Polycarbonate resin prepreg and laminate comprising same

Abstract

According to the present invention, provided is a polycarbonate resin prepreg which contains a polycarbonate resin (A) and a continuous carbon fiber-reinforced material (B), and which contains 1-30 mass% of a polyalkylene glycol (C) relative to the polycarbonate resin (A). A preferred embodiment of the present invention contains 20-80 vol% of the continuous carbon fiber-reinforced material (B), and also contains 80-20 vol% of the polycarbonate resin (A) and the polyalkylene glycol (C) in total.

Description

Technical Field

[0001] The present invention relates to a polycarbonate resin prepreg applicable to aircraft parts, spacecraft parts, automotive parts, marine parts, electronic device parts, and sports-related parts, and a laminate including the prepreg. Background Art

[0002] Compared with metals, carbon fibers, glass fibers, and aramid fibers not only have a low specific gravity but also excellent elastic modulus and strength. Therefore, composite materials composed of these fibers and various matrix resins can be used in many fields such as aircraft parts, spacecraft parts, automotive parts, marine parts, civil engineering and construction parts, and sporting goods. In particular, carbon fiber reinforced resin (CFRP), which is a composite material composed of carbon fibers and epoxy resin or unsaturated polyester resin, is widely used.

[0003] Existing carbon fiber reinforced resins based on thermosetting resins have the disadvantage that thermosetting requires a large amount of time. However, in recent years, carbon fiber reinforced thermoplastic resins (hereinafter sometimes referred to as "CFRTP") based on thermoplastic resins are expected to be composite materials capable of realizing high-cycle molding, and research and development are being carried out on them.

[0004] Although short fiber reinforced thermoplastic resins capable of forming complex shapes have been put into practical use, since the fiber length of the reinforcing fibers is short, there is a problem that the elastic modulus is significantly reduced compared with light metals. Therefore, there is a strong demand for continuous fiber reinforced thermoplastic resins. In addition, when forming a laminate using such a resin, excellent adhesion is required.

[0005] Although a sheet made of a carbon fiber reinforced thermoplastic resin with high moldability (large thermal deformation at low temperatures) is obtained in Patent Document 1, there is still room for further improvement in its adhesion.

[0006] Prior Art Documents

[0007] Patent Documents

[0008] Patent Document 1: WO2018 / 216516 Summary of the Invention

[0009] Problems to be Solved by the Invention

[0010] An object of the present invention is to provide a polycarbonate resin prepreg with good adhesion and a laminate including the prepreg.

[0011] Technical Means for Solving the Problems

[0012] In order to solve the above problems, the inventors of the present invention conducted in-depth research and found that by using a specified amount of polyalkylene glycol when forming a prepreg containing a polycarbonate resin and a continuous carbon fiber reinforcing material, a polycarbonate resin prepreg with good adhesion and a laminate containing the prepreg can be obtained, thereby completing the present invention. That is, the above problems can be solved by the following present invention.

[0013] <1> A polycarbonate resin prepreg containing a polycarbonate resin (A) and a continuous carbon fiber reinforcing material (B), wherein 1 to 30% by mass of polyalkylene glycol (C) is contained relative to the above polycarbonate resin (A).

[0014] <2> The prepreg according to <1> above, wherein 20 to 80% by volume of the above continuous carbon fiber reinforcing material (B) is contained, and the above polycarbonate resin (A) and the above polyalkylene glycol (C) are contained in a total of 80 to 20% by volume.

[0015] <3> The prepreg according to <1> or <2> above, wherein the glass transition temperature of the above polycarbonate resin (A) is 110 to 170 °C.

[0016] <4> The prepreg according to any one of <1> to <3> above, wherein the viscosity-average molecular weight of the above polycarbonate resin (A) is 10,000 to 100,000.

[0017] <5> The prepreg according to any one of <1> to <4> above, wherein the above polycarbonate resin (A) has a terminal structure derived from a monohydric phenol represented by the following general formula (1).

[0018]

[0019] (In general formula (1), R 1 represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms, and R 2 to R 5 each independently represent hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 12 carbon atoms which may have a substituent.)

[0020] <6> The prepreg according to any one of <1> to <5> above, wherein the above polycarbonate resin (A) has a structural unit derived from a dihydric phenol represented by the following general formula (2).

[0021]

[0022] (In general formula (2), R 6 to R 9Each independently represents hydrogen, a halogen, a nitro group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, an aralkyl group having 7 to 17 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms which may have a substituent.

[0023] X is —O—, —S—, —SO—, —SO 2 —, —CO—, or a divalent group represented by any one of the following formulas (3) to (6).)

[0024]

[0025] (In formula (3), R 10 and R 11 each independently represents hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, an aralkyl group having 7 to 17 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms which may have a substituent, or R 10 and R 11 are bonded to each other to form a carbocyclic ring having 3 to 20 carbon atoms or a heterocyclic ring having 1 to 20 carbon atoms, and c represents an integer of 0 to 20;

[0026] In formula (4), R 12 and R 13 each independently represents hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, an aralkyl group having 7 to 17 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms which may have a substituent, or R 12 and R 13 are bonded to each other to form a carbocyclic ring having 3 to 20 carbon atoms or a heterocyclic ring having 1 to 20 carbon atoms;

[0027] In formula (5), R 14 to R 17 each independently represents hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, an aralkyl group having 7 to 17 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms which may have a substituent, or R 14 and R 15 , and R 16 and R 17 are respectively bonded to each other to form a carbocyclic ring having 3 to 20 carbon atoms or a heterocyclic ring having 1 to 20 carbon atoms;

[0028] In formula (6), R 18 ~R 27 each independently represents hydrogen or an alkyl group having 1 to 3 carbon atoms, and at least one of R 18 ~R 27 is an alkyl group having 1 to 3 carbon atoms.)

[0029] <7> The prepreg according to any one of <1> to <6> above, wherein the polyalkylene glycol (C) is polypropylene glycol.

[0030] <8> The prepreg according to <7> above, wherein the polypropylene glycol is trihydroxy polyoxypropylene ether.

[0031] <9> A laminate comprising the prepreg according to any one of <1> to <8> above.

[0032] <10> The laminate according to <9> above, comprising a laminate composed only of the prepreg and a composite laminate of the prepreg and a polycarbonate sheet.

[0033] <11> A method for manufacturing a molded article, comprising a step of shaping the laminate according to <9> or <10> above, and the shaping temperature for the shaping is 150 to 185 °C.

[0034] <12> A molded article obtained by shaping the laminate according to <9> or <10> above.

[0035] Effects of the Invention

[0036] According to the present invention, a polycarbonate resin prepreg having good adhesion and a laminate containing the prepreg can be provided. Detailed Embodiments

[0037] Hereinafter, the present invention will be described in detail with reference to production examples and examples, etc. However, the present invention is not limited to the exemplified production examples and examples, etc., and can be implemented by any method as long as it does not deviate significantly from the content of the present invention.

[0038] One embodiment of the present invention is a polycarbonate resin prepreg containing a polycarbonate resin (A) and a continuous carbon fiber reinforcing material (B), wherein 1 to 30% by mass of a polyalkylene glycol (C) is contained relative to the polycarbonate resin (A).

[0039] <Polycarbonate Resin (A)>

[0040] The polycarbonate resin (A) used in the present invention is not particularly limited and can be any type of polycarbonate resin.

[0041] In the present invention, the polycarbonate resin (A) preferably has a terminal structure derived from a monohydric phenol represented by the following general formula (1). Herein, in the present specification, examples of the substituent when "may have a substituent" include a halogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

[0042]

[0043] In the general formula (1), R 1 represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms. As the upper limit value of the number of carbon atoms of R 1 , it is preferably 35, more preferably 22, and particularly preferably 18. As the lower limit value of the number of carbon atoms of R 1 , it is preferably 9, more preferably 12.

[0044] In the general formula (1), R 2 to R 5 each independently represent hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms that may have a substituent, or an aryl group having 6 to 12 carbon atoms that may have a substituent. It is preferably hydrogen, a halogen, an alkyl group having 1 to 9 carbon atoms that may have a substituent, or an aryl group having 6 to 8 carbon atoms that may have a substituent, and particularly preferably hydrogen.

[0045] The monohydric phenol represented by the above general formula (1) can be introduced into the polycarbonate resin of the present invention by being used as a terminal terminator in the polymerization reaction. Examples of the monohydric phenol represented by the above general formula (1) include cetyl-4-hydroxybenzoate (CEPB), 2-ethylhexyl p-hydroxybenzoate (EHPB), cetyl p-hydroxybenzoate, 2-hexyldecyl p-hydroxybenzoate, etc., but are not limited to these.

[0046] For example, when the monohydric phenol represented by the above general formula (1) having an alkyl group with 16 carbon atoms as R 1 is used as a terminal terminator, the resulting polycarbonate resin has excellent glass transition temperature, melt fluidity, moldability, and sag resistance, and the solvent solubility of the monohydric phenol is excellent when manufacturing the polycarbonate resin. It is particularly preferably used as the terminal terminator for the polycarbonate resin of the present invention.

[0047] On the other hand, when the number of carbon atoms of R 1 in the general formula (1) is too large, there is a tendency for the organic solvent solubility of the monohydric phenol to decrease, and the productivity when manufacturing the polycarbonate resin may be reduced. For example, when the number of carbon atoms of R 1 is 36 or less, the productivity is high and the economy is good when manufacturing the polycarbonate resin. When R 1When the number of carbon atoms is 22 or less, the solubility of the monohydric phenol in an organic solvent is particularly excellent, and the productivity can be greatly improved and the economy can also be improved when producing a polycarbonate resin. On the other hand, when the number of carbon atoms in R in the general formula (1) 1 is too small, the glass transition temperature of the polycarbonate resin cannot reach a sufficiently low value, and the thermoformability may be reduced.

[0048] According to the properties required for the material, within the scope not departing from the gist of the present invention, it is allowed to use the main skeleton and the end terminator in combination with other structures, or to mix them with other polycarbonate resins and other transparent resins. It is preferred that 80 mol% or more of all the end terminators used have the structure shown in the above formula (1), more preferably 90 mol% or more of all the end terminators used have the structure shown in the above formula (1), and particularly preferably all the end terminators used have the structure shown in the above formula (1).

[0049] Examples of other end terminators that can be used in combination include phenol, p-cresol, o-cresol, 2,4-xylenol, p-tert-butylphenol, o-allylphenol, p-allylphenol, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-propylphenol, p-cumylphenol, p-phenylphenol, o-phenylphenol, p-trifluoromethylphenol, p-nonylphenol, p-dodecylphenol, eugenol, amylphenol, hexylphenol, heptylphenol, octylphenol, nonylphenol, decylphenol, dodecylphenol, myristylphenol, palmitylphenol, stearylphenol, behenylphenol and other alkylphenols, and methyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, propyl p-hydroxybenzoate, butyl p-hydroxybenzoate, pentyl p-hydroxybenzoate, hexyl p-hydroxybenzoate, heptyl p-hydroxybenzoate and other alkyl p-hydroxybenzoates. In addition, two or more of the above monohydric phenols can be used in combination.

[0050] In a preferred embodiment of the present invention, the polycarbonate resin used in the present invention preferably has a structural unit derived from a dihydric phenol represented by the following general formula (2).

[0051]

[0052] In the general formula (2), R 6 ~R 9 each independently represents hydrogen, a halogen, a nitro group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, an aralkyl group having 7 to 17 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms which may have a substituent, and preferably represents hydrogen or a methyl group.

[0053] In the general formula (2), X represents -O-, -S-, -SO-, -SO 2 -, -CO- or a divalent group represented by any one of the following formulas (3) to (6).

[0054]

[0055] In formula (3), R 10 and R 11 each independently represent hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, an aralkyl group having 7 to 17 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms which may have a substituent, or R 10 and R 11 are bonded to each other to form a carbocyclic ring having 3 to 20 carbon atoms or a heterocyclic ring having 1 to 20 carbon atoms.

[0056] From the viewpoint of the availability of raw materials, it is preferable that R 10 represents an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 12 carbon atoms.

[0057] From the viewpoint of the availability of raw materials, it is preferable that R 11 represents an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 12 carbon atoms.

[0058] Moreover, from the viewpoint of the availability of raw materials, it is preferable that R 10 and R 11 are bonded to each other to form a carbocyclic ring having 6 to 12 carbon atoms.

[0059] c represents an integer of 0 to 20, and from the viewpoint of the availability of raw materials, it is preferably 1 or 2.

[0060] In formula (4), R 12 and R 13 each independently represent hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, an aralkyl group having 7 to 17 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms which may have a substituent, or R 12 and R 13 are bonded to each other to form a carbocyclic ring having 3 to 20 carbon atoms or a heterocyclic ring having 1 to 20 carbon atoms.

[0061] From the viewpoint of the availability of raw materials, it is preferable that R 12 represents hydrogen or methyl.

[0062] From the viewpoint of the availability of raw materials, it is preferable that R 13 represents hydrogen or methyl.

[0063] Moreover, from the viewpoint of the availability of raw materials, it is preferable that R 12 and R 13Bond with each other to form a carbon ring having 5 to 12 carbon atoms.

[0064] In formula (5), R 14 ~R 17 Each independently represents: hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, preferably 1 to 9 carbon atoms, which may have a substituent, an alkoxy group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, which may have a substituent, an aryl group having 6 to 12 carbon atoms, preferably 6 to 8 carbon atoms, which may have a substituent, an aralkyl group having 7 to 17 carbon atoms, preferably 7 to 12 carbon atoms, or an alkenyl group having 2 to 15 carbon atoms, preferably 2 to 5 carbon atoms, which may have a substituent. And, R 14 and R 15 , and R 16 and R 17 may bond with each other to form a carbon ring having 3 to 20 carbon atoms or a heterocyclic ring having 1 to 20 carbon atoms.

[0065] In formula (6), R 18 ~R 27 Each independently represents hydrogen or an alkyl group having 1 to 3 carbon atoms, and at least one of R 18 ~R 27 is an alkyl group having 1 to 3 carbon atoms.

[0066] From the perspective of raw material availability, it is preferred that R 18 ~R 27 each independently represents hydrogen or methyl.

[0067] From the perspective of the moldability of the obtained prepreg, the polycarbonate resin in the present invention preferably contains 20 to 100% by mass, more preferably 40 to 100% by mass, and particularly preferably 60 to 100% by mass of the structural unit derived from the diphenol represented by the above general formula (2). When the above polycarbonate resin is a copolymer, within the range not impairing the effects of the present invention, it may also contain structural units other than the structural unit derived from the diphenol represented by the above general formula (2).

[0068] From the viewpoints of raw material availability and raw material purity, the diphenols represented by the above general formula (2) preferably used as the polycarbonate resin in the present invention include, for example, 2,2-bis(4-hydroxyphenyl)propane [= bisphenol A], bis(4-hydroxyphenyl)diisopropylbenzene, 4,4'-dihydroxybiphenyl, 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-ethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-diphenylphenyl)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-hydroxyphenyl)pentane, 2,4'-dihydroxydiphenylmethane, bis(4-hydroxy-3-methylphenyl)methane, bis(4-hydroxy-3-nitrophenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxy-3-methylphenyl)ethane, 3,3-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)cyclohexane [= bisphenol Z], bis(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenylsulfone, 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-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. Among them, bis(4-hydroxyphenyl)alkanes are preferred, and 2,2-bis(4-hydroxyphenyl)propane [bisphenol A] is particularly preferred. These aromatic dihydroxy compounds can be used alone or in combination of two or more.

[0069] From the viewpoint of solution viscosity that is easy to handle in the form of a resin solution, the viscosity-average molecular weight of the polycarbonate resin used in the present invention is preferably 10,000 to 100,000, more preferably 14,000 to 60,000, and further preferably 16,000 to 40,000.

[0070] From the viewpoint of improving the formability, the glass transition temperature of the polycarbonate resin used in the present invention is preferably 110 to 170 °C, more preferably 110 to 150 °C, further preferably 110 to 140 °C, and particularly preferably 110 to 130 °C.

[0071] <Continuous carbon fiber reinforced material (B)>

[0072] The continuous carbon fiber reinforced material (B) used in the present invention is a continuous fiber. The average fiber length of the continuous fiber is preferably 10 mm or more, more preferably 30 mm or more. In addition, examples of the form of the continuous fiber include unidirectional sheets, woven sheets, multi-axial laminated sheets, etc.

[0073] Regarding carbon fiber, the number of single fibers included in a fiber bundle (filament), the number of filaments included in a tow, and its constitution are diverse. In the present invention, the number of single fibers, the number of filaments, and its constitution are not limited, and various carbon fibers can be used.

[0074] The proportion of the continuous carbon fiber reinforced material (B) in the polycarbonate resin prepreg of the present invention is preferably 20 to 80% by volume, more preferably 40 to 80% by volume, and further preferably 50 to 70% by volume from the perspective of the mechanical properties of the prepreg.

[0075] <Polyalkylene glycol (C)>

[0076] The polyalkylene glycol (C) used in the present invention is not particularly limited and can be any type of polyalkylene glycol.

[0077] The polycarbonate resin prepreg of the present invention is characterized by containing 1 to 30% by mass of polyalkylene glycol (C) relative to the polycarbonate resin (A). It is preferably to contain 2 to 20% by mass of polyalkylene glycol (C) relative to the polycarbonate resin (A), and more preferably to contain 3 to 15% by mass of polyalkylene glycol (C) relative to the polycarbonate resin (A).

[0078] When the content of the polyalkylene glycol (C) is less than 1% by mass, the adhesiveness of the laminate decreases, and it is difficult to achieve precise forming; when it exceeds 30% by mass, the mechanical strength of the prepreg or laminate decreases, and plastic deformation is likely to occur.

[0079] The polyalkylene glycol (C) used in the present invention is preferably a 2-4 functional polyalkylene glycol as shown below, and more preferably a 3-functional one from the perspective of easy forming and excellent adhesiveness. Each of n1 to n4 shown below is independently preferably an integer of 1 to 100, more preferably an integer of 1 to 50, and particularly preferably an integer of 1 to 30. R shown below is preferably propylene, butylene, ethylene, methylene, etc., and more preferably propylene.

[0080] Polyalkylene glycol

[0081]

[0082] In the present invention, among the above-mentioned polyalkylene glycols, polypropylene glycols having 2 to 4 functional groups as shown below are more preferred.

[0083] Polypropylene glycol

[0084]

[0085] In the present invention, among the above-mentioned polypropylene glycols, trihydroxy polyoxypropylene ethers having 3 functional groups as shown below are further preferred.

[0086] Trihydroxy polyoxypropylene ether

[0087]

[0088] The polyalkylene glycol (C) used in the present invention preferably has an OH group content of 20 to 700 mg-KOH / g, more preferably 30 to 500 mg-KOH / g.

[0089] The number average molecular weight (Mn) of the polyalkylene glycol (C) used in the present invention is preferably 200 to 5000, more preferably 500 to 4000.

[0090] <Prepreg made of polycarbonate resin>

[0091] In the prepreg made of polycarbonate resin of the present invention, the proportion of the continuous carbon fiber reinforcing material (B) to the total of the polycarbonate resin (A) and the polyalkylene glycol (C) is preferably such that the continuous carbon fiber reinforcing material (B) is 20 to 80% by volume, and the total of the polycarbonate resin (A) and the polyalkylene glycol (C) is 80 to 20% by volume. From the perspective of the mechanical strength of the prepreg, it is more preferably that the continuous carbon fiber reinforcing material (B) is 40 to 80% by volume, and the total of the polycarbonate resin (A) and the polyalkylene glycol (C) is 60 to 20% by volume; further preferably, the continuous carbon fiber reinforcing material (B) is 50 to 70% by volume, and the total of the polycarbonate resin (A) and the polyalkylene glycol (C) is 50 to 30% by volume.

[0092] When the proportion of the continuous carbon fiber reinforcing material (B) is less than this range, the mechanical properties of the prepreg will be equivalent to or even lower than those of light metals; when the proportion of the continuous carbon fiber reinforcing material (B) is greater than this range, the resin amount decreases, and the matrix resin cannot play a role in bundling the carbon fibers, which may lead to a reduction in mechanical strength.

[0093] Within the scope not detrimental to the effects of the present invention, the prepreg made of polycarbonate resin of the present invention may also contain components other than the polycarbonate resin (A), continuous carbon fiber reinforcing material (B), and polyalkylene glycol (C). Examples of these components include other resins and various additives such as mold release agents, flame retardants, antioxidants, heat stabilizers, flame retardant aids, ultraviolet absorbers, colorants, antistatic agents, fluorescent brighteners, antifogging agents, fluidity improvers, plasticizers, dispersants, antibacterial agents, etc.

[0094] Examples of the above-mentioned other resins include: thermoplastic polyester resins such as polyarylate resin, polyethylene terephthalate resin (PET resin), polytrimethylene terephthalate (PTT resin), polybutylene terephthalate resin (PBT resin); styrene-based resins such as polystyrene resin (PS resin), high-impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), methyl methacrylate-styrene copolymer (MS resin); elastomers such as core / shell type elastomers like methyl methacrylate-acrylic rubber-styrene copolymer (MAS), polyester-based elastomers; polyolefin resins such as cyclic olefin resin (COP resin), cyclic olefin (COP) copolymer 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); polysulfone resin (PSU resin); polymethyl methacrylate resin (PMMA resin); polycaprolactone, etc.

[0095] The thickness of the prepreg made of polycarbonate resin of the present invention is not particularly limited, and is preferably 0.01 mm to 1 mm, more preferably 0.05 mm to 0.5 mm.

[0096] As a method for manufacturing a laminate by laminating the prepreg made of polycarbonate resin of the present invention, a compression molding method, etc. can be cited.

[0097] A preferred embodiment of the present invention relates to a laminate, which includes a laminate composed only of the above-mentioned prepreg and a composite laminate of the above-mentioned prepreg and a polycarbonate sheet.

[0098] <Manufacturing method of prepreg made of polycarbonate resin>

[0099] The manufacturing method of the prepreg made of polycarbonate resin of the present invention preferably includes: a step of manufacturing a resin solution in which the polycarbonate resin (A) is dissolved in dichloromethane by an interfacial polymerization method; a step of adding the polyalkylene glycol (C) to the resin solution to manufacture a resin solution containing glycol; and a step of impregnating the continuous carbon fiber reinforcing material (B) with the resin solution containing glycol.

[0100] In a preferred embodiment of the present invention, after the impregnation is completed, it is dried in a constant temperature chamber at 25 °C for about 5 to 15 minutes, and then dried in a hot air dryer at 100 to 150 °C for about 0.5 to 4 hours.

[0101] In the manufacturing method of the present invention, the concentration of the polycarbonate resin in the above resin solution is preferably 10 to 30% by mass, more preferably 12 to 25% by mass. When the concentration of the polycarbonate resin is less than 10% by mass, foaming sometimes occurs during drying in subsequent processes; when it is higher than 30% by mass, the solution viscosity significantly increases, and sometimes the treatment in the impregnation process becomes difficult.

[0102] (Manufacturing process of resin solution)

[0103] When reacting by the interfacial polymerization method, in the presence of dichloromethane and an alkaline aqueous solution, the pH value is usually maintained above 10, and a reaction raw material containing a dihydric phenol, a monohydric phenol as a terminal terminator, an antioxidant for preventing oxidation of the dihydric phenol as needed, and phosgene or triphosgene as a carbonate bond binder is mixed, and then a polymerization catalyst such as a tertiary amine or a quaternary ammonium salt is added for interfacial polymerization, and the obtained resin solution is refined, whereby a polycarbonate resin solution can be obtained. The addition of the terminal terminator is not particularly limited and can be carried out during the period from the phosgenation to the start of the polymerization reaction. In addition, the reaction temperature is 0 to 35 °C, and the reaction time is several minutes to several hours.

[0104] (Manufacturing process of resin solution containing diol)

[0105] This process is a process of manufacturing a resin solution containing a polyalkylene glycol (C) by adding the polyalkylene glycol (C) to the resin solution obtained as described above. The method of mixing the polyalkylene glycol (C) is not particularly limited, and any mixing method can be adopted.

[0106] In the present invention, it is mixed in such a manner that the polyalkylene glycol (C) is contained in an amount of 1 to 30% by mass based on the polycarbonate resin (A). It is preferably mixed in such a manner that the polyalkylene glycol (C) is contained in an amount of 2 to 20% by mass based on the polycarbonate resin (A), and more preferably mixed in such a manner that the polyalkylene glycol (C) is contained in an amount of 3 to 15% by mass based on the polycarbonate resin (A).

[0107] (Impregnation process)

[0108] This step is to impregnate the resin solution containing diol in the present invention into the continuous carbon fiber reinforced material (B). The impregnation method is not particularly limited, and various methods can be adopted, such as a method of immersing the fiber in a tank filled with the solution, a method of passing the fiber through a tank filled with solution spray, and a method of spraying the solution onto the fiber. Among them, the method of immersing the fiber in a tank filled with the solution is the simplest and most likely to achieve uniform attachment of the solution, so it is preferred.

[0109] (Drying step)

[0110] This step is to dry the continuous carbon fiber reinforced material impregnated with the resin solution containing diol. For example, drying treatment without external heating or with less external heating such as air drying is carried out, and then external heating drying is carried out. Air drying can be carried out by simply placing it at room temperature or by blowing air to accelerate drying.

[0111] (Manufacturing method of the molded body)

[0112] The manufacturing method of the molded body of the present invention includes a step of shaping the laminate containing the above-mentioned polycarbonate resin prepreg. Among them, shaping means heating the laminate containing the polycarbonate resin prepreg to a temperature above the glass transition temperature of the polycarbonate resin by using a heater or the like, pressing it using a mold such as a metal mold, and then cooling it to a temperature below the glass transition temperature of the polycarbonate resin to form it, which is a method of deforming and forming it.

[0113] The molding temperature for the above-mentioned shaping is preferably 150 - 185 °C, more preferably 160 - 180 °C.

[0114] Examples

[0115] The present invention will be specifically described below through examples and comparative examples. However, as long as the effects of the present invention can be achieved, the specific implementation manners can be appropriately changed.

[0116] (Viscosity-average molecular weight (Mv))

[0117] Measuring instrument: Ubbelohde capillary viscometer

[0118] Solvent: Dichloromethane

[0119] Resin solution concentration: 0.5 g / dl

[0120] Measuring temperature: 25 °C

[0121] Measurement is carried out under the above conditions, and the intrinsic viscosity [η] dl / g is obtained with a Huggins constant of 0.45 and calculated by the following formula.

[0122] η = 1.23×10 -4 ×Mv 0.83

[0123] <Carbon fiber content (Vf)>

[0124] The carbon fiber content is measured according to JIS K 7075.

[0125] <Glass transition temperature (Tg)>

[0126] It is measured using a differential scanning calorimeter (DSC).

[0127] Measuring instrument: Differential scanning calorimeter (DSC) (DSC-50 manufactured by Shimadzu Corporation)

[0128] Heating rate: 10 °C / min

[0129] Gas flow environment: Nitrogen 20 ml / min

[0130] Sample pretreatment: Heat and melt at 300 °C

[0131] <Peel test (adhesion test)>

[0132] After removing the film sandwiched between the laminates, hold both ends of the laminate with hands and peel the bonded surface of the laminate. Confirm the force felt during peeling and the gloss of the peeled surface at this time.

[0133] For products with good adhesion, force can be felt during peeling, and the peeled surface loses its gloss when visually observed, and it is evaluated as "〇"; while products with poor adhesion, no force is felt during peeling, and the peeled surface still has gloss when visually observed, are evaluated as "×".

[0134] (Synthesis example of polycarbonate resin)

[0135] In 650 ml of a 9 mass / mass% aqueous sodium hydroxide solution, 100 g (0.44 mol) of bisphenol A (BPA) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. and 0.3 g of sodium dithionite as an antioxidant were added and dissolved. 385 ml of dichloromethane was added thereto, and while stirring, the solution temperature was maintained in the range of 15 °C to 25 °C, and 60.0 g of phosgene was blown in over 40 minutes.

[0136] After the phosgene blowing was completed, 100 ml of a 9 mass / mass% aqueous sodium hydroxide solution and a solution obtained by dissolving 9.92 g (0.027 mol) of cetyl-4-hydroxybenzoate (CEPB) manufactured by Ueno Pharmaceutical Co., Ltd. in 315 ml of dichloromethane were added. After vigorously stirring to emulsify, 0.5 ml of triethylamine as a polymerization catalyst was added and polymerization was carried out for about 40 minutes. The polymerization solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washed repeatedly with pure water until the pH value of the washing solution reached neutral. The concentration of the refined polycarbonate resin solution was 14 mass%.

[0137] The viscosity-average molecular weight was measured using the obtained polycarbonate resin solution, and the viscosity-average molecular weight was 18,000. The Tg of the polycarbonate resin obtained by drying the obtained polycarbonate resin solution and removing the solvent was 116°C.

[0138] (Example 1)

[0139] 18.2 g of polypropylene glycol (Sannix GP-3000 manufactured by Sanyo Chemical Industries, OH group: 56 mg-KOH / g, number-average molecular weight (Mn) of about 3000) represented by the following structural formula was mixed into 2.6 kg of the polycarbonate resin solution obtained in the above synthesis example. That is, a resin solution containing diol was produced, containing 364 g of polycarbonate resin and 18.2 g of polypropylene glycol (5 mass% with respect to the polycarbonate resin).

[0140] A continuous carbon fiber reinforced material (TORAYCA Cloth CO6347B manufactured by Toray Industries, Inc.) was cut into a size of 10 cm × 10 cm. In an impregnation tank, the resin solution containing diol was impregnated into the continuous carbon fiber reinforced material. After the impregnation was completed, it was dried in a constant temperature room at 25°C for 10 minutes, and then dried in a hot air dryer at 120°C for 2 hours to obtain a polycarbonate resin prepreg (carbon fiber reinforced polycarbonate prepreg, CFRTP).

[0141] The obtained prepreg was made into 15 cm × 20 cm and two pieces were overlapped, and pressed with a hot press at 175°C and 0.5 MPa for 15 minutes, and then at 175°C and 2 MPa for 5 minutes. After cooling, the laminate was taken out.

[0142] The physical properties of the obtained prepreg and laminate are shown in Table 1.

[0143] GP-3000 trifunctional polyol

[0144]

[0145] (Example 2)

[0146] Except for using a diol-containing resin solution containing 364 g of polycarbonate resin and 36.4 g of polypropylene glycol (10% by mass relative to the polycarbonate resin), the same operations as in Example 1 were carried out to obtain a prepreg and a laminate. The physical properties of the obtained prepreg and laminate are shown in Table 1.

[0147] (Comparative Example 1)

[0148] Except for not using polypropylene glycol, the same operations as in Example 1 were carried out to obtain a prepreg and a laminate. The physical properties of the obtained prepreg and laminate are shown in Table 1.

[0149] [Table 1]

[0150]

Claims

1. A prepreg made of a polycarbonate resin, characterized in that, it contains polycarbonate resin A and a continuous carbon fiber reinforcing material B, and contains 1 to 30% by mass of a polyalkylene glycol C relative to the polycarbonate resin A.

2. The prepreg according to claim 1, characterized in that, it contains 20 to 80% by volume of the continuous carbon fiber reinforcing material B, and contains a total of 80 to 20% by volume of the polycarbonate resin A and the polyalkylene glycol C.

3. The prepreg according to claim 1 or 2, characterized in that, the glass transition temperature of the polycarbonate resin A is 110 to 170 °C.

4. The prepreg according to any one of claims 1 to 3, characterized in that, the viscosity-average molecular weight of the polycarbonate resin A is 10,000 to 100,000.

5. The prepreg according to any one of claims 1 to 4, characterized in that, the polycarbonate resin A has a terminal structure derived from a monohydric phenol represented by the following general formula (1), In general formula (1), R 1 represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms, and R 2 to R 5 each independently represent hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 12 carbon atoms which may have a substituent.

6. The prepreg according to any one of claims 1 to 5, characterized in that, the polycarbonate resin A has a structural unit derived from a dihydric phenol represented by the following general formula (2), In general formula (2), R 6 ~R 9 each independently represents hydrogen, halogen, nitro, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, an aralkyl group having 7 to 17 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms which may have a substituent, X is -O-, -S-, -SO-, -SO 2 -, -CO- or a divalent group represented by any one of the following formulas (3) to (6); In formula (3), R 10 and R 11 each independently represent hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, an aralkyl group having 7 to 17 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms which may have a substituent, or R 10 and R 11 are bonded to each other to form a carbocyclic ring having 3 to 20 carbon atoms or a heterocyclic ring having 1 to 20 carbon atoms, and c represents an integer of 0 to 20; In formula (4), R 12 and R 13 each independently represent hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, an aralkyl group having 7 to 17 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms which may have a substituent, or R 12 and R 13 are bonded to each other to form a carbocyclic ring having 3 to 20 carbon atoms or a heterocyclic ring having 1 to 20 carbon atoms; In formula (5), R 14 ~R 17 each independently represents hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, an aralkyl group having 7 to 17 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms which may have a substituent, or R 14 and R 15 , and R 16 and R 17 are bonded to each other to form a carbocyclic ring having 3 to 20 carbon atoms or a heterocyclic ring having 1 to 20 carbon atoms; In formula (6), R 18 ~R 27 each independently represents hydrogen or an alkyl group having 1 to 3 carbon atoms, and at least one of R 18 ~R 27 is an alkyl group having 1 to 3 carbon atoms.

7. The prepreg according to any one of claims 1 to 6, characterized in that, the polyalkylene glycol C is polypropylene glycol.

8. The prepreg according to claim 7, characterized in that, the polypropylene glycol is trihydroxy polyoxypropylene ether.

9. A laminate, characterized in that, it comprises the prepreg according to any one of claims 1 to 8.

10. The laminate according to claim 9, characterized in that, it includes a laminate composed only of the prepreg and a composite laminate of the prepreg and a polycarbonate sheet.

11. A method for manufacturing a molded article, characterized in that, it includes a step of shaping the laminate according to claim 9 or 10, and the shaping temperature for the shaping is 150 to 185 °C.

12. A molded article, characterized in that, it is obtained by shaping the laminate according to claim 9 or 10.

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