Composite laminate and method for manufacturing the same

Abstract

To provide a composite laminate which is excellent in productivity, and can effectively enhance flame retardancy.SOLUTION: In a composite laminate 1 containing an inorganic fiber and a thermoplastic resin, the composite laminate 1 is obtained by integrating laminates including films (A) and sheets (B) by thermocompression bonding. The film (A) is composed of a resin composition containing an inorganic fiber (a1) having an average fiber length of 1 μm to 300 μm, a thermoplastic resin (a2) and a flame retardant (a3). The resin composition has a melt volume flow rate value (MVR value) measured under the condition of 280°C and a load of 2.16 kg of 0.5 cm3 / 10 min to 7 cm3 / 10 min. The sheet (B) contains a reinforcement fiber (b1) having an average fiber length of 1 mm to 100 mm.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a fiber-reinforced composite laminate and a method for manufacturing the composite laminate.

Background Art

[0002] Fiber-reinforced resins are used in various fields such as golf clubs, tennis rackets, aircraft, and automobiles as materials to replace metals because they are light and strong. In recent years, due to the demand for weight reduction of automobiles to achieve low fuel consumption, fiber-reinforced resins have attracted attention in the automotive field. However, there are various problems in using fiber-reinforced resins for automotive members. For example, since fiber-reinforced resins made of thermosetting resins require heat treatment (curing reaction) after molding, high productivity and low cost, which are essential in the manufacture of automotive members, cannot be achieved. Therefore, there is a need for fiber-reinforced thermoplastics (hereinafter also referred to as "FRTP") using thermoplastic resins that are easy to mold instead of thermosetting resins.

[0003] As a typical form of FRTP, a molded product (composite laminate) is obtained by laminating a sheet impregnated with a thermoplastic resin on a reinforced fiber base material in which continuous reinforcing fibers are arranged in one direction or a reinforced fiber base material obtained by weaving continuous reinforcing fibers, and then shaping it into a desired shape by heating and pressing with a press or the like. The composite laminate thus obtained can be designed to have excellent mechanical properties because continuous reinforcing fibers are used, and the variation in mechanical properties is also small. However, when a polycarbonate resin with low fluidity during melting is used as the thermoplastic resin, there is a problem that it is difficult to obtain a good-quality composite laminate because the polycarbonate resin has poor impregnation properties into continuous fibers.

[0004] On the other hand, in Patent Document 1, by using a mixture of a polycarbonate resin adjusted to a specific melt viscosity and a flame retardant as an impregnating agent for a continuous fiber reinforcing material, a polycarbonate resin composition having excellent resin impregnability and excellent flame retardancy, which has never existed before, and a highly flame-retardant polycarbonate prepreg using a resin composition having such excellent performance can be provided.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, in a composite laminate obtained by molding a polycarbonate resin composition such as that of Patent Document 1, the flame retardancy may not be sufficiently enhanced. Further, when using a polycarbonate resin composition such as that of Patent Document 1, gas may be generated during melt kneading, or the film-forming property when forming a film may be poor, and thus the productivity of the composite laminate may not be sufficiently enhanced.

[0007] The present invention has been made in view of the above circumstances, and an object thereof is to provide a composite laminate having excellent productivity and capable of effectively enhancing flame retardancy, and a method for manufacturing the composite laminate.

Means for Solving the Problems

[0008] The present invention provides the following composite laminate and a method for manufacturing the same.

[0009] Item 1. In a composite laminate comprising an inorganic fiber and a thermoplastic resin, the composite laminate is formed by integrating a laminate including a film (A) and a sheet (B) by thermocompression bonding. The film (A) is composed of a resin composition containing inorganic fibers (a1) having an average fiber length of 1 μm to 300 μm, a thermoplastic resin (a2), and a flame retardant (a3). The melt volume flow rate value (MVR value) measured under the conditions of 280 °C and a load of 2.16 kg of the resin composition is 0.5 cm 3 / 10 min to 7 cm 3 / 10 min, and the sheet (B) is a composite laminate containing reinforcing fibers (b1) having an average fiber length of 1 mm to 100 mm.

[0010] Item 2. The composite laminate according to Item 1, wherein the laminate has a portion where the film (A) is laminated and arranged so as to be in direct contact with the sheet (B) between a plurality of the sheets (B).

[0011] Item 3. The composite laminate according to Item 1 or Item 2, wherein the average aspect ratio of the inorganic fibers (a1) is 3 to 200.

[0012] Item 4. The composite laminate according to any one of Items 1 to 3, wherein the inorganic fibers (a1) are at least one of potassium titanate fibers or wollastonite fibers.

[0013] Item 5. The composite laminate according to any one of Items 1 to 4, wherein the flame retardant (a3) contains at least one selected from the group consisting of phosphate ester flame retardants, phosphazene flame retardants, and silicone flame retardants.

[0014] Item 6. The composite laminate according to any one of Items 1 to 5, wherein the content of the inorganic fibers (a1) is 1 mass% to 40 mass% in 100 mass% of the total amount of the components contained in the film (A).

[0015] Item 7. The composite laminate according to any one of Items 1 to 6, wherein the thermoplastic resin (a2) is a polycarbonate resin.

[0016] Item 8. The composite laminate according to any one of Items 1 to 7, wherein the content of the reinforcing fiber (b1) is 75% by mass to 100% by mass in 100% by mass of the total amount of the components contained in the sheet (B).

[0017] Item 9. The composite laminate according to any one of Items 1 to 8, wherein the reinforcing fiber (b1) is at least one selected from the group consisting of carbon fiber, glass fiber, and aramid fiber.

[0018] Item 10. The composite laminate according to any one of Items 1 to 9, wherein the content of the reinforcing fiber (b1) is 15% by volume to 50% by volume as a volume content value (Vf) in 100% by volume of the total amount of the components contained in the composite laminate.

[0019] Item 11. The composite laminate according to any one of Items 1 to 10, which is for electrical / electronic members or automotive members.

[0020] Item 12. A method for manufacturing a composite laminate according to any one of Items 1 to 11, comprising: a step of preparing a laminate by laminating and arranging a film (A) containing an inorganic fiber (a1) having an average fiber length of 1 μm to 300 μm, a thermoplastic resin (a2), and a flame retardant (a3), and a sheet (B) containing a reinforcing fiber (b1) having an average fiber length of 1 mm to 100 mm; and a step of obtaining a composite laminate by integrating the laminate by thermocompression bonding.

[0021] Item 13. The method for manufacturing a composite laminate according to Item 12, wherein the thickness of the film (A) is less than 500 μm.

[0022] Item 14. The method for manufacturing a composite laminate according to Item 12 or Item 13, wherein the thickness of the sheet (B) is 0.3 mm to 15 mm.

Advantages of the Invention

[0023] According to the present invention, it is possible to provide a composite laminate excellent in productivity and capable of effectively enhancing flame retardancy, and a method for producing the composite laminate.

Brief Description of the Drawings

[0024]

Figure 1

Embodiments for Carrying Out the Invention

[0025] Hereinafter, preferred embodiments will be described. However, the following embodiments are merely illustrative, and the present invention is not limited to the following embodiments. Also, in the drawings, members having substantially the same function may be referred to by the same reference numerals.

[0026] The composite laminate of the present invention contains inorganic fibers and a thermoplastic resin. Further, the composite laminate of the present invention is formed by integrating a laminate containing a film (A) and a sheet (B) by thermocompression bonding. In the composite laminate of the present invention, the film (A) may be laminated on the sheet (B), or a part or all of the film (A) may be impregnated in the sheet (B).

[0027] The film (A) is composed of a resin composition containing inorganic fibers (a1), a thermoplastic resin (a2), and a flame retardant (a3). The inorganic fibers (a1) have an average fiber length of 1 μm to 300 μm.

[0028] Also, the melt volume flow rate (hereinafter, may be referred to as "MVR") value measured under the conditions of 280 °C and a load of 2.16 kg of the resin composition constituting the film (A) is 0.5 cm 3 / 10 min to 7 cm 3 / 10 min.

[0029] The sheet (B) contains reinforcing fibers (b1) having an average fiber length of 1 mm to 100 mm.

[0030] Since the composite laminate of the present invention has the above-described configuration, it is excellent in productivity and can effectively enhance the flame retardancy.

[0031] In the present invention, since the laminate including the film (A) and the sheet (B) is integrated by thermocompression bonding, part or all of the constituent materials of the film (A) are mixed with the sheet (B), and it is considered that the inorganic fibers (a1), which are microfibers constituting the film (A), are filled in the voids between the reinforcing fibers (b1) constituting the sheet (B). At this time, when the MVR value measured under the conditions of 280°C and a load of 2.16 kg of the resin composition constituting the film (A) is within the above range, the impregnation property of the resin composition constituting the film (A) into the reinforcing fibers (b1) constituting the sheet (B) can be improved without reducing the reinforcing effect by the reinforcing fibers (b1) constituting the sheet (B), so that the mechanical properties of the obtained composite laminate can be enhanced.

[0032] Further, in the present invention, since the MVR value of the resin composition constituting the film (A) is not more than the above upper limit value, the film-forming property of the film (A) is excellent and the productivity of the composite laminate can be improved. In addition, by setting the MVR value of the resin composition constituting the film (A) to not more than the above upper limit value, surprisingly, the flame retardancy of the composite laminate can also be effectively enhanced.

[0033] Note that generally, a "sheet" refers to a flat product that is thin and generally has a thickness small relative to its length and width, as defined in JIS. Also, generally, a "film" refers to a thin, flat product with a thickness extremely small compared to its length and width, and with its maximum thickness arbitrarily limited, and is usually supplied in the form of a roll (Japanese Industrial Standard JIS K6900). For example, in terms of thickness, in a narrow sense, those with a thickness of 100 μm or more may be referred to as "sheets", and those with a thickness of less than 100 μm may be referred to as "films". However, the boundary between "sheet" and "film" is not clear, and there is no need to completely distinguish between the two in terms of language. Therefore, in the present invention, even when referring to a "sheet", it may include "film" in its meaning, and even when referring to a "film", it may include "sheet" in its meaning.

[0034] Hereinafter, an example of the laminate constituting the composite laminate of the present invention will be described.

[0035] FIG. 1 is a schematic cross-sectional view showing a laminate constituting a composite laminate according to an embodiment of the present invention.

[0036] As shown in FIG. 1, the laminate 1 includes a film (A) and a sheet (B). The laminate 1 is composed of one layer of film (A) and one layer of sheet (B). Also, in the laminate 1, the film (A) is provided on the sheet (B). Such a laminate 1 can be used as a composite laminate by being integrated by thermocompression bonding.

[0037] In the present invention, the thickness of the entire laminate is not particularly limited, but is preferably 0.6 mm or more, more preferably 0.8 mm or more, preferably 10 mm or less, and more preferably 4 mm or less. When the thickness of the entire laminate is within the above range, the mechanical properties, flame retardancy, and productivity of the composite laminate can be further improved.

[0038] In the present invention, the MVR value measured under the conditions of 280 °C and a load of 2.16 kg for the resin composition constituting the film (A) is 0.5 cm 3 / Above 10 min, preferably 1 cm 3 / Above 10 min and 7 cm 3 / Below 10 min, preferably 5 cm 3 / Below 10 min. When the MVR value of the resin composition is within the above range, without reducing the reinforcing effect of the reinforcing fiber (b1), the impregnation property and mechanical properties of the resin composition constituting the film (A) with respect to the reinforcing fiber (b1) constituting the sheet (B) can be further improved. Also, when the MVR value of the resin composition is within the above range, the flame retardancy and productivity of the composite laminate can be further improved. Note that if the MVR value of the resin composition constituting the film (A) is greater than the above upper limit value, the resin composition may flow out to the surroundings during thermocompression bonding, and the impregnation property of the resin composition into the reinforcing fiber (b1) may deteriorate.

[0039] Note that the MVR value measured under the conditions of 280 °C and a load of 2.16 kg for the resin composition constituting the film (A) can be adjusted, for example, by changing the type and content of the inorganic fiber (a1), thermoplastic resin (a2), or flame retardant (a3) contained in the resin composition constituting the film (A).

[0040] In the composite laminate of the present invention, the content of the reinforcing fiber (b1) is preferably 15% by volume to 50% by volume, more preferably 20% by volume to 45% by volume, and even more preferably 30% by volume to 40% by volume as the volume content value (Vf) in 100% by volume of the total amount of the components contained in the composite laminate. In this case, the mechanical properties of the composite laminate can be further improved.

[0041] The respective components and the like of the composite laminate of the present invention will be described below.

[0042] <Film (A)> The film (A) used in the composite laminate of the present invention is a film containing an inorganic fiber (a1) having an average fiber length of 1 μm to 300 μm, a thermoplastic resin (a2), and a flame retardant (a3), and may contain other additives as necessary.

[0043] (Inorganic fiber (a1)) The inorganic fiber (a1) is a powder composed of fibrous particles. The average fiber length of the inorganic fiber (a1) is from 1 μm to 300 μm, preferably from 1 μm to 200 μm, more preferably from 3 μm to 100 μm, and even more preferably from 5 μm to 50 μm.

[0044] The average fiber diameter of the inorganic fiber (a1) is preferably 0.01 μm or more and 15 μm or less, more preferably 0.05 μm or more and 10 μm or less, and even more preferably 0.1 μm or more and 7 μm or less.

[0045] The average aspect ratio of the inorganic fiber (a1) is preferably from 3 to 200, more preferably from 3 to 100, even more preferably from 3 to 50, and particularly preferably from 3 to 40.

[0046] In this specification, fibrous particles refer to particles for which, when the longest side of the rectangular parallelepiped with the smallest volume circumscribing the particle (circumscribing rectangular parallelepiped) is defined as the major axis L, the next longest side as the minor axis B, and the shortest side as the thickness T (B > T), both L / B and L / T are 3 or more. The major axis L corresponds to the fiber length, and the minor axis B corresponds to the fiber diameter. Non-fibrous particles refer to particles for which L / B is less than 3. Among non-fibrous particles, particles for which L / B is less than 3 and L / T is 3 or more are referred to as plate-like particles.

[0047] The above-mentioned average fiber length and average fiber diameter can be measured by observation with a scanning electron microscope (SEM), and the average aspect ratio (average fiber length / average fiber diameter) can be calculated using the average fiber length and average fiber diameter. For example, using a scanning electron microscope, a plurality of inorganic fibers (a1) are photographed, 300 inorganic fibers (a1) are arbitrarily selected from the observed images, their fiber lengths and fiber diameters are measured, the sum of all the fiber lengths is divided by the number to obtain the average fiber length, and the sum of all the fiber diameters is divided by the number to obtain the average fiber diameter.

[0048] The inorganic fiber (a1) is not particularly limited as long as its average fiber length is 1 μm to 300 μm. However, from the viewpoint of further improving the impregnation property of the resin composition constituting the film (A) into the reinforcing fiber (b1), it is preferably an inorganic fiber having a Mohs hardness of 5 or less. The Mohs hardness is an index representing the hardness of a substance. When minerals are rubbed against each other, the substance that is damaged is the one with a lower hardness. Examples of inorganic fibers having a Mohs hardness of 5 or less include potassium titanate fibers, wollastonite fibers, zinc oxide, basic magnesium sulfate, alumina fibers, silicon carbide fibers, boron fibers, and the like. These inorganic fibers may be used alone or in combination of two or more.

[0049] From the viewpoint of further improving the impregnation property of the resin composition constituting the film (A) into the reinforcing fiber (b1) without reducing the reinforcing effect of the inorganic fiber (a1) and further improving the mechanical properties of the composite laminate, the inorganic fiber (a1) is preferably at least one of potassium titanate fibers and wollastonite fibers, more preferably potassium titanate fibers or wollastonite fibers, and even more preferably potassium titanate fibers. In addition to at least one of potassium titanate fibers and wollastonite fibers, the inorganic fiber (a1) can be further used in combination with inorganic fibers, organic fibers, metal fibers, or two or more of these other than potassium titanate fibers and wollastonite fibers. In addition to at least one of potassium titanate fibers and wollastonite fibers, the inorganic fiber (a1) can be used in combination with, for example, aluminum borate, magnesium borate, zonoite, zinc oxide, basic magnesium sulfate, and the like.

[0050] As the potassium titanate, conventionally known ones can be widely used, and examples include potassium tetratitanate, potassium hexatitanate, potassium octatitanate, etc. The dimensions of the potassium titanate are not particularly limited as long as they are within the range of the dimensions of the above-mentioned inorganic fiber (a1). The average fiber length of the potassium titanate is preferably 1 μm to 50 μm, more preferably 3 μm to 30 μm, and even more preferably 10 μm to 20 μm. The average fiber diameter of the potassium titanate is preferably 0.01 μm to 1 μm, more preferably 0.05 μm to 0.8 μm, and even more preferably 0.1 μm to 0.7 μm. The average aspect ratio of the potassium titanate is preferably 10 or more, more preferably 10 to 100, and even more preferably 15 to 35.

[0051] Wollastonite is an inorganic fiber composed of calcium metasilicate. The dimensions of the wollastonite are not particularly limited as long as they are within the range of the dimensions of the above-mentioned inorganic fiber (a1). The average fiber length of the wollastonite is preferably 1 μm to less than 100 μm, more preferably 10 μm to 70 μm, and even more preferably 20 μm to 40 μm. The average fiber diameter of the wollastonite is preferably 0.1 μm to 15 μm, more preferably 1 μm to 10 μm, and even more preferably 2 μm to 7 μm. Also, the average aspect ratio of the wollastonite is preferably 3 or more, more preferably 3 to 30, and even more preferably 5 to 15.

[0052] In the inorganic fiber (a1), for the purpose of enhancing the wettability with the thermoplastic resin (a2) and further improving the physical properties such as the mechanical physical properties of the composite laminate, a treatment layer composed of a surface treatment agent may be formed on the surface of the inorganic fiber (a1).

[0053] Examples of the surface treatment agent include silane coupling agents and titanium coupling agents. Among these, the surface treatment agent is preferably a silane coupling agent, and particularly preferably an amino-based silane coupling agent, an epoxy-based silane coupling agent, or an alkyl-based silane coupling agent. These surface treatment agents may be used alone or in combination of two or more.

[0054] Examples of the amino-based silane coupling agent include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, and the like.

[0055] Examples of the epoxy-based silane coupling agent include 3-glycidyloxypropyl(dimethoxy)methylsilane, 3-glycidyloxypropyltrimethoxysilane, diethoxy(3-glycidyloxypropyl)methylsilane, triethoxy(3-glycidyloxypropyl)silane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and the like.

[0056] Examples of the alkyl-based silane coupling agent include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, and the like.

[0057] As a method for forming a treatment layer composed of a surface treatment agent on the surface of the inorganic fiber (a1), a known surface treatment method can be used. For example, the surface treatment agent is dissolved in a solvent that promotes hydrolysis (for example, water, alcohol, or a mixed solvent thereof) to form a solution, and the solution is sprayed onto the inorganic fiber (a1).

[0058] When treating the surface of the inorganic fiber (a1), the amount of the surface treatment agent is not particularly limited. For example, a solution of the surface treatment agent may be sprayed so that the amount of the surface treatment agent is 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the inorganic fiber (a1). By setting the amount of the surface treatment agent within the above range, the adhesion between the inorganic fiber (a1) and the thermoplastic resin (a2) can be further improved, and the dispersibility of the inorganic fiber (a1) in the resin composition can be further improved.

[0059] The content of the inorganic fiber (a1) is preferably 1% by mass to 40% by mass, more preferably 2% by mass to 35% by mass, and even more preferably 5% by mass to 25% by mass in 100% by mass of the total amount of the components contained in the film (A).

[0060] By setting the content of the inorganic fiber (a1) to be not less than the above lower limit value, the mechanical properties of the composite laminate can be further improved. Also, by setting the content of the inorganic fiber (a1) to be not more than the above upper limit value, the film-forming property of the film (A) can be further improved.

[0061] (Thermoplastic resin (a2)) The thermoplastic resin (a2) is not particularly limited as long as it is a thermoplastic resin that can be formed into a film. Examples include polyolefin resins such as polypropylene (PP) resin, polyethylene (PE) resin, cyclic polyolefin (COP) resin, and cyclic olefin copolymer (COC) resin; polystyrene (PS) resin, syndiotactic polystyrene (SPS) resin, high-impact polystyrene (HIPS) resin, acrylonitrile-butadiene-styrene copolymer (ABS) resin, methyl methacrylate / styrene copolymer (MS), methyl methacrylate / butadiene / styrene copolymer (MBS), styrene / butadiene copolymer (SBR), styrene / isoprene copolymer (SIR), styrene / isoprene / butadiene copolymer (SIBR), styrene / butadiene / styrene copolymer (SBS), styrene / isoprene / styrene copolymer (SIS), styrene / ethylene / butylene / styrene copolymer (SEBS), and styrene / ethylene / propylene / styrene copolymer (SEPS); polyester resins such as polylactic acid (PLA) resin, polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, and polycyclohexylene dimethylene terephthalate (PCT) resin; polyacetal (POM) resin; polycarbonate (PC) resin; aliphatic polyamide (PA) resins such as polyamide 6 resin, polyamide 66 resin, polyamide 11 resin, polyamide 12 resin, polyamide 46 resin, polyamide 6C resin, polyamide 9C resin, and copolymer of polyamide 6 resin and polyamide 66 resin (polyamide 6 / 66 resin), and copolymer of polyamide 6 resin and polyamide 12 resin (polyamide 6 / 12 resin); semi-aromatic polyamide (PA) resins composed of structural units having an aromatic ring and structural units not having an aromatic ring, such as polyamide MXD6 resin, polyamide MXD10 resin, polyamide 6T resin, polyamide 9T resin, and polyamide 10T resin; polyphenylene sulfide (PPS) resin; polyether sulfone (PES) resin; liquid crystal polyester (LCP) resin; polyether aromatic ketone resins such as polyether ketone (PEK) resin, polyether ether ketone (PEEK) resin, polyether ketone ketone (PEKK) resin, and polyether ether ketone ketone (PEEKK);Polyetherimide (PEI) resin; polyamideimide (PAI) resin; thermoplastic polyimide (TPI) resin; fluororesins such as polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), ethylene / tetrafluoroethylene copolymer (ETFE), etc. As the thermoplastic resin (a2), a mixture of two or more compatible thermoplastic resins selected from the above-mentioned thermoplastic resins, that is, a polymer alloy or the like may be used.

[0062] Among these, the thermoplastic resin (a2) is preferably at least one selected from the group consisting of polyolefin resins, polystyrene resins, polyester resins, polycarbonate (PC) resins, aliphatic polyamide (PA) resins, semi-aromatic polyamide (PA) resins, polyphenylene sulfide (PPS) resins, polyethersulfone (PES) resins, polyether aromatic ketone resins, polyetherimide (PEI) resins, and thermoplastic polyimide (TPI) resins. More preferably, it contains at least one polycarbonate (PC) resin, and even more preferably, it is a polycarbonate (PC) resin.

[0063] Here, the polycarbonate (PC) resin is a polymer obtained by a phosgene method in which various dihydroxydiaryl compounds are reacted with phosgene, or a transesterification method in which a dihydroxydiaryl compound is reacted with a carbonate ester such as diphenyl carbonate. Representative polycarbonate (PC) resins include polycarbonate resins produced from 2,2-bis(4-hydroxyphenyl)propane (bisphenol A).

[0064] Examples of the dihydroxydiaryl compound include, in addition to bisphenol A, bis(hydroxyaryl)alkanes such as bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxyphenyl-3-methylphenyl)propane, 1,1-bis(4-hydroxy-3-tert-butylphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane; bis(hydroxyaryl)cycloalkanes such as 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane; dihydroxydiaryl ethers such as 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether; dihydroxydiaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide; dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide; dihydroxydiaryl sulfones such as 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone. These compounds may be used alone or in combination of two or more.

[0065] The dihydroxydiaryl compound may be used in admixture with piperazine, dipiperidyl hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, etc.

[0066] Also, the dihydroxyaryl compound may be used in admixture with a phenol compound having a valence of 3 or higher. Examples of the phenol compound having a valence of 3 or higher include phloroglucinol, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptene, 2,4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptane, 1,3,5-tri-(4-hydroxyphenyl)-benzole, 1,1,1-tri-(4-hydroxyphenyl)-ethane, 2,2-bis-[4,4-(4,4'-dihydroxydiphenyl)-cyclohexyl]-propane, and the like.

[0067] The viscosity average molecular weight (Mv) of the polycarbonate (PC) resin is not particularly limited, but from the viewpoint of further improving the productivity and mechanical properties of the composite laminate, it is preferably 10,000 to 100,000, and more preferably 15,000 to 35,000.

[0068] The viscosity average molecular weight (Mv) of the polycarbonate (PC) resin is determined as a 0.5 mass% methylene chloride solution of the polycarbonate (PC) resin. Using a Cannon-Fenske type viscometer tube, the specific viscosity (ηsp) is measured at a temperature of 20°C, and the intrinsic viscosity [η] is obtained by concentration conversion. It is the value calculated from the SCHNELL equation of the following formula (1).

[0069] [η]=1.23×10 -4 ×Mv 0.83 …Formula (1)

[0070] The MVR value of the polycarbonate (PC) resin can be measured in accordance with ISO1133. The temperature for measuring the MVR value is 300°C, and the load is 1.20 kg. Note that the general load for measuring the MVR value is 2.16 kg, but in this measurement, it is set to 1.20 kg.

[0071] The MVR of the thermoplastic resin (a2) used in the present invention at 300°C and a load of 1.20 kg is preferably 0.5 cm 3 / 10 min or more, more preferably 1.0 cm 3 / 10 minutes or more, preferably 10cm 3 / 10 minutes or less, preferably 7cm 3 / 10 minutes or less.

[0072] The shape of the thermoplastic resin (a2) is not particularly limited as long as it can be melt-kneaded. Examples of the shape of the thermoplastic resin (a2) include powder, granules, pellets, flakes, and beads.

[0073] The content of the thermoplastic resin (a2) is preferably from 5 to 88% by mass, and more preferably from 50 to 85% by mass, in 100% by mass of the total amount of the components contained in the film (A).

[0074] (Flame retardant (a3)) Examples of the flame retardant (a3) ​​include halogen-based flame retardants, inorganic flame retardants, phosphate-based flame retardants, phosphazene-based flame retardants, silicone-based flame retardants, etc. The flame retardant (a3) ​​preferably includes at least one selected from the group consisting of phosphate-based flame retardants, phosphazene-based flame retardants, and silicone-based flame retardants.

[0075] Examples of halogen-based flame retardants include polycarbonate from tetrabromobisphenol A [2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane], copolycarbonate of tetrabromobisphenol A and bisphenol A, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, tetrabromodiphenyl ether, hexabromocyclododecane, ethylenebistetrabromophthalimide, tris(pentabromobenzyl)isocyanurate, brominated polystyrene, and tetrabromobisphenol A-epoxy resin.

[0076] Examples of inorganic flame retardants include magnesium hydroxide, aluminum hydroxide, zinc hydroxystannate, zinc stannate, metatitanic acid, tin oxide, tin oxide salts, zinc sulfate, zinc oxide, ferrous oxide, ferric oxide, stannous oxide, stannic oxide, zinc borate, ammonium borate, ammonium octamolybdate, metal salts of tungstic acid, complex oxide acids of tungsten and metalloids, ammonium sulfamate, ammonium bromide, zirconium-based compounds, guanidine-based compounds, fluorine-based compounds, graphite, or expandable graphite. Among these, as the flame retardant (a3), from the viewpoint of further enhancing the flame retardancy and mechanical properties of the composite laminate, magnesium hydroxide, fluorine-based compounds, or expandable graphite is preferable, and magnesium hydroxide or fluorine-based compounds are more preferable.

[0077] Examples of fluorine-based compounds include polytetrafluoroethylene, polyhexafluoropropylene, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / ethylene copolymer, hexafluoropropylene / propylene copolymer, polyvinylidene fluoride, or vinylidene fluoride / ethylene copolymer. The fluorine-based compound may be a polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene particles and an organic polymer.

[0078] Examples of phosphate-based flame retardants include phenyl resorcinol polyphosphate, cresyl resorcinol polyphosphate, phenyl cresyl resorcinol polyphosphate, phenyl hydroquinone polyphosphate, cresyl hydroquinone polyphosphate, phenyl cresyl hydroquinone polyphosphate, phenyl 2,2-bis(4-hydroxyphenyl)propane (bisphenol A type) polyphosphate, cresyl 2,2-bis(4-hydroxyphenyl)propane (bisphenol A type) polyphosphate, phenyl cresyl 2,2-bis(4-hydroxyphenyl)propane (bisphenol A type) polyphosphate, xylyl resorcinol polyphosphate, phenyl p-t-butylphenyl resorcinol polyphosphate, phenyl isopropylphenyl resorcinol polyphosphate, cresyl xylyl resorcinol polyphosphate, or phenyl isopropylphenyl diisopropylphenyl resorcinol polyphosphate, etc.

[0079] Examples of phosphazene-based flame retardants include phosphazene-based compounds such as cyclic phenoxyphosphazene compounds, chain phenoxyphosphazene compounds, or crosslinked phenoxyphosphazene compounds.

[0080] As the silicone-based flame retardant, for example, a silicone compound described in JP-A-11-217494, having a branched main chain and having an aromatic group in the organic functional group it contains, is preferred.

[0081] More specifically, as the silicone compound, a compound having a structure in which the main chain is a branched structure and contains an aromatic group as an organic functional group, as shown in the following formula (2), that is, a compound having a structure containing T units and / or Q units as branching units is preferred.

[0082]

Chemical formula

[0083] (Here, R1, R2, and R3 represent organic functional groups in the main chain, and X represents a terminal functional group. l, m, and n are each an integer of 1 or more.)

[0084] It is more preferable that the silicone compound contains the structure of formula (2) in a proportion of 30 mol% or more and 95 mol% or less of the total siloxane units. When the structure of formula (2) is 30 mol% or more, the heat resistance of the silicone compound is further improved, and the flame retardancy of the composite laminate containing this is further improved. However, when the structure of formula (2) exceeds 95 mol%, the degree of freedom of the main chain of the silicone decreases, and condensation of aromatic groups during combustion of the composite laminate may be less likely to occur, and it may be difficult to exhibit a remarkable flame retardancy by the silicone compound.

[0085] Also, the organic functional group of the silicone compound preferably contains 20 mol% or more of an aromatic group. When the content of the aromatic group is less than 20 mol%, condensation between aromatic groups during combustion becomes less likely to occur, and the flame retardant effect by the silicone compound may decrease.

[0086] Examples of the aromatic group include a phenyl group, a biphenyl group, a naphthalene group, or derivatives thereof. Among them, from the viewpoint of safety, the aromatic group is preferably a phenyl group. Among the organic functional groups in the silicone compound, among those attached to the main chain or branched side chains, the organic group other than the aromatic group is preferably a methyl group. Further, the end group in the silicone compound is preferably a mixture containing at least one selected from the group consisting of a methyl group, a phenyl group, a hydroxyl group, and an alkoxy group (particularly a methoxy group). In this case, since the reactivity of the end group is low, gelation (crosslinking) of the silicone compound hardly occurs during kneading of the thermoplastic resin (a2) and the silicone compound, so that the silicone compound can be more uniformly dispersed in the resin composition. As a result, a further better flame retardant effect by the silicone compound is achieved, and the moldability of the film (A) is further improved. The end group in the silicone compound is more preferably a methyl group. In this case, since the reactivity of the methyl group is extremely low, the dispersibility of the silicone compound in the thermoplastic resin (a2) becomes extremely good, and the flame retardancy of the composite laminate can be further improved.

[0087] The weight average molecular weight (Mw) of the silicone compound is preferably from 5,000 to 500,000. When the weight average molecular weight (Mw) of the silicone compound is less than 5,000, the heat resistance of the silicone compound itself may decrease, and the effect of imparting flame retardancy by the silicone compound may decrease. Further, the melt viscosity of the silicone compound decreases, and when forming the film (A), the silicone compound may ooze out onto the surface of the thermoplastic resin (a2) to deteriorate the moldability. Further, when the weight average molecular weight (Mw) of the silicone compound exceeds 500,000, the melt viscosity of the silicone compound increases, the uniform dispersion in the resin composition of the silicone compound is impaired, and the flame retardancy effect and the moldability may decrease. Further, the weight average molecular weight (Mw) of the silicone compound is more preferably from 10,000 to 270,000. When the weight average molecular weight of the silicone compound is within this range, since the melt viscosity of the silicone compound becomes more optimum, the silicone compound can be dispersed extremely uniformly in the resin composition, and excessive bleeding of the silicone compound onto the surface of the thermoplastic resin (a2) can be reduced. Therefore, the flame retardancy and the moldability of the composite laminate can be further enhanced.

[0088] Halogen-based flame retardants may generate toxic halogen gases or corrode metals during incineration. Therefore, the flame retardant (a3) is preferably a non-halogen-based flame retardant, and from the viewpoint of further improving the compatibility with the thermoplastic resin (a2), it is preferably a phosphate ester-based flame retardant, a phosphazene-based flame retardant, or a silicone-based flame retardant.

[0089] These flame retardants may be used alone or in combination of two or more.

[0090] In the present invention, the content of the flame retardant (a3) is preferably 5% by mass to 40% by mass in 100% by mass of the total amount of the components contained in the film (A). The content of the flame retardant (a3) is preferably 5% by mass or more, more preferably 10% by mass or more, preferably 40% by mass or less, and more preferably 35% by mass or less in 100% by mass of the total amount of the components contained in the film (A).

[0091] When the content of the flame retardant (a3) is less than 5% by mass, a sufficient flame retardant effect may not be obtained for the composite laminate. When the content of the flame retardant (a3) exceeds 40% by mass, the mechanical properties of the composite laminate may deteriorate, the appearance may become defective, or the film-forming property of the film (A) may deteriorate.

[0092] (Other additives) The film (A) may contain other additives as long as the preferable physical properties thereof are not impaired.

[0093] Examples of other additives include fillers other than the above inorganic fibers (a1) such as aramid fibers, polyphenylene benzoxazole (PBO) fibers, glass fibers, carbon fibers, alumina fibers, boron fibers, silicon carbide fibers, calcium carbonate, mica, mica, sericite, illite, talc, kaolinite, montmorillonite, boehmite, smectite, vermiculite, titanium dioxide, potassium titanate, lithium potassium titanate, boehmite, etc.; solid lubricants such as polytetrafluoroethylene (PTFE), polyolefin resins such as low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, ultra-high molecular weight polyethylene, etc., graphite, molybdenum disulfide, tungsten disulfide, boron nitride, etc.; heat stabilizers such as copper compounds; light stabilizers such as hindered phenol-based light stabilizers; nucleating agents; antistatic agents such as anionic antistatic agents, cationic antistatic agents, nonionic antistatic agents, etc.; antioxidants (anti-aging agents); weathering agents; light-resistant agents; metal deactivators; ultraviolet absorbers such as benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, etc.; antibacterial and antifungal agents; deodorants; conductivity-imparting agents such as carbon-based conductive agents, metal-based conductive agents, metal oxide-based conductive agents, surfactants, etc.; dispersants; plasticizers (softening agents) such as polyester-based plasticizers, glycerin-based plasticizers, polyvalent carboxylic acid ester-based plasticizers, phosphate ester-based plasticizers other than the above flame retardants (a3), polyalkylene glycol-based plasticizers, epoxy-based plasticizers, etc.; pigments such as carbon black, titanium dioxide, etc., colorants such as dyes; flame retardants other than the above flame retardants (a3) such as phosphazene-based compounds, phosphate esters, condensed phosphate esters, inorganic phosphorus-based flame retardants, halogen-based flame retardants, silicone-based flame retardants, metal oxide-based flame retardants, metal hydroxide-based flame retardants, organic metal salt-based flame retardants, nitrogen-based flame retardants, boron compound-based flame retardants, etc.; anti-dripping agents; vibration damping agents; neutralizing agents; anti-blocking agents; fluidity improvers; mold release agents such as fatty acids, fatty acid metal salts, etc.; lubricants; impact resistance improvers, etc. These may be used alone or in combination of two or more.

[0094] When the film (A) contains other additives, the content thereof is not particularly limited as long as it does not impair the preferable physical properties of the composite laminate of the present invention. The content of the other additives is preferably 5% by mass or less, more preferably 1% by mass or less, in 100% by mass of the total amount of the components contained in the film (A).

[0095] (Method for producing the film (A)) The method for producing the film (A) is not particularly limited, and for example, known melt film-forming methods such as the T-die casting method, the calendar method, and the press method can be employed.

[0096] More specifically, a method of directly mixing the inorganic fiber (a1), the thermoplastic resin (a2), the flame retardant (a3), and, if necessary, other additives and melt film-forming; a method of previously melt-kneading the inorganic fiber (a1), the thermoplastic resin (a2), the flame retardant (a3), and, if necessary, other additives to produce pellets of a resin composition and using this for melt film-forming, etc. can be mentioned.

[0097] In addition, the ratio (mixture / thermoplastic resin (a2)) of the melt viscosity of the mixture constituting the above pellets to the melt viscosity of the thermoplastic resin (a2) before mixing is preferably 1.01 or more, preferably 5 or less. When the melt viscosity ratio (mixture / thermoplastic resin (a2)) is within the above range, the mechanical properties of the composite laminate can be further improved. The measurement temperature of the melt viscosity is set to a temperature suitable for melt-kneading at a temperature higher than the melting point when the thermoplastic resin (a2) constituting the above pellets has a melting point, or at a temperature higher than the glass transition temperature when the thermoplastic resin (a2) constituting the above pellets does not have a melting point but has a glass transition temperature. For example, when the thermoplastic resin (a2) is an aliphatic polyamide (PA) resin and a semi-aromatic polyamide (PA) resin, the melt viscosity is measured at a temperature 25°C higher than the melting point, when it is a polyetherimide (PEI) resin, the melt viscosity is measured at a temperature 150°C higher than the glass transition temperature, and when it is a polycarbonate (PC) resin, the melt viscosity is measured at a temperature 100°C to 150°C higher than the glass transition temperature.

[0098] The film (A) can be either a stretched film or an unstretched film. However, a stretched film is preferred because shrinkage during heat melting can prevent wrinkles and sagging, further improving the appearance of the molded product. The stretching ratio of the stretched film is preferably 2 times or more and 15 times or less. In this specification, the stretching ratio is defined as the area ratio obtained by multiplying the stretching ratio in the transverse direction by the stretching ratio in the longitudinal direction, with the area ratio being the stretching ratio, based on the film dimensions as they come out of the casting roll during film formation.

[0099] The thickness per sheet of the film (A) is preferably less than 500 μm, more preferably 30 μm to 450 μm, even more preferably 50 μm to 300 μm, and most preferably 50 μm to 200 μm. If the thickness per sheet of the film (A) is less than the above upper limit or within the above range, the mechanical properties of the composite laminate can be further improved.

[0100] <Sheet (B)> The sheet (B) used in the composite laminate of the present invention is a sheet containing reinforcing fibers (b1) with an average fiber length of 1 mm to 100 mm and, optionally, a thermoplastic resin (b2).

[0101] The basis weight of the sheet (B) is preferably 100 g / m 2 ~1500 g / m 2 for smooth molding processing of the composite laminate of the present invention.

[0102] (Reinforcing fibers (b1)) The reinforcing fiber (b1) is not particularly limited as long as the average fiber length is 1 mm to 100 mm, and inorganic fibers, organic fibers, metal fibers, or a combination of two or more of these can be used. Examples of inorganic fibers include carbon fibers, graphite fibers, silicon carbide fibers, alumina fibers, tungsten carbide fibers, boron fibers, glass fibers, and the like. Examples of organic fibers include aramid fibers, poly(paraphenylene benzoxazole) (PBO) fibers, high-density polyethylene fibers, other general polyamide fibers, polyester fibers, and the like. Examples of metal fibers include fibers such as stainless steel and iron, or carbon fibers coated with a metal may also be used. Among these, the reinforcing fiber (b1) is preferably at least one selected from the group consisting of carbon fibers, glass fibers, and aramid fibers. The reinforcing fiber (b1) is more preferably a carbon fiber from the viewpoint of further improving the mechanical properties such as the strength of the obtained composite laminate. Carbon fiber is a fiber produced by carbonizing acrylic fiber, pitch (by-products such as petroleum, coal, and coal tar) or the like at a high temperature. In the JIS standard, it is defined as a fiber obtained by heat-treating the precursor of organic fiber and composed of 90% or more carbon by mass ratio. Carbon fiber using acrylic fiber is called PAN-based carbon fiber, and carbon fiber using pitch is called pitch-based carbon fiber.

[0103] If the fiber length of the reinforcing fiber (b1) is too long, the fluidity during molding may decrease, and if the fiber length is too short, the production of the mat of the reinforcing fiber (b1) may be difficult. Considering these points, from the viewpoint of further improving the moldability of the sheet (B), the reinforcing fiber (b1) is preferably a discontinuous fiber. Further, the average fiber length of the reinforcing fiber (b1) is preferably 1 mm to 100 mm, more preferably 10 mm to 90 mm, and even more preferably 40 mm to 80 mm. The average fiber diameter of the reinforcing fiber (b1) is preferably 1 μm to 50 μm, more preferably 3 μm to 20 μm, and even more preferably 5 μm to 15 μm. The reinforcing fiber (b1) may be in the form of a bundle of reinforcing fibers aggregated with a sizing agent or the like as long as it has the above average fiber diameter.

[0104] The content of the reinforcing fiber (b1) is preferably 75% by mass to 100% by mass, more preferably 80% by mass to 98% by mass or less, and still more preferably 85% by mass to 95% by mass in 100% by mass of the total amount of the components contained in the sheet (B).

[0105] By setting the content of the reinforcing fiber (b1) to 75% by mass or more, a further reinforcing effect by the reinforcing fiber (b1) can be obtained.

[0106] (Thermoplastic resin (b2)) As the thermoplastic resin (b2), there is no particular limitation as long as it is a thermoplastic resin that can be fibrillated or formed into a film. For example, polyolefin resins such as polypropylene (PP) resin, polyethylene (PE) resin, cyclic polyolefin (COP) resin, and cyclic olefin copolymer (COC) resin; polystyrene (PS) resin, syndiotactic polystyrene (SPS) resin, high-impact polystyrene (HIPS) resin, acrylonitrile-butadiene-styrene copolymer (ABS) resin, methyl methacrylate / styrene copolymer (MS), methyl methacrylate / butadiene / styrene copolymer (MBS), styrene / butadiene copolymer (SBR), styrene / isoprene copolymer (SIR), styrene / isoprene / butadiene copolymer (SIBR), styrene / butadiene / styrene copolymer (SBS), styrene / isoprene / styrene copolymer (SIS), styrene / ethylene / butylene / styrene copolymer (SEBS), styrene / ethylene / propylene / styrene copolymer (SEPS), etc.; polyester resins such as polylactic acid (PLA) resin, polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, polycyclohexylene dimethylene terephthalate (PCT) resin, etc.; polyacetal (POM) resin; polycarbonate (PC) resin; aliphatic polyamide (PA) resins such as polyamide 6 resin, polyamide 66 resin, polyamide 11 resin, polyamide 12 resin, polyamide 46 resin, polyamide 6C resin, polyamide 9C resin, copolymer of polyamide 6 resin and polyamide 66 resin (polyamide 6 / 66 resin), copolymer of polyamide 6 resin and polyamide 12 resin (polyamide 6 / 12 resin), etc.; semi-aromatic polyamide (PA) resins composed of structural units having an aromatic ring and structural units not having an aromatic ring, such as polyamide MXD6 resin, polyamide MXD10 resin, polyamide 6T resin, polyamide 9T resin, polyamide 10T resin, etc.; polyphenylene sulfide (PPS) resin; polyethersulfone (PES) resin; liquid crystal polyester (LCP) resin; polyether aromatic ketone resins such as polyether ketone (PEK) resin, polyether ether ketone (PEEK) resin, polyether ketone ketone (PEKK) resin, polyether ether ketone ketone (PEEKK), etc.;Examples of the thermoplastic resin include polyetherimide (PEI) resin, polyamideimide (PAI) resin, thermoplastic polyimide (TPI) resin, and fluorine-based resins such as polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), and ethylene / tetrafluoroethylene copolymer (ETFE). As the thermoplastic resin (b2), a mixture of two or more compatible thermoplastic resins selected from the above-mentioned thermoplastic resins, i.e., a polymer alloy, may be used.

[0107] Among these, the thermoplastic resin (b2) is preferably at least one selected from the group consisting of polyolefin resins, polystyrene-based resins, polyester-based resins, polycarbonate (PC) resins, aliphatic polyamide (PA) resins, semi-aromatic polyamide (PA) resins, polyphenylene sulfide (PPS) resins, polyethersulfone (PES) resins, polyether aromatic ketone resins, polyetherimide (PEI) resins, and thermoplastic polyimide (TPI) resins.

[0108] The shape of the thermoplastic resin (b2) is not particularly limited as long as it can be melt-kneaded, and for example, any of powder, granules, pellets, flakes, beads, etc. can be used.

[0109] The content of the thermoplastic resin (b2) is preferably 2% by mass to 25% by mass, more preferably 2% by mass to 20% by mass, and even more preferably 5% by mass to 15% by mass, based on 100% by mass of the total amount of the components contained in the sheet (B). The thermoplastic resin (b2) may not be substantially contained in the sheet (B). The fact that the thermoplastic resin (b2) is substantially not contained in the sheet (B) means that the content of the thermoplastic resin (b2) is 0.5% by mass or less based on 100% by mass of the total amount of the components contained in the sheet (B). In this case, the sheet (B) may be a woven fabric or nonwoven fabric composed of reinforcing fibers (b1).

[0110] (Method of manufacturing sheet (B)) The sheet (B) can use as it is a woven fabric or non-woven fabric composed of reinforcing fibers (b1). Further, when the sheet (B) contains a thermoplastic resin (b2), it can be obtained by laminating a plurality of prepregs in which the reinforcing fibers (b1) are impregnated with the thermoplastic resin (b2) and integrating the obtained laminate by heating and pressing with a molding machine.

[0111] As the method for manufacturing the non-woven fabric, a known method can be used. For example, it is preferably a method including at least any one selected from the group consisting of a papermaking method, a carding method, and an air-laid method, more preferably any one of the papermaking method, the carding method, and the air-laid method, and even more preferably the carding method. When using the carding method, a commercially available carding machine can be used.

[0112] As the method for manufacturing the prepreg, known methods can be used and it is not limited to the manufacturing method described below. For example, two sheets of thermoplastic resin (b2) in the form of a sheet such as a film, non-woven fabric, mat, woven or knitted fabric, etc. are prepared, and between the two sheets, a sheet with reinforcing fibers (b1) arranged in a sheet form, or a sheet (non-woven material) produced by a method including at least one selected from the group consisting of the papermaking method, carding method, and air-laid method by cutting the reinforcing fibers (b1) is sandwiched, and the obtained product is obtained by heating and pressurizing. More specifically, two sheets of thermoplastic resin sheets are fed out from two rolls, and after sandwiching the sheet of reinforcing fibers supplied from the roll of the sheet of reinforcing fibers between the two sheets of thermoplastic resin sheets, heating and pressurizing are performed. As the means for heating and pressurizing, known ones can be used, and it may require multi-step processes such as using two or more hot rolls or using a plurality of pairs of a preheating device and a hot roll. In this case, the method for manufacturing the sheet (non-woven material) when the reinforcing fibers (b1) are cut is more preferably any one of the papermaking method, carding method, and air-laid method, and even more preferably the carding method. Here, the thermoplastic resin constituting the sheet does not have to be of one type, and a sheet made of another type of thermoplastic resin may be further laminated using the above-described apparatus.

[0113] As another manufacturing method of the prepreg, there can be mentioned a method in which the reinforcing fiber (b1) obtained by opening the fiber bundle of the reinforcing fiber (b1) and, if necessary, the fibrous thermoplastic resin (b2) are mixed in a desired mass ratio to form a sheet, and if necessary, further laminated to obtain a nonwoven fabric, and then the prepreg is obtained by heating and pressing the nonwoven fabric. For the mixing, a commercially available blender can be used. For the sheet formation and lamination, a carding method can be used, and a commercially available carding machine can be used. Also, as the means for heating and pressing the nonwoven fabric, known means can be used. The average fiber length of the fibrous thermoplastic resin (b2) used for manufacturing the nonwoven fabric can be the same as that of the reinforcing fiber (b1) to be mixed. Also, the fineness of the thermoplastic resin (b2) is preferably 2.2 dtex to 22 dtex. By setting the fineness of the thermoplastic resin (b2) within the above range, the dispersibility of the fibrous thermoplastic resin (b2) into the reinforcing fiber (b1) is improved, and it becomes easier to form a more uniform nonwoven fabric. Also, from the viewpoint of further suppressing the phenomenon that the sheet expands in the thickness direction when obtaining a molded body using the prepreg, the prepreg preferably has 5 traces / cm by a needle punch machine generally used in the mixing. 2 The following is preferred. Further, in the cross-section of the prepreg, the number of cases where a part and another part of the reinforcing fiber (b1) are displaced by 1 mm or more in the thickness direction is 80 pieces / cm 2 The following is preferred.

[0114] When the sheet (B) contains the thermoplastic resin (b2), the heating temperature of the nonwoven fabric is usually preferably 100°C to 400°C, although it depends on the type of the thermoplastic resin (b2). On the other hand, the pressure during the pressing of the nonwoven fabric is usually preferably 0.1 MPa to 10 MPa. If it is within this range, it is preferable because the thermoplastic resin (b2) can be further impregnated between the reinforcing fibers (b1) contained in the prepreg, if necessary.

[0115] In a prepreg containing reinforcing fibers (b1) and a thermoplastic resin (b2), when the reinforcing fibers (b1) are continuous fibers oriented in one direction, the prepreg that can be used for the composite laminate of the present invention is preferably obtained by making incisions using a laser marker, a cutting plotter, a die, or the like. Although the reinforcing fibers (b1) are cut by the incisions, from the viewpoints of the mechanical properties and fluidity of the reinforcing fibers (b1), the length of the cut reinforcing fibers (b1) is preferably 5 mm to 100 mm, and more preferably 10 mm to 50 mm.

[0116] Two or more of the prepregs obtained as described above may be laminated so that the directions of the reinforcing fibers (b1) are pseudo-isotropic or alternately laminated to produce a laminated base material. It is preferable to laminate the prepregs in 1 to 96 layers. A more preferable range of the number of prepreg layers is 1 to 32 layers. By setting the number of prepreg layers to be equal to or greater than the above lower limit value, the directions of the reinforcing fibers can be laminated in a pseudo-isotropic manner. Further, by setting the number of prepreg layers to be equal to or less than the above upper limit value, the work load of the lamination process can be further reduced.

[0117] The sheet (B) may be manufactured by heating and pressing the laminated base material obtained as described above to integrate and form the laminated base material. At this time, the composite laminate of the present invention can also be manufactured simultaneously with the manufacture of the sheet (B) by disposing the film (A) between the sheets (B) or by disposing the film (A) between the laminated base material of the sheet (B) and the sheet (B). After the heating step, it is preferable to carry out a cooling step. By performing the cooling step, the thermoplastic resin is solidified, making it even easier to handle the sheet (B).

[0118] The heating temperature of the laminated base material depends on the type of the thermoplastic resin (b2) contained in the prepreg, but is preferably 100°C to 400°C, and more preferably 150°C to 350°C. Further, preheating may be performed prior to the above heating. The temperature of the preheating is usually 150°C to 400°C, and preferably desirably 200°C to 380°C.

[0119] As the pressure during the pressing of the laminated substrate, it is preferably 0.1 MPa to 10 MPa, more preferably 0.2 MPa to 2 MPa. Regarding this pressure, it is the value obtained by dividing the pressing force by the area of the laminated substrate.

[0120] The heating and pressing time of the laminated substrate is preferably 0.1 minute to 30 minutes, more preferably 0.5 minute to 20 minutes. Also, the cooling time provided after heating and pressing is preferably 0.5 minute to 30 minutes.

[0121] The thickness of the sheet (B) can be arbitrarily selected according to the shape of the target member, but from the viewpoint of further improving the formability of the sheet (B) and the mechanical properties of the composite laminate, it is preferably 0.3 mm to 15 mm, more preferably 1 mm to 12 mm.

[0122] <Method for manufacturing a composite laminate> The composite laminate of the present invention can be manufactured by laminating and arranging the film (A) and the sheet (B) to prepare a laminate, and integrating the prepared laminate by thermocompression bonding by heating and pressing. The composite laminate of the present invention can be manufactured, for example, by thermocompression bonding a laminate in which the film (A) is directly laminated and arranged between a plurality of sheets (B) by heating and pressing to integrate the film (A) and the sheet (B). At this time, the film (A) can be laminated and arranged on one side or both sides of the sheet (B). In the manufacturing method of the composite laminate of the present invention, it is preferable to carry out a cooling step after the heating step. By carrying out the cooling step, the thermoplastic resin solidifies, making the handling of the composite laminate easier.

[0123] In heating the laminate, depending on the types of the thermoplastic resin (a2) contained in the film (A) and the thermoplastic resin (b2) contained in the sheet (B), it is preferably heated at 100°C to 400°C, more preferably at 150°C to 350°C. Further, preheating may be performed prior to heating the laminate. In preheating, it is desirably heated usually at 150°C to 400°C, preferably at 200°C to 380°C.

[0124] The pressure during pressing of the laminate is preferably 0.1 MPa to 10 MPa, more preferably 0.2 MPa to 2 MPa. This pressure is taken as the value obtained by dividing the press force by the area of the laminate.

[0125] The time for heating and pressing the laminate is preferably 0.1 minute to 30 minutes, more preferably 0.5 minute to 20 minutes. Also, the cooling time provided after heating and pressing the laminate is preferably 0.5 minute to 30 minutes.

[0126] When the thermoplastic resin contained in the laminate has a melting point (Tm), the mold temperature (Th) of the molding machine during heating of the laminate is preferably Tm ≤ Th ≤ (Tm + 100) (°C), more preferably (Tm + 10) ≤ Th ≤ (Tm + 80) (°C). When the thermoplastic resin contained in the laminate does not have a melting point (Tm) but has a glass transition temperature (Tg), the mold temperature (Th) of the molding machine during heating of the laminate is preferably Tg ≤ Th ≤ (Tg + 100) (°C), more preferably (Tg + 10) ≤ Th ≤ (Tg + 80) (°C). By setting the mold temperature (Th) of the molding machine within the above range, the laminate can be integrated while preventing the expansion of the mold and suppressing the deterioration of the resin.

[0127] The difference (Th - Tc) between the mold temperature (Th) of the molding machine during heating of the laminate and the mold temperature (Tc) of the molding machine during cooling of the laminate is preferably 10 ≦ (Th - Tc) ≦ 250 (°C), more preferably 30 ≦ (Th - Tc) ≦ 200 (°C). By setting the difference in mold temperature within the above range, more uniform melting and solidification of the thermoplastic resin (a2) can be achieved, and the durability of the resulting composite laminate can be further improved.

[0128] The thickness of the entire composite laminate of the present invention can be arbitrarily selected according to the shape of the target member, and from the viewpoint of further improving the moldability and mechanical properties of the composite laminate, for example, it is preferably 0.6 mm or more and 10 mm or less, more preferably 0.7 mm or more and 3 mm or less.

[0129] The composite laminate of the present invention can be used as an intermediate material for molding that can be shaped into an arbitrary shape by press molding such as stamping molding, and can be shaped and used for various parts and members such as electric and electronic devices (computer cases, tablets, etc.) and automobiles (housings for EV batteries).

Examples

[0130] Specific descriptions will be given below based on examples and comparative examples, but the present invention is not limited thereto. The raw materials used in the present examples and comparative examples are specifically as follows.

[0131] <Raw materials used for manufacturing film (A)> (Inorganic fiber (a1)) Potassium titanate fiber: manufactured by Otsuka Chemical Co., Ltd., trade name "TISMO N102", average fiber length 15 μm, average fiber diameter 0.5 μm, average aspect ratio 30

[0132] The average fiber length, average fiber diameter, and aspect ratio of the potassium titanate fiber were determined from the average values of arbitrarily selected 300 measured by observation with a scanning electron microscope (SEM).

[0133] (Thermoplastic resin (a2)) Polycarbonate (PC) resin A: manufactured by Mitsubishi Engineering Plastics Corporation, trade name "Novarex 7027A", viscosity average molecular weight (Mv) 26,700, MVR value 5.7 cm 3 / 10 min (compliant with JIS K7210, 300 °C, 1.20 kg load) Polycarbonate (PC) resin B: manufactured by Mitsubishi Engineering Plastics Corporation, trade name "Novarex 7025A", viscosity average molecular weight (Mv) 23,000, MVR value 7.0 cm 3 / 10 min (compliant with JIS K7210, 300 °C, 1.20 kg load)

[0134] (Flame retardant (a3)) Phosphate ester-based flame retardant: aromatic phosphate ester, manufactured by Daihachi Chemical Industry Co., Ltd., trade name "PX200" Silicone-based flame retardant: manufactured by Kaneka Corporation, trade name "Kanace MR-01" Fluorine-based compound: polytetrafluoroethylene, manufactured by AGC Inc., trade name "Fluon PTFECD145E"

[0135] (Other additives) Carbon black: manufactured by Ohta Kasei Co., Ltd., trade name "Grain Black NoPC2045G" Antioxidant: manufactured by Songwon Industrial Co., Ltd., trade name "SONGNOX6260"

[0136] (Raw materials used in the production of sheet (B)) (Sheet containing reinforcing fiber (b1)) Carbon fiber non-woven fabric: manufactured by Yuho Co., Ltd., recycled carbon fiber content 100% by mass, sheet thickness 3 mm, recycled carbon fiber (average fiber length 80 mm, average fiber diameter 7 μm, carbon fiber content: 100% by mass)

[0137] (Examples 1, 2 and Comparative Examples 1, 2) Using a twin-screw extruder, melt-kneading was carried out at the compounding ratios shown in Table 1 to produce pellets of the resin composition. The cylinder temperature of the twin-screw extruder was 250 °C.

[0138] After drying the obtained pellets, using a film extruder (manufactured by Toyo Seiki Seisaku-sho, Ltd., with a single-screw extruder D2020 (L / D = 20) connected to Laboplastomill 4C150-01), the molten resin composition extruded from a T-die (width: 150 mm, thickness: 0.2 mm) at a cylinder temperature of 250°C was uniaxially stretched through a film take-up device so that the film reached the target thickness, and a film was obtained. The thickness of the film was 100 μm.

[0139] The obtained film was designated as film (A), and a sheet formed from a non-woven fabric containing recycled carbon fibers was designated as sheet (B).

[0140] The above film (A) and sheet (B) were laminated and sandwiched between two imide films (manufactured by Ube Industries, Ltd., trade name "UPILEX 75S"). The obtained laminate was pressed using a press machine (manufactured by Discharge Precision Machining Laboratory, trade name "ZENFormer" 75t double-slide machine) under the conditions of a top plate temperature of 280°C, a preheating time of 5 minutes, a pressure of 9.6 MPa, and a pressurization time of 3 minutes. After pressing, the imide films were peeled off to produce a composite laminate. The thickness of the obtained composite laminate was measured and shown in Table 1. In the total 100% by volume of the components contained in the composite laminates of Example 1, Example 2, and Comparative Example 1, excluding Comparative Example 2 where film formation was not possible, the volume content value (Vf) of the reinforcing fiber (b1) was 35% by volume, 35% by volume, and 31% by volume, respectively. In Comparative Example 2, due to foaming making melt kneading difficult, film formation was not possible, and the volume content value (Vf) of the reinforcing fiber (b1) contained in the composite laminate could not be measured.

[0141] <Evaluation> (Flowability) Regarding the pellets of the resin composition before forming film (A) prepared in the examples and comparative examples, the melt volume flow rate (MVR) value was measured. The measurement of the MVR value was carried out in accordance with ISO1133 using a semi-automatic melt indexer (manufactured by Toyo Seiki Seisaku-sho, Ltd., product number "Meltindexes F-F01") under the conditions of a temperature of 280°C and a load of 2.16 kg.

[0142] (Formability) The formability during the production of film (A) in the examples and comparative examples was evaluated according to the following evaluation criteria.

[0143] Evaluation criteria; 〇…Film (A) can be formed (film-formed) without problems ×…Due to reasons such as foaming, it is difficult to melt-knead the resin composition, and film (A) cannot be formed (film-formed)

[0144] (Flame retardancy) The flame retardancy of the film (A) and the composite laminate produced in the examples and comparative examples was evaluated.

[0145] The evaluation of flame retardancy was carried out according to "IEC60695-11-10 Method B, ASTM D3801". Specifically, test pieces (125 ± 5 mm × 13 ± 0.5 mm × t mm) of each of the film (A) and the composite laminate were prepared, and the obtained test pieces were vertically attached to a clamp, and a 10-second flame contact with a 20-mm flame was performed twice. Based on the combustion behavior, the judgment described in the UL94 test method was carried out. In addition, the obtained judgment results were evaluated according to the following evaluation criteria.

[0146] Evaluation criteria; 〇…When t = 0.8 mm, it meets the V-0 judgment in the judgment described in the UL94 test method ×…When t = 0.8 mm, the judgment result in the judgment described in the UL94 test method is V-1, V-2, or Not judgment, and does not meet the V-0 judgment

[0147] The results are shown in Table 1 below.

[0148]

Table 1

[0149] As is clear from Table 1, in Example 1 and Example 2, the MVR value measured under the conditions of 280 °C and a load of 2.16 kg of the pellets of the resin composition was 0.5 cm 3 / 10 min to 7 cm3 Since it was within the range of / 10 min, it had excellent film-forming properties of the film (A) and also excellent flame retardancy of the obtained composite laminate. On the other hand, in Comparative Example 1, the MVR value measured under the conditions of 280 °C and a load of 2.16 kg of the pellets of the resin composition was greater than 7, and the flame retardancy of the obtained composite laminate was not sufficient. Further, in Comparative Example 2, melt kneading was difficult due to foaming and the film (A) could not be formed, and the MVR value could not be measured. Although not described in Table 1, in the comparative example with an MVR value of 14.7, it was observed that the fluidity was high and the film-forming property of the film deteriorated, and in the comparative example with an MVR value of 29.5, the fluidity was too high and the film could not be formed.

Explanation of symbols

[0150] 1... laminate

Claims

1. In a composite laminate comprising an inorganic fiber and a thermoplastic resin, the composite laminate is formed by integrating a laminate including a film (A) and a sheet (B) by thermocompression bonding, the film (A) is composed of a resin composition containing an inorganic fiber (a1) having an average fiber length of 1 μm to 300 μm, a thermoplastic resin (a2), and a flame retardant (a3), The melt volume flow rate value (MVR value) measured under the conditions of 280 °C and a load of 2.16 kg of the resin composition is 0.5 cm ３ / 10 min to 7 cm ３ / 10 min, and the sheet (B) is a composite laminate containing a reinforcing fiber (b1) having an average fiber length of 1 mm to 100 mm.

2. The laminate has a portion where the film (A) is laminated and arranged so as to be in direct contact with the sheet (B) between a plurality of the sheets (B), the composite laminate according to claim 1.

3. The composite laminate according to claim 1 or claim 2, wherein the average aspect ratio of the inorganic fiber (a1) is 3 to 200.

4. The composite laminate according to claim 1 or claim 2, wherein the inorganic fiber (a1) is at least one of potassium titanate fiber or wollastonite fiber.

5. The composite laminate according to claim 1 or claim 2, wherein the flame retardant (a3) contains at least one selected from the group consisting of a phosphate ester-based flame retardant, a phosphazene-based flame retardant, and a silicone-based flame retardant.

6. The composite laminate according to claim 1 or claim 2, wherein the content of the inorganic fiber (a1) is 1 mass% to 40 mass% in 100 mass% of the total amount of the components contained in the film (A).

7. The composite laminate according to claim 1 or claim 2, wherein the thermoplastic resin (a2) is a polycarbonate resin.

8. The composite laminate according to claim 1 or claim 2, wherein the content of the reinforcing fiber (b1) is 75 mass% to 100 mass% in 100 mass% of the total amount of the components contained in the sheet (B).

9. The composite laminate according to claim 1 or claim 2, wherein the reinforcing fiber (b1) is at least one selected from the group consisting of carbon fiber, glass fiber, and aramid fiber.

10. The composite laminate according to claim 1 or claim 2, wherein the content of the reinforcing fiber (b1) is 15 volume% to 50 volume% as a volume content value (Vf) in 100 volume% of the total amount of the components contained in the composite laminate.

11. The composite laminate according to claim 1 or claim 2, which is for electrical / electronic members or automotive members.

12. A method for manufacturing a composite laminate according to claim 1 or claim 2, comprising: preparing a laminate by laminating and arranging a film (A) containing inorganic fibers (a1) having an average fiber length of 1 μm to 300 μm, a thermoplastic resin (a2), and a flame retardant (a3), and a sheet (B) containing reinforcing fibers (b1) having an average fiber length of 1 mm to 100 mm; obtaining a composite laminate by integrating the laminate by thermocompression bonding; A method for manufacturing a composite laminate, comprising the above steps.

13. The method for manufacturing a composite laminate according to claim 12, wherein the thickness of the film (A) is less than 500 μm.

14. The method for manufacturing a composite laminate according to claim 12, wherein the thickness of the sheet (B) is 0.3 mm to 15 mm.

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