Thermosetting resin composition, non-flammable molded body, pultrusion molded body, and method for producing pultrusion molded body

Abstract

To provide an incombustible molding and a drawn molding, a method for manufacturing a drawn molding, and a thermosetting resin composition used in the moldings.SOLUTION: A thermosetting resin composition contains a phenol resin, an organic halogen compound, and a curing agent as organic components, and an inorganic filler and an antimony compound as inorganic components. The content of the curing agent is 1-25 pts.wt. with respect to 100 pts.wt. of the phenol resin. The average particle diameter (D50) of the inorganic filler is 0.5-11 μm. The content of the inorganic filler is 20-130 pts.wt. with respect to 100 pts.wt. of the phenol resin. The content ratio of halogen contained in the thermosetting resin composition is 2-35 wt.% with respect to the organic components. The content of the antimony compound is 2-95 pts.wt. with respect to 100 pts.wt. of the phenol resin.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a thermosetting resin composition, a non-flammable molded article, a pultrusion molded article, and a method for producing the pultrusion molded article. [Background technology]

[0002] In recent years, there has been an increasing demand for fiber reinforced plastic (FRP) molded bodies as an alternative to metal building materials. These FRP molded bodies are lighter than metal building materials and have excellent workability and strength. However, FRP molded bodies have the disadvantage of being more flammable than metal building materials. To overcome this drawback, research is underway to develop non-combustible FRP molded bodies.

[0003] For example, Patent Document 1 discloses a non-flammable fiber-reinforced resin molding obtained by impregnating fibers with an unsaturated polyester resin containing aluminum hydroxide. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2019-6852 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the non-combustible fiber reinforced resin molding disclosed in Patent Document 1 has a total calorific value of 8 MJ / m in a 20-minute heating period in an evaluation test for non-combustible materials. 2 The problem is that the following does not hold true: Evaluation tests for non-combustible materials, etc. refer to evaluation tests for non-combustible materials, etc. in accordance with the Building Standards Act of Japan, which is in accordance with ISO5660-1:2002.

[0006] The present invention has been made in consideration of the above circumstances, and aims to provide a non-combustible molded article and a non-combustible pultrusion molded article, a thermosetting resin composition to be used for these molded articles, and a method for producing the pultrusion molded article. [Means for solving the problem]

[0007] The present invention is as follows. [1] The thermosetting resin composition according to the present invention comprises, as organic components, a phenolic resin, an organic halogen compound, and a curing agent, and, as inorganic components, an inorganic filler and an antimony compound, wherein the content of the curing agent is 1 to 25 parts by weight relative to 100 parts by weight of the phenolic resin, the average particle size (D50) of the inorganic filler is 0.5 to 11 μm, and the content of the inorganic filler is 20 to 130 parts by weight relative to 100 parts by weight of the phenolic resin, the content of halogen in the thermosetting resin composition is 2 to 35% by weight relative to the organic components, and the content of the antimony compound is 2 to 95 parts by weight relative to 100 parts by weight of the phenolic resin.

[0008] [2] The phenolic resin may include a resol type phenolic resin.

[0009] [3] The inorganic filler may contain at least one selected from the group consisting of aluminum hydroxide and magnesium hydroxide.

[0010] [4] The non-combustible molded body according to the present invention is a non-combustible molded body made of a fiber-reinforced plastic in which a matrix resin is impregnated into a substrate made of fibers, wherein the fibers are made of at least one type selected from the group consisting of glass, carbon, and basalt, the volume ratio of the substrate is 40 to 85 volume % relative to 100 volume % of the non-combustible molded body, and the matrix resin is a thermosetting resin composition according to any one of [1] to [3].

[0011] [5] The substrate may be made of at least one material selected from the group consisting of threads, fabrics made by weaving threads, and unidirectional fiber sheets made by aligning threads in one direction.

[0012] [6] The average particle size (D50) of the inorganic filler may be 1 / 33 to 1 / 2 of the diameter of the thread.

[0013] [7] The diameter of the thread may be 4 to 30 μm.

[0014] [8] The non-combustible molded body may be provided with a skin layer formed by impregnating a non-woven fabric or a woven fabric with a binder resin.

[0015] [9] The fibers constituting the nonwoven fabric or the woven fabric may be made of at least one type selected from the group consisting of glass, carbon, and basalt.

[0016]

[10] The binder resin may be composed of at least one selected from the group consisting of epoxy resin, phenolic resin, and the thermosetting resin composition.

[0017]

[11] The pultrusion molded article according to the present invention is a pultrusion molded article obtained by pultrusion from a mold, and is composed of the non-combustible molded article according to [4].

[0018]

[12] The method for producing a pultrusion molded body according to the present invention includes a substrate supplying step of supplying a substrate composed of fibers, a matrix resin impregnation step of impregnating the substrate with a matrix resin composed of the thermosetting resin composition according to any one of [1] to [3], a heat-molding step of drawing the substrate impregnated with the matrix resin into a heated mold and molding it, a drawing step of drawing the molded substrate from the mold, and a cutting step of cutting the molded substrate.

[0019]

[13] The method may further include a sheet-like substrate supplying step of supplying a sheet-like substrate after the matrix resin impregnation step, and in the heat molding step, the substrate impregnated with the matrix resin and the sheet-like substrate may be drawn into a heated mold and molded. [Effects of the Invention]

[0020] According to the present invention, a non-combustible molded article and a non-combustible pultrusion molded article are provided, and a thermosetting resin composition for use in these molded articles and a method for producing the pultrusion molded article are also provided. Furthermore, such non-combustible molded articles and pultrusion molded articles can be used not only for building materials but also for vehicles. [Brief explanation of the drawings]

[0021] [Figure 1] FIG. 1 is a schematic front view of a unidirectional fiber sheet. [Figure 2] 1 is a schematic cross-sectional view of a non-combustible molded article according to an embodiment. [Figure 3] 1 is a schematic cross-sectional view of a non-combustible molded article having a skin layer according to an embodiment. [Figure 4] 1 is a front view showing a manufacturing apparatus for a pultruded body according to an embodiment. [Figure 5] 1 is a front view showing an apparatus for manufacturing a pultruded body having a skin layer according to an embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0022] Hereinafter, modes for carrying out the present invention (hereinafter referred to as embodiments) will be described in detail. The following embodiments are merely examples for explaining the present invention, and are not intended to limit the present invention to the following content. The present invention can be practiced by appropriately modifying it within the scope of its gist. Unless otherwise specified, "parts by weight" or "number of parts by weight" used in the following description refers to the weight of only the solid content excluding volatile content such as solvents.

[0023] [Thermosetting resin composition] The thermosetting resin composition of the embodiment is suitably used as a matrix resin constituting the non-combustible molded article and the pultrusion molded article.

[0024] The thermosetting resin composition of the embodiment contains a phenolic resin, an organic halogen compound, and a curing agent as organic components, and contains an inorganic filler and an antimony compound as inorganic components.

[0025] (phenolic resin) From the viewpoint of improving non-flammability, the phenolic resin preferably contains a resol-type phenolic resin. The content of the resol-type phenolic resin is preferably 80 parts by weight or more, more preferably 90 parts by weight or more, per 100 parts by weight of the phenolic resin contained in the thermosetting resin composition of the embodiment.

[0026] The viscosity of the phenolic resin is 500 to 20,000 mPa·s at 25° C., and from the viewpoint of facilitating impregnation of the thermosetting resin composition into the substrate, it is preferably 500 to 8,000 mPa / s. The viscosity of the phenolic resin can be measured in accordance with JIS Z8803 "Method for measuring viscosity of liquids" of the Japanese Industrial Standards (hereinafter referred to as JIS).

[0027] (organohalogen compounds) Examples of the organic halogen compound include halogenated aliphatic compounds and halogenated aromatic compounds. Examples of the halogenated aliphatic compound include vinyl chloride resin (halogen content 57%) and polyvinyl bromide (halogen content 75%). Examples of the halogenated aromatic compound include tetrachlorobisphenol A (halogen content 39%), tetrabromobisphenol A (halogen content 59%), decabromodiphenyl ether (halogen content 83%), tribromophenol (halogen content 72%), tetrachlorobisphenol S (halogen content 56%), tetrabromobisphenol S (halogen content 56%), and brominated triazine (halogen content 67%). From the viewpoints of improving non-flammability and improving the bending strength of non-flammable molded articles and pultrusion molded articles, the organic halogen compound is preferably a halogenated aromatic compound. Non-flammable molded articles and pultrusion molded articles using halogenated aromatic compounds are non-flammable and have a bending strength (in accordance with JIS K6911) of 500 MPa or more.

[0028] The content of halogen in the thermosetting resin composition is 2 to 35 wt % of the organic components from the viewpoint of improving non-combustibility and improving the processability of the non-combustible molded article and the pultrusion processability of the pultrusion molded article. Here, the organic components refer to the phenolic resin, organic halogen compound, and curing agent contained in the thermosetting resin composition. In addition, when the thermosetting resin composition further contains resins other than the phenolic resin, curing accelerators, etc., these are also treated as organic components.

[0029] The halogen content can be determined by adding up the amount of halogen contained in the organic halogen compound and the amount of halogen contained in compounds other than the organic halogen compound, dividing this total amount of halogen by the total amount of organic components, and multiplying the result by 100. Here, the total amount of organic components refers to the total amount of only the solid content excluding volatile components such as solvents contained in the organic components.

[0030] (hardening agent) Examples of the curing agent include hexamethylenetetramine, resorcinol, imidazole-based curing agents, hexamethylenetetramine, and amine-based curing agents. From the viewpoint of improving non-flammability and ensuring good drawing processability, the curing agent is preferably resorcinol. Furthermore, the non-flammability can be improved by using the curing agent in combination with a curing accelerator.

[0031] The content of the curing agent is 1 to 25 parts by weight relative to 100 parts by weight of the phenolic resin, and from the viewpoint of improving non-combustibility and ensuring good drawing processability, it is more preferably 2 to 20 parts by weight, and even more preferably 4 to 20 parts by weight.

[0032] The gel time of the thermosetting resin composition containing the curing agent at 150°C is 60 to 420 seconds, preferably 80 to 300 seconds, from the viewpoint of heating and curing the thermosetting resin composition at a predetermined timing, thereby curing the thermosetting resin composition at the timing of heating and molding, and improving drawability.

[0033] Here, the gel time refers to the time it takes for a thermosetting resin composition to harden after being heated. The shorter the gel time, the faster the hardening rate. The method for measuring the gel time will be described later.

[0034] (inorganic filler) The inorganic filler includes at least one selected from the group consisting of aluminum hydroxide and magnesium hydroxide. From the viewpoint of improving non-combustibility, the inorganic filler is preferably aluminum hydroxide or magnesium hydroxide, and from the viewpoint of improving mass productivity, more preferably aluminum hydroxide.

[0035] The inorganic filler has an average particle size (D50) of 0.5 to 11 μm, and from the viewpoint of improving drawability, it is preferably 1.0 to 11 μm.

[0036] Here, the average particle size (D50) refers to the particle size at which, when the cumulative distribution of particle sizes is divided into two at a certain particle size, the proportion of the cumulative distribution on the larger particle size side is equal to the proportion of the cumulative distribution on the smaller particle size side. Particle size can be measured by dynamic light scattering. The average particle size (D50) is also called the median size.

[0037] The content of the inorganic filler is 20 to 130 parts by weight relative to 100 parts by weight of the phenolic resin, and from the viewpoint of improving non-combustibility, 30 to 100 parts by weight is more preferable.

[0038] (antimony compounds) Examples of the antimony compound include antimony trioxide and antimony pentoxide. From the viewpoint of improving non-flammability, the antimony compound is preferably antimony trioxide. Furthermore, the antimony compound can improve non-flammability by being used in combination with an organic halogen compound.

[0039] The content of the antimony compound is 2 to 95 parts by weight relative to 100 parts by weight of the phenolic resin, from the viewpoint of improving non-combustibility and ensuring good drawing processability.

[0040] (Other ingredients) The thermosetting resin composition may contain, for example, a resin other than a phenolic resin, a silane coupling agent, an internal mold release agent, a crack inhibitor, a heat aging inhibitor, an antioxidant, etc. Examples of resins other than phenolic resins include vinyl ester resins, unsaturated polyester resins, and epoxy resins. When a vinyl ester resin or an unsaturated polyester resin is contained, an organic peroxide, azobisisobutyronitrile, etc. may be contained as a radical generator. When an epoxy resin is contained, an amine-based curing agent or an imidazole-based curing agent may be contained as a curing agent.

[0041] [Nonflammable molded body] The noncombustible molded article 37 of the embodiment is made of a fiber-reinforced plastic in which a base material made of fibers is impregnated with a matrix resin made of a thermosetting resin composition. The noncombustible molded article 37 is made of a plate-shaped fiber-reinforced plastic having a rectangular cross section, for example, as shown in FIG.

[0042] The fibers are composed of at least one material selected from the group consisting of glass, carbon, and basalt. Preferably, the fibers are composed of glass, which has excellent processability. Hereinafter, fibers composed of glass will be referred to as glass fibers, fibers composed of carbon as carbon fibers, and fibers composed of basalt as basalt fibers.

[0043] The substrate is made of at least one material selected from the group consisting of threads, woven fabrics made from woven threads, nonwoven fabrics, and unidirectional fiber sheets made from threads aligned in one direction.

[0044] The yarn made of glass fiber or basalt fiber is a yarn in which single fibers (monofilaments) are bundled to have a weight of 100 to 9600 g / 1000 m. The diameter of the yarn is 10 to 30 μm, preferably 10 to 25 μm. A binder may be used to bundle multiple single fibers.

[0045] The carbon fiber yarn is made by aligning and bundling 1,000 to 60,000 single fibers. The diameter of the yarn is 4 to 15 μm. A binder may also be used for the carbon fiber yarn. An example of a commercially available carbon fiber yarn is STS40-24K (yarn diameter 7 μm) manufactured by Teijin Limited.

[0046] Examples of the woven fabric include satin weave fabric, plain weave fabric, and twill weave fabric.

[0047] The unidirectional fiber sheet is made of a plurality of threads 66 aligned in one direction. The threads 66 are, for example, twisted threads or flattened threads. As shown in FIG. 1, the unidirectional fiber sheet may be held by a stopper thread 65 to prevent the aligned threads 66 from collapsing.

[0048] The volume ratio of the base material to the entire non-combustible molded body 37 is 40 to 85 volume % relative to 100 volume % of the non-combustible molded body 37 (100 volume % non-combustible molded body) from the viewpoints of exhibiting non-combustibility, improving drawing processability, and exhibiting rigidity of the non-combustible molded body 37.

[0049] The volume fraction of the substrate is calculated by dividing the volume of the substrate by the volume of the non-combustible molded body 37 (i.e., the total volume of the substrate and the resin component), and multiplying the result by 100. The volume of the substrate is calculated by dividing the weight of the substrate used by the true density (true specific gravity) of the material. The volume of the non-combustible molded body 37 is calculated by submerging the non-combustible molded body 37 in a measuring cylinder filled with pure water and measuring the change in the liquid level before and after submersion. Here, true density refers to the density of the material itself, excluding the volume of pores, voids, etc. within the material.

[0050] The average particle size (D50) of the inorganic filler contained in the matrix resin is 1 / 33 to 1 / 2 of the diameter of the thread, and preferably 1 / 27 to 1 / 2.

[0051] The noncombustible molded body 37 can be produced, for example, by the following method. First, a thermosetting resin composition is prepared. The thermosetting resin composition is obtained by adding predetermined amounts of a phenolic resin, an organic halogen compound, an inorganic filler, an antimony compound, a curing agent, and an organic solvent to a container and stirring them. Next, the thermosetting resin composition is impregnated into a substrate, and the substrate is placed in a rectangular mold and heated. After that, the substrate is cooled to obtain the noncombustible molded body 37. The heating conditions are, for example, 100 to 250°C and 1 to 15 minutes, and the temperature and time are adjusted depending on the size of the noncombustible molded body 37.

[0052] The cross-sectional shape of the noncombustible molded body 37 may be, other than a rectangle, a circle, a triangle, a square, or a C-shape (cross-sectional shape 25 shown in FIG. 2). The cross-sectional shape is not limited to these, and any shape can be selected depending on the application.

[0053] As shown in Fig. 3, the noncombustible molded body 37 may have a skin layer 36 formed on the noncombustible molded body 37, the skin layer 36 being made of a nonwoven fabric or a woven fabric impregnated with a binder resin. The noncombustible molded body 37 shown in Fig. 3 has the skin layer 36 formed so as to cover the entire surface. The noncombustible molded body 37 may also have the skin layer 36 formed so as to cover only a portion of the surface.

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

[0055] Examples of the woven fabric include satin weave fabric, plain weave fabric, and twill weave fabric.

[0056] The fibers constituting the nonwoven fabric and woven fabric are made of at least one type selected from the group consisting of glass, carbon, and basalt. From the viewpoint of excellent processability, the fibers are preferably made of glass.

[0057] Examples of the binder resin include epoxy resin, phenol resin, and the matrix resin constituting the non-combustible molded body 37 described above.

[0058] The thickness of the skin layer 36 is, for example, 10 to 500 μm.

[0059] By providing the noncombustible molded body 37 with the skin layer 36, it is possible to prevent fluffing around the hole when a hole is made in the noncombustible molded body 37 with, for example, a drill.

[0060] Another method for producing the noncombustible molded article 37 is a method for producing the noncombustible molded article 37 by pultrusion molding. Specifically, a substrate composed of fibers is supplied (substrate supplying step). The substrate is impregnated with a separately prepared thermosetting resin composition (matrix resin) (matrix resin impregnation step). The substrate impregnated with the matrix resin is drawn into a heated mold and molded (heat molding step). The molded substrate is drawn out of the mold (pulling step). The substrate is cut (cutting step) to obtain the noncombustible molded article 37. The heating conditions are 100 to 250°C and 1 to 15 minutes. The noncombustible molded article 37 thus obtained by drawing it out of a mold or other form is called a pultrusion molded article. When producing the pultrusion molded article 37 having the skin layer 36, for example, a sheet-like substrate supplying step is included after the matrix resin impregnation step, in which a sheet-like substrate is supplied. Furthermore, in the heat molding step, the substrate impregnated with the matrix resin and the sheet-like substrate are drawn into a heated mold and molded.

[0061] The pultruded body and its manufacturing method will be described in more detail below.

[0062] [Method of manufacturing pultruded body] A manufacturing apparatus 10 used in the manufacturing method for a pultruded body according to an embodiment will be described below with reference to Fig. 4. Upstream and downstream refer to the upstream and downstream in the conveying direction, and top and bottom refer to the top and bottom directions in the manufacturing apparatus 10.

[0063] The manufacturing apparatus 10 includes a substrate supply section 20, a resin impregnation section 30, a heat forming section 40, a pulling section 50, and a cutting section 60.

[0064] The substrate supply section 20 includes a roving 21 in which a thread 9 is wound around a bobbin (not shown). The thread 9 serves as the substrate that constitutes the pultrusion molded body 97. The number of rovings 21 arranged in the substrate supply section 20 varies depending on the shape of the pultrusion molded body 97, but is generally 10 to 2000 pieces. The thread 9 is pulled downstream from the roving 21 by operation of a tensioning machine 51, which will be described later. The thread 9 travels through guide rolls 11, 12, 13, 14, and 15 to the resin impregnation section 30. The substrate supply section 20 is also called a creel.

[0065] A reed 18 for aligning the yarns 9 is installed between the base material supply section 20 and the resin impregnation section 30. In the manufacturing apparatus 10, the reed 18 is installed upstream of the guide roll 15. The multiple yarns 9 are aligned by the reed 18 and move to the resin impregnation section 30. At this time, the yarns 9 are aligned while being spread in the width direction by the reed 18. The width direction refers to the direction perpendicular to the direction in which the yarns 9 flow in a horizontal plane including the direction in which the yarns 9 flow.

[0066] The resin impregnation unit 30 includes a container 32 filled with resin 33 and an impregnation roll 31 for impregnating the yarn 9 with the resin 33. The impregnation roll 31 is at least partially immersed in the resin 33. The resin 33 is, for example, a thermosetting resin composition according to the embodiment. The container 32 may be equipped with a heating device for heating the resin 33.

[0067] The yarn 9 passes through the resin 33 via the impregnation roll 31. The yarn 9 coming out of the resin 33 passes through the guide roll 16 and moves to the hot molding section 40.

[0068] Between the resin impregnation section 30 and the heat molding section 40, a reed 19 is installed to scrape off excess resin 33 adhering to the yarn 9 and align the yarn 9. In the manufacturing apparatus 10, the reed 19 is installed downstream of the guide roll 16.

[0069] The hot molding section 40 includes a mold 41 in which a predetermined shape is formed, and hot plates 42 and 43 installed on the upper and lower surfaces of the mold 41. The mold 41 is heated by the hot plates 42 and 43. The temperature of the heated mold 41 is, for example, 100°C to 250°C.

[0070] The yarn 9, from which excess resin 33 has been scraped off by the reed 19, is drawn into the mold 41. When the yarn 9 enters the heated mold 41, the resin 33 hardens and a pultruded body 97 is formed along the shape of the mold 41. The formed pultruded body 97 is pulled out of the mold 41 by a pulling machine 51.

[0071] The pulling section 50 includes a pulling machine 51. The pulling machine 51 includes belts 54 and 55 for pulling out the pultruded body 97, a drive unit 53 that rotates belt 54 counterclockwise in FIG. 4, and a drive unit 56 that rotates belt 55 clockwise in FIG. 4. In FIG. 4, the pultruded body 97 is sandwiched between belts 54 and 55. The drive units 53 and 56 operate synchronously. When the drive units 53 and 56 operate, the belts 54 and 55 rotate in unison. As a result, the pultruded body 97 moves so as to be extruded downstream. The extruded pultruded body 97 moves to the cutting section 60.

[0072] The rotation speed of the belts 54 and 55 is adjusted depending on the hardening speed of the resin 33 .

[0073] The cutting unit 60 includes a cutter 61. The cutter 61 includes a blade 62 that moves up and down. The rotation speed of the belts 54 and 55 is linked to the vertical movement of the blade 62 of the cutter 61. The pultruded body 97 is cut to a predetermined length by the blade 62 depending on the application.

[0074] Next, the manufacturing apparatus 20 used in the method for manufacturing the pultruded body 37 having the skin layer 36 will be described with reference to Figure 5. The manufacturing apparatus 20 is substantially the same as the manufacturing apparatus 10, except that the manufacturing apparatus 20 further includes a sheet-like substrate introduction section 70 downstream of the resin impregnation section 30 of the manufacturing apparatus 10. Similar components are given the same reference numerals, and detailed description thereof will be omitted.

[0075] The sheet-like substrate introduction section 70 is provided between the resin impregnation section 30 and the heat molding section 40. The sheet-like substrate introduction section 70 includes a sheet-like substrate supply section 94 and a sheet-like substrate supply section 96. The sheet-like substrate supply section 94 supplies the sheet-like substrate 93 via guide rolls 131 and 132 to the upper side of the yarn 9 to which the resin 33 is attached. The sheet-like substrate supply section 96 supplies the sheet-like substrate 95 via guide rolls 133 and 134 to the lower side of the yarn 9 to which the resin 33 is attached.

[0076] The sheet-like substrates 93 and 95 are nonwoven fabrics or woven fabrics.

[0077] The yarn 9 immediately before entering the heat forming section 40 has a structure in which the sheet-like substrate 93 is laminated on the upper side of the yarn 9 and the sheet-like substrate 95 is laminated on the lower side.

[0078] The yarn 9, the sheet-like substrate 93, and the sheet-like substrate 95 are simultaneously drawn into the mold 41 and heated, causing the resin 33 adhering to the yarn 9 to melt. The molten resin 33 soaks into the sheet-like substrate 93 and the sheet-like substrate 95 that are layered on the yarn 9. The resin 33 then hardens through a curing reaction caused by heat. The pultruded body 98 pulled out of the mold 41 has a skin layer on its surface made of fiber-reinforced plastic in which the resin 33 has soaked into the sheet-like substrate 93 and the sheet-like substrate 95.

[0079] The sheet-like base material 93 and the sheet-like base material 95 may be prepreg sheets in which a nonwoven fabric or a woven fabric is impregnated with a resin. Examples of the resin include an epoxy resin, a phenolic resin, and the thermosetting resin composition of the embodiment.

[0080] [Pultruded body] The pultruded body 97 of this embodiment is produced, for example, by the above-described method for producing a pultruded body.

[0081] The average particle diameter (D50) of the inorganic filler contained in the matrix resin that constitutes the pultrusion molded body 97 is 1 / 33 to 1 / 2 of the diameter of the thread. Because the relationship between the average particle diameter of the inorganic filler and the diameter of the thread satisfies the above-mentioned relationship, the pultrusion molded body 97 can be easily pulled out of the mold in the pultrusion step in the above-mentioned method for producing the pultrusion molded body.

[0082] The reason the pultrusion molded body 97 can be easily pulled out is thought to be due to the following phenomenon occurring between the inorganic filler contained in the matrix resin and the yarn. The inorganic filler flows within the matrix resin until the heated matrix resin melts and hardens. At this time, the inorganic filler, whose average particle diameter (D50) is smaller than the diameter of the yarn, easily penetrates into gaps between the yarns, gaps between the yarns and the mold, and so on. In other words, a low proportion of the inorganic filler is exposed to the surface, while a high proportion of the matrix resin is exposed to the surface. This reduces contact between the inorganic filler and the mold, reducing friction between the pultrusion molded body 97 and the mold. As a result, the pultrusion molded body 97 can be easily pulled out of the mold.

[0083] The cross-sectional shape of the pultruded body 97 can be selected arbitrarily depending on the application. Examples include rectangular, circular, triangular, and square shapes, which are the same as the cross-sectional shapes of the noncombustible molded body 37. Here, the cross-sectional shape of the pultruded body 97 refers to the shape in a plane perpendicular to the longitudinal direction of the pultruded body 97.

[0084] A skin layer made of fiber reinforced plastic, in which nonwoven fabric or woven fabric is impregnated with a binder resin, may be formed on the entire or part of the pultruded body 97 . [Example]

[0085] The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples in any way.

[0086] The following components were used as the resin compositions in the examples and comparative examples. (phenolic resin) Phenolic resin FA: resol type phenolic resin, viscosity at 25°C 600 mPa·s (Gunei Chemical Industry Co., Ltd., PL-4222), Phenolic resin FB: resol-type phenolic resin, viscosity at 25°C: 4000 mPa·s (Meiwa Kasei Co., Ltd., MWF-2620).

[0087] (inorganic filler) Inorganic filler IA: aluminum hydroxide, D50 average particle size 0.75 μm (Showa Denko, Hijilite H-43M), Inorganic filler IB: aluminum hydroxide, D50 average particle size 1.0 μm (Nippon Light Metal Co., Ltd., BF013), Inorganic filler IC: aluminum hydroxide, D50 average particle size 3.0 μm (Nippon Light Metal Co., Ltd., B703), Inorganic filler ID: aluminum hydroxide, D50 average particle size 10.5 μm (manufactured by Armolix, B-308), Inorganic filler IE: aluminum hydroxide, D50 average particle size 12 μm (manufactured by Armolix, B-309), Inorganic filler IF: aluminum hydroxide, D50 average particle size 27 μm (manufactured by Armolix, B-325), Inorganic filler IG: magnesium hydroxide, D50 average particle size 0.8 μm (Kisuma 5P, manufactured by Kyowa Chemical Industry Co., Ltd.).

[0088] (organohalogen compounds) Organic halogen compound HA: Tetrabromobisphenol A, halogen content 59% (manufactured by LANXESS, BA-59P(TBBPA)).

[0089] (antimony compounds) Antimony compound AA: antimony trioxide, D50 average particle size 0.5 μm (PATOX-M, manufactured by Nippon Seiko Co., Ltd.).

[0090] (hardening agent) Curing agent: resorcinol, molecular weight 110 (Sumitomo Chemical Co., Ltd., Resorcin).

[0091] The following substrates were used in the examples and comparative examples. (base material) Glass fiber yarn (GA yarn): yarn diameter 20 μm (Nitto Boseki Co., Ltd., RS440 RR-520), Nonwoven fabric made of glass fiber (nonwoven fabric GC): weight 450 g / m 2 (Kurabo Kuramasu Stitch Mat #450, manufactured by Kurabo Industries, Ltd.).

[0092] (Preparation of Thermosetting Resin Composition) Example 1 The thermosetting resin composition used in Example 1 was prepared as follows: 100 parts by weight of phenolic resin FB, 6.0 parts by weight of curing agent, 7.0 parts by weight of antimony compound AA, and 70 parts by weight of inorganic filler IA were added to a container. Next, a solution prepared by dissolving 14.3 parts by weight of organic halogen compound HA in 8.0 parts by weight of acetone as an organic solvent was added to the container, and the mixture was stirred at room temperature for 5 minutes to obtain a thermosetting resin composition.

[0093] (Example 2) to (Example 36), (Comparative Example 1) to (Comparative Example 7) The thermosetting resin compositions used in the examples and comparative examples other than Example 1 were prepared in the same manner as in Example 1, except that the types and contents of the components shown in Tables 1 to 8 were changed. The units of contents in the tables are "parts by weight" unless otherwise specified.

[0094] (Preparation of non-combustible molded body without skin layer) Example 1 190 rovings of glass fiber yarn (GA yarn) were placed on a creel. The GA yarn was pulled out from the roving and passed through a reed to straighten it. The GA yarn was then immersed in a resin vat filled with the thermosetting resin composition used in Example 1 for 120 seconds to impregnate the GA yarn with the thermosetting resin composition. Next, excess resin adhering to the GA yarn was scraped off, and the GA yarn was passed through a reed to spread it in the width direction. The GA yarn was then passed through a mold heated to 150°C for 5 minutes to cure the thermosetting resin composition. The GA yarn was then cooled to obtain a non-combustible molded article. A plate-shaped non-combustible molded article was obtained as the non-combustible molded article. The plate-shaped non-combustible molded article had a longitudinal length of 1000 mm, a transverse length of 100 mm, and a thickness of 5 mm. A mold was used such that the cross-sectional shape of the non-combustible molded article after passing through the mold was a rectangle of 100 mm x 5 mm. This non-combustible molded article is a pultrusion molded article because it is molded by being pulled out from a mold.

[0095] (Production of non-combustible molded body with skin layer) Example 2 170 rovings of glass fiber yarn (GA yarn) were placed on a creel. The GA yarn was pulled out from the roving and passed through a reed to straighten it. The GA yarn was then immersed in a resin vat filled with the thermosetting resin composition used in Example 2 for 120 seconds to impregnate the GA yarn with the thermosetting resin composition. Next, excess resin adhering to the GA yarn was scraped off, and the GA yarn was passed through a reed to spread it in the width direction. A nonwoven fabric (GC nonwoven fabric) made of glass fiber was then laminated on the top and bottom surfaces of the GA yarn, and the GA yarn was passed through a mold heated to 150°C for 5 minutes to harden the thermosetting resin composition. The GA yarn was then cooled to obtain a noncombustible molded article with a skin layer. A plate-shaped noncombustible molded article was obtained as the noncombustible molded article. The plate-shaped noncombustible molded article had a longitudinal length of 1000 mm, a transverse length of 100 mm, and a thickness of 5 mm. The same mold as used in Example 1 was used. This non-combustible molded article is also a pultrusion molded article because it is molded by being pulled out from a mold.

[0096] (Production of non-combustible molded body with skin layer) (Example 3) to (Example 36), (Comparative Example 1) to (Comparative Example 7) The noncombustible molded articles of the other Examples and Comparative Examples were produced in the same manner as the noncombustible molded article of Example 2. The same substrate (yarn GA) as in Example 2 was used. The thermosetting resin compositions were prepared by changing the types and contents of each component shown in Tables 1 to 8.

[0097] The viscosity of the phenolic resin, the gel time of the thermosetting resin composition, and the evaluation and measurement methods were as follows.

[0098] <Viscosity measurement of phenolic resin> The viscosity of the phenolic resin was measured in accordance with JIS Z8803 "Method for measuring viscosity of liquids."

[0099] <Gel time measurement> The gel time of the thermosetting resin composition used in Example 23 was measured as follows. First, 100 parts by weight of phenolic resin FB and 10 parts by weight of curing agent were added to a container and mixed thoroughly to prepare a resin composition. Next, 1 ml of this resin composition was dropped onto a hot plate heated to 150°C and kneaded with an awl at approximately 1 stroke per second until the composition no longer formed strings. The gel time was measured as the time from when the resin composition was dropped onto the hot plate until the composition no longer formed strings. The results are shown in Table 6. The gel times of the thermosetting resin compositions of Examples 24 to 28 were measured in the same manner as in Example 23, except that the amount of curing agent was changed.

[0100] Here, the main reaction in a thermosetting resin composition is the curing reaction between the phenolic resin and the curing agent. The speed of this curing reaction affects the processability of the non-flammable molded article. Therefore, the gel time of a resin composition obtained by removing the inorganic components from the thermosetting resin composition, i.e., a resin composition consisting only of the phenolic resin and the curing agent, was measured. This gel time was also defined as the gel time of the thermosetting resin composition.

[0101] <Non-flammability evaluation> The non-combustible molded body prepared in Example 1 was cut into 100 mm x 100 mm pieces using a diamond cutter. Samples for evaluating non-combustibility were obtained by polishing the end faces of the cut non-combustible molded body with sandpaper of No. 800. Samples for Examples 2 to 36 and Comparative Examples 1 to 7 were prepared in the same manner.

[0102] The non-combustibility evaluation was carried out based on the evaluation test for non-combustible materials in the Building Standards Act of Japan, which conforms to ISO5660-1:2002. The measurement device used was a cone calorimeter (C4, manufactured by Toyo Seiki Seisakusho Co., Ltd.). The evaluation criteria were as follows: Excellent: Total heat output for the first 20 minutes after heating starts is 8MJ / m 2 It was as follows. Poor: The total heat generated within 20 minutes after the start of heating is 8MJ / m 2 It was bigger.

[0103] <Viscosity measurement> The viscosity of the thermosetting resin composition was measured at 25° C. using a rotational viscometer (TVC-10 type viscometer, manufactured by Toki Sangyo Co., Ltd.) at 20 rpm.

[0104] <Drawing processability> The drawing processability was evaluated from three perspectives: resin impregnation, mold clogging, and the presence or absence of resin chipping.

[0105] <Resin impregnation> The resin impregnation property was evaluated as follows. First, a GA thread drawn from a roving was immersed in a resin vat filled with a thermosetting resin composition for 120 seconds to impregnate the GA thread with the thermosetting resin composition. Then, the GA thread was drawn from the resin vat and loosened by hand. At this time, the presence or absence of voids between the fibers constituting the GA thread was visually confirmed. Excellent: No voids were observed. Good: Voids were observed (at a level that does not pose a problem in practical use). Poor: Voids were observed (at a level that is problematic for practical use). The level that does not pose any practical problems refers to a level that does not affect the non-combustibility evaluation or strength.

[0106] <Mold clogging> Mold clogging was evaluated by determining the degree of mold clogging during the production of the noncombustible molded articles of Examples and Comparative Examples. Specifically, during the hot molding process for producing the pultrusion molded article, visual observation was made to determine whether the thread GA impregnated with the thermosetting resin composition or the laminate in which the nonwoven fabric GC was laminated on both the top and bottom surfaces of the thread GA impregnated with the thermosetting resin composition was smoothly drawn into the mold. Excellent: The laminate was pulled in smoothly without bulging at the entrance of the mold. Poor: The laminate bulged at the entrance of the mold and was not drawn in smoothly.

[0107] <Presence or absence of resin chipping> The presence or absence of resin chipping was evaluated by examining the surface condition of the noncombustible molded article when it was pulled out of the mold during the hot molding process for producing the pultrusion molded article. Specifically, the presence or absence of resin chipping (resin deficiency) on the surface of the noncombustible molded article pulled out of the mold was visually observed. Excellent: No resin shortage (chipping). Good: There is a lack of resin (chipping) (to a level that does not cause any problems in practical use). Poor: Resin deficiency (chipping) is present (to a level that is problematic for practical use). The level that does not pose any practical problems refers to a level that does not affect the non-combustibility evaluation or strength.

[0108] [Table 1]

[0109] Table 1 shows the results of evaluating the non-combustibility, resin viscosity, and drawability of non-combustible molded articles produced from thermosetting resin compositions prepared using inorganic fillers with different average particle sizes (D50). The non-combustible molded articles of Examples and Comparative Examples other than Example 1 have a skin layer. The inorganic filler IG used in Example 6 was magnesium hydroxide, and the inorganic fillers IA to IF used in the other Examples and Comparative Examples were aluminum hydroxide. The results of Examples 1 to 6 show that when the inorganic filler had an average particle size (D50) of 0.5 to 11 μm, the evaluation results of the non-combustible molded articles for non-combustible properties and drawability were good.

[0110] [Table 2]

[0111] Thermosetting resin compositions containing different amounts of inorganic filler were prepared, and the non-combustibility and drawability of non-combustible molded articles made from these thermosetting resin compositions were evaluated, as shown in Table 2. The results of Examples 7 to 9 show that when the amount of inorganic filler was 20 to 130 parts by weight per 100 parts by weight of the phenolic resin, the evaluation results for the non-combustibility and drawability of the non-combustible molded articles were good.

[0112] [Table 3]

[0113] Table 3 shows the results of evaluating the non-combustibility and drawability of non-combustible molded articles produced from thermosetting resin compositions prepared by varying the halogen content in the thermosetting resin composition. The results of Examples 10 to 14 show that when the halogen content was 2 to 35 wt% relative to the organic components, the evaluation results of the non-combustible molded articles were good in terms of non-combustibility and drawability.

[0114] [Table 4]

[0115] Thermosetting resin compositions containing different amounts of antimony compound were prepared, and the non-combustibility and drawability of non-combustible molded articles made from these thermosetting resin compositions were evaluated. Table 4 shows the results. From the results of Examples 15 to 20, when the amount of antimony compound was 2 to 95 parts by weight per 100 parts by weight of the phenolic resin, the evaluation results for the non-combustible property and drawability of the non-combustible molded articles were good.

[0116] [Table 5]

[0117] Table 5 shows the results of preparing thermosetting resin compositions using phenolic resins with different viscosities and evaluating the non-combustibility and drawability of non-combustible molded articles made from these thermosetting resin compositions. The results of Examples 21 and 22 show that the evaluation results for the non-combustible properties and drawability of the non-combustible molded articles were good even when the viscosity of the phenolic resin was changed.

[0118] [Table 6]

[0119] Table 6 shows the results of evaluating the non-combustibility and drawability of non-combustible molded articles produced from thermosetting resin compositions prepared with different amounts of curing agent. The results of Examples 23 to 28 show that the evaluation results for the non-combustible properties and drawability of non-combustible molded articles were good when the gel time was at least in the range of 60 to 420 seconds.

[0120] [Table 7]

[0121] Table 7 shows the results of evaluating the noncombustibility and drawability of noncombustible molded bodies with different volume ratios of the substrate to the noncombustible molded body. From the results of Examples 29 to 32, when the volume ratio of the substrate was 40 to 85 volume %, the evaluation results of the noncombustibility and drawability of the noncombustible molded body were good.

[0122] [Table 8]

[0123] Table 8 shows the results of evaluating the noncombustibility and drawability of noncombustible molded articles depending on the ratio of the average particle diameter (D50) of the inorganic filler to the diameter of the thread. From the results of Examples 33 to 36, when the ratio was 1 / 33 to 1 / 2, the evaluation results of the noncombustible molded articles for noncombustibility and drawability were good.

[0124] From the above results, the present invention can provide a non-combustible molded article, a non-combustible pultrusion molded article, and a method for producing the pultrusion molded article. The present invention can also provide a thermosetting resin composition for use in these molded articles. Furthermore, the non-combustible molded article and pultrusion molded article provided by the present invention can be used not only for building materials but also for vehicles.

[0125] The present invention allows various embodiments and modifications without departing from the broad spirit and scope of the present invention. Furthermore, the above-described embodiments are intended to illustrate the present invention and do not limit the scope of the present invention. That is, the scope of the present invention is defined by the claims, not the embodiments. Various modifications made within the scope of the claims and within the scope of the meaning of the invention equivalent thereto are considered to be within the scope of the present invention. [Explanation of symbols]

[0126] 9, 66 thread, 65 stop thread, 10, 20 manufacturing equipment, 11, 12, 13, 14, 15, 16 Guide roll, 18, 19 Reed, 20 Base material supply section, 21 Roving, 25 Cross-sectional shape, 30 resin impregnation part, 31 impregnation roll, 32 container, 33 resin, 36 skin layer, 37 non-combustible molded body, 40 heating forming section, 41 mold, 42, 43 hot plate, 50 tensioning section, 51 tensioning machine, 53, 56 driving section, 54, 55 belt, 60 cutting section, 61 cutting machine, 62 blade, 70 sheet-shaped substrate introduction section, 93, 95 sheet-shaped substrate, 94, 96 sheet-shaped substrate supply section, 97, 98 pultrusion molding body, 131, 132, 133, 134 Guide rolls.

Claims

1. The organic component includes a phenolic resin, an organic halogen compound, and a curing agent, A thermosetting resin composition containing an inorganic filler and an antimony compound as inorganic components, the organic halogen compound is a halogenated aromatic compound, The content of the curing agent is 1 to 25 parts by weight based on 100 parts by weight of the phenolic resin, The inorganic filler has an average particle size (D50) of 0.5 to 11 μm, The content of the inorganic filler is 20 to 130 parts by weight based on 100 parts by weight of the phenolic resin, the content of halogen in the thermosetting resin composition is 2 to 35% by weight based on the organic component; The thermosetting resin composition has a content of the antimony compound of 2 to 95 parts by weight based on 100 parts by weight of the phenolic resin.

2. The thermosetting resin composition according to claim 1 , wherein the phenolic resin comprises a resol-type phenolic resin.

3. The thermosetting resin composition according to claim 1 , wherein the inorganic filler comprises at least one selected from the group consisting of aluminum hydroxide and magnesium hydroxide.

4. A non-combustible molded body made of fiber reinforced plastic in which a matrix resin is impregnated into a substrate made of fibers, the fibers are made of at least one material selected from the group consisting of glass, carbon, and basalt; The volume ratio of the base material is 40 to 85% by volume relative to 100% by volume of the noncombustible molded body, A non-combustible molded article, wherein the matrix resin is the thermosetting resin composition according to claim 1 .

5. The non-combustible molded body according to claim 4, wherein the substrate is composed of at least one material selected from the group consisting of yarn, a woven fabric made of woven yarn, and a unidirectional fiber sheet made of yarns aligned in one direction.

6. The non-combustible molded body according to claim 5, wherein the average particle diameter (D50) of the inorganic filler is 1 / 33 to 1 / 2 of the diameter of the thread.

7. The non-combustible molded article according to claim 5, wherein the diameter of the thread is 4 to 30 μm.

8. The non-combustible molded article according to claim 4, further comprising a skin layer formed on the non-combustible molded article, the skin layer being made of a non-woven fabric or a woven fabric impregnated with a binder resin.

9. The noncombustible molded article according to claim 8, wherein the fibers constituting the nonwoven fabric or the woven fabric are composed of at least one type selected from the group consisting of glass, carbon, and basalt.

10. The noncombustible molded article according to claim 8, wherein the binder resin is at least one selected from the group consisting of an epoxy resin, a phenolic resin, and the thermosetting resin composition.

11. A pultrusion molded body that is molded by being pulled out of a mold, The pultrusion molded article is formed from the noncombustible molded article according to claim 4.

12. a substrate supplying step of supplying a substrate composed of fibers; a matrix resin impregnation step of impregnating the substrate with a matrix resin composed of the thermosetting resin composition according to any one of claims 1 to 3; a heat molding step of drawing the substrate impregnated with the matrix resin into a heated mold and molding it; a drawing step of drawing the molded substrate from the mold; a cutting step of cutting the substrate after molding; A method for producing a pultruded body comprising the steps of:

13. a sheet-like substrate supplying step of supplying a sheet-like substrate after the matrix resin impregnation step, The method for producing a pultruded body according to claim 12, wherein in the hot molding step, the substrate impregnated with the matrix resin and the sheet-like substrate are pulled into a heated mold and molded.

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