Method for manufacturing continuous fiber reinforced thermoplastic resin sheets

Abstract

This invention relates to a manufacturing method for producing a large number of continuous fiber reinforced thermoplastic resin sheets that can be carried out with simple equipment and efficiently in a short time. The aforementioned problems can be solved by the following manufacturing method for continuous fiber reinforced thermoplastic resin sheets, which includes: an impregnation step of impregnating a thermoplastic resin containing at least one of polycarbonate resin and polyaryl ester resin, and a thermoplastic resin solution containing a halogenated organic solvent, into continuous fibers; and a solvent removal step of removing the halogenated organic solvent from the continuous fibers impregnated with the aforementioned thermoplastic resin solution by irradiation with infrared light; wherein in the solvent removal step, the distance between the heater irradiating the aforementioned infrared light and the aforementioned continuous fibers is 400 mm or less, and the temperature of the heating element radiating the aforementioned infrared light in the aforementioned heater is 260°C or higher.

Description

Technical Field

[0001] This invention relates to a method for manufacturing continuous fiber-reinforced thermoplastic resin sheets, with prepreg as an example. Prior Technology

[0002] Fiber-reinforced thermoplastic resins with thermoplastic resins as the matrix are known in the past. For example, intermediate materials for composite materials made of reinforcing fibers such as glass fibers and thermoplastic polymers are known (Patent Document 1), fiber-reinforced composite materials with thermoplastic resins reinforced by conductive fibers as the matrix are known (Patent Document 2), and carbon fiber reinforced plastic resins (CFRTP: Patent Documents 3-5) are known as composite materials combining carbon fibers and thermoplastic resins and are used in various fields. Carbon fiber reinforced thermoplastic resin is suitable for aerospace components, space components, automotive components, marine components, electronic components, and motion-related components.

[0003] Most of the fiber-reinforced thermoplastic resins such as CFRTP mentioned above can be used to manufacture continuous fiber-reinforced thermoplastic resin sheets, such as general prepregs. Continuous fiber-reinforced thermoplastic resin sheets manufactured from these resins are widely used as materials for products for the aforementioned purposes. [Previous Technical Documents] [Patent Literature]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 4-85337 [Patent Document 2] Japanese Patent Application Publication No. 2005-225993 [Patent Document 3] International Publication No. 2018 / 216516 [Patent Document 4] International Publication No. 2018 / 216517 [Patent Document 5] International Publication No. 2018 / 216518 Summary of the Invention

[0005] [The problem solved by the invention]

[0006] The manufacturing process of traditional continuous fiber reinforced thermoplastic resin sheets was not necessarily efficient. That is, the manufacturing process of traditional continuous fiber reinforced thermoplastic resin sheets required relatively large equipment, and the manufacturing efficiency of the production line in the traditional method was not sufficiently improved. The main problem solved by this invention is to provide a manufacturing method that can be carried out with simple equipment, namely, to efficiently manufacture continuous fiber-reinforced thermoplastic resin sheets in a short time. [Methods for solving the problem]

[0007] The inventors, in order to solve the above-mentioned problems, conducted a detailed review and found that a method for producing fiber-reinforced thermoplastic resin sheets in which the solvent-containing intermediate material can be efficiently removed through a simple process can improve the manufacturing efficiency of fiber-reinforced thermoplastic resin sheets.

[0008] The present invention comprises the following. [1] A method for manufacturing a continuous fiber reinforced thermoplastic resin sheet, comprising: an impregnation step in which a thermoplastic resin having at least one of a polycarbonate resin and a polyaryl ester resin and a thermoplastic resin solution containing a halogenated organic solvent are impregnated in a continuous fiber; and a solvent removal step in which the halogenated organic solvent is removed from the continuous fiber impregnated with the aforementioned thermoplastic resin solution by irradiation with infrared rays; wherein the distance between the heater irradiating the aforementioned infrared rays in the aforementioned solvent removal step and the aforementioned continuous fiber is 400 mm or less, and the temperature of the heating element radiating the aforementioned infrared rays in the aforementioned heater is 260°C or more. [2] The aforementioned method for manufacturing continuous fiber reinforced thermoplastic resin sheets containing dichloromethane in a halogenated organic solvent as described in [1] above. [3] In the aforementioned solvent removal step, the distance between the aforementioned heater and the aforementioned continuous fiber is 100 mm or more and 410 mm or less, as described in the above [1] or [2] method for manufacturing continuous fiber reinforced thermoplastic resin sheets. [4] In the aforementioned solvent removal step, the temperature of the aforementioned heating element in the aforementioned heater is 300°C or higher and 400°C or lower, as described in any of the above [1] to [3] methods for manufacturing continuous fiber reinforced thermoplastic resin sheets. [5] In the aforementioned solvent removal step, the aforementioned heater is a method for manufacturing continuous fiber reinforced thermoplastic resin sheets as described in any of [1] to [4] above, which irradiates far-infrared rays containing wavelengths of 2 μm to 20 μm. [6] The method for manufacturing continuous fiber reinforced thermoplastic resin sheets as described in any of [1] to [5] above, wherein the concentration of the aforementioned thermoplastic resin in the aforementioned thermoplastic resin solution is 10 to 30% by mass. [7] In the aforementioned impregnation step, the speed at which the aforementioned thermoplastic resin solution is impregnated in the aforementioned continuous fiber is 0.3 m / min to 3.0 m / min, as described in any of [1] to [6] above, for the manufacture of continuous fiber reinforced thermoplastic resin sheets. [8] The method for manufacturing continuous fiber reinforced thermoplastic resin sheets described in any of [1] to [7] above, wherein the infrared irradiation time in the solvent removal step is 2 minutes to 15 minutes. [9] The aforementioned continuous fiber reinforced thermoplastic resin sheet contains 15 to 50% by mass of the aforementioned thermoplastic resin as described in any of [1] to [8] above.

[10] The manufacturing method of continuous fiber reinforced thermoplastic resin sheets described in any of [1] to [9] above, wherein the content of residual halogenated organic solvent in the aforementioned continuous fiber reinforced thermoplastic resin sheets is less than 1000 ppm by mass.

[0009]

[11] The aforementioned thermoplastic resin has a method for manufacturing a continuous fiber-reinforced thermoplastic resin sheet as described in any of [1] to

[10] above, which is a structural unit derived from a divalent phenol as shown in the following general formula (1). (in general formula (1), R1 to R4 each independently represent hydrogen, halogen, nitro, alkyl with 1 to 20 carbon atoms that may have substituents, alkoxy with 1 to 5 carbon atoms that may have substituents, aryl with 6 to 12 carbon atoms that may have substituents, aralkyl with 7 to 17 carbon atoms that may have substituents, or alkenyl with 2 to 15 carbon atoms that may have substituents; X is -O-, -S-, -SO-, -SO 2-, -CO-, or any of the divalent groups shown in equations (2) to (5) below. (In formula (2), R5 and R6 each independently represent hydrogen, halogen, alkyl with 1 to 20 carbon atoms that may have substituents, alkoxy with 1 to 5 carbon atoms that may have substituents, aryl with 6 to 12 carbon atoms that may have substituents, aralkyl with 7 to 17 carbon atoms that may have substituents, or alkenyl with 2 to 15 carbon atoms that may have substituents, or R5 and R6 bonded together to form a carbon ring with 3 to 20 carbon atoms or a heterocycle with 1 to 20 carbon atoms; c represents an integer from 0 to 20. (In formula (3), R7 and R8 each independently represent hydrogen, halogen, alkyl with 1 to 20 carbon atoms that may have substituents, alkoxy with 1 to 5 carbon atoms that may have substituents, aryl with 6 to 12 carbon atoms that may have substituents, aralkyl with 7 to 17 carbon atoms that may have substituents, or alkenyl with 2 to 15 carbon atoms that may have substituents, or R7 and R8 bonded together to form a carbon ring with 3 to 20 carbon atoms or a heterocycle with 1 to 20 carbon atoms). (In formula (4), R9 to R12 each independently represent hydrogen, halogen, alkyl with 1 to 20 carbon atoms that may have substituents, alkoxy with 1 to 5 carbon atoms that may have substituents, aryl with 6 to 12 carbon atoms that may have substituents, aralkyl with 7 to 17 carbon atoms that may have substituents, or alkenyl with 2 to 15 carbon atoms that may have substituents. The aforementioned substituents are each independently halogen, alkyl with 1 to 20 carbon atoms, or aryl with 6 to 12 carbon atoms. R9 and R10 and R11 and R12 can be bonded to each other to form a carbon ring with 3 to 20 carbon atoms or a heterocycle with 1 to 20 carbon atoms). (In formula (5), each of R13 to R22 independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and one of R13 to R22 is an alkyl group having 1 to 3 carbon atoms.)

[12] Further comprising a solution manufacturing step of dissolving the aforementioned thermoplastic resin in the aforementioned halogen-containing organic solvent to produce a thermoplastic resin solution, as described in any of [1] to

[11] above, a method for manufacturing continuous fiber reinforced thermoplastic resin sheets.

[13] After the aforementioned solvent removal step, the method for manufacturing continuous fiber reinforced thermoplastic resin sheets further includes a step of determining the content of residual halogenated organic solvents in the aforementioned continuous fiber reinforced thermoplastic resin sheets, as described in any of [1] to

[12] above.

[14] After the aforementioned solvent removal step, the method for manufacturing continuous fiber reinforced thermoplastic resin sheets further includes a comparison step of comparing the content of residual halogenated organic solvent in the aforementioned continuous fiber reinforced thermoplastic resin sheet with a predetermined threshold, as described in any of [1] to

[13] above.

[15] The aforementioned continuous fiber is any of the single-strand, unidirectional sheet, or fabric, as described in any of [1] to

[14] above, and is a method for manufacturing continuous fiber reinforced thermoplastic resin sheets.

[16] The aforementioned continuous fiber is any one of carbon fiber, glass fiber, or aramid fiber, as described in any of [1] to

[15] above, and is a method for manufacturing continuous fiber reinforced thermoplastic resin sheets.

[17] The aforementioned continuous fiber reinforced thermoplastic resin sheet is a prepreg and is manufactured by any of the continuous fiber reinforced thermoplastic resin sheets described in [1] to

[16] above. [Effects of the Invention]

[0010] According to the present invention, the intermediate material for fiber-reinforced thermoplastic resin sheets is a continuous fiber impregnated with a thermoplastic resin solution containing a specified organic solvent. The organic solvent is efficiently removed by infrared irradiation, thereby improving the manufacturing efficiency of fiber-reinforced thermoplastic resin sheets. Implementation

[0011] [Types of Invention Implementation]

[0012] The method for manufacturing continuous fiber reinforced thermoplastic resin sheets of the present invention comprises the following steps: an impregnation step in which a thermoplastic resin solution containing a predetermined thermoplastic resin and a halogenated organic solvent is impregnated into continuous fibers; and a solvent removal step in which the halogenated organic solvent is removed from the continuous fibers impregnated with the thermoplastic resin solution by irradiation with infrared light. In the solvent removal step, the distance between the heater irradiating with infrared light and the continuous fibers is adjusted to 400 mm or less, and the temperature of the infrared light irradiated by the heater is adjusted to 260°C or higher. By employing this continuous method for manufacturing fiber-reinforced thermoplastic resin sheets, the solvent can be efficiently removed from the intermediate material containing solvent in a simple step, thereby improving the manufacturing efficiency of fiber-reinforced thermoplastic resin sheets. In particular, according to the manufacturing method of this invention, the solvent removal step from the intermediate material, which is in the rate-determining step, can be efficiently achieved in a large-scale production line for fiber-reinforced thermoplastic resin sheets, thus improving the manufacturing efficiency of fiber-reinforced thermoplastic resin sheets on an industrial scale. The following is a detailed description of the manufacturing method of the continuous fiber reinforced thermoplastic resin sheet of the present invention.

[0013] <1. Continuous fiber reinforced thermoplastic resin sheets> The continuous fiber reinforced thermoplastic resin sheet manufactured by the method of the present invention comprises a thermoplastic resin and continuous fibers, and is a thermoplastic resin sheet reinforced by the continuous fibers. The thermoplastic resin comprises at least one of polycarbonate resin and polyarylate resin, which will be described in detail later. Furthermore, in the manufacturing process of continuous fiber reinforced thermoplastic resin sheets, as will be described in detail later, since there is an impregnation step in which a solution of thermoplastic resin dissolved in a halogen-containing organic solvent is impregnated in the continuous fibers, the continuous fiber reinforced thermoplastic resin sheets may contain a small amount of solvents such as halogen-containing organic solvents. Continuous fiber-reinforced thermoplastic resin sheets, such as prepregs.

[0014] 1-1. Thermoplastic resin At least one of the polycarbonate resin and polyaryl ester resin contained in the thermoplastic resin of the present invention has a structural unit derived from a divalent phenol as shown in the following general formula (1). For either the polycarbonate resin or the polyaryl ester resin, a single polymer, a copolymer, or a mixture of multiple single polymers or copolymers may also be used. Furthermore, as a thermoplastic resin, any one of polycarbonate resin only, a mixture of polycarbonate resins, polyaryl ester resin only, a mixture of polyaryl ester resins, or a mixture of polycarbonate resin and polyaryl ester resin may be used. (in general formula (1), R1 to R4 each independently represent hydrogen, halogen, nitro, alkyl with 1 to 20 carbon atoms that may have substituents, alkoxy with 1 to 5 carbon atoms that may have substituents, aryl with 6 to 12 carbon atoms that may have substituents, aralkyl with 7 to 17 carbon atoms that may have substituents, or alkenyl with 2 to 15 carbon atoms that may have substituents; X is -O-, -S-, -SO-, -SO2-, -CO-, or any of the divalent groups shown in equations (2) to (5) below. R1 to R4 are preferably hydrogen, an alkyl group having 1 to 10 carbon atoms that may have substituents, an alkoxy group having 1 to 3 carbon atoms that may have substituents, an aryl group having 6 to 10 carbon atoms that may have substituents, an aralkyl group having 7 to 12 carbon atoms that may have substituents, or an alkenyl group having 2 to 10 carbon atoms that may have substituents. More preferably, they are hydrogen, an alkyl group having 1 to 10 carbon atoms that may have substituents, an alkoxy group having 1 or 2 carbon atoms that may have substituents, an aryl group having 6 to 8 carbon atoms that may have substituents, an aralkyl group having 7 to 9 carbon atoms that may have substituents, or an alkenyl group having 2 to 6 carbon atoms that may have substituents. In formula (2), R5 and R6 each independently represent hydrogen, halogen, alkyl with 1 to 20 carbon atoms that may have substituents, alkoxy with 1 to 5 carbon atoms that may have substituents, aryl with 6 to 12 carbon atoms that may have substituents, aralkyl with 7 to 17 carbon atoms that may have substituents, or alkenyl with 2 to 15 carbon atoms that may have substituents, or R5 and R6 bonded together to form a carbon ring with 3 to 20 carbon atoms or a heterocycle with 1 to 20 carbon atoms. From the viewpoint of ease of obtaining raw materials, it is preferable that R5 represents an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 12 carbon atoms. From the viewpoint of ease of obtaining raw materials, it is preferable that R6 represents an alkyl group with 1 to 3 carbon atoms, or an aryl group with 6 to 12 carbon atoms. Furthermore, from the perspective of the ease of obtaining raw materials, it is preferable for R5 and R6 to be bonded together to form a carbon ring with 6 to 12 carbon atoms. In equation (2), c represents an integer from 0 to 20. From the perspective of the ease of obtaining raw materials, it is preferable to represent 1 or 2.

[0015] In the above formula (3), R7 and R8 each independently represent hydrogen, halogen, alkyl with 1 to 20 carbon atoms that may have substituents, alkoxy with 1 to 5 carbon atoms that may have substituents, aryl with 6 to 12 carbon atoms that may have substituents, aralkyl with 7 to 17 carbon atoms that may have substituents, or alkenyl with 2 to 15 carbon atoms that may have substituents, or R7 and R8 are bonded together to form a carbon ring with 3 to 20 carbon atoms or a heterocycle with 1 to 20 carbon atoms. From the perspective of the ease of obtaining raw materials, it is preferable that R 7 represents hydrogen or methyl. From the perspective of the ease of obtaining raw materials, it is preferable that R8 represents hydrogen or methyl. Furthermore, from the perspective of the ease of obtaining raw materials, it is preferable for R7 and R8 to be bonded together to form a carbon ring with 5 to 12 carbon atoms.

[0016] In the above formula (4), R9~R12 each independently represent hydrogen, halogen, alkyl with 1~20 carbons (preferably 1~9 carbons) that may have substituents, alkoxy with 1~5 carbons (preferably 1~3 carbons) that may have substituents, aryl with 6~12 carbons (preferably 6~8 carbons) that may have substituents, aralkyl with 7~17 carbons (preferably 7~12 carbons) that may have substituents, or alkenyl with 2~15 carbons (preferably 2~5 carbons) that may have substituents. Furthermore, R9 and R10, as well as R11 and R12, can bond with each other to form carbon rings with 3 to 20 carbon atoms or heterocycles with 1 to 20 carbon atoms.

[0017] In formulas (1) to (4) above, each substituent is independently a halogen, an alkyl group with 1 to 20 carbon atoms, or an aryl group with 6 to 12 carbon atoms. Furthermore, the number of carbon atoms mentioned above when substituents are present is the total number of carbon atoms containing the substituents.

[0018] In the above formula (5), each of R13 to R22 independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and at least one of R13 to R22 is an alkyl group having 1 to 3 carbon atoms. From the viewpoint of ease of obtaining raw materials, it is preferable that R 13 to R 22 each independently represent hydrogen or methyl.

[0019] Examples of divalent phenols of the general formula (1) above include 2,2-bis(4-hydroxyphenyl)propane [=bisphenol A], bis(4-hydroxyphenyl)-p-diisopropylbenzene, 4,4'-dihydroxydiphenyl, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3,5-diethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-diethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-diethylphenyl)propane, and 2,2-bis(4-hydroxy-3-ethylphenyl)propane. 2,2-bis(4-hydroxy-3-phenylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxyphenyl)pentane, 2,4'-dihydroxy-diphenylmethane, bis(4-hydroxy-3-methylphenyl)methane, bis(4-hydroxy-3-nitrophenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)ethane, 3,3-Bis(4-hydroxyphenyl)ethane, 1,1-Bis(4-hydroxyphenyl)cyclohexane [=Bisphenol Z], bis(4-hydroxyphenyl) sulfide, 2,4'-dihydroxydiphenyl sulfide, bis(4-hydroxyphenyl) sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-dihydroxy-2,5-diethoxydiphenyl ether, 1-phenyl-1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)ethane (4-Hydroxy-3-methylphenyl)cyclohexane, 1-phenyl-1,1-bis(4-hydroxy-3-methylphenyl)ethane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxy-3-methylphenyl)diphenylmethane, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, etc., preferably bis(4-hydroxyphenyl)alkanes, especially 2,2-bis(4-hydroxyphenyl)propane [bisphenol A]. These aromatic dihydroxy compounds can be used alone or in mixtures of two or more. Polycarbonate resins, for example, are polymerized by interfacial polycondensation of the above-mentioned divalent phenol and phosgene (chlorinated carbonyl), or polymerized by transesterification reaction of the above-mentioned divalent phenol and diphenyl carbonate. Furthermore, the polyarylate resin is a divalent phenol and a dicarboxylic acid, for example, generated by reacting with dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, tartaric acid, glutamic acid, o-phthalic acid, isophthalic acid, and terephthalic acid.

[0020] From the viewpoint of solution viscosity that allows for easy handling of the resin solution, the polycarbonate resin used in this invention preferably has an average molecular weight of 10,000 to 100,000, more preferably 14,000 to 60,000, and even more preferably 16,000 to 40,000.

[0021] Furthermore, from the viewpoint of the viscosity of the polyarylate resin used in this invention, the average molecular weight of the viscosity is preferably 10,000 to 100,000, more preferably 14,000 to 60,000, and even more preferably 16,000 to 40,000.

[0022] The thermoplastic resin may contain at least one component other than the aforementioned polycarbonate resin and polyarylate resin, provided that the effects of the invention can be achieved. Other resins, mold release agents, flame retardants, antioxidants, heat stabilizers, flame retardant additives, ultraviolet absorbers, colorants, anti-static agents, fluorescent whitening agents, anti-fogging agents, flow improvers, plasticizers, dispersants, antibacterial agents, and other additives may also be added.

[0023] Other resins include, for example, thermoplastic polyester resins such as polyethylene terephthalate resin (PET resin), polytrimethylene terephthalate (PTT resin), and polybutene terephthalate resin (PBT resin); styrene-based resins such as polystyrene resin (PS resin), high-impact polystyrene resin (HIPS resin), acrylonitrile-styrene copolymer (AS resin), and methyl methacrylate-styrene copolymer (MS resin); core / shell elastomers such as methyl methacrylate-acrylic rubber-styrene copolymer (MAS), and polyester elastomers; polyolefin resins such as cyclic olefin resin (COP resin) and cyclic olefin copolymer (COP) resin; polyamide resin (PA resin); polyimide resin (PI resin); polyetherimide resin (PEI resin); polyurethane resin (PU resin); polyphenylene ether resin (PPE resin); polyphenylene sulfide resin (PPS resin); polyurethane resin (PSU resin); polymethyl methacrylate resin (PMMA resin); and polycaprolactone, etc. The proportion of these components, namely, components other than the aforementioned polycarbonate resin and polyarylate resin, in 100% by mass of the thermoplastic resin is preferably 0-50% by mass, and more preferably 0-20% by mass. Furthermore, the total mass ratio of polycarbonate resin and polyarylate resin in 100% by mass of the thermoplastic resin is preferably 50-100% by mass, more preferably 70-100% by mass, and particularly preferably 80-100% by mass. The thermoplastic resin is preferably composed of only one of the polycarbonate resin and the polyarylate resin, or only both.

[0024] The proportion of thermoplastic resin in continuous fiber reinforced thermoplastic resin sheets is preferably 15-50% by mass, more preferably 20-45% by mass, even more preferably 25-40% by mass, and especially preferably 30-35% by mass, based on the total mass of the continuous fiber reinforced thermoplastic resin sheets. Thus, when the content of thermoplastic resin in the continuous fiber reinforced thermoplastic resin sheet is adjusted to an appropriate range, even with the solvent removal steps described in detail later, the amount of residual solvent that has not been removed can be easily suppressed, and the elasticity, strength and other properties of the continuous fiber reinforced thermoplastic resin sheet can also be kept at a good level.

[0025] 1-2. Continuous fibers Examples of continuous fibers used in this invention include carbon fiber, nylon or polyamide fibers such as aramid, organic fibers such as polyester fibers, and inorganic fibers such as glass fibers, with carbon fiber being preferred. As carbon fiber, it can be derived from polyacrylonitrile (PAN) fiber or pitch fiber, or it can be PAN-based carbon fiber made from PAN fiber, or it can be pitch-based hydrocarbon. The carbon content in carbon fiber is preferably 90% by mass or more, preferably 95% by mass or more, and practically 100% by mass is even better.

[0026] For continuous fibers, an average fiber length of 10mm or more is preferred, 30mm or more is better, and 50mm or more is even better. Furthermore, as forms of continuous fibers, examples include single fibers, unidirectional sheets, fabric sheets, and multiaxial laminates. As a continuous fiber, the number of single fibers contained in the fiber bundle (filament), the number of filaments contained in the filament bundle (silk bundle), or various other configurations can be used. In this invention, a wide variety of continuous fibers can be used.

[0027] The proportion of continuous fibers in continuous fiber reinforced thermoplastic resin sheets is based on the total mass of the continuous fiber reinforced thermoplastic resin sheets, with 50-85% by mass being preferred. From the viewpoint of the mechanical properties of continuous fiber reinforced thermoplastic resin, 55-80% by mass is preferred, 60-75% by mass is more preferred, and 65-70% by mass is especially preferred.

[0028] When taking the total mass of the continuous fiber reinforced thermoplastic resin sheet as a reference, the components other than continuous fiber and thermoplastic resin in the continuous fiber reinforced thermoplastic resin sheet are preferably 0-20% by mass, better 0-10% by mass, even better 0-5% by mass, and particularly good 0-2% by mass. Furthermore, when using the total mass of continuous fiber reinforced thermoplastic resin sheets as a basis, the ratio of the total mass of continuous fibers and thermoplastic resin is preferably 80-100% by mass, more preferably 90-100% by mass, even more preferably 95-100% by mass, and particularly preferably 98-100% by mass. Continuous fiber reinforced thermoplastic resin sheets are preferably substantially composed only of continuous fibers and thermoplastic resin.

[0029] 1-3. Residual organic solvents In the manufacturing process of continuous fiber reinforced thermoplastic resin sheets, as detailed later, an impregnation step is included, in which a solution of dissolved thermoplastic resin in a halogenated organic solvent is impregnated into the continuous fibers. Therefore, the continuous fiber reinforced thermoplastic resin sheets may contain a certain amount of solvents such as halogenated organic solvents. Thus, the percentage of residual halogenated organic solvents in the continuous fiber reinforced thermoplastic resin sheets, based on the total mass of the continuous fiber reinforced thermoplastic resin sheets, is preferably 1000 ppm or less, preferably 1000 ppm or less, more preferably 800 ppm or less, even better 500 ppm or less, particularly preferably 200 ppm or less, and particularly preferably 150 ppm or less, 100 ppm or less, or less than 100 ppm or less. According to the manufacturing method of the present invention, the content of residual halogenated organic solvents can be adjusted to the above-mentioned range even if the continuous fiber-reinforced thermoplastic resin sheet is produced immediately after the solvent removal step or immediately after manufacturing, without natural drying.

[0030] 1-4. Properties of Continuous Fiber Reinforced Thermoplastic Resin Sheets The thickness of the continuous fiber reinforced thermoplastic resin sheet of the present invention is not particularly limited, but is preferably 0.01mm to 1mm, more preferably 0.05mm to 0.5mm, and even more preferably 0.1mm to 0.3mm. The continuous fiber reinforced thermoplastic resin sheet of the present invention can be a single layer of sheet or a laminate formed by directly laminating multiple sheets. A laminate formed by laminating only multiple continuous fiber reinforced thermoplastic resin sheets is particularly preferred. Examples of steps in manufacturing a laminate by laminating the continuous fiber-reinforced thermoplastic resin sheet of the present invention include a pressing molding step.

[0031] <2. Method for manufacturing continuous fiber reinforced thermoplastic resin sheets> The manufacturing process of continuous fiber reinforced thermoplastic resin sheets includes an impregnation step of impregnating continuous fibers with a solution of dissolved thermoplastic resin in a halogenated organic solvent, and a solvent removal step of removing the halogenated organic solvent from the continuous fibers by infrared irradiation. Through this solvent removal step, the intermediate material of the continuous fiber reinforced thermoplastic resin sheet, the continuous fibers impregnated with the solvent-containing thermoplastic resin, can be efficiently dried.

[0032] 2-1. Preparation of thermoplastic resin solutions (solution manufacturing steps) The manufacturing method of continuous fiber reinforced thermoplastic resin sheets may also include a solution manufacturing step. The thermoplastic resin solution is preferably prepared by dissolving the aforementioned thermoplastic resin in a halogen-containing organic solvent. Although the thermoplastic resin may contain at least one of polycarbonate resin and polyarylate resin, the method of preparation of these resins is not particularly limited. For example, polycarbonate resins prepared by methods such as phosgene polymerization (interfacial polymerization) and melt transesterification can be used. For example, polycarbonate resin can be manufactured by interfacial polymerization under the following reaction conditions: In the presence of dichloromethane and an alkaline aqueous solution, typically maintaining the pH above 10, a mixture of reactants containing divalent phenol, monovalent phenol as a terminator, an antioxidant to prevent oxidation of the divalent phenol (if necessary), and phosgene or triphosgene as a carbonate bonding agent is added. A polymerization catalyst such as a tertiary amine or quaternary ammonium salt is then added, followed by interfacial polymerization. The resulting resin solution is purified to obtain a polycarbonate resin solution. The terminator can be added between the start of phosgenation and the start of the polymerization reaction; there is no particular limitation. Furthermore, the reaction temperature is 0–35°C, and the reaction time is several minutes to several hours.

[0033] When the concentration of thermoplastic resin in the thermoplastic resin solution is based on the total mass of the thermoplastic resin solution, it is preferably 10-30% by mass, more preferably 10-20% or 12-25% by mass, and particularly preferably 10-18% or 12-20% by mass. If the concentration of thermoplastic resins such as polycarbonate resin is within the above range, foaming during the drying of the solvent in the next step can be prevented, and poor impregnation caused by excessively high solution viscosity can also be prevented.

[0034] 2-2. Halogen-containing organic solvents As a halogenated organic solvent for forming a thermoplastic resin solution, various types can be used. For example, halogenated organic solvents with a total carbon number of 3 or less, preferably 2 or less, and even more preferably 1; halogenated organic solvents containing 3 or less halogen atoms per molecule, preferably 2 or less; and halogens containing any one of chlorine, fluorine, and iodine, preferably chlorine and fluorine. Preferred examples of halogenated organic solvents include dichloromethane, chloromethane, trichloromethane, trichloroethylene, and tetrachloroethylene, with dichloromethane being a preferred halogenated organic solvent.

[0035] Furthermore, solvents other than those that are considered to be compatible with halogenated organic solvents may be contained up to 0-20% by mass, 0-10% by mass, 0-5% by mass, or 0-2% by mass, when the total mass of the solvent is taken as the basis.

[0036] 2-3. Impregnation steps The impregnation step involves impregnating continuous fibers with a thermoplastic resin solution, such as a polycarbonate resin solution. The method for impregnating the thermoplastic resin solution in this step is not particularly limited; various methods can be used, such as impregnating the fibers in a tank containing the solution, passing the fibers through a tank containing the solution, or spraying the solution onto the fibers. Among these methods, impregnating the continuous fibers in a tank containing the solution is the simplest and allows for uniform solution adhesion, and is therefore preferred.

[0037] In the impregnation step, the impregnation speed of the thermoplastic resin solution into the continuous fiber is preferably 0.3 m / min to 3.0 m / min, more preferably 0.3 m / min to 2.0 m / min or 0.3 m / min to 1.5 m / min, even more preferably 0.4 m / min to 2.0 m / min, 0.4 m / min to 1.5 m / min or 0.4 m / min to 1.2 m / min, and particularly preferably 0.5 m / min to 1.5 m / min or 0.5 m / min to 1.0 m / min. When the impregnation step is carried out continuously for a relatively long time, for example, impregnating the continuous fiber with the thermoplastic resin solution at a speed of approximately 1.0 m / min is preferable.

[0038] 2-4. Solvent Removal Steps In the solvent removal step, an infrared irradiation device, such as an infrared-irradiating heater, is used to dry the continuous fibers containing a thermoplastic resin solution in the intermediate material of the continuous fiber-reinforced thermoplastic resin sheet. The distance between the heater and the continuous fibers being dried—that is, the distance between the infrared irradiation surface of the heater and the drying surface of the continuous fibers—is preferably 100 mm to 410 mm. The distance between the heater and the continuous fibers being dried is preferably 150 mm to 380 mm, more preferably 180 mm to 360 mm, and ideally 200 mm to 320 mm, for example, 220 mm to 300 mm.

[0039] In the solvent removal step, the temperature of the infrared-emitting heating element in the heater is above 260°C, preferably between 300°C and 400°C. The preferred temperature of the infrared-emitting heater is between 325°C and 375°C, approximately 350°C. Furthermore, in the solvent removal step, it is preferable to use a heater that irradiates far-infrared rays with a wavelength range of 2μm to 20μm, and more preferably, the heater can irradiate infrared rays with a wavelength range of 3μm to 15μm, and even more preferably, the heater can irradiate infrared rays with a wavelength range of 5μm to 12μm. In the solvent removal step, it is preferable to further use far-infrared light with an absorption peak wavelength of 2.0 μm to 6.0 μm, more preferably with an absorption peak wavelength of 2.5 μm to 5.5 μm, even more preferably with an absorption peak wavelength of 3.0 μm to 5.2 μm, and most preferably with an absorption peak wavelength of 3.5 μm to 5.0 μm or 4.0 μm to 4.9 μm. Furthermore, the absorption peak wavelength value is the value immediately after the infrared irradiation surface of the heater is irradiated, and the infrared wavelength can vary with the distance between the heater and the continuous fiber being dried. When irradiated with infrared light of the wavelength region or absorption peak wavelength of the above-mentioned distance range, the solvent removal efficiency can be improved.

[0040] In the solvent removal step, the infrared irradiation time is preferably 2 to 15 minutes. The infrared irradiation time is preferably 3 to 12 minutes, even better is 3 to 6 minutes or 4 to 10 minutes, and the best is 5 to 6 minutes.

[0041] In the solvent removal step, the area of ​​the infrared irradiated surface of the heater, relative to the area of ​​the dried surface of the continuous fibers, is preferably 10% or more, preferably 20% or more, and especially preferably 30% or more. This area ratio, i.e., the ratio of the area of ​​the infrared irradiated surface of the heater (area of ​​dried surface (m²) / area of ​​infrared irradiated surface (m²) × 100 (%)) to the area of ​​the dried surface of the continuous fibers, is more preferably 35% or more. The upper limit of the above area ratio is not particularly important; for example, it can be 80%, 70%, 60%, or 50%, etc. Furthermore, in the solvent removal step, a maximum energy density of 20-200 kW / m² is preferred, 30-150 kW / m² or 35-120 kW / m² is even better, and 45-120 kW / m² or 50-150 kW / m² is even more desirable. Alternatively, the maximum energy density of the heater can also be 40-100 kW / m² or 45-80 kW / m².

[0042] 2-5. Measurement Procedure In the method for manufacturing continuous fiber reinforced thermoplastic resin sheets, it is preferable to further include a determination step after the solvent removal step to measure the content of residual halogenated organic solvents in the continuous fiber reinforced thermoplastic resin sheets. As mentioned above, since it is better to have a lower content of residual halogenated organic solvents in continuous fiber reinforced thermoplastic resin sheets, the determination of whether the desired properties of continuous fiber reinforced thermoplastic resin sheets can be confirmed by the testing procedure.

[0043] 2-6. Comparison Steps In the method for manufacturing continuous fiber reinforced thermoplastic resin sheets, after the solvent removal step, it is preferable to have a comparative step that compares the content of residual halogenated organic solvents in the continuous fiber reinforced thermoplastic resin sheets with a predetermined threshold. As mentioned above, it is necessary to suppress the content of residual halogenated organic solvents in continuous fiber reinforced thermoplastic resin sheets. The established benchmark value is mainly the upper limit value (such as the above-mentioned 1000 ppm by mass) as the threshold. By comparing it with the actual content of residual halogenated organic solvents, it can be confirmed whether the desired properties of continuous fiber reinforced thermoplastic resin sheets can be manufactured.

[0044] The present invention will be specifically described below through embodiments, but the present invention is not limited thereto. [Example]

[0045] <Resin content by weight> The resin mass content in the carbon fiber reinforced resin prepreg obtained in the following examples and comparative examples will be calculated based on the fiber mass content obtained according to JIS K 7075. That is, the resin mass content is obtained by subtracting the fiber mass content (mass%) from 100 (%).

[0046] <Residual dichloromethane content (ppm)> The carbon fiber reinforced resin prepreg obtained in the examples and comparative examples described later was cut into 6.0 cm × 4.0 cm pieces. The dichloromethane portion of the sample was extracted by dissolving it in 20 mL of chloroform. After extraction, the sample was filtered using a 0.45 μm filter (RJF3245NH) to obtain a sample for gas chromatography. GC analysis was performed under the following conditions to obtain the absorption peak area at a retention time of 4.7 minutes, and the dichloromethane content was calculated using a standard curve. Measuring instrument: Gas chromatography (Shimadzu Corporation GC-2014) Solvent: Chloroform Sample vaporization chamber: 200℃, 252kPa Column temperature and time: 60℃ at the start of the measurement, 120℃ at the end of the measurement, and the measurement time is 10 minutes. Detector temperature: 320℃

[0047] <Manufacturing Example 1: Manufacturing Example of Polycarbonate Resin (PC-1)> To 40 kg of a 9% (w / w%) sodium hydroxide aqueous solution, 6.5 kg (28.47 mol) of bisphenol A (BPA) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., and 30 g of bisulfite as an antioxidant were added and dissolved. 17 kg of dichloromethane was added to the resulting solution, and while stirring, the solution temperature was maintained between 15°C and 25°C. 3.7 kg of phosgene was then introduced for 30 minutes. After the phosgene blowing is completed, add 3 kg of sodium hydroxide aqueous solution (pre-dissolved at 9% by mass), 16 kg of dichloromethane, and 167.7 g (1.12 mol) of p-tert-butylphenol to the 1 kg solution of dichloromethane. After vigorous stirring and emulsification, add 10 ml of triethylamine as a polymerization catalyst to the reaction solution and carry out the polymerization reaction for about 40 minutes. The resulting polymer solution was separated into an aqueous phase and an organic phase. The organic phase was neutralized with phosphoric acid and repeatedly washed with pure water until the pH of the washing solution became neutral. The resulting polymer solution was added dropwise to warm water maintained at 47°C, and the solvent was removed by evaporation to obtain a white powdery precipitate. The obtained precipitate was filtered and dried at 105°C for 24 hours to obtain polycarbonate resin (PC-1). The obtained polycarbonate resin (PC-1) was used in the following examples and comparative examples. The viscosity-average molecular weight of the obtained polycarbonate resin (PC-1) was determined to be 21,500.

[0048] <Manufacturing Example 2: Manufacturing Example of Polycarbonate Resin (PC-2)> To 36 kg of a 9 w / w% sodium hydroxide aqueous solution, 6.7 kg (23.10 mol) of 1,1-bis(4-hydroxyphenyl)-1-phenylethane (BPAP) manufactured by Honshu Chemical Industry Co., Ltd., and 40 g of bisulfite as an antioxidant were added and dissolved. To the resulting solution, 16 kg of dichloromethane was added, and while stirring, the solution temperature was maintained between 15°C and 25°C. Then, 3.2 kg of phosgene was introduced and the mixture was allowed to stand for 30 minutes. After the phosgene blowing is completed, add 13 kg of dichloromethane and 132.8 g (0.89 mol) of p-tert-butylphenol to a solution of 1 kg of dichloromethane. After vigorous stirring and emulsification, add 15 ml of triethylamine as a polymerization catalyst to the reaction solution and carry out the polymerization reaction for about 40 minutes. The resulting polymer solution was separated into an aqueous phase and an organic phase. The organic phase was neutralized with phosphoric acid and repeatedly washed with pure water until the pH of the washing solution became neutral. The resulting polymer solution was added dropwise to warm water maintained at 60°C, and the solvent was removed by evaporation to obtain a white powdery precipitate. The precipitate was filtered and dried at 120°C for 24 hours to obtain polycarbonate resin (PC-2). The obtained polycarbonate resin (PC-2) was used in the following examples and comparative examples. The viscosity-average molecular weight of the obtained polycarbonate resin (PC-2) was determined to be 21,000.

[0049] <Methods for determining viscosity-average molecular weight> The method for determining and calculating the viscosity-average molecular weight (Mv) is as follows. Measuring instrument: Ubbelohde capillary viscometer Solvent: dichloromethane Resin solution concentration: 0.5 g / dL Measurement temperature: 25℃ The determination was carried out under the above conditions, and the limiting viscosity [η] ppm / g at Hagins definite number 0.45 was obtained by the following formula (1). η=1.23×10 -4×Mv 0.83･･･(1)

[0050] <Example 1> 15 parts by weight of polycarbonate resin (PC-1) were dissolved in 85 parts by weight of dichloromethane to prepare a polycarbonate resin solution. A 2 / 2 woven carbon fiber fabric (Treka (registered trademark) Cross CO6347B, manufactured by Toray Co., Ltd.) was cut into 6.0cm × 16.0cm dimensions (thickness 0.22mm; weight 198g / m²) using continuous carbon fibers derived from polyacrylonitrile. The fabric was then impregnated with a polycarbonate resin solution using a dip-coating machine at a tensile speed of 0.6m / min. The prepreg intermediate material (prepreg substrate) of the impregnated carbon fiber fabric was dried for 5 minutes on both sides using a pair of face-to-face far-infrared heater panels (electric ceramic heater PLC (PLC-328), manufactured by Noritake Company Limited), to obtain a carbon fiber reinforced thermoplastic resin prepreg. The far-infrared heaters were surrounded by aluminum plates. The distance between the heater panels and the prepreg substrate, as well as the heater temperature, were as described in Table 1. A solvent removal step was performed. Furthermore, in the solvent removal step, four far-infrared heater panels are used. The infrared irradiation area of ​​each far-infrared heater panel is 0.0144 m² (12 cm × 12 cm). These four far-infrared heater panels are arranged side-by-side on the outer and inner sides of two pieces of prepreg intermediate material, roughly on the same surface, so that they face each other. The impregnated portion of the two pieces of prepreg intermediate material, i.e., the dried surface to be removed by solvent, is 0.0060 m² (10 cm × 6 cm). Therefore, the ratio of the area of ​​the far-infrared irradiation surface of the heater panel to the area of ​​the dried surface of the continuous fiber (area of ​​dried surface (m²) / area of ​​far-infrared irradiation surface (m²) × 100 (%)) is approximately 41.7%.

[0051] Furthermore, the electrical capacity of the far-infrared heater panel is 800W, and the area of ​​the infrared irradiation surface is 0.0144m² as mentioned above. Therefore, the maximum energy density is calculated to be 55.6kW / m² (0.8kW / 0.0144m²).

[0052] As described above, in Example 1, a pair of far-infrared heater panels are used, and the prepreg substrate is placed at the middle of the pair of far-infrared heater panels. Therefore, the value in the column "Distance between heater and prepreg substrate" in Table 1 represents the distance between the surface (drying surface) of the prepreg substrate and either of the far-infrared heater panels, and thus the values ​​in Table 2 are the same as in Table 1. Furthermore, the value in the "Infrared Heater Temperature" column of Table 1 indicates the temperature of the heating element that emits infrared rays in the heater, and the values ​​in Table 2 are the same as those in Table 1. As shown in the table below, the infrared heater temperature in the embodiment is 300~400°C, and the absorption peak wavelength of the irradiated far-infrared light, calculated using Wien's displacement law of the far-infrared heater panel used, is approximately 4.96~4.21 μm. In contrast, the infrared heater temperature in the comparative example is 250~300°C, and the absorption peak wavelength of the irradiated far-infrared light is approximately 5.43~4.96 μm.

[0053] The obtained carbon fiber reinforced resin prepreg (continuous fiber reinforced thermoplastic resin sheet) had a resin content of 33% by mass, and the dichloromethane content in the prepreg was 100 ppm by mass after the determination of dichloromethane content in the prepreg. The evaluation results are shown in Table 1.

[0054] <Examples 2-14, Examples 1-1-1-7, Comparative Examples 1-4> Except for any changes in the type of polycarbonate resin, the distance between the heater panel and the prepreg substrate, and the heater temperature as described in Table 1, carbon fiber reinforced resin prepregs were produced and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1 or Table 2. The results of Examples 1-1 to 1-7, which are included in Examples 1 and 2, are collectively shown in Table 2.

[0055] <Comparative Example 5> Similar to Example 1, impregnation with a polycarbonate resin solution was performed. After impregnation, the material was dried for 5 minutes in a multi-stage hot air dryer to obtain carbon fiber reinforced resin prepreg. The evaluation results are shown in Table 1.

[0056] As can be seen from the results of the examples and comparative examples shown in Table 1, when infrared light is irradiated, it can be confirmed that the solvent is efficiently removed from the intermediate material (prepreg intermediate material, prepreg substrate) containing halogenated organic solvents (see Examples and Comparative Examples 5). Furthermore, in embodiments where conditions in the solvent removal step, such as the distance between the infrared irradiation heater and the dried surface of the continuous fiber, the infrared heater temperature, and the drying time, are adjusted, it has been confirmed that even by performing the continuous fiber drying more efficiently, and by adjusting the conditions in the impregnation step prior to the solvent removal step, such as the resin solution concentration or impregnation rate, the drying of the continuous fiber can be further improved (see Tables 1 and 2).

[0057] Furthermore, not only in the examples using bisphenol-based polycarbonate resin (PC-1), but also in the examples using bisphenol AP-based polycarbonate resin (PC-2), which is generally not easy to dry, it was confirmed that the solvent could be removed efficiently.

Claims

1. A method for manufacturing a continuous fiber reinforced thermoplastic resin sheet, comprising: an impregnation step of impregnating a thermoplastic resin containing at least one of polycarbonate resin and polyaryl ester resin, and a thermoplastic resin solution containing a halogenated organic solvent into a continuous fiber; and a solvent removal step of removing the halogenated organic solvent from the continuous fiber impregnated with the aforementioned thermoplastic resin solution by irradiation with infrared rays; wherein the distance between the heater irradiating the aforementioned infrared rays in the aforementioned solvent removal step and the aforementioned continuous fiber is 400 mm or less, and the temperature of the heating element radiating the aforementioned infrared rays in the aforementioned heater is 260°C or higher.

2. The method for manufacturing continuous fiber reinforced thermoplastic resin sheets as claimed in claim 1, wherein the aforementioned halogenated organic solvent contains dichloromethane.

3. The method for manufacturing continuous fiber reinforced thermoplastic resin sheets as claimed in claim 1 or 2, wherein in the aforementioned solvent removal step, the distance between the aforementioned heater and the aforementioned continuous fiber is 100 mm or more and 410 mm or less.

4. A method for manufacturing continuous fiber reinforced thermoplastic resin sheets as claimed in claim 1 or 2, wherein in the aforementioned solvent removal step, the temperature of the aforementioned heating element in the aforementioned heater is 300°C or higher and 400°C or lower.

5. A method for manufacturing continuous fiber reinforced thermoplastic resin sheets as claimed in claim 1 or 2, wherein in the aforementioned solvent removal step, the aforementioned heater is a far-infrared irradiator containing a wavelength region of 2μm to 20μm.

6. A method for manufacturing continuous fiber reinforced thermoplastic resin sheets as claimed in claim 1 or 2, wherein the concentration of the aforementioned thermoplastic resin in the aforementioned thermoplastic resin solution is 10 to 30% by mass.

7. A method for manufacturing a continuous fiber reinforced thermoplastic resin sheet as claimed in claim 1 or 2, wherein in the aforementioned impregnation step, the speed at which the aforementioned thermoplastic resin solution impregnates the aforementioned continuous fiber is 0.3 m / min to 3.0 m / min.

8. A method for manufacturing continuous fiber reinforced thermoplastic resin sheets as claimed in claim 1 or 2, wherein the irradiation time of the aforementioned infrared radiation in the solvent removal step is 2 to 15 minutes.

9. A method for manufacturing a continuous fiber reinforced thermoplastic resin sheet as claimed in claim 1 or 2, wherein the proportion of the aforementioned thermoplastic resin in the continuous fiber reinforced thermoplastic resin sheet is 15 to 50 by mass.

10. A method for manufacturing continuous fiber reinforced thermoplastic resin sheets as claimed in claim 1 or 2, wherein the content of residual halogenated organic solvents in the aforementioned continuous fiber reinforced thermoplastic resin sheets is less than 1000 ppm by mass.

11. A method for manufacturing a continuous fiber-reinforced thermoplastic resin sheet as claimed in claim 1 or 2, wherein the aforementioned thermoplastic resin has a structural unit derived from a divalent phenol as shown in the following general formula (1); (in general formula (1), R1 to R4 each independently represent hydrogen, halogen, nitro, alkyl with 1 to 20 carbon atoms that may have substituents, alkoxy with 1 to 5 carbon atoms that may have substituents, aryl with 6 to 12 carbon atoms that may have substituents, aralkyl with 7 to 17 carbon atoms that may have substituents, or alkenyl with 2 to 15 carbon atoms that may have substituents; X is -O-, -S-, -SO-, -SO2-, -CO- or any divalent group shown in formulas (2) to (5) below) (In formula (2), R5 and R6 each independently represent hydrogen, halogen, alkyl with 1 to 20 carbon atoms that may have substituents, alkoxy with 1 to 5 carbon atoms that may have substituents, aryl with 6 to 12 carbon atoms that may have substituents, aralkyl with 7 to 17 carbon atoms that may have substituents, or alkenyl with 2 to 15 carbon atoms that may have substituents, or R5 and R6 bonded together to form a carbon ring with 3 to 20 carbon atoms or a heterocycle with 1 to 20 carbon atoms; c represents an integer from 0 to 20) (In formula (3), R7 and R8 each independently represent hydrogen, halogen, alkyl with 1 to 20 carbon atoms that may have substituents, alkoxy with 1 to 5 carbon atoms that may have substituents, aryl with 6 to 12 carbon atoms that may have substituents, aralkyl with 7 to 17 carbon atoms that may have substituents, or alkenyl with 2 to 15 carbon atoms that may have substituents, or R7 and R8 bonded together to form a carbon ring with 3 to 20 carbon atoms or a heterocycle with 1 to 20 carbon atoms) (In formula (4), R9 to R12 each independently represent hydrogen, halogen, alkyl with 1 to 20 carbon atoms that may have substituents, alkoxy with 1 to 5 carbon atoms that may have substituents, aryl with 6 to 12 carbon atoms that may have substituents, aralkyl with 7 to 17 carbon atoms that may have substituents, or alkenyl with 2 to 15 carbon atoms that may have substituents, Each of the aforementioned substituents is independently a halogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms. R9 and R10 and R11 and R12 are bonded to each other to form a carbon ring having 3 to 20 carbon atoms or a heterocycle having 1 to 20 carbon atoms. (In formula (5), R13 to R22 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and at least one of R13 to R22 is an alkyl group having 1 to 3 carbon atoms.) 12. A method for manufacturing continuous fiber reinforced thermoplastic resin sheets as claimed in claim 1 or 2, further comprising a solution manufacturing step of dissolving the aforementioned thermoplastic resin in the aforementioned halogen-containing organic solvent to produce a thermoplastic resin solution.

13. A method for manufacturing a continuous fiber reinforced thermoplastic resin sheet as claimed in claim 1 or 2, wherein after the aforementioned solvent removal step, a step is further included to determine the content of residual halogenated organic solvents in the aforementioned continuous fiber reinforced thermoplastic resin sheet.

14. A method for manufacturing a continuous fiber reinforced thermoplastic resin sheet as claimed in claim 1 or 2, wherein after the aforementioned solvent removal step, a comparison step is further provided to compare the content of residual halogenated organic solvent in the aforementioned continuous fiber reinforced thermoplastic resin sheet with a predetermined threshold.

15. A method for manufacturing a continuous fiber reinforced thermoplastic resin sheet as claimed in claim 1 or 2, wherein the aforementioned continuous fiber is any one of a single-strand, a unidirectional sheet, or a fabric.

16. A method for manufacturing a continuous fiber reinforced thermoplastic resin sheet as claimed in claim 1 or 2, wherein the aforementioned continuous fiber is any one of carbon fiber, glass fiber, or aramid fiber.

17. A method for manufacturing a continuous fiber reinforced thermoplastic resin sheet as claimed in claim 1 or 2, wherein the aforementioned continuous fiber reinforced thermoplastic resin sheet is a prepreg.