Glass chopped strand mats, glass fiber reinforced resin molded products, and automotive molded headliner materials.

Abstract

The glass chopped strand mat comprises a glass chopped strand 2a consisting of a first glass composition and a glass chopped strand 2b consisting of a second glass composition, wherein the content P1 of the glass chopped strand 2a is 20.0 to 95.0% by mass, the content P2 of the glass chopped strand 2b is 5.0 to 80.0% by mass, the ratio SC1 of the SiO2 content to the CaO content in the first glass composition is 1.5 to 150.0, and the ratio SC2 of the SiO2 content to the CaO content in the second glass composition is 1.5 to 150.0, satisfying the following equation (1). 0.20≦(P1·SC1) / (P2·SC2)≦1.80 …(1)

Description

[Technical Field]

[0001] This disclosure relates to glass chopped strand mats, glass fiber reinforced resin molded articles, and automotive molded ceiling materials. [Background technology]

[0002] In recent years, there has been a growing demand for the recycling of discarded glass products from the perspective of reducing environmental impact. In particular, from the perspective of reducing CO2 emissions, there is a demand for the recycling of discarded glass products that do not undergo processes that produce high CO2 emissions, such as heating. In this context, it has been proposed to manufacture glass fibers using all or part of discarded glass products that can be reused without processes that produce high CO2 emissions, such as heating, as glass raw materials (see, for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2024-133149 [Overview of the project] [Problems that the invention aims to solve]

[0004] However, according to the inventors' research, when glass chopped strand mats used in components requiring high safety, such as automotive molded ceiling materials, are manufactured using glass fibers derived from recycled glass products as described above, the mechanical strength may be insufficient. On the other hand, glass fibers capable of forming glass chopped strand mats with sufficient mechanical strength are often used integrated with resin as glass fiber reinforced resin molded products. Therefore, it is difficult to reuse such glass fibers as glass raw materials without processing that generates a lot of CO2, such as heating. Furthermore, since the glass raw materials must be melted at high temperatures during the manufacture of such glass fibers, it has been difficult to reduce CO2 emissions during manufacturing. Therefore, the present disclosure aims to provide glass chopped strand mats, glass fiber reinforced resin molded products, and automotive molded ceiling materials that have sufficiently high mechanical strength while reducing CO2 emissions during manufacturing. [Means for solving the problem]

[0005] The gist of this disclosure is found in the following [1] to [6].

[0006] [1] Glass chopped strand mat, A first glass chopped strand consisting of a first glass composition, A second glass chopped strand comprising a second glass composition having a lower elastic modulus than the first glass composition, The content P1 of the first glass chopped strand relative to the total amount of the glass chopped strand mat is in the range of 20.0 to 95.0% by mass. The content P2 of the second glass chopped strand relative to the total amount of the glass chopped strand mat is in the range of 5.0 to 80.0% by mass. In the first glass composition, the ratio SC1 of the SiO2 content to the CaO content is in the range of 1.5 to 150.0. In the second glass composition, the ratio of SiO2 content to CaO content, SC2, is in the range of 1.5 to 150.0. A glass chopped strand mat characterized in that P1, P2, SC1, and SC2 satisfy the following formula (1). 0.20≦(P1·SC1) / (P2·SC2)≦1.80 (1)

[0007] [2] The glass chopped strand mat according to [1], characterized in that P1, P2, SC1, and SC2 satisfy the following formula (2). 0.30≦(P1·SC1) / (P2·SC2)≦1.50 (2)

[0008] [3] The glass chopped strand mat according to [1], characterized in that P1, P2, SC1, and SC2 satisfy the following formula (3). 0.60≦(P1·SC1) / (P2·SC2)≦1.20 (3)

[0009] [4] The glass chopped strand mat according to [1], characterized in that P1, P2, SC1, and SC2 satisfy the following formula (4). 0.95≦(P1·SC1) / (P2·SC2)≦1.05 (4)

[0010] [5] A glass fiber reinforced resin molded article containing a glass chopped strand mat as described in any one of items [1] to [4].

[0011] [6] Automotive molded ceiling material including a glass chopped strand mat as described in any one of items [1] to [4]. [Effects of the Invention]

[0012] According to this disclosure, it is possible to provide glass chopped strand mats, glass fiber reinforced resin molded products, and automotive molded ceiling materials that have sufficiently high mechanical strength while reducing CO2 emissions during manufacturing. [Brief explanation of the drawing]

[0013] [Figure 1] It is a diagram showing a glass chopped strand mat according to the present disclosure. [Figure 2] It is a diagram showing a glass chopped strand mat roll from the axial direction of the core. [Figure 3] It is a schematic cross-sectional view of an automotive molded ceiling material provided with a glass chopped strand mat according to the present disclosure. [Figure 4] It is an explanatory diagram showing the manufacturing process of a glass chopped strand mat according to the present disclosure.

Mode for Carrying Out the Invention

[0014] Hereinafter, a glass chopped strand mat, a glass fiber reinforced resin molded product, and an automotive molded ceiling material according to the present disclosure will be described in detail with reference to the drawings.

[0015] As shown in FIGS. 1 to FIG. 4, the glass chopped strand mat 1 according to the present embodiment is formed by binding a large number of glass chopped strands 2 deposited in a sheet shape with a binder 3 (see FIG. 4) of a thermoplastic resin. The glass chopped strand mat 1 is used, for example, as a reinforcing material in an automotive molded ceiling material 31 (see FIG. 3). The automotive molded ceiling material 31 is an example of a glass fiber reinforced resin molded product including the glass chopped strand mat 1.

[0016] The mass per unit area of the glass chopped strand mat 1 is, for example, in the range of 50.0 to 200.0 g / m 2 and preferably in the range of 60.0 to 150.0 g / m 2 The mass per unit area of the glass chopped strand mat 1 can be measured based on JIS R3420:2023.

[0017] Furthermore, the ignition loss of the glass chopped strand mat 1 is, for example, in the range of 5.0 to 25.0 mass%, preferably in the range of 10.0 to 20.0 mass%. The ignition loss of the glass chopped strand mat 1 can be measured by the method specified in the examples described later.

[0018] The mat tensile strength of the glass chopped strand mat 1 is in the range of 100 to 400 N, preferably in the range of 130 to 380 N, more preferably in the range of 140 to 340 N, even more preferably in the range of 150 to 330 N, particularly preferably in the range of 180 to 320 N, and most preferably in the range of 200 to 300 N. The mat tensile strength of the glass chopped strand mat 1 can be measured by the method specified in the examples described later.

[0019] Furthermore, the glass chopped strand mat 1 can be used as a molded ceiling material for automobiles. Therefore, in order to ensure sufficient mechanical strength of the glass chopped strand mat 1, the tensile strength per unit area per mass (tensile strength / mass per unit area) of the glass chopped strand mat 1 is 1.50 N·m. 2 It is greater than or equal to 1.70 N·m 2 It is preferable that it be 2.00 N·m or more. 2 It is more preferable that it be 2.15 N·m or more. 2 It is even more preferable that the strength is 1 / g or more. There is no particular upper limit to the tensile strength per unit area per mass of the glass chopped strand mat 1, but it may be, for example, 3.00 or less, or 2.50 or less.

[0020] The glass filaments constituting the glass chopped strand mat 1 have, for example, filament diameters in the range of 3.0 to 30.0 μm.

[0021] The glass chopped strands 2 that make up the glass chopped strand mat 1 are made by cutting glass fibers, and the glass fibers are made by melting and spinning glass raw materials. The mass per unit length of the glass chopped strands 2 is, for example, in the range of 10.0 to 60.0 tex (g / 1000m), and preferably in the range of 12.0 to 50.0 tex.

[0022] There are two types of glass chopped strands 2 that make up glass chopped strand mat 1, each with a different glass composition. In the following, when distinguishing between these two types, the one with the higher elastic modulus will be referred to as glass chopped strand 2a (first glass chopped strand), and the one with the lower elastic modulus will be referred to as glass chopped strand 2b (second glass chopped strand). Glass chopped strand mat 1 contains glass chopped strand 2a and glass chopped strand 2b, each in predetermined proportions.

[0023] The glass chopped strand 2a will now be described. The content (P1) of glass chopped strand 2a relative to the total amount of glass chopped strand mat 1 is in the range of 15.0 to 99.0 mass%, preferably in the range of 20.0 to 95.0 mass%, more preferably in the range of 40.0 to 85.0 mass%, even more preferably in the range of 45.0 to 80.0 mass%, particularly preferably in the range of 47.5 to 77.5 mass%, especially preferably in the range of 51.0 to 77.0 mass%, and most preferably in the range of 60.0 to 75.0 mass%.

[0024] In the glass composition of the glass chopped strand 2a (first glass composition), the ratio of the SiO2 content to the CaO content (SC1) is in the range of 1.5 to 150.0, preferably in the range of 2.0 to 10.0, and more preferably in the range of 2.0 to 3.0.

[0025] Examples of the glass composition (first glass composition) of glass chopped strand 2a include, for example, glass composition E and acid-resistant glass composition. Glass composition E contains SiO2 in the range of 52.0 to 56.0 mass%, Al2O3 in the range of 12.0 to 16.0 mass%, MgO and CaO in total in the range of 20.0 to 25.0 mass%, and B2O3 in the range of 0.0 to 10.0 mass% relative to the total amount of glass fibers. Acid-resistant glass composition contains SiO2 in the range of 52.0 to 62.0 mass%, Al2O3 in the range of 12.0 to 16.0 mass%, and MgO and CaO in total in the range of 16.0 to 30.0 mass%, relative to the total amount of glass fibers.

[0026] The glass composition of glass chopped strand 2a can be measured as follows. First, glass chopped strand 2a extracted from the glass chopped strand mat is placed in a platinum crucible and melted in an electric furnace at a temperature in the range of 1200 to 1650°C for 6 hours while stirring, at a temperature where the glass fibers or recycled glass cullet are completely melted into molten glass without any unmelted residue, and where the molten glass can flow out of the platinum crucible when the crucible containing the molten glass is tilted 60° upward from a direction horizontal to the opening surface, thereby obtaining homogeneous molten glass. Next, the obtained molten glass is poured onto a carbon plate to produce glass cullet, which is then crushed and powdered to obtain glass powder. For the light element Li, the obtained glass powder is heated and decomposed with acid, and then quantitatively analyzed using an ICP emission spectrometer. For other elements, the glass powder is formed into a disc shape using a press, and then quantitatively analyzed using a wavelength-dispersive X-ray fluorescence spectrometer. These quantitative analysis results are converted to oxides to calculate the content and total amount of each component, and the glass composition is determined from these values. Furthermore, SC1 (the ratio of SiO2 content to CaO content) can be calculated from the obtained glass composition.

[0027] The glass raw materials for glass chopped strand 2a may be mineral-derived raw materials designed to achieve a desired glass composition based on the components of each mineral. For example, glass raw materials commonly used by those skilled in the art, designed for the manufacture of glass fibers, can be used as the glass raw materials for glass chopped strand 2a. Alternatively, for example, silica sand, feldspar, clay, limestone, silica powder, dolomite, talc, clay, alumina or soda ash, or mixtures thereof, can be used as glass raw materials.

[0028] The average strand count T of the glass chopped strands 2a constituting the glass chopped strand mat 1 is in the range of 5.0 to 70.0 g / 1000 m, preferably in the range of 7.0 to 65.0 g / 1000 m, more preferably in the range of 8.0 to 60.0 g / 1000 m, even more preferably in the range of 9.0 to 50.0 g / 1000 m, particularly preferably in the range of 10.0 to 50.0 g / 1000 m, and most preferably in the range of 12.0 to 48.0 g / 1000 m. The average strand count T of the glass chopped strands 2a and 2b constituting the glass chopped strand mat 1 can be measured by the method specified in the examples described later.

[0029] The glass chopped strands 2a are formed by cutting the glass fiber bundles 5a drawn from the glass cake 4a to a predetermined length. For example, glass chopped strands 2a with an average length of 1 to 3 inches (25.4 to 76.2 mm) are used. The average length is the average length of the glass chopped strands 2a after cutting. It is preferable that the coefficient of variation of the length of the glass chopped strands 2a (standard deviation of length / average length) is 0.1 or less. A coefficient of variation of length of 0.1 or less is preferable because it improves the accuracy of weight control of the glass chopped strand mat 1.

[0030] Furthermore, in order to facilitate the formation of glass chopped strands 2a by cutting the glass fiber bundles, it is preferable that the moisture content of the glass cake 4a be 5.0 wt% or less.

[0031] The glass chopped strand 2b will now be described. The content (P2) of glass chopped strand 2b relative to the total amount of glass chopped strand mat 1 is in the range of 1.0 to 85.0 mass%, preferably in the range of 5.0 to 80.0 mass%, more preferably in the range of 15.0 to 60.0 mass%, even more preferably in the range of 20.0 to 55.0 mass%, particularly preferably in the range of 22.5 to 52.5 mass%, especially preferably in the range of 23.0 to 49.0 mass%, and most preferably in the range of 25.0 to 40.0 mass%.

[0032] In the glass composition of glass chopped strand 2b (second glass composition), the ratio of SiO2 content to CaO content (SC2) is in the range of 1.5 to 150.0, preferably in the range of 2.0 to 10.0, and more preferably in the range of 7.0 to 9.0.

[0033] An example of the glass composition (second glass composition) of glass chopped strand 2b is the easily recyclable glass composition. The above easily recyclable glass composition contains SiO2 in the range of 60.0 to 74.0 mass%, Al2O3 in the range of 0.1 to 6.0 mass%, MgO and CaO in total in the range of 6.0 to 20.0 mass%, B2O3 in the range of 0.0 to 8.0 mass%, and Na2O and K2O in total in the range of 8.0 to 20.0 mass% relative to the total amount of glass fibers. In addition, glass compositions C and A can be cited as glass compositions included in the easily recyclable glass composition. The above C glass composition contains SiO2 in the range of 60.0 to 67.0 mass%, Al2O3 in the range of 2.0 to 6.0 mass%, MgO and CaO in total in the range of 10.0 to 20.0 mass%, B2O3 in the range of 0.0 to 8.0 mass%, and Na2O and K2O in total in the range of 8.0 to 15.0 mass%, relative to the total amount of glass fibers. The above A glass composition contains SiO2 in the range of 70.0 to 74.0 mass%, Al2O3 in the range of 0.1 to 3.0 mass%, CaO in the range of 7.0 to 11.0 mass%, MgO in the range of 0.0 to 4.0 mass%, and Na2O and K2O in total in the range of 12.0 to 16.0 mass%, relative to the total amount of glass fibers.

[0034] The glass composition of glass chopped strand 2b can be measured in the same manner as the glass composition of glass chopped strand 2a described above. Furthermore, SC2 (the ratio of SiO2 content to CaO content) can be calculated from the determined glass composition.

[0035] The glass fibers of glass chopped strand 2b can be obtained from waste glass in the market, and it is preferable that they be obtained from waste glass in the market. Waste glass in the market refers to glass recovered from waste in the market (for example, waste containing 30% or more by mass of glass of unspecified shape relative to the total amount) without including a process of heating at 500°C or higher. Waste in the market includes not only waste that has been used in the market and then discarded, but also waste that has been manufactured and completed as a product but has been discarded without being used or distributed in the market. Waste glass in the market as per this disclosure does not include waste glass generated in factories, etc., during the manufacturing process of glass or products using glass. Examples of waste glass in the market as per this disclosure include glass cullet recovered by crushing fluorescent tubes, glass cullet recovered by crushing automobile windshields, glass cullet recovered by crushing screens of digital devices, glass cullet recovered by crushing glass bottles used as containers for beverages, etc., and glass cullet recovered by crushing solar panels for solar power generation.

[0036] Such discarded glass from the city may be glass made from a glass composition having SiO2, Al2O3, and B2O3 as its basic composition, and further containing at least one of CaO and MgO, and at least one of Na2O and K2O.

[0037] "Waste glass from the city" refers to glass recovered from city waste by methods commonly used by those skilled in the art, as long as the process does not involve heating to 500°C or higher. Such waste glass from the city may be recovered by, for example, separating the recovered waste into glass portions that can be recycled as glass raw materials and other portions. In the separation process, the waste may be crushed to recover the glass as glass cullet. Organic matter derived from the non-glass portions of the waste may also be removed by dissolving it in a solvent such as benzyl alcohol, if necessary. When recovering glass from city waste, heating the glass to 500°C or higher may increase carbon dioxide (CO2) emissions. However, using glass recovered without a process involving heating to 500°C or higher as glass raw material can reduce carbon dioxide (CO2) emissions and, consequently, reduce the environmental burden.

[0038] The average strand count T of the glass chopped strands 2b constituting the glass chopped strand mat 1 is in the range of 5.0 to 70.0 g / 1000 m, preferably in the range of 7.0 to 65.0 g / 1000 m, more preferably in the range of 8.0 to 60.0 g / 1000 m, even more preferably in the range of 9.0 to 50.0 g / 1000 m, particularly preferably in the range of 10.0 to 50.0 g / 1000 m, and most preferably in the range of 12.0 to 48.0 g / 1000 m.

[0039] The glass chopped strands 2b are formed by cutting the glass fiber bundles 5b, which are drawn from the glass cake 4b, to a predetermined length. For example, glass chopped strands 2b with an average length of 1 to 3 inches (25.4 to 76.2 mm) are used. The average length is the average length of the glass chopped strands 2b after cutting. It is preferable that the coefficient of variation of the length of the glass chopped strands 2b (standard deviation of length / average length) is 0.1 or less. A coefficient of variation of length of 0.1 or less is preferable because it improves the accuracy of weight control of the glass chopped strand mat 1.

[0040] Furthermore, in order to facilitate the formation of glass chopped strands 2b by cutting the glass fiber bundles, it is preferable that the moisture content of the glass cake 4b be 5.0 wt% or less.

[0041] Furthermore, a powder of a thermoplastic resin such as an unsaturated polyester resin is used as the binder 3 that joins the glass chopped strands 2. The powder preferably has a weight-average particle size of 50 to 300 μm. The binder 3 melts when heated at a temperature of 170 to 280°C for 20 to 70 seconds, and then solidifies when cooled, joining the glass chopped strands 2 together.

[0042] Furthermore, the binder 3 is sprayed onto the glass chopped strand mat 1 after manufacturing so that the ratio of the mass of the binder 3 to the glass chopped strand 2 to which the binder 3 is attached is 5.0 to 25.0% by mass.

[0043] As shown in Figure 2, the glass chopped strand mat 1 is shipped as a glass chopped strand mat roll (hereinafter referred to as mat roll) 21, which is wound in a roll shape around a core 22.

[0044] Figure 3 is a schematic cross-sectional view of an automotive molded ceiling material 31 equipped with a glass chopped strand mat 1. The automotive molded ceiling material 31 is equipped with a glass chopped strand mat 1 as a reinforcing material. The automotive molded ceiling material 31 comprises a foamed resin sheet 32 ​​and a surface layer 33 that is bonded to the foamed resin sheet 32 ​​via the glass chopped strand mat 1. For the foamed resin sheet 32, for example, a foamed urethane material can be used. For the surface layer 33, for example, a nonwoven fabric can be used. Before processing as an automotive molded ceiling material 31, a resin (for example, isocyanate) is applied to the glass chopped strand mat 1, and the glass chopped strand mat 1 is aged for 2 to 3 days to reach a semi-cured state.

[0045] The semi-cured glass chopped strand mat 1 is placed on both sides of the foamed resin sheet 32 ​​in the thickness direction, and the surface layer 33 is placed on the surface of the glass chopped strand mat 1 that will be the front (inside the vehicle interior) side of the automotive molded ceiling material 31. The automotive molded ceiling material 31 is then manufactured by press molding. The glass chopped strand mat 1 functions as an adhesive for bonding the foamed resin sheet 32 ​​and the surface layer 33, and also functions as a reinforcing material to improve the strength of the automotive molded ceiling material 31. When press molding the automotive molded ceiling material 31, the male mold is usually on the inside of the vehicle interior and the female mold is on the outside. That is, compressive stress is applied to the inside of the vehicle interior and tensile stress is applied to the outside.

[0046] Here, we introduce a parameter Q to represent the properties of glass chopped strand matte, Q = (P1·SC1) / (P2·SC2) Let's assume that. however, P1 is the content (mass%) of glass chopped strand 2a relative to the total amount of glass chopped strand mat. SC1 is the ratio of the SiO2 content (mass%) to the CaO content (mass%) in the glass composition of glass chopped strand 2a. P2 is the percentage (by mass) of glass chopped strand 2b relative to the total amount of glass chopped strand mat. SC2 is the ratio of the SiO2 content (mass%) to the CaO content (mass%) in the glass composition of glass chopped strand 2b.

[0047] The value of parameter Q of the glass chopped strand mat 1 in this embodiment satisfies the following equation (1). 0.20 ≤ Q ≤ 1.80 ···(1) Furthermore, the value of parameter Q of the glass chopped strand mat 1 in this embodiment preferably satisfies the following equation (2), more preferably satisfies the following equation (3), and even more preferably satisfies the following equation (4). 0.30 ≤ Q ≤ 1.50 ···(2) 0.60 ≤ Q ≤ 1.20 ···(3) 0.95 ≤ Q ≤ 1.05 ···(4)

[0048] Next, a method for manufacturing the glass chopped strand mat 1 according to this embodiment will be described.

[0049] First, in the manufacturing method of the glass chopped strand mat 1 according to this embodiment, glass raw material for glass chopped strand 2a is placed in a platinum container equipped with 500 to 2500 nozzle tips at the bottom, and the platinum container is heated to a temperature in the range of 1000°C to 1800°C at which the glass raw material completely melts, thereby melting the glass raw material and obtaining molten glass. Next, the molten glass is drawn out from the nozzle tips of the platinum container to obtain a number of glass filament groups corresponding to the number of nozzle tips. Next, a sizing agent is applied to the obtained glass filament groups using an applicator. Then, in a gathering shoe, the glass filament groups are gathered, or divided into multiple groups and then gathered, to obtain 1 to 200 glass fiber bundles. Next, the obtained glass fiber bundles are reciprocated using a traverse device and wound onto a rotating collet to obtain a glass cake 4a.

[0050] The glass filaments in the glass cake 4a may have a filament diameter of 3.0 to 30.0 μm. The cross-sectional shape of the glass filaments may be circular, elliptical, or oblong. If the cross-sectional shape of the glass filaments is other than circular, the filament diameter refers to the equivalent fiber diameter (the diameter of a circle having the same cross-sectional area as the cross-sectional area of ​​the said cross-sectional shape).

[0051] Examples of glass compositions for the glass filaments that form the glass fiber bundles constituting the glass cake 4a include E-glass composition and acid-resistant glass composition.

[0052] Similarly, glass cake 4b is obtained separately from a different glass raw material than that used for glass cake 4a. Specifically, the glass raw material for glass chopped strand 2b is placed in a platinum container equipped with 500 to 2500 nozzle tips at the bottom, and the platinum container is heated to a temperature in the range of 1000°C to 1800°C at which the glass raw material completely melts, thereby melting the glass raw material and obtaining molten glass. Next, the molten glass is drawn out from the nozzle tips of the platinum container to obtain a number of glass filament groups corresponding to the number of nozzle tips. Next, a sizing agent is applied to the obtained glass filament groups using an applicator. Then, in a gathering shoe, the glass filament groups are gathered, or divided into multiple groups and then gathered, to obtain 1 to 200 glass fiber bundles. Next, the obtained glass fiber bundles are reciprocated using a traverse device and wound onto a rotating collet to obtain glass cake 4b.

[0053] The glass filaments in the glass cake 4b may have a filament diameter of 3.0 to 30.0 μm. The cross-sectional shape of the glass filaments may be circular, elliptical, or oblong. If the cross-sectional shape of the glass filaments is other than circular, the filament diameter refers to the equivalent fiber diameter (the diameter of a circle having the same cross-sectional area as the cross-sectional area of ​​the said cross-sectional shape).

[0054] The glass composition of the glass filaments that form the glass fiber bundles constituting the glass cake 4b includes an easily recyclable glass composition, a C glass composition, and an A glass composition.

[0055] Next, as shown in Figure 4, in the manufacturing method of the glass chopped strand mat 1 according to this embodiment, the glass fiber bundle 5a drawn from the glass cake 4a is fed to the cutter 11a of the cutting device 10 and cut to a predetermined length to form the glass chopped strand 2a. Similarly, the glass fiber bundle 5b drawn from the glass cake 4b is fed to the cutter 11b of the cutting device 10 and cut to a predetermined length to form the glass chopped strand 2b. The order in which the glass cakes 4a and 4b are cut is not particularly limited, and as shown in Figure 4, the glass cake 4a may be cut first, the glass cake 4b may be cut first, or the glass cakes 4a and 4b may be arranged alternately and cut alternately.

[0056] The glass chopped strands 2a cut by cutter 11a and 2b cut by cutter 11b fall onto the belt 13a of the first conveyor (accumulation belt conveyor) 13 located below the cutting device 10. The belt 13a of the first conveyor 13 rotates at a constant speed, and the glass chopped strands 2a and 2b that fall from the cutting device 10 accumulate on the belt 13a in a uniform sheet-like manner. This causes the glass chopped strands 2a and 2b to accumulate and form a chopped strand layer.

[0057] The first conveyor 13 transports the glass chopped strands 2 in a predetermined transport direction and has four drive rollers 13b extending in the width direction of the conveyor. An endless roller chain 13c is stretched across each end of these drive rollers 13b, forming a trapezoidal shape with the four drive rollers 13b as the vertices. Two roller chains 13c mesh with the gears at both ends of the drive rollers 13b. The two roller chains 13c are connected in a ladder-like manner by a plurality of connecting rods 13d, and an endless belt 13a is stretched across the outside of these connecting rods 13d.

[0058] In the first conveyor 13 configured in this way, when one of the drive rollers 13b is rotated by a motor (not shown), the roller chain 13c rotates in a predetermined direction. When the connecting rod 13d rotates together with the roller chain 13c, the belt 13a on the connecting rod 13d rotates, and the glass chopped strands 2 on the upper surface of the belt 13a are conveyed in a predetermined conveying direction.

[0059] In the conveying direction of the first conveyor 13, a second conveyor (a belt conveyor for binder application) 14 is positioned, connected to the first conveyor 13 to form a conveying path for the glass chopped strands 2. This second conveyor 14 has the same configuration as the first conveyor 13. The glass chopped strands 2 on the belt 13a of the first conveyor 13 are conveyed onto the belt 14a of the second conveyor 14 while maintaining a sheet-like accumulation.

[0060] Water sprayers 15 are positioned above and below the second conveyor 14 to spray water onto the glass chopped strands 2. The water sprayers 15 uniformly spray water onto both the upper and lower surfaces of the glass chopped strands 2, which are piled up in a sheet-like manner on the belt 14a (water spraying process). Here, the water sprayers 15 adjust the amount and state of water spraying so that the ratio of the mass of water adhering to the glass chopped strands 2 to the glass chopped strands 2 is 30 to 90 wt% (more preferably 50 to 80 wt%). By spraying water in this way, the water droplets are selectively placed at the intersections of the glass chopped strands constituting the glass chopped strand mat 1 by capillary action, and the binder 3 is moved and positioned as if attracted by these water droplets, so that the binder 3 can be efficiently adhered to the intersections of the glass chopped strands.

[0061] Furthermore, a binder sprayer 16 is positioned above the second conveyor 14 to spray powdered binder 3 onto the glass chopped strands 2. The binder sprayer 16 is positioned behind the water sprayer 15 and uniformly sprays the binder 3 onto the glass chopped strands 2 that have water adhering to them (binder spraying process). Here, the binder sprayer 16 adjusts the amount and state of the binder 3 sprayed so that the mass ratio of binder 3 to glass chopped strands 2 in the glass chopped strand mat 1 after manufacturing is less than 10%. Preferably, the amount of binder 3 sprayed is adjusted so that the mass ratio of binder 3 to glass chopped strands 2 is 5.0 to 25.0 mass%. Here, the mass ratio of binder 3 to glass chopped strands 2 can be measured by ignition loss based on JIS R3420:2023.

[0062] Furthermore, the binder 3 can be used in fibrous form rather than powder form. A fibrous binder 3 is less likely to fall through the gaps between the glass chopped strands 2, and can connect and bond distant glass chopped strands 2 with less mass than a powder, which is advantageous for improving the yield of the binder 3. On the other hand, if the binder is used as an emulsion instead of a solid, it is difficult to suppress its outflow from the gaps between the glass chopped strands 2.

[0063] In the conveying direction of the second conveyor 14, a third conveyor (heating belt conveyor) 17 is positioned, which is connected to the second conveyor 14 to form a conveying path for the glass chopped strands 2. Similar to the first conveyor 13, this third conveyor 17 has four drive rollers 17b extending in the width direction of the conveyor. At both ends of these drive rollers 17b, an endless roller chain 17c is stretched across in a trapezoidal shape with the four drive rollers 17b as the vertices. The two roller chains 17c mesh with the gears at both ends of the drive rollers 17b. The two roller chains 17c are connected in a ladder-like manner by a plurality of connecting rods 17d, and an endless belt 17a is stretched across the outside of these connecting rods 17d.

[0064] The glass chopped strands 2 and binder 3 on the belt 14a of the second conveyor 14 are transported onto the belt 17a of the third conveyor 17 while maintaining a dispersed state in a sheet-like manner.

[0065] A heating device 18 for heating the binder 3 is positioned along the third conveyor 17. The heating device 18 heats the glass chopped strands 2 and binder 3, which have been transported by the third conveyor 17, to a temperature of 170 to 280°C for 20 to 70 seconds (heating process). This heating melts the binder 3 attached to the glass chopped strands 2 and fills the areas where the glass chopped strands 2 come into contact with each other.

[0066] In the conveying direction of the third conveyor 17, a pair of upper and lower cooling rollers 19 are arranged to draw in the glass chopped strands 2 and binder 3 on the belt 17a. These cooling rollers 19 cool the glass chopped strands 2 and binder 3 while applying pressure to form a mat (cooling process). This cooling causes the molten binder 3 to solidify, bonding the glass chopped strands 2 together and producing a glass chopped strand mat 1. The cooling rollers 19 then feed the produced glass chopped strand mat 1 toward the winding machine 20, where the glass chopped strand mat 1 is wound onto a core 22 in a roll shape to obtain a mat roll 21 (winding process).

[0067] In the production of the glass chopped strand mat 1 described above, it is preferable that the maximum melting temperature during glass fiber production be kept below 1500°C, from the viewpoint of reducing CO2 emissions during glass fiber production.

[0068] In the above manufacturing method, by adjusting the glass raw materials used for the glass chopped strands 2a and 2b, the specifications and deposition amounts of the glass chopped strands 2a and 2b, the type of binder 3, the amount of water and binder sprayed, and the heating and cooling temperatures, the content P1 of glass chopped strands 2a relative to the total amount of glass chopped strand mat 1 can be adjusted, and P1 can be adjusted to a range of 20.0 to 95.0 mass%. Furthermore, by adjusting the above manufacturing conditions, the content P2 of glass chopped strands 2b relative to the total amount of glass chopped strand mat 1 can be adjusted, and P2 can be adjusted to a range of 5.0 to 80.0 mass%.

[0069] Furthermore, by adjusting the above manufacturing conditions, the ratio SC1 of SiO2 content to CaO content in the glass composition (first glass composition) of the glass chopped strand 2a can be adjusted, and SC1 can be adjusted within the range of 1.5 to 150.0. Also, by adjusting the above manufacturing conditions, the ratio SC2 of SiO2 content to CaO content in the glass composition (second glass composition) of the glass chopped strand 2b can be adjusted, and SC2 can be adjusted within the range of 1.5 to 150.0.

[0070] Furthermore, by adjusting P1, P2, SC1, and SC2 as described above, the parameter Q can be adjusted to the range of equation (1), equation (2), equation (3), or equation (4).

[0071] Next, the effects and benefits obtained by the glass chopped strand mat 1 in this embodiment will be explained. The value of parameter Q of the glass chopped strand mat 1 is within the range expressed by equation (1). As a result, the glass chopped strand mat 1 has sufficiently high mechanical strength while reducing CO2 emissions during manufacturing. Therefore, glass fiber reinforced resin molded products and automotive molded ceiling materials containing this glass chopped strand mat 1 also have sufficiently high mechanical strength while reducing CO2 emissions during manufacturing. Among the above, it is preferable if the value of parameter Q is within the range of equation (2), as this further improves the mechanical strength of the glass chopped strand mat 1 while achieving a reduction in CO2 emissions during manufacturing. Furthermore, it is even more preferable if the value of parameter Q is within the range of equation (3), as this further improves the mechanical strength of the glass chopped strand mat 1 while achieving a reduction in CO2 emissions during manufacturing. Furthermore, if the value of parameter Q falls within the range of equation (4), it is even more preferable because the reduction in CO2 emissions during manufacturing is achieved, and the mechanical strength of the glass chopped strand mat 1 is further improved.

[0072] The glass fiber reinforced resin molded product in this embodiment includes the glass chopped strand mat 1 of this embodiment described above and a resin impregnated into the glass chopped strand mat 1. The resin may be a thermoplastic resin or a thermosetting resin.

[0073] Here, the thermoplastic resins include polyethylene, polypropylene, polystyrene, styrene / maleic anhydride resin, styrene / maleimide resin, polyacrylonitrile, acrylonitrile / styrene (AS) resin, acrylonitrile / butadiene / styrene (ABS) resin, chlorinated polyethylene / acrylonitrile / styrene (ACS) resin, acrylonitrile / ethylene / styrene (AES) resin, acrylonitrile / styrene / methyl acrylate (ASA) resin, styrene / acrylonitrile (SAN) resin, methacrylic resin, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyamide, polyacetal, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), and polycarbonate. Examples include nates, polyarylene sulfides, polyethersulfones (PES), polyphenylsulfones (PPSU), polyphenylene ethers (PPE), modified polyphenylene ethers (m-PPE), polyarylether ketones, liquid crystal polymers (LCP), fluororesins, polyetherimides (PEI), polyarylates (PAR), polysulfones (PSF), polyamideimides (PAI), polyaminobismaleimides (PABM), thermoplastic polyimides (TPI), polyethylene naphthalates (PEN), ethylene / vinyl acetate (EVA) resins, ionomer (IO) resins, polybutadiene, styrene / butadiene resins, polybutylene, polymethylpentene, olefin / vinyl alcohol resins, cyclic olefin resins, cellulose resins, and polylactic acid.

[0074] Specifically, examples of polyethylene include high-density polyethylene (HDPE), medium-density polyethylene, low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and ultra-high molecular weight polyethylene.

[0075] Examples of the aforementioned polypropylene include isotactic polypropylene, atactic polypropylene, syndiotactic polypropylene, and mixtures thereof.

[0076] Examples of the aforementioned polystyrene include general-purpose polystyrene (GPPS), which is atactic polystyrene having an atactic structure; high-impact polystyrene (HIPS), which is GPPS with a rubber component added; and syndiotactic polystyrene having a syndiotactic structure.

[0077] Examples of the methacrylic resin include polymers obtained by homopolymerizing one of the following: acrylic acid, methacrylic acid, styrene, methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, and fatty acid vinyl ester, or polymers obtained by copolymerizing two or more of these.

[0078] Examples of the polyvinyl chloride include vinyl chloride homopolymers polymerized by conventionally known methods such as emulsion polymerization, suspension polymerization, microsuspension polymerization, and bulk polymerization, copolymers of vinyl chloride monomer and copolymerizable monomers, and graft copolymers obtained by graft polymerization of vinyl chloride monomer onto a polymer.

[0079] The aforementioned polyamides include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46), polytetramethylene sevacamide (nylon 410), polypentamethylene adipamide (nylon 56), polypentamethylene sevacamide (nylon 510), polyhexamethylene sevacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polydecamethylene adipamide (nylon 106), and polydecamethylene. Methylene sevacamide (Nylon 1010), Polydecamethylene dodecamide (Nylon 1012), Polyundecaneamide (Nylon 11), Polyundecamethylene adipamide (Nylon 116), Polydodecaneamide (Nylon 12), Polyxylene adipamide (Nylon XD6), Polyxylene sevacamide (Nylon XD10), Polymetaxylylene adipamide (Nylon MXD6), Polyparaxylylene adipamide (Nylon PXD6), Polytetramethylene terephthalamide (Nylon Nylon 4T), Polypentamethylene terephthalamide (Nylon 5T), Polyhexamethylene terephthalamide (Nylon 6T), Polyhexamethylene isophthalamide (Nylon 6I), Polynonamethylene terephthalamide (Nylon 9T), Polydecamethylene terephthalamide (Nylon 10T), Polyundecamethylene terephthalamide (Nylon 11T), Polydodecamethylene terephthalamide (Nylon 12T), Polytetramethylene isophthalamide (Nylon 4I), Polybis( Examples include copolymers or mixtures thereof, consisting of one or more of the following components: 3-methyl-4-aminohexyl)methaneterephthalamide (nylon PACMT), polybis(3-methyl-4-aminohexyl)methaneisophthalamide (nylon PACMI), polybis(3-methyl-4-aminohexyl)methanendodecamido (nylon PACM12), polybis(3-methyl-4-aminohexyl)methanetetradecamide (nylon PACM14).

[0080] Examples of the polyacetal include homopolymers having oxymethylene units as the main repeating units, and copolymers that mainly consist of oxymethylene units and contain oxyalkylene units having 2 to 8 adjacent carbon atoms in the main chain.

[0081] Examples of polyethylene terephthalate include polymers obtained by polycondensation of terephthalic acid or its derivatives with ethylene glycol.

[0082] Examples of the aforementioned polybutylene terephthalate include polymers obtained by polycondensation of terephthalic acid or its derivatives with 1,4-butanediol.

[0083] Examples of the aforementioned polytrimethylene terephthalate include polymers obtained by polycondensation of terephthalic acid or its derivatives with 1,3-propanediol.

[0084] Examples of the polycarbonate include polymers obtained by a transesterification method in which a dihydroxydiaryl compound is reacted with a carbonate ester such as diphenyl carbonate in a molten state, or polymers obtained by a phosgene method in which a dihydroxyaryl compound is reacted with phosgene.

[0085] Examples of the aforementioned polyarylene sulfides include linear polyphenylene sulfides, cross-linked polyphenylene sulfides with high molecular weight obtained by curing reactions after polymerization, polyphenylene sulfide sulfones, polyphenylene sulfide ethers, and polyphenylene sulfide ketones.

[0086] The aforementioned polyphenylene ethers include poly(2,3-dimethyl-6-ethyl-1,4-phenylene ether), poly(2-methyl-6-chloromethyl-1,4-phenylene ether), poly(2-methyl-6-hydroxyethyl-1,4-phenylene ether), poly(2-methyl-6-n-butyl-1,4-phenylene ether), poly(2-ethyl-6-isopropyl-1,4-phenylene ether), poly(2-ethyl-6-n-propyl-1,4-phenylene ether), poly(2,3,6-trimethyl-1,4-phenylene ether), poly[2-(4'-methylphenyl)-1,4-phenylene ether], poly(2-bromo-6-phenyl-1,4-phenylene ether), poly(2-methyl-6-phenyl-1,4-phenylene ether), and poly(2-phenyl-1,4-phenylene ether). Examples include poly(2-chloro-1,4-phenylene ether), poly(2-methyl-1,4-phenylene ether), poly(2-chloro-6-ethyl-1,4-phenylene ether), poly(2-chloro-6-bromo-1,4-phenylene ether), poly(2,6-di-n-propyl-1,4-phenylene ether), poly(2-methyl-6-isopropyl-1,4-phenylene ether), poly(2-chloro-6-methyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2,6-dibromo-1,4-phenylene ether), poly(2,6-dichloro-1,4-phenylene ether), poly(2,6-diethyl-1,4-phenylene ether), and poly(2,6-dimethyl-1,4-phenylene ether).

[0087] Examples of the modified polyphenylene ether include polymer alloys of poly(2,6-dimethyl-1,4-phenylene ether) and polystyrene, polymer alloys of poly(2,6-dimethyl-1,4-phenylene ether) and styrene / butadiene copolymer, polymer alloys of poly(2,6-dimethyl-1,4-phenylene ether) and styrene / maleic anhydride copolymer, polymer alloys of poly(2,6-dimethyl-1,4-phenylene ether) and polyamide, polymer alloys of poly(2,6-dimethyl-1,4-phenylene ether) and styrene / butadiene / acrylonitrile copolymer, polyphenylene ether with functional groups such as amino groups, epoxy groups, carboxyl groups, and styryl groups introduced at the polymer chain ends, and polyphenylene ether with functional groups such as amino groups, epoxy groups, carboxyl groups, styryl groups, and methacrylic groups introduced at the polymer chain side chains.

[0088] Examples of the polyaryl ether ketone include polyether ketone (PEK), polyether ether ketone (PEEK), polyether ketone ketone (PEKK), and polyether ether ketone ketone (PEEKK).

[0089] Examples of the liquid crystal polymer (LCP) include (co)polymers consisting of one or more structural units selected from thermotropic liquid crystal polyesters such as aromatic hydroxycarbonyl units, aromatic dihydroxy units, aromatic dicarbonyl units, aliphatic dihydroxy units, and aliphatic dicarbonyl units.

[0090] Examples of the aforementioned fluororesins include polytetrafluoroethylene (PTFE), perfluoroalkoxy resin (PFA), fluoroethylene propylene resin (FEP), fluoroethylene tetrafluoroethylene resin (ETFE), polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), and ethylene / chlorotrifluoroethylene resin (ECTFE).

[0091] Examples of the ionomer (IO) resin include polymers obtained by copolymerizing an olefin or styrene with an unsaturated carboxylic acid, wherein some of the carboxyl groups are neutralized with metal ions.

[0092] Examples of the olefin / vinyl alcohol resin include ethylene / vinyl alcohol copolymer, propylene / vinyl alcohol copolymer, ethylene / vinyl acetate copolymer saponified, and propylene / vinyl acetate copolymer saponified.

[0093] Examples of the cyclic olefin resin include monocyclic compounds such as cyclohexene, polycyclic compounds such as tetracyclopentadiene, and polymers of cyclic olefin monomers.

[0094] Examples of the aforementioned polylactic acid include poly-L-lactic acid, which is a homopolymer of the L-isomer; poly-D-lactic acid, which is a homopolymer of the D-isomer; or stereocomplex-type polylactic acid, which is a mixture thereof.

[0095] Examples of the cellulose resin include methylcellulose, ethylcellulose, hydroxycellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, cellulose acetate, cellulose propionate, and cellulose butyrate.

[0096] Furthermore, examples of thermosetting resins include unsaturated polyester resins, vinyl ester resins, epoxy (EP) resins, melamine (MF) resins, phenolic (PF) resins, urethane (PU) resins, polyisocyanates, polyisocyanurates, modified polyimide (PI) resins, urea (UF) resins, silicone (SI) resins, furan (FR) resins, benzoguanamine (BR) resins, alkyd resins, xylene resins, bismalade triazine (BT) resins, diallyl phthalate (PDAP) resins, and the like.

[0097] Specifically, examples of the unsaturated polyester resin include resins obtained by esterifying an aliphatic unsaturated dicarboxylic acid and an aliphatic diol.

[0098] Examples of the vinyl ester resins mentioned above include bis-based vinyl ester resins and novolac-based vinyl ester resins.

[0099] The epoxy resins mentioned above include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, bisphenol M type epoxy resin (4,4'-(1,3-phenylenediisopridiene)bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4'-(1,4-phenylenediisopridiene)bisphenol type epoxy resin), bisphenol Z type epoxy resin (4,4'-cyclohexydiene bisphenol type epoxy resin), phenol novolac type epoxy resin, cresol novolac type epoxy resin, and tetraphenol group ethane type novolac type epoxy resin. Examples of epoxy resins include novolac-type epoxy resins having a condensed ring aromatic hydrocarbon structure, biphenyl-type epoxy resins, aralkyl-type epoxy resins such as xylylene-type epoxy resins and phenylaralkyl-type epoxy resins, naphthylene ether-type epoxy resins, naphthol-type epoxy resins, naphthalenediol-type epoxy resins, bifunctional or tetrafunctional epoxy-type naphthalene resins, binaphthyl-type epoxy resins, naphthalenearalkyl-type epoxy resins, anthracene-type epoxy resins, phenoxy-type epoxy resins, dicyclopentadiene-type epoxy resins, norbornene-type epoxy resins, adamantane-type epoxy resins, and fluorene-type epoxy resins.

[0100] Examples of the melamine resin include polymers formed by the polycondensation of melamine (2,4,6-triamino-1,3,5-triazine) and formaldehyde.

[0101] Examples of the phenolic resin include novolac-type phenolic resins such as phenol novolac resin, cresol novolac resin, and bisphenol A type novolac resin; resol-type phenolic resins such as methylol-type resol resin and dimethylene ether-type resol resin; and arylalkylene-type phenolic resins. One of these, or a combination of two or more, may be used.

[0102] Examples of the urea resin mentioned above include resins obtained by the condensation of urea and formaldehyde.

[0103] The thermoplastic resin or the thermosetting resin may be used alone or in combination of two or more types.

[0104] The glass fiber reinforced resin molded product in this embodiment may contain other additives in addition to the glass chopped strand mat 1 and resin of this embodiment described above.

[0105] Other additives include reinforcing fibers other than glass fibers, fillers other than glass fibers, flame retardants, UV absorbers, heat stabilizers, antioxidants, antistatic agents, flow improvers, antiblocking agents, lubricants, nucleating agents, antibacterial agents, pigments, and the like.

[0106] Examples of reinforcing fibers other than the aforementioned glass fibers include carbon fibers and metal fibers.

[0107] Examples of fillers other than the aforementioned glass fibers include glass powder, talc, and mica.

[0108] In the glass fiber reinforced resin molded product of this embodiment, the glass chopped strand mat 1 of this embodiment described above may be present in an amount of 10.0 to 90.0% by mass, the resin in an amount of 90.0 to 10.0% by mass, and the other additives in an amount of 0 to 40.0% by mass, relative to the total amount of the glass fiber reinforced resin molded product.

[0109] This disclosure is not limited to the embodiments described above, and various modifications are possible without departing from the gist of this disclosure, as described below.

[0110] For example, the water spraying onto the glass chopped strands 2 may be carried out on the first conveyor 13 almost simultaneously with the accumulation of the glass chopped strands 2. Furthermore, the water sprayer 15 may be configured to spray from below rather than from above the belt. Also, the glass chopped strand mat 1 may be manufactured using a single conveyor without dividing it into three conveyors. In this case, the conveyor belt is preferably made of a mesh fabric composed of aramid fibers, carbon fibers, or glass fibers.

[0111] Furthermore, although the above embodiment describes an automotive molded ceiling material 31 having a glass chopped strand mat 1, the glass chopped strand mat 1 may be processed into other glass fiber reinforced resin molded products. For example, it may be used in other automobile parts, and the glass chopped strand mat 1 may be used in aircraft and ships. The glass chopped strand mat 1 can be used for other applications, such as waterproofing work.

[0112] The following describes examples of the glass chopped strand mat related to this disclosure.

[0113] The inventors used the equipment shown in Figure 4 and the method for manufacturing glass chopped strand mat 1 described above to produce the glass chopped strand mats according to Examples 1 to 9 and Comparative Examples 1 to 3, as shown in Table 1 below. For reference, they also produced the glass chopped strand mats according to Reference Example 1. The glass chopped strand mat of Reference Example 1 contains only one type of glass chopped strand as shown in Table 1.

[0114] Table 1 shows the characteristic values ​​for glass chopped strands 2a and 2b in each glass chopped strand mat (content P1, P2, SiO2 content in the glass composition, CaO content in the glass composition, mass per unit length, elastic modulus of the glass composition, and maximum melting temperature during glass fiber production). Table 1 also shows the ratio of SiO2 content to CaO content (SC1, SC2) and the parameter Q value calculated from the above characteristic values. The glass filaments forming each glass chopped strand mat had a filament diameter of 11-12 μm. The first glass composition in Examples 1, 3-9, and Comparative Examples 1-2 corresponds to the E glass composition. The first glass composition in Example 2 corresponds to the acid-resistant glass composition. The second glass composition in Examples 1-9 and Comparative Examples 1-3 corresponds to the easily recyclable glass composition.

[0115] The average strand count T of the glass chopped strands 2a and 2b in each glass chopped strand mat was adjusted by the following method: the number of nozzle tips provided in the platinum container and the number of divisions of the glass filament group in the gathering shoe were adjusted, thereby adjusting the number of glass filaments forming the glass fiber bundles that make up the glass cakes 4a and 4b, and thus adjusting the average strand count T.

[0116] Furthermore, Table 1 shows the tensile strength, tensile strength / mass per unit area, and evaluation results for the potential to reduce CO2 emissions when obtaining glass raw materials, measured for each glass chopped strand mat.

[0117] The mass per unit area of ​​each glass chopped strand mat was measured by the following method: A 30cm (length) x 30cm (width) test piece was cut from the glass chopped strand mat, and its weight was read to two decimal places using a balance. Then, this weight was divided by the area of ​​30cm (length) x 30cm (width), and the result was obtained in units of g / m². 2 The mass per unit area was calculated using this method.

[0118] The tensile strength of each glass chopped strand mat was measured using the following method. First, a 15cm (length) x 30cm (width) piece was cut out of the glass chopped strand mat, with the winding direction as the longitudinal side. Next, this piece was tested using a tensile and compression testing machine (manufactured by Imada Seisakusho Co., Ltd.) with both the top and bottom ends gripped, at a span distance of 200mm and a test speed of 200mm / min. The maximum load was measured as the tensile strength (N) in the longitudinal direction of the mat.

[0119] The tensile strength / mass per unit area of ​​each glass chopped strand mat was calculated from the measured values ​​of mass per unit area and tensile strength, as described above.

[0120] The average strand count T of each glass chopped strand mat was measured and calculated using the following method: A 300mm (length) x 300mm (width) section was cut from the glass chopped strand mat to serve as a test specimen. The specimen was then heated to 625°C to burn off the binder. After the specimen cooled to room temperature, a single strand was removed from the specimen, and its weight and length were measured. The strand count (g / 1000m) was calculated by converting the measured values ​​to the weight per 1000m (g).

[0121] Furthermore, the ignition loss of each glass chopped strand mat was measured and calculated using the following method, and was found to be between 10.0 and 13.0 mass%. First, a 30 cm (length) x 30 cm (width) section was cut from glass chopped strand mat 1 to serve as a test specimen. Next, the weight of the test specimen was read to three decimal places using a balance, and it was heated at 625°C according to JIS R3420:2023 until there was no further weight change, burning off the binder 3. After heating, the test specimen cooled to room temperature, and then the weight was read again to three decimal places using a balance. The weight loss from before heating was expressed as a percentage as ignition loss (weight loss / weight before heating × 100; unit: %).

[0122] Furthermore, the elastic modulus of the glass composition (first glass composition) of glass chopped strand 2a and the elastic modulus of the glass composition (first glass composition) of glass chopped strand 2b in each glass chopped strand mat were measured by the following method. When obtaining the aforementioned glass cake 4a or 4b, one glass filament (monofilament) was taken from the group of glass filaments present between the nozzle tip and the winding device. From the monofilaments obtained in this way, those that were not degraded due to contact or friction were selected, and at least 20 monofilaments were selected as measurement samples for each example and comparative example. The fiber diameter of at least 10 of each measurement sample was measured by observing them with a scanning electron microscope (Hitachi High-Tech Corporation, product name: S-3400N). From the obtained measured values, the two largest and two smallest measured values ​​were excluded, and the numerical average of the remaining measured values ​​was taken as the average fiber diameter, and the fiber cross-sectional area was calculated assuming a circular cross-sectional shape. Next, each measurement sample was attached to a predetermined cardboard base with a rectangular hole in the center measuring 50 mm on the long side and 10 mm on the short side, so that the fiber length within the hole was 50 mm, to create a test specimen. Under a temperature condition of 23°C, the obtained test specimens were set in the grips of a tensile testing machine (manufactured by A&D Co., Ltd., product name: Single Column Tensile Testing Machine STB-1225S), the edges of the cardboard base were cut off, and a tensile test was performed at a crosshead speed of 5 mm / min. The initial strength fluctuation value and the corresponding elongation rate were calculated. Test specimens in which threads came loose or broke during measurement were excluded. When measuring the elastic modulus of the glass composition from a glass chopped strand mat, glass chopped strands can be extracted from the glass chopped strand mat and used as glass raw materials, and as described above, molten glass and glass filaments can be obtained.

[0123] Furthermore, the potential for CO2 reduction during the acquisition of glass raw materials for each glass chopped strand mat was evaluated as follows: When manufacturing the glass fibers of glass chopped strand 2a and glass chopped strand 2b using the maximum amount of waste glass from the market as glass raw material, the numerical value corresponding to the volume-based emission intensity for No. 32, column code 62909 "Other non-metallic minerals" in the "Input-Output Table-Based Emission Intensity Database for Calculating Greenhouse Gas Emissions, etc. of Organizations Through the Supply Chain (Ver. 2.5)" was evaluated as "OK" if it fell within the range of 0 to 0.0050 t-CO2eq / ton, and as "NG" if it exceeded 0.0050 t-CO2eq / ton.

[0124] [Table 1]

[0125] As shown in Table 1, Examples 1 to 9 satisfy equation (1) for the value of parameter Q, of which Examples 1 to 8 further satisfy equation (2) for the value of parameter Q, of which Examples 1 to 5 further satisfy equation (3) for the value of parameter Q, and of which Examples 1 to 3 further satisfy equation (4) for the value of parameter Q. Comparative Examples 1 to 3 do not satisfy equation (1) for the value of parameter Q. Reference Example 1 includes only one type of glass chopped strand, that is, it does not include two types of glass chopped strand.

[0126] As shown in Table 1, in Examples 1-9, the evaluation of the potential for CO2 reduction when obtaining glass raw materials was "OK," and the maximum melting temperature during glass fiber production was kept below 1500°C, so it can be said that a sufficient reduction in CO2 emissions in the production of glass chopped strand mats can be achieved. Furthermore, the tensile strength / mass per unit area is 1.50 N·m 2 Since the value is above / g, it can be said that the mechanical strength of the glass chopped strand mat is also sufficiently ensured.

[0127] Among these, in Examples 1 to 8, since the tensile strength / mass per unit area is 1.70 N·m 2 / g or more, it can be said that the mechanical strength of the glass chopped strand mat can be further ensured, and it is preferable. Furthermore, in Examples 1 to 5, since the tensile strength / mass per unit area is 2.00 N·m 2 / g or more, it can be said that the mechanical strength of the glass chopped strand mat can be further ensured, and it is more preferable. Furthermore, in Examples 1 to 3, since the tensile strength / mass per unit area is 2.15 N·m 2 / g or more, it can be said that the mechanical strength of the glass chopped strand mat can be further ensured, and it is even more preferable.

[0128] In Comparative Example 1, the evaluation of the possibility of CO2 reduction at the time of obtaining the glass raw material is an "OK" evaluation, and the maximum melting temperature during glass fiber production can also be suppressed to 1500°C or less. Therefore, it can be said that the reduction of CO2 emissions in the production of the glass chopped strand mat can be sufficiently achieved. However, the mass per unit area of the tensile strength in Comparative Example 1 is 1.50 N·m 2 / g or less, so it cannot be said that the mechanical strength of the glass chopped strand mat can be sufficiently ensured.

[0129] In Comparative Example 2, the mass per unit area of the tensile strength is 1.50 N·m 2 / g or more, so it can be said that the mechanical strength of the glass chopped strand mat can be sufficiently ensured. Also, in Comparative Example 2, the maximum melting temperature during glass fiber production can be suppressed to 1500°C or less, but the evaluation of the possibility of CO2 reduction at the time of obtaining the glass raw material is an "NG" evaluation. Therefore, it cannot be said that the reduction of CO2 emissions in the production of the glass chopped strand mat can be sufficiently achieved.

[0130] Comparative Example 3 received an "OK" rating for its CO2 reduction potential when obtaining glass raw materials, and the maximum melting temperature during glass fiber production was kept below 1500°C, so it can be said that a sufficient reduction in CO2 emissions during the production of glass chopped strand mats can be achieved. However, the tensile strength / mass per unit area is 1.50 N·m 2 Since the value is less than / g, it cannot be said that the mechanical strength of the glass chopped strand mat is sufficiently ensured.

[0131] Reference Example 1 shows an "OK" rating for the potential to reduce CO2 emissions when obtaining glass raw materials, and the maximum melting temperature during glass fiber production can be kept below 1500°C, so it can be said that a sufficient reduction in CO2 emissions during the production of glass chopped strand mats can be achieved. However, the tensile strength / mass per unit area in Comparative Example 1 is 1.50 N·m 2 Since the value is less than / g, it cannot be said that the mechanical strength of the glass chopped strand mat is sufficiently ensured.

[0132] From the above results, if the value of parameter Q of the glass chopped strand mat is within the range expressed by equation (1), it can be said that the glass chopped strand mat has sufficiently high mechanical strength while reducing CO2 emissions during manufacturing. Among these, if the value of parameter Q is within the range of equation (2), it is preferable because the reduction in CO2 emissions during manufacturing is achieved while the mechanical strength of the glass chopped strand mat is further improved. Furthermore, if the value of parameter Q is within the range of equation (3), it is even more preferable because the reduction in CO2 emissions during manufacturing is achieved while the mechanical strength of the glass chopped strand mat is further improved. Moreover, if the value of parameter Q is within the range of equation (4), it is even more preferable because the reduction in CO2 emissions during manufacturing is achieved while the mechanical strength of the glass chopped strand mat is further improved. [Explanation of Symbols]

[0133] 1... Glass chopped strand mat, 2... Glass chopped strand, 2a... Glass chopped strand (first glass chopped strand), 2b... Glass chopped strand (second glass chopped strand), 31... Automotive molded ceiling material (glass fiber reinforced resin molded product).

Claims

1. It is a glass chopped strand mat, A first glass chopped strand consisting of a first glass composition, A second glass chopped strand comprising a second glass composition having a lower elastic modulus than that of the first glass composition, The content P1 of the first glass chopped strand relative to the total amount of the glass chopped strand mat is in the range of 20.0 to 95.0% by mass. The content P2 of the second glass chopped strand relative to the total amount of the glass chopped strand mat is in the range of 5.0 to 80.0% by mass. The SiO content relative to the CaO content in the first glass composition ２ The percentage SC1 of the content is in the range of 1.5 to 150.

0. The SiO content relative to the CaO content in the second glass composition ２ The percentage SC2 of the content is in the range of 1.5 to 150.

0. A glass chopped strand mat characterized in that P1, P2, SC1, and SC2 satisfy the following formula (1). 0.20≦(P1・SC1) / (P2・SC2)≦1.80 (1)

2. The glass chopped strand mat according to claim 1, characterized in that P1, P2, SC1, and SC2 satisfy the following formula (2). 0.30≦(P1・SC1) / (P2・SC2)≦1.50 (2)

3. The glass chopped strand mat according to claim 1, characterized in that P1, P2, SC1, and SC2 satisfy the following formula (3). 0.60≦(P1・SC1) / (P2・SC2)≦1.20 (3)

4. The glass chopped strand mat according to claim 1, characterized in that P1, P2, SC1, and SC2 satisfy the following formula (4). 0.95≦(P1・SC1) / (P2・SC2)≦1.05 (4)

5. A glass fiber reinforced resin molded article comprising a glass chopped strand mat according to any one of claims 1 to 4.

6. Automotive molded ceiling material comprising a glass chopped strand mat according to any one of claims 1 to 4.

Images