] The resin-impregnated section 40 comprises a container 42 filled with a matrix resin composition 41 and an impregnation roll 43 for impregnating the planar substrate 2 with the matrix resin composition 41. At least a portion of the impregnation roll 43 is immersed in the matrix resin composition 41. The matrix resin composition 41 is, for example, the matrix resin composition of the embodiment.

[0079] The planar substrate 2 passes through the matrix resin composition 41 via the impregnation roll 43. The planar substrate 2, having exited the matrix resin composition 41, moves to the heat molding section 50 via the guide roll 10.

[0080] The heat molding section 50 includes a mold 51 in which a predetermined shape is formed, and heating plates 52 installed on the upper and lower surfaces of the mold 51. The mold 51 is heated by the heating plates 52. The temperature of the heated mold 51 is, for example, 60°C to 180°C.

[0081] The planar substrate 2 is integrated by guide rolls in front of the mold 51 and then drawn into the mold 51. When the planar substrate 2 enters the heated mold 51, the matrix resin composition 41 hardens, and an extruded molded body 81 is formed along the mold of the mold 51. The formed extruded molded body 81 is pulled out of the mold 51 by a tensile machine 61.

[0082] The tensioning section 60 is equipped with a tensioning machine 61. The tensioning machine 61 includes a belt 62 for pulling out the pultruded molded body 81 and a drive unit 63 for rotating the belt 62 in the direction of the arrow in Figure 3. In Figure 3, the belt 62 is sandwiching the pultruded molded body 81. When the drive unit 63 is activated, the belt 62 rotates in conjunction. As a result, the pultruded molded body 81 moves so as to be pushed downstream. The pushed-out pultruded molded body 81 moves to the cutting section 70.

[0083] The rotational speed of the belt 62 and the drive unit 63 is adjusted by the curing speed of the matrix resin composition 41.

[0084] The cutting section 70 is equipped with a cutting machine 71. The rotational speed of the belt 62 and the movement of the cutting machine 71 are linked. Depending on the application, the pultruded molded body 81 is cut to a predetermined length by the cutting machine 71.

[0085] The extruded molded body of the present invention can be used, for example, by laminating it onto the structural frame of a building (columns, beams, floors, walls, etc.), and is particularly suitable for use by laminating it onto a structural frame made of organic materials such as wood.

[0086] The thickness of the pultruded body can be set according to the desired fire resistance, and is preferably 3 mm to 60 mm, more preferably 4 mm to 50 mm, even more preferably 5 mm to 30 mm, and most preferably 6 mm to 25 mm.

[0087] Furthermore, the pultruded molded body of the present invention can also be used in conjunction with laminated materials such as gypsum board, concrete board, mortar board, fiber-reinforced cement board, cement calcium silicate board, slag cement perlite board, ALC board, siding board, extruded board, steel plate, plastic board, natural flat board, plywood, thermal insulation foam, heat-expandable coating material, and heat-expandable sheet.

[0088] The present invention will be further described in detail by the following examples. However, the present invention is not limited in any way by the following examples.

[0089] The following components were used as the matrix resin compositions in the examples and comparative examples.

[0090] (Composition of Matrix Resin Composition 1) Thermosetting resin: Unsaturated polyester resin / styrene (mass ratio 60 / 40) Endothermic component: Sodium tetraborate decahydrate Polymerization initiator: tert-butyl peroxypivalate (Composition of Matrix Resin Composition 2) Thermosetting resin: Unsaturated polyester resin / styrene (mass ratio 55 / 45) Endothermic component: Boric acid Polymerization initiator: Methyl ethyl ketone peroxide

[0091] (Fire Resistance Test) A portion of the pultruded molded body obtained in the following examples and comparative examples was cut out (100 mm x 100 mm x 13 mm), and a test specimen was prepared by bonding it to a gypsum board (100 mm x 100 mm x 12.5 mm) with acrylic adhesive. A fire resistance test was then conducted using this specimen with a cone calorimeter as specified in ISO 5660. The heating intensity in the fire resistance test was 50 kW / m².２ The heating time was 60 minutes. In the fire resistance test, the temperature of the back surface of the test specimen was measured during heating, and the fire resistance was evaluated based on the highest temperature reached. The back surface of the test specimen refers to the side facing the gypsum board (the non-heated side). (Evaluation criteria) If the highest temperature reached is 250°C or less: It is at a practical level and has excellent fire resistance. If the highest temperature reached exceeds 250°C: It is not at a practical level and has poor fire resistance.

[0092] [Example 1] (Preparation of Matrix Resin Composition 1) 50 parts by mass of thermosetting resin and 50 parts by mass of sodium tetraborate decahydrate were added to a container. Next, the mixture was stirred in a warm room (23°C) for 30 minutes, and then 1 part by mass of polymerization initiator was added and stirred for 10 minutes to obtain Matrix Resin Composition 1.

[0093] (Manufacturing of pultruded molded body 1) Using the manufacturing apparatus shown in Figure 1, glass fiber roving (manufactured by Nitto Boseki Co., Ltd., RS440 RR-520) and glass fiber nonwoven fabric (manufactured by Kurashiki Spinning Co., Ltd., Kurabo Kuramas Stitch Mat #450) were supplied to form the laminated structure shown in Figure 2, and the laminated structure consisting of roving and nonwoven fabric was used as the base material (the content ratio (mass ratio) of roving to nonwoven fabric was 14:86). Subsequently, the obtained base material was immersed in a resin vat filled with matrix resin composition 1 to impregnate the base material with the matrix resin composition 1. Next, the excess matrix resin composition 1 that had impregnated and adhered to the base material was scraped off, and then the base material was passed through a mold heated to 80°C for 6 minutes to cure the matrix resin composition 1, and then cooled to obtain the pultruded molded body 1. The mold used was one in which the cross-sectional shape of the pultruded molded body 1 after passing through the mold was a rectangle of 260 mm × 13 mm. The obtained pultruded molded body 1 had a longitudinal length of 1000 mm, a width of 260 mm, a thickness of 13 mm, and a base material content of 15% by mass. It was confirmed that pultruded molded bodies with a constant thickness could be continuously manufactured, demonstrating excellent mass productivity (continuous productivity, moldability). Furthermore, in a fire resistance test of the obtained pultruded molded body 1, the maximum temperature reached was in the range of over 150°C and 200°C or less, showing excellent results at a practical level and confirming that it possesses fire resistance.

[0094] [Example 2] An extruded molded body 2 was manufactured in the same manner as in Example 1, except that the content of the base material in the extruded molded body was 11.5% by mass. It was confirmed that extruded molded bodies with a constant thickness could be continuously manufactured, demonstrating mass productivity (continuous productivity, moldability). Furthermore, in a fire resistance test of the obtained extruded molded body 2, the maximum temperature reached was in the range of over 150°C and 200°C or less, showing excellent results at a practical level and confirming that it possesses fire resistance.

[0095] [Example 3] An extruded molded body 3 was manufactured in the same manner as in Example 1, except that the content of the base material in the extruded molded body was 23% by mass. It was confirmed that extruded molded bodies with a constant thickness could be manufactured continuously, and that they had excellent mass productivity (continuous productivity, moldability). Furthermore, in a fire resistance test of the obtained extruded molded body 3, the maximum temperature reached was in the range of over 200°C and 250°C or less, showing excellent results at a practical level and confirming that it has fire resistance.

[0096] [Example 4] (Preparation of Matrix Resin Composition 2) 50 parts by mass of thermosetting resin and 50 parts by mass of boric acid were added to a container. Next, the mixture was stirred in a warm room (23°C) for 30 minutes, and then 1 part by mass of polymerization initiator was added and stirred for 10 minutes to obtain Matrix Resin Composition 2.

[0097] (Manufacturing of pultruded molded body 4) Using the manufacturing apparatus shown in Figure 3, a nonwoven fabric made of glass fibers (Kurabo Kuramas Stitch Mat #450, manufactured by Kurabo Industries Ltd.) was supplied to form the laminated structure shown in Figure 4, and the laminated structure made of the nonwoven fabric was used as the base material (the content ratio (mass ratio) of roving to nonwoven fabric was 0:100). The obtained base material was then immersed in a resin vat filled with matrix resin composition 2 to impregnate the base material with the matrix resin composition 2. Subsequently, the excess matrix resin composition 2 that had impregnated and adhered to the base material was scraped off, and then the base material was passed through a mold heated to 110°C for 3 minutes to harden the matrix resin composition, and then cooled to obtain the pultruded molded body 4. The mold used was one in which the cross-sectional shape of the pultruded molded body after passing through the mold was a rectangle of 260 mm × 13 mm. The obtained pultruded molded article had a longitudinal length of 1000 mm, a width of 260 mm, a thickness of 13 mm, and a base material content of 15% by mass. It was confirmed that pultruded molded articles with a constant thickness could be continuously manufactured, demonstrating excellent mass productivity (continuous productivity and moldability). Furthermore, in a fire resistance test of the obtained pultruded molded article 4, the maximum temperature reached was in the range of over 150°C and under 200°C, showing excellent results at a practical level and confirming that it possesses fire resistance.

[0098] [Comparative Example 1] An attempt was made to manufacture an pultruded molded article using the same method as in Example 1, except that the content of the base material in the pultruded molded article was 5% by mass. However, due to the low content of the base material, it was difficult to manufacture an pultruded molded article with a constant thickness, and therefore evaluation was not possible.

[0099] [Comparative Example 2] An extruded molded article was manufactured in the same manner as in Example 1, except that the content of the base material in the extruded molded article was 40% by mass. The extruded molded article produced had a consistent thickness and was confirmed to be suitable for mass production. However, in the fire resistance test, the maximum temperature reached exceeded 250°C, and a practical level was not achieved, so fire resistance was not obtained.

[0100] [Comparative Example 3] A test specimen made by laminating two sheets of gypsum board (100 mm x 100 mm x 12.5 mm) was subjected to the same fire resistance test as in Example 1. The maximum temperature reached exceeded 250°C, and a practical level was not achieved, meaning that fire resistance was not obtained.

Claims

1. An extruded molded article obtained by impregnating a substrate made of fibers with a matrix resin composition and extruding the substrate impregnated with the matrix resin composition, wherein the matrix resin composition comprises one or more selected from inorganic acids, hydroxide compounds, and hydrated compounds, a thermosetting resin, and a polymerization initiator, and the content ratio of the substrate in the extruded molded article is 10% by mass or more and 35% by mass or less.

2. The pultruded article according to claim 1, wherein the inorganic acid contains boric acid.

3. The pultruded article according to claim 1, wherein the thermosetting resin comprises an unsaturated polyester resin and / or a vinyl ester resin, and an unsaturated monomer.

4. The pultruded article according to claim 1, wherein the polymerization initiator comprises an organic peroxide.

5. A method for manufacturing an extruded molded article according to any one of claims 1 to 4, comprising: (1) a substrate supply step of supplying a substrate composed of the fibers; (2) an impregnation step of impregnating the substrate with the matrix resin composition; (3) a heat molding step of drawing the substrate impregnated with the matrix resin composition into a heated mold and heat molding it; (4) an extrusion step of drawing the substrate from the mold after heat molding; and (5) a cutting step of cutting the substrate after heat molding.

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