Laminate, molded article including same, and method for manufacturing laminate

Abstract

The present invention provides a laminate or the like in which carbon fibers are not likely to protrude from the surface or are not likely to be scattered to the outside even when a strong impact is applied thereto.　The present invention specifically provides a laminate in which a first non-reinforced polycarbonate resin layer that contains a first polycarbonate resin, a carbon fiber-reinforced resin layer, and a second non-reinforced polycarbonate resin layer that contains a second polycarbonate resin are arranged in this order, wherein: the carbon fiber-reinforced resin layer contains carbon fibers and a third polycarbonate resin; the third polycarbonate resin contains a polycarbonate that is obtained by reacting a bisphenol, a carbonate binder, and a monohydric phenol chain terminator represented by formula (5); and the ratio of the thickness of the first non-reinforced polycarbonate resin layer to the thickness of the carbon fiber-reinforced resin layer ((thickness of first non-reinforced polycarbonate resin layer) / (thickness of carbon fiber-reinforced resin layer)) is 0.05 to 4.

Description

Laminate, molded article including same, and method for manufacturing laminate

[0001] The present invention relates to a laminate, a molded article including the same, and a method for producing the laminate.

[0002] Carbon fiber, glass fiber, and aramid fiber have low specific gravity compared to metals, yet are excellent in elastic modulus and strength, and therefore composite materials combining these with various matrix resins are used in many fields, such as mobility components, spacecraft components, ship components, civil engineering and construction materials, sporting goods, etc. In particular, carbon fiber reinforced plastic (CFRP), which is a composite material combining carbon fiber with a thermosetting resin such as an epoxy resin, is widely used.

[0003] However, carbon fiber reinforced plastic (CFRP) that is combined with thermosetting resin has drawbacks such as requiring a long time for thermosetting and the fact that the curing reaction is irreversible, making it impossible to change the shape once molded. Therefore, in recent years, so-called carbon fiber reinforced thermoplastic plastic (CFRTP), which combines carbon fiber and thermoplastic resin, has been studied.

[0004] For example, Patent Document 1 describes an invention relating to a fiber-reinforced composite molding comprising a reinforcing fiber and a thermoplastic resin, wherein the thermoplastic resin is a resin composition containing 70 to 99 parts by weight of (A) a polycarbonate resin (component A) and 30 to 1 part by weight of (B) a phosphazene (component B) containing 98.5 mol % or more of a phosphazene cyclic trimer, and the content of the reinforcing fiber is 15 to 400 parts by weight per 100 parts by weight of the resin component comprising components A and B of the thermoplastic resin.

[0005] Patent Document 1 describes that a fiber-reinforced composite molded product having excellent mechanical properties such as bending strength and shear strength, long-term durability thereof, flame retardancy, and appearance can be obtained by laminating a predetermined thermoplastic resin sheet and a reinforcing fiber sheet. Patent Document 1 also describes that carbon fiber is preferable as the reinforcing fiber from the viewpoint of finally obtaining a high-strength molded product.

[0006] Japanese Patent Application Laid-Open No. 2023-128655

[0007] Carbon fiber reinforced thermoplastic resin (CFRTP) has excellent mechanical properties, as described in Patent Document 1. However, when a molded article using such CFRTP is subjected to a strong impact, for example, the carbon fibers may break, and the broken carbon fibers may protrude from the surface of the molded article or fly off to the outside.

[0008] Generally, thermoplastic resins have excellent impact resistance, and thus molded articles containing CFRTP also have excellent impact resistance. However, when used in applications such as aircraft, bicycles, drones, and helmets, the molded articles may be subjected to strong impacts, and therefore, safer components in which carbon fibers are less likely to protrude from the surface or scatter to the outside are required.

[0009] Therefore, the present invention provides a laminate or the like in which carbon fibers are less likely to protrude from the surface or fly off to the outside even when a strong impact is applied.

[0010] The present invention is, for example, as follows.

[0011] [1] A laminate comprising: a first unreinforced polycarbonate resin layer containing a first polycarbonate resin; a carbon fiber reinforced resin layer; and a second unreinforced polycarbonate resin layer containing a second polycarbonate resin, arranged in this order; wherein the carbon fiber reinforced resin layer contains carbon fiber and a third polycarbonate resin; and the third polycarbonate resin is a polycarbonate resin containing a bisphenol, a carbonate binder, and a carboxylic acid represented by the following formula (5): (In the above formula, R ３ is an alkyl group having 1 to 30 carbon atoms or an alkenyl group having 8 to 30 carbon atoms, R ４are each independently a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and c is 0 to 4), wherein the thickness of the first unreinforced polycarbonate resin layer relative to the thickness of the carbon fiber reinforced resin layer (thickness of the first unreinforced polycarbonate resin layer / thickness of the carbon fiber reinforced resin layer) is 0.05 to 4. [2] The laminate according to [1] above, wherein the thickness of the second unreinforced polycarbonate resin layer relative to the thickness of the carbon fiber reinforced resin layer (thickness of the second unreinforced polycarbonate resin layer / thickness of the carbon fiber reinforced resin layer) is 0.05 to 4. [3] The laminate according to [1] above or [2], wherein the thickness of the carbon fiber reinforced resin layer is 0.1 to 3 mm, and the thickness of the first unreinforced polycarbonate resin layer is 0.05 to 1 mm. [4] The laminate according to any one of [1] to [3] above, wherein the thickness of the second unreinforced polycarbonate resin layer is 0.05 to 1 mm. [5] The laminate according to any one of [1] to [4] above, wherein the bisphenol includes bisphenol A. [6] The monohydric phenol end-terminator represented by formula (5) is a monohydric phenol end-terminator represented by formula (5-1): (In the above formula, R ３

[0013] The laminate according to any one of [1] to [5] above, comprising a monohydric phenol end-terminator represented by the formula (5): (wherein R represents an alkyl group having 1 to 30 carbon atoms or an alkenyl group having 8 to 30 carbon atoms). [7] The laminate according to [6] above, wherein the monohydric phenol end-terminator represented by formula (5) comprises cetyl parahydroxybenzoate. [8] The laminate according to any one of [1] to [7] above, which is in the form of a torus. [9] A molded product comprising the laminate according to any one of [1] to [8] above.

[10] A method for producing the laminate according to any one of [1] to [8] above, comprising a press-molding step of arranging a first unreinforced polycarbonate resin layer, a carbon fiber-reinforced resin layer, and a second unreinforced polycarbonate resin layer in this order and integrating them by press-molding, wherein the press-molding temperature is 160°C or higher and lower than 200°C.

[0012] According to the present invention, a laminate or the like is provided in which carbon fibers are unlikely to protrude from the surface or fly off to the outside even when a strong impact is applied.

[0013] 1A shows the results of Example 2, FIG. 1B shows the results of Example 3, FIG. 1C shows the results of Example 4, and FIG. 1D shows the results of Comparative Example 1. 1B shows the results of Example 3, FIG. 1C shows the results of Example 4, and FIG. 1D shows the results of Comparative Example 1. 1C shows the results of Example 2, FIG. 1B shows the results of Example 3, FIG. 1C shows the results of Example 4, and FIG. 1D shows the results of Comparative Example 1. 1D ...

[0014] Hereinafter, embodiments of the present invention will be described in detail.

[0015] 1. Laminate The laminate according to the present invention comprises a first unreinforced polycarbonate resin layer containing a first polycarbonate resin, a carbon fiber reinforced resin layer, and a second unreinforced polycarbonate resin layer containing a second polycarbonate resin, arranged in this order. The carbon fiber reinforced resin layer contains carbon fiber and a third polycarbonate resin. The third polycarbonate resin contains a polycarbonate obtained by reacting a bisphenol, a carbonate binder, and a monohydric phenol end-terminator represented by the following formula (5). The ratio of the thickness of the first unreinforced polycarbonate resin layer to the thickness of the carbon fiber reinforced resin layer (thickness of the first unreinforced polycarbonate resin layer / thickness of the carbon fiber reinforced resin layer) is 0.05 to 4.

[0016] In the laminate according to the present invention, the carbon fiber reinforced resin layer contains a polycarbonate (third polycarbonate resin) having excellent impact resistance as a thermoplastic resin. The third polycarbonate resin has a terminal structure derived from a predetermined terminal terminator. The laminate also includes a first unreinforced polycarbonate resin layer and a second unreinforced polycarbonate resin layer, each having excellent impact resistance, on both sides of the carbon fiber reinforced resin layer. The thickness ratio of the carbon fiber reinforced resin layer to the first unreinforced polycarbonate resin layer is adjusted to a predetermined range.

[0017] When a strong impact is applied to the laminate of the present invention, the first unreinforced polycarbonate resin layer, the carbon fiber reinforced resin layer, and the second unreinforced polycarbonate resin layer all contain polycarbonate resins with excellent impact resistance, so the impact can be absorbed. Therefore, when the laminate breaks, it tends to undergo ductile fracture accompanied by plastic deformation, which can lead to bending failure. As a result, the carbon fibers are less likely to protrude from the surface or scatter to the outside. In addition, in conventional carbon fiber reinforced plastics (CFRP) using thermosetting resins such as epoxy resins, the thermosetting resin is harder and more brittle than thermoplastic resins, and tends to break suddenly upon impact. When a CFRP laminate using a thermosetting resin breaks, it tends to undergo brittle fracture without plastic deformation, which can lead to breakage. As a result, the carbon fibers are more likely to protrude from the surface or scatter to the outside. Furthermore, even if the carbon fibers contained in the carbon fiber reinforced resin layer are broken or shortened by impact, the carbon fiber reinforced resin layer has a first unreinforced polycarbonate resin layer and a second unreinforced polycarbonate resin layer on both sides. Therefore, even if carbon fibers protrude from the carbon fiber reinforced resin layer, the carbon fibers can be contained within the first unreinforced polycarbonate resin layer and the second unreinforced polycarbonate resin layer. Furthermore, by having the thickness ratio of the carbon fiber reinforced resin layer and the first unreinforced polycarbonate resin layer within a predetermined range, the impact resistance of the laminate is improved, and the carbon fibers are more likely to remain within the first unreinforced polycarbonate resin layer. As a result, the laminate of the present invention is less likely to have carbon fibers protrude from the surface or scatter to the outside even when subjected to a strong impact, making it safer. Therefore, the laminate of the present invention can be suitably applied to applications where strong impacts may be applied, in addition to conventional applications.

[0018] <First Unreinforced Polycarbonate Resin Layer> The first unreinforced polycarbonate resin layer contains a first polycarbonate resin. The first unreinforced polycarbonate resin layer may further contain other resins, additives, and the like. In this specification, the term "unreinforced polycarbonate resin layer" refers to a polycarbonate resin layer that is substantially free of reinforcing fibers such as carbon fiber, glass fiber, and aramid fiber. In this context, "substantially free of reinforcing fibers" means that the reinforcing fiber content is less than 5% by mass, preferably 1% by mass or less, and more preferably 0% by mass (no reinforcing fibers) relative to the total mass of the polycarbonate resin layer. Furthermore, the term "polycarbonate resin layer" means that the polycarbonate resin content is 50% by mass or more relative to the total mass of the resin layer.

[0019] [First Polycarbonate Resin] The first polycarbonate resin is not particularly limited as long as it contains a carbonate bond, i.e., a -[O-R-OCO]- unit (where R may contain an aliphatic group, an aromatic group, or both an aliphatic group and an aromatic group, and may have a linear or branched structure) in the molecular main chain.

[0020] In one embodiment, the first polycarbonate resin is preferably a polycarbonate obtained by reacting a bisphenol, a carbonate binder, and a terminal capping agent.

[0021] (Bisphenol) The bisphenol is not particularly limited, but is represented by the following formula (1).

[0022] In the above formula, R １ are each independently selected from the group consisting of a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and a substituted or unsubstituted aralkyl group having 7 to 17 carbon atoms; each a is independently an integer of 0 to 4; and X is -O-, -S-, -SO-, -SO ２ -, -CO-, and the following formulas (2) to (4): (In the above formula, R ２ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 17 carbon atoms, or two R ２ together with the same carbon atom or an adjacent carbon atom to which it is bonded, form a substituted or unsubstituted carbocyclic group having 5 to 20 carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 12 atoms, and b is an integer of 1 to 20. In this specification, the "halogen atom" is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and more preferably a fluorine atom or a chlorine atom.

[0023] The alkyl group having 1 to 20 carbon atoms is not particularly limited, but examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group.

[0024] The alkoxy group having 1 to 5 carbon atoms is not particularly limited, but examples thereof include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, and a pentyloxy group.

[0025] The aryl group having 6 to 12 carbon atoms is not particularly limited, but examples thereof include a phenyl group, a tolyl group, a xylyl group, a trimethylphenyl group, a tetramethylphenyl group, an ethylphenyl group, an ethylmethylphenyl group, a diethylphenyl group, a propylphenyl group, an isopropylphenyl group, an isopropylmethylphenyl group, a benzyl group, a phenethyl group, a phenylpropyl group, a naphthyl group, and a biphenyl group.

[0026] The aralkyl group having 7 to 17 carbon atoms is not particularly limited, but examples thereof include a benzyl group, a 1-methylbenzyl group, a 1,1-dimethylbenzyl group, a 1-ethylbenzyl group, a 1-ethyl-1-methylbenzyl group, a phenethyl group, a 1-methylphenethyl group, a 2-methylphenethyl group, and a 1-ethylphenethyl group.

[0027] The carbocyclic group having 5 to 20 carbon atoms is not particularly limited, and examples thereof include cycloalkylidene groups such as a cyclopentylidene group, a cyclohexylidene group, a cycloheptylidene group, a cyclooctylidene group, a methylcyclopentylidene group, an ethylcyclopentylidene group, a methylcyclohexylidene group, an ethylcyclohexylidene group, and a 3,3,5-trimethylcyclohexylidene group; and arylalkylidene groups such as a benzylidene group, a phenethylidene group, and a phenylpropylidene group.

[0028] The heterocyclic group having 5 to 12 elements is not particularly limited, and examples thereof include a furanyl group, a benzofuranyl group, an isobenzofuranyl group, a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a triazolyl group, a pyridyl group, a pyrazyl group, a pyrimidyl group, a pyridazyl group, a pyrrolidyl group, an indolyl group, an isoindolyl group, an indazolyl group, a quinolyl group, an isoquinolyl group, a naphthyridyl group, a quinoxalyl group, a quinazolyl group, a pteridyl group, a phenanthridyl group, and an acridinyl group. , a pyrimidinyl group, a phenanthrolinyl group, a phenazinyl group, a thiophenyl group, a thiopyranyl group, a benzothiophenyl group, a benzothiopyranyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, a furazanyl group, an oxadiazolyl group, a dithiazolyl group, a benzoxazolyl group, a benzisoxazolyl group, a benzothiazolyl group, a benzisothiazolyl group, a benzimidazolyl group, a benzotriazolyl group, and the like.

[0029] Here, when an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 5 carbon atoms has a substituent, examples of the substituent include a halogen atom, a cyano group, a nitro group, an alkoxy group having 1 to 5 carbon atoms, an alkyloxycarbonyl group having 2 to 5 carbon atoms, and an alkylcarbonyloxy group having 2 to 5 carbon atoms. Furthermore, when an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 17 carbon atoms, a carbocyclic group having 5 to 20 carbon atoms, or a heterocyclic group having 5 to 12 elements has a substituent, examples of the substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkyloxycarbonyl group having 2 to 5 carbon atoms, and an alkylcarbonyloxy group having 2 to 5 carbon atoms. These substituents may be present alone or in combination of two or more. In this specification, the number of carbon atoms of a substituent is not included in the number of carbon atoms of the functional group to be substituted. For example, when an ethyl group (carbon number: 2) is substituted with a methoxy group (carbon number: 1), the substituted ethyl group has two carbon atoms.

[0030] The alkoxy group having 1 to 5 carbon atoms is not particularly limited, but examples thereof include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, and a pentyloxy group.

[0031] The alkyloxycarbonyl group having 2 to 5 carbon atoms is not particularly limited, but examples thereof include a methyloxycarbonyl group, an ethyloxycarbonyl group, a propyloxycarbonyl group, an isopropyloxycarbonyl group, a butyloxycarbonyl group, an isobutyloxycarbonyl group, a sec-butyloxycarbonyl group, and a tert-butyloxycarbonyl group.

[0032] The alkylcarbonyloxy group having 2 to 5 carbon atoms is not particularly limited, but examples thereof include a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, an isopropylcarbonyloxy group, and a butylcarbonyloxy group.

[0033] Examples of the alkyl group having 1 to 5 carbon atoms include, but are not limited to, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and a pentyl group.

[0034] In one embodiment, a is preferably 0. In another embodiment, a is 1 and R １ is preferably selected from the group consisting of a halogen atom and a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, more preferably a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, even more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. １ are each preferably independently selected from the group consisting of a halogen atom and a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

[0035] In one embodiment, X is preferably a group represented by formula (2), more preferably at least one selected from the group consisting of the following formulae (2-1) to (2-9), and even more preferably the following formula (2-1):

[0036] b is preferably 1 or 2, and more preferably 1.

[0037] Specific examples of bisphenols include, but are not limited to, bisphenol compounds in which X is —O—, such as bis(4-hydroxyphenyl) ether; bisphenol compounds in which X is —S—, such as bis(4-hydroxyphenyl) sulfide; bisphenol compounds in which X is —SO—, such as bis(4-hydroxyphenyl) sulfoxide; and bisphenol compounds in which X is —SO , such as bis(4-hydroxyphenyl) sulfone, 2,4′-dihydroxydiphenyl sulfone, bis(2-hydroxyphenyl) sulfone, and bis(4-hydroxy-3-methylphenyl) sulfone. ２-; bisphenol compounds where X is -CO- such as bis(4-hydroxyphenyl)ketone; 2,2-bis(4-hydroxyphenyl)propane (bisphenol A: BPA), bis(4-hydroxyphenyl)methane (bisphenol F: BPF), bis(2-hydroxyphenyl)methane, 2,4'-dihydroxydiphenylmethane, bis(4-hydroxy-3-methylphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane (bisphenol E: BPE), 1,1 -bis(4-hydroxy-3-methylphenyl)ethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane (bisphenol C: BPC), 2,2-bis(4-hydroxy-3-isopropylphenyl)propane (bisphenol G: BPG), 2,2-bis(4-hydroxyphenyl)butane (bisphenol B: BPB), 2,2-bis(4-hydroxy-3-tert-butylphenyl)propane, 5,5'-(1-methylethylidene)-bis[1,1'-(bisphenyl)-2-ol] Propane (bisphenol PH: BPPH), 1,1-bis(4-hydroxyphenyl)-2-methylpropane (bisphenol IBTD), 2,2-bis(4-hydroxyphenyl)-4-methylpentane (bisphenol MIBK), 1,1-bis(4-hydroxyphenyl)-2-ethylhexane (bisphenol IOTD), 1,1-bis(4-hydroxyphenyl)decane, 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z: BPZ), 1,1-bis(4-hydroxyphenyl)-2-ethylhexane (bisphenol IOTD), bisphenol compounds in which X is represented by formula (2), such as 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol TMC), 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cycloundecane, 1,1-bis(4-hydroxyphenyl)cyclododecane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane (bisphenol AP: BPAP), and bis(4-hydroxyphenyl)diphenylmethane (bisphenol BP; BPBP);Examples of suitable bisphenol compounds include bisphenol compounds in which X is represented by formula (3), such as 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, and 9,9-bis(4-hydroxy-3-ethylphenyl)fluorene; and bisphenol compounds in which X is represented by formula (4), such as 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisphenol and 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisphenol. These bisphenols may be used alone or in combination of two or more.

[0038] Of these, the bisphenol preferably includes a bisphenol compound in which X is represented by formula (2), more preferably at least one selected from the group consisting of bisphenol A (BPA), bisphenol F (BPF), bisphenol E (BPE), bisphenol C (BPC), bisphenol G (BPG), bisphenol B (BPB), bisphenol PH (BPPH), bisphenol IBTD), bisphenol MIBK, bisphenol IOTD), bisphenol Z (BPZ), bisphenol TMC, bisphenol AP (BPAP), and bisphenol BP (BPBP), and even more preferably includes bisphenol A. The above-mentioned bisphenols may be used alone or in combination of two or more.

[0039] The content of the bisphenol is preferably 1 mol% or more, more preferably 2 to 100 mol%, even more preferably 5 to 100 mol%, and particularly preferably 10 to 100 mol%, based on all structural units of the first polycarbonate resin.

[0040] The content of the bisphenol is preferably 2 to 99.8 mol %, more preferably 5 to 99 mol %, based on the total number of moles of the structural units and terminal structures of the first polycarbonate resin.

[0041] (Compound for deriving other structural units) The first polycarbonate resin may be formed by further reacting a compound for deriving other structural units. By using the compound for deriving other structural units, the physical properties of the polycarbonate can be adjusted.

[0042] Compounds from which other structural units are derived include alicyclic diol compounds and organosiloxanes.

[0043] The alicyclic diol compound is not particularly limited, but examples thereof include cyclohexanedimethanol, tricyclodecanedimethanol, adamantanediol, and pentacyclopentadecanedimethanol.

[0044] The organosiloxane is not particularly limited, but examples thereof include α,ω-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane, α,ω-bis[3-(o-hydroxyphenyl)propyl]polydimethyldiphenyl random copolymerized siloxane, and the like.

[0045] The compounds from which other structural units are derived may be used alone or in combination of two or more.

[0046] The content of the compound that derives other structural units is preferably 50 moles or less, and more preferably 0.1 to 40 moles, per mole of bisphenol.

[0047] (Carbonate Binder) The carbonate binder is not particularly limited, and examples thereof include carbonyl compounds such as phosgene, triphosgene, carbon monoxide, carbon dioxide, and carbonate diesters.

[0048] Examples of the carbonic acid diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate, and substituted diphenyl carbonates such as diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, and di-p-chlorophenyl carbonate.

[0049] Among these, the carbonate binder preferably contains at least one of phosgene, triphosgene, diphenyl carbonate, and substituted diphenyl carbonate, and more preferably contains at least one of phosgene and diphenyl carbonate. The carbonate binders may be used alone or in combination of two or more.

[0050] (End Capper) The end capper has a function of adjusting the physical properties such as the viscosity average molecular weight of the first polycarbonate resin.

[0051] The terminal terminator is not particularly limited, and examples thereof include a monohydric phenol terminal terminator represented by the following formula (5) and a monohydric phenol terminal terminator having no unsaturated group.

[0052]

[0053] In the above formula, R ３ is an alkyl group having 1 to 30 carbon atoms or an alkenyl group having 8 to 30 carbon atoms, R ４ are each independently a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and c is 0 to 4, preferably 0 or 1, and more preferably 0.

[0054] The alkyl group having 1 to 30 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a 2-hexyldecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an eicosyl group.

[0055] The alkenyl group having 8 to 30 carbon atoms is not particularly limited, but examples thereof include an octenyl group, a nonenyl group, a decenyl group, a dodecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a 2-hexyldecenyl group, a heptadecenyl group, an octadecenyl group, a nonadecenyl group, and an eicosenyl group.

[0056] The alkyl group having 1 to 20 carbon atoms is not particularly limited, but examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group.

[0057] The aryl group having 6 to 12 carbon atoms is not particularly limited, but examples thereof include a phenyl group, a tolyl group, a xylyl group, a trimethylphenyl group, a tetramethylphenyl group, an ethylphenyl group, an ethylmethylphenyl group, a diethylphenyl group, a propylphenyl group, an isopropylphenyl group, an isopropylmethylphenyl group, a benzyl group, a phenethyl group, a phenylpropyl group, a naphthyl group, and a biphenyl group.

[0058] When the alkyl group having 1 to 20 carbon atoms has a substituent, examples of the substituent include a halogen atom and an aryl group having 6 to 12 carbon atoms. When the aryl group having 6 to 12 carbon atoms has a substituent, examples of the substituent include a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms. These substituents may be present alone or in combination of two or more.

[0059] In one embodiment, R ３ is preferably an alkyl group having 8 to 30 carbon atoms or an alkenyl group having 8 to 30 carbon atoms, more preferably an alkyl group having 12 to 20 carbon atoms or an alkenyl group having 12 to 20 carbon atoms, even more preferably an alkyl group having 12 to 20 carbon atoms, particularly preferably a tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group or octadecyl group, and most preferably a hexadecyl group.

[0060] In another embodiment, R ３ is preferably an alkyl group having 8 to 22 carbon atoms or an alkenyl group having 8 to 22 carbon atoms, more preferably an alkyl group having 12 to 22 carbon atoms or an alkenyl group having 12 to 22 carbon atoms, and even more preferably an alkyl group having 12 to 18 carbon atoms or an alkenyl group having 12 to 18 carbon atoms. ３When the carbon number of R is 8 or more, the glass transition temperature of the monohydric phenol end terminator represented by formula (5) is not too high, and favorable thermoformability is obtained, which is preferable. ３ When the carbon number is 22 or less, the solubility in organic solvents tends to be high, which is preferable from the viewpoints of increasing the productivity during production of the polycarbonate resin, increasing the transparency of the polycarbonate resin, etc. Note that alkyl groups having 12 to 18 carbon atoms and alkenyl groups having 12 to 18 carbon atoms, preferably alkyl groups having 12 to 18 carbon atoms, and more preferably alkyl groups having 14 to 18 carbon atoms, are preferred because they are excellent in glass transition temperature, melt fluidity, moldability, drawdown resistance, and solvent solubility.

[0061] In one embodiment, c is preferably 0. In another embodiment, c is 1 and R ４ is preferably a methyl group or an ethyl group, and more preferably a methyl group.

[0062] In one embodiment, the monohydric phenol end-terminator represented by formula (5) is preferably a monohydric phenol end-terminator represented by the following formula (5-1):

[0063] In the above formula, R ３ is the same as defined in equation (5).

[0064] In one embodiment, the monohydric phenol end-stopper represented by formula (5) is selected from the group consisting of methyl parahydroxybenzoate, ethyl parahydroxybenzoate, propyl parahydroxybenzoate, butyl parahydroxybenzoate, amyl parahydroxybenzoate, hexyl parahydroxybenzoate, heptyl parahydroxybenzoate, decyl parahydroxybenzoate, dodecyl parahydroxybenzoate, tetradecyl parahydroxybenzoate, hexadecyl parahydroxybenzoate (cetyl parahydroxybenzoate), and tetradecyl parahydroxybenzoate. Preferably, the hydroxybenzoic acid ester contains at least one selected from the group consisting of parahydroxybenzoic acid 2-hexyldecyl ester, and parahydroxybenzoic acid octadecyl ester, more preferably contains at least one selected from the group consisting of parahydroxybenzoic acid tetradecyl ester, parahydroxybenzoic acid hexadecyl ester (parahydroxybenzoate cetyl), parahydroxybenzoic acid 2-hexyldecyl ester, and parahydroxybenzoic acid octadecyl ester, and even more preferably contains parahydroxybenzoic acid hexadecyl ester (parahydroxybenzoate cetyl).

[0065] The monohydric phenol end-terminator represented by the formula (5) may be used alone or in combination of two or more kinds.

[0066] The amount of the monohydric phenol end-terminator represented by formula (5) used is preferably 0.02 to 0.07 mol, more preferably 0.025 to 0.06 mol, per 1 mol of bisphenol.

[0067] The amount of the monohydric phenol end-terminator represented by formula (5) used is preferably 0.02 to 0.07 mol, more preferably 0.025 to 0.06 mol, per 1 mol of the carbonate binder.

[0068] Examples of the monohydric phenol end-terminator having no unsaturated group include a monohydric phenol end-terminator represented by the following formula (6).

[0069]

[0070] In the above formula, R ５ are each independently a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkylcarbonyloxy group having 1 to 8 carbon atoms. d is 0 to 5, preferably 0 to 3, more preferably 0 to 2, even more preferably 0 to 1, and particularly preferably 1.

[0071] The alkyl group having 1 to 20 carbon atoms is not particularly limited, but examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group.

[0072] The aryl group having 6 to 12 carbon atoms is not particularly limited, but examples thereof include a phenyl group, a tolyl group, a xylyl group, a trimethylphenyl group, a tetramethylphenyl group, an ethylphenyl group, an ethylmethylphenyl group, a diethylphenyl group, a propylphenyl group, an isopropylphenyl group, an isopropylmethylphenyl group, a benzyl group, a phenethyl group, a phenylpropyl group, a naphthyl group, and a biphenyl group.

[0073] The alkoxy group having 1 to 10 carbon atoms is not particularly limited, but examples thereof include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, and a 2-ethylhexyloxy group.

[0074] Examples of alkylcarbonyloxy groups having 1 to 8 carbon atoms include methylcarbonyloxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, pentylcarbonyloxy, hexylcarbonyloxy, and heptylcarbonyloxy. The number of carbon atoms in an "alkylcarbonyloxy" refers to the total number of carbon atoms in the alkyl group and the carbonyl group (C=O). Therefore, the number of carbon atoms in an octylcarbonyloxy group is 9, which is the total number of carbon atoms in the octyl (8 carbon atoms) and carbonyl group (1 carbon atom).

[0075] When the alkyl group having 1 to 20 carbon atoms, the alkoxy group having 1 to 10 carbon atoms, or the alkylcarbonyloxy group having 1 to 8 carbon atoms has a substituent, examples of the substituent include a halogen atom, an aryl group having 6 to 12 carbon atoms, etc. When the aryl group having 6 to 12 carbon atoms has a substituent, examples of the substituent include a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms, etc. These substituents may be present alone or in combination of two or more.

[0076] In one embodiment, d is preferably 0. In another embodiment, d is 1 and R ５ is preferably a methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, amyl group, trifluoromethyl group, 2-phenylpropan-2-yl group, methylcarbonyloxy group, ethylcarbonyloxy group, propylcarbonyloxy group, isopropylcarbonyloxy group, butylcarbonyloxy group, amylcarbonyloxy group, hexylcarbonyloxy group, or heptylcarbonyloxy group, and more preferably a methyl group, isopropyl group, or tert-butyl group.

[0077] In one embodiment, examples of the monohydric phenol end-stopper having no unsaturated group include phenol, p-cresol, o-cresol, 2,4-xylenol, p-tert-butylphenol, p-propylphenol, p-cumylphenol, p-hexylphenol, p-heptylphenol, p-trifluoromethylphenol, p-octylphenol, p-nonylphenol, p-decylphenol, p-dodecylphenol, p-amylphenol, 4-tetradecylphenol, 4-hexadecylphenol, 4-octadecylphenol (stearylphenol), 4-docosylphenol (behenylphenol), p-phenylphenol, o-phenylphenol, 4-methylcarbonyloxyphenol, 4-ethylcarbonyloxyphenol, 4-propylcarbonyloxyphenol, 4-isopropylcarbonyloxyphenol, 4-butylcarbonyloxyphenol, and 4-tert-butylcarbonyloxyphenol. Of these, the monohydric phenol end-terminator having no unsaturated group preferably contains at least one selected from the group consisting of phenol, p-isopropylbutylphenol, p-tert-butylphenol, and p-octylphenol, more preferably contains at least one of p-tert-butylphenol and p-octylphenol, and even more preferably contains p-tert-butylphenol.

[0078] The above-mentioned monohydric phenol end-stoppers having no unsaturated group may be used alone or in combination of two or more kinds.

[0079] The amount of the monohydric phenol end-terminator having no unsaturated group used is preferably 0.02 to 0.07 mol, more preferably 0.025 to 0.06 mol, per 1 mol of bisphenol.

[0080] The amount of the monohydric phenol end-terminator having no unsaturated group used is preferably 0.5 mol or less, more preferably 0.2 mol or less, and even more preferably 0.1 mol or less, per 1 mol of the end-terminator represented by formula (5).

[0081] In one embodiment, the first polycarbonate resin preferably contains a bisphenol A polycarbonate resin. In this case, the bisphenol A polycarbonate resin is a polycarbonate obtained by reacting bisphenol A, a carbonate binder, and a terminal terminator. The bisphenol A polycarbonate resin may optionally be further reacted with a bisphenol other than bisphenol A, a compound that derives another structural unit, or the like, in addition to the bisphenol A, the carbonate binder, and the terminal terminator.

[0082] In the first polycarbonate resin, the bisphenol A polycarbonate resin preferably has a terminal structure derived from at least one selected from the group consisting of parahydroxybenzoic acid tetradecyl ester, parahydroxybenzoic acid hexadecyl ester (parahydroxybenzoate cetyl), parahydroxybenzoic acid 2-hexyldecyl ester, parahydroxybenzoic acid octadecyl ester, phenol, p-isopropylbutylphenol, p-tert-butylphenol, and p-octylphenol, more preferably has a terminal structure derived from at least one selected from the group consisting of parahydroxybenzoic acid hexadecyl ester (parahydroxybenzoate cetyl), para-tert-butylphenol, and p-octylphenol, and even more preferably has a terminal structure derived from parahydroxybenzoate cetyl.

[0083] In one embodiment, the bisphenol A polycarbonate resin preferably contains structural units derived from bisphenol A in an amount of 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more, even more preferably 97% by mass or more, and particularly preferably 98 to 100% by mass, based on the mass of all structural units of the bisphenol A polycarbonate resin excluding terminal structures.

[0084] The above-mentioned first polycarbonate resins may be used alone or in combination of two or more kinds.

[0085] From the viewpoint of ease of handling, the first polycarbonate resin preferably has a viscosity 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. In this specification, the "viscosity average molecular weight" is calculated using Schnell's viscosity formula. Specifically, first, the intrinsic viscosity [η] (dL / g) of the resin is measured using methylene chloride as a solvent. At this time, the temperature is set to 25°C. Using an Ubbelohde viscometer, the specific viscosity [η] at each solution concentration [C] (g / dL) is measured. ｓｐ ] is measured, and the intrinsic viscosity can be calculated from the obtained specific viscosity value and concentration using the following formula. Next, the viscosity average molecular weight [Mv] was calculated using Schnell's viscosity formula, i.e., η = 1.23 × 10 －４ Mv ０．８３ When the polycarbonate resin is a mixture of two or more polycarbonate resins having different molecular weights, the viscosity average molecular weight after mixing is used.

[0086] From the viewpoint of improving moldability, the polycarbonate resin used in the present invention preferably has a glass transition temperature of 110 to 170 ° C, more preferably 110 to 150 ° C, even more preferably 110 to 140 ° C, and particularly preferably 110 to 130 ° C. In this specification, the "glass transition temperature" is measured by a differential scanning calorimeter (DSC). In this case, a differential scanning calorimeter (DSC) DSC-50 (manufactured by Shimadzu Corporation) is used as the measuring instrument, and the measurement conditions are a heating temperature of 10 ° C / min, a gas flow environment of nitrogen of 20 mL / min, and sample pretreatment by heating and melting at 300 ° C.

[0087] [Other Resins] The first unreinforced polycarbonate resin layer may contain other resins. In this specification, "other resins" refers to resins other than polycarbonate resins.

[0088] Examples of other resins include, but are not limited to, thermoplastic polyester resins such as polyacrylate resin, polyethylene terephthalate resin (PET resin), polytrimethylene terephthalate (PTT resin), and polybutylene terephthalate resin (PBT resin); styrene-based resins such as polystyrene resin (PS resin), high-impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), and methyl methacrylate-styrene copolymer (MS resin); and core / shell resins such as methyl methacrylate-acrylic rubber-styrene copolymer (MAS). Examples of such resins include elastomers such as olefin-type elastomers and polyester-based elastomers; polyolefin resins such as cyclic cycloolefin resins (COP resins) and cyclic cycloolefin (COP) copolymer resins; polyamide resins (PA resins); polyimide resins (PI resins); polyetherimide resins (PEI resins); polyurethane resins (PU resins); polyphenylene ether resins (PPE resins); polyphenylene sulfide resins (PPS resins); polysulfone resins (PSU resins); polymethacrylate resins (PMMA resins); polycaprolactone, etc. These other resins may be used alone or in combination of two or more.

[0089] [Additives] The first unreinforced polycarbonate resin layer may contain additives. The additives are not particularly limited, but include antioxidants, transesterification inhibitors, release agents, heat stabilizers, flame retardants, flame retardant aids, ultraviolet absorbers, colorants, antistatic agents, fluorescent brighteners, antifogging agents, flow improvers, plasticizers, dispersants, antibacterial agents, antiblocking agents, impact improvers, sliding improvers, color improvers, and acid trapping agents. These additives may be used alone or in combination of two or more.

[0090] The content of the additive is preferably 4% by mass or less, more preferably 3% by mass or less, and even more preferably 0.1 to 2% by mass, based on the total mass of the first unreinforced polycarbonate resin layer.

[0091] [Configuration of the First Unreinforced Polycarbonate Resin Layer] The first unreinforced polycarbonate resin layer may have a single layer structure or a laminated structure. For example, a laminated first unreinforced polycarbonate resin layer can be obtained by laminating first unreinforced polycarbonate resin layers having a predetermined thickness and fusing them together. In the case of a laminated structure, the first unreinforced polycarbonate resin layers may be the same or different, but are preferably the same from the viewpoint of improving mechanical properties.

[0092] The shape of the first unreinforced polycarbonate resin layer is not particularly limited and may be any of a flat plate shape, a curved shape, a circular ring shape (cylindrical shape), etc. The shape of the first unreinforced polycarbonate resin layer can be appropriately set depending on the application of the laminate, etc. In this specification, "circular ring" or "cylindrical" means a cylindrical shape having a cavity, the cross section of which is a perfect circle, an ellipse, etc.

[0093] The thickness of the first unreinforced polycarbonate resin layer is not particularly limited, but is preferably 0.01 to 5 mm, more preferably 0.05 to 1 mm, and even more preferably 0.05 to 0.8 mm, 0.05 to 0.6 mm, 0.05 to 0.4 mm, 0.05 to 0.2 mm, 0.1 to 1 mm, 0.1 to 0.8 mm, 0.1 to 0.6 mm, 0.1 to 0.4 mm, 0.1 to 0.2 mm, 0.2 to 1 mm, 0.2 to 0.8 mm, 0.2 to 0.6 mm, 0.2 to 0.4 mm, 0.4 to 1 mm, 0.4 to 0.8 mm, 0.4 to 0.6 mm, 0.6 to 1 mm, 0.6 to 0.8 mm, or 0.8 to 1 mm.

[0094] <Second Unreinforced Polycarbonate Resin Layer> The second unreinforced polycarbonate resin layer contains a second polycarbonate resin. In addition, the second unreinforced polycarbonate resin layer may further contain other resins, additives, etc.

[0095] [Second Polycarbonate Resin] The second polycarbonate resin may be the same as the first polycarbonate resin. In one embodiment, the second polycarbonate resin is preferably a polycarbonate obtained by reacting a bisphenol, a carbonate binder, and a terminal capping agent. In this case, the second polycarbonate resin may be further reacted with a compound that derives another structural unit.

[0096] The bisphenol, compound for deriving other structural units, carbonate binder, and end-capping agent used in the second polycarbonate resin are the same as those described for the first polycarbonate resin, and the second polycarbonate resin may be used alone or in combination of two or more.

[0097] In one embodiment, the second polycarbonate resin preferably contains a bisphenol A polycarbonate resin. In this case, the bisphenol A polycarbonate resin is a polycarbonate obtained by reacting bisphenol A, a carbonate binder, and a terminal terminator. The bisphenol A polycarbonate resin may optionally be further reacted with a bisphenol other than bisphenol A, a compound that derives another structural unit, or the like, together with bisphenol A, the carbonate binder, and the terminal terminator.

[0098] In the second polycarbonate resin, the bisphenol A polycarbonate resin preferably has a terminal structure derived from at least one selected from the group consisting of tetradecyl parahydroxybenzoate, hexadecyl parahydroxybenzoate (cetyl parahydroxybenzoate), 2-hexyldecyl parahydroxybenzoate, octadecyl parahydroxybenzoate, phenol, p-isopropylbutylphenol, and p-tert-butylphenol, more preferably has a terminal structure derived from at least one of hexadecyl parahydroxybenzoate (cetyl parahydroxybenzoate) and para-tert-butylphenol, and even more preferably has a terminal structure derived from cetyl parahydroxybenzoate.

[0099] The second polycarbonate resin may be the same as or different from the first polycarbonate resin, but is preferably the same as the first polycarbonate resin from the viewpoint of improving mechanical properties.

[0100] [Other Resins and Additives] The other resins and additives may be the same as those used in the first polycarbonate resin layer. In this case, the other resins and additives may be used alone or in combination of two or more.

[0101] [Configuration of the second unreinforced polycarbonate resin layer] The second unreinforced polycarbonate resin layer may have a single layer structure or a laminated structure. For example, a laminated second unreinforced polycarbonate resin layer can be obtained by laminating second unreinforced polycarbonate resin layers having a predetermined thickness and fusing them together. In the case of a laminated structure, the second unreinforced polycarbonate resin layers may be the same or different, but are preferably the same from the viewpoint of improving mechanical properties.

[0102] The shape of the second unreinforced polycarbonate resin layer is not particularly limited and may be any of a flat plate shape, a curved shape, a circular ring shape (cylindrical shape), etc. The shape of the second unreinforced polycarbonate resin layer can be appropriately set depending on the use of the laminate, etc.

[0103] The thickness of the second unreinforced polycarbonate resin layer is not particularly limited, but is preferably 0.01 to 5 mm, more preferably 0.05 to 1 mm, and even more preferably 0.05 to 0.8 mm, 0.05 to 0.6 mm, 0.05 to 0.4 mm, 0.05 to 0.2 mm, 0.1 to 1 mm, 0.1 to 0.8 mm, 0.1 to 0.6 mm, 0.1 to 0.4 mm, 0.1 to 0.2 mm, 0.2 to 1 mm, 0.2 to 0.8 mm, 0.2 to 0.6 mm, 0.2 to 0.4 mm, 0.4 to 1 mm, 0.4 to 0.8 mm, 0.4 to 0.6 mm, 0.6 to 1 mm, 0.6 to 0.8 mm, or 0.8 to 1 mm.

[0104] The ratio of the thickness of the first unreinforced polycarbonate resin layer to the thickness of the second unreinforced polycarbonate resin layer (thickness of first unreinforced polycarbonate resin layer / thickness of second unreinforced polycarbonate resin layer) is preferably 0.5 to 2, more preferably 0.7 to 1.5, even more preferably 0.8 to 1.2, particularly preferably 0.9 to 1.1, or 0.9 to 1.2, and most preferably 1. A thickness ratio within the above range is preferable from the viewpoints of improved mechanical properties, ability to be used on both sides, suppression of bending, etc.

[0105] <Carbon fiber reinforced resin layer> The carbon fiber reinforced resin layer includes carbon fibers and a third polycarbonate resin. In this specification, the term "carbon fiber reinforced resin layer" refers to a resin layer having a carbon fiber content of 5 mass% or more relative to the total mass of the carbon fiber reinforced resin layer.

[0106] [Carbon Fiber] Carbon fiber has a function of improving the mechanical properties of the carbon fiber reinforced resin layer.

[0107] The carbon fiber is not particularly limited, but examples thereof include polyacrylonitrile (PAN)-based carbon fiber, pitch-based carbon fiber, pitch-based hydrocarbon, and rayon-based carbon fiber. The surface of the carbon fiber may be oxidized. The oxidization treatment can improve the adhesion between the carbon fiber and the resin. The adhesion between the carbon fiber and the resin can also be improved by applying a silane coupling agent to the carbon fiber.

[0108] The carbon fibers may be discontinuous or continuous, but are preferably continuous from the viewpoint of further improving the strength of the carbon fiber reinforced resin layer. In this specification, "discontinuous fibers" means fibers having a fiber length of less than 15 mm. Also, "continuous fibers" means fibers having a fiber length of 15 mm or more.

[0109] The form of carbon fiber is not particularly limited, and examples thereof include spun yarns (spun yarns) made by bundling short fibers into a thread; filaments made by bundling long fibers; unidirectional sheets (sheets in which carbon fibers are aligned parallel to one direction) obtained by spinning spun yarns, nonwoven fabrics (sheets in which carbon fibers are arranged in random directions and fixed without being woven), woven fabrics (sheets in which carbon fibers are woven by crossing warp and weft threads), multiaxial (sheets in which two or more unidirectional sheets are stacked in different directions and stitched together); tows obtained by bundling filaments; unidirectional sheets, nonwoven fabrics, woven fabrics, and braids (string-like structures formed by braiding multiple carbon fibers while crossing them diagonally) obtained by spinning filaments; and multiaxial. The orientation direction within the multiaxial sheet can be, for example, 0°, 90°, or ±45°, or these may be combined (for example, [0° / 90°], [0° / ±45°], or [0° / 90° / ±45°]). Of these, the form of the carbon fiber is preferably a continuous fiber from the viewpoint of excellent impact resistance, more preferably a tow obtained by bundling filaments; a unidirectional sheet, nonwoven fabric, woven fabric, knitted cord, or multiaxial obtained by spinning filaments, and even more preferably a unidirectional sheet or woven fabric obtained by spinning filaments.

[0110] In one embodiment, the carbon fibers constituting the spunbond, filament, tow, unidirectional sheet, nonwoven fabric, woven fabric, multiaxial, and braided cords can be partially replaced with other fibers, as described below. That is, in one embodiment, the spunbond, filament, tow, unidirectional sheet, nonwoven fabric, woven fabric, multiaxial, and braided cord contain carbon fibers and other fibers (e.g., at least one selected from the group consisting of nylon fibers, aramid fibers, polyester fibers, and glass fibers). In one embodiment, the spunbond, filament, tow, unidirectional sheet, nonwoven fabric, woven fabric, multiaxial, and braided cord can contain other resins, additives, and the like to hold the carbon fibers and other components and maintain their shape. That is, in one embodiment, the spunbond, filament, tow, unidirectional sheet, nonwoven fabric, woven fabric, multiaxial, and braided cord contain carbon fibers, optionally other fibers, and at least one of other resins and additives.

[0111] The above-mentioned unidirectional sheets, nonwoven fabrics, woven fabrics, multiaxial fiber sheets, etc. can be laminated. In this case, the laminated fiber sheets may be the same or different fiber sheets. Furthermore, the laminated fiber sheets may contain other resins, additives, etc., from the viewpoint of improving the adhesion between the sheets and maintaining the shape. By laminating the fiber sheets, the thickness of the carbon fiber reinforced resin layer, the carbon fiber orientation, etc. can be controlled.

[0112] The above carbon fibers may be used alone or in combination of two or more kinds.

[0113] The fiber length of the spun yarn is preferably 0.1 mm or more, more preferably 3 mm or more, even more preferably 10 mm or more, and particularly preferably 15 mm or more. The fiber length of the filament is preferably 10 mm or more, more preferably 30 mm or more, and even more preferably 50 mm or more. In this specification, "fiber length" means the longest distance between two points on the surface of an object (fiber), and is the average fiber length of 50 objects randomly included in one field of view of a scanning electron microscope (SEM).

[0114] The diameter of a single carbon fiber fiber constituting a spun fabric (nonwoven fabric, woven fabric, etc.) of spun spun yarn (spun yarn) is preferably 3 to 11 μm, more preferably 5 to 7 μm. The diameter of a single carbon fiber fiber constituting a spun fabric (nonwoven fabric, woven fabric, knitted cord, etc.) of filaments is preferably 3 to 11 μm, more preferably 5 to 7 μm. In this specification, "diameter" refers to the longest distance between two points on the cross section of an object (carbon fiber, etc.), and is the average value of the diameters of any 50 objects contained in one field of view of a scanning electron microscope (SEM).

[0115] The carbon fiber content is preferably 20 to 80 mass %, more preferably 40 to 80 mass %, and even more preferably 50 to 70 mass %, based on the total mass of the carbon fiber reinforced resin layer.

[0116] [Other Fibers] The carbon fiber reinforced resin layer may further contain other fibers. In this specification, "other fibers" refers to reinforcing fibers other than carbon fibers.

[0117] The other fibers are not particularly limited, but include nylon fibers, aramid fibers, polyester fibers, glass fibers, and the like.

[0118] The form of the other fibers may be discontinuous fibers or continuous fibers, but from the viewpoint of excellent impact resistance, continuous fibers are preferred, and tows obtained by bundling filaments; unidirectional sheets, nonwoven fabrics, woven fabrics, knitted cords, and multiaxial fibers obtained by spinning filaments are more preferred, and unidirectional sheets, nonwoven fabrics, woven fabrics, knitted cords, and multiaxial fibers obtained by spinning filaments are even more preferred.

[0119] In one embodiment, filaments, tows, unidirectional sheets, nonwoven fabrics, woven fabrics, multiaxial, and braided cords made of other fibers may contain other resins, additives, etc. to hold the carbon fibers, etc. that make them up and maintain their shape.

[0120] Fiber sheets such as unidirectional sheets, nonwoven fabrics, woven fabrics, and multiaxial sheets made of the above-mentioned other fibers can be laminated. In this case, the laminated fiber sheets may be the same or different. Furthermore, the laminated fiber sheets may contain other resins, additives, etc., in order to improve the adhesion between the sheets and maintain their shape.

[0121] The above-mentioned other fibers may be used alone or in combination of two or more.

[0122] The fiber length of the spun yarn of the other fiber is preferably 0.1 mm or more, more preferably 3 mm or more, even more preferably 10 mm or more, and particularly preferably 15 mm or more. The fiber length of the filament of the other fiber is preferably 10 mm or more, more preferably 30 mm or more, and even more preferably 50 mm or more.

[0123] The diameter of a single fiber of the other fiber constituting a spun product (nonwoven fabric, woven fabric, etc.) of a span (spun yarn) of the other fiber is preferably 3 to 11 μm, more preferably 5 to 7 μm. The diameter of a single fiber of the other fiber constituting a spun product (nonwoven fabric, woven fabric, knitted cord, etc.) of a filament of the other fiber is preferably 3 to 11 μm, more preferably 5 to 7 μm.

[0124] The content of the other fibers is preferably 1 to 80 mass %, more preferably 3 to 70 mass %, and even more preferably 5 to 50 mass %, based on the total mass of the carbon fiber reinforced resin layer.

[0125] [Third Polycarbonate Resin] The third polycarbonate resin may be the same as the first polycarbonate resin. However, the third polycarbonate resin contains a terminal structure derived from a monohydric phenol end-blocking agent represented by formula (5). That is, the third polycarbonate resin contains a polycarbonate obtained by reacting a bisphenol, a carbonate binder, and a monohydric phenol end-blocking agent represented by formula (5). In this case, the third polycarbonate resin may be further reacted with a compound that derives another structural unit, or a monohydric phenol end-blocking agent that does not have an unsaturated group as an end-blocking agent.

[0126] The bisphenol, compound for deriving other structural units, carbonate binder, and end-capping agent used in the third polycarbonate resin are the same as those described for the first polycarbonate resin, and the third polycarbonate resin may be used alone or in combination of two or more.

[0127] In one embodiment, the bisphenol used in the third polycarbonate resin preferably includes a bisphenol compound where X is represented by formula (2), more preferably includes at least one selected from the group consisting of bisphenol A (BPA), bisphenol F (BPF), bisphenol E (BPE), bisphenol C (BPC), bisphenol G (BPG), bisphenol B (BPB), bisphenol PH (BPPH), bisphenol IBTD), bisphenol MIBK), bisphenol IOTD), bisphenol Z (BPZ), bisphenol TMC, bisphenol AP (BPAP), and bisphenol BP (BPBP), and even more preferably includes bisphenol A.

[0128] In one embodiment, the carbonate binder used in the third polycarbonate resin preferably comprises at least one of phosgene, triphosgene, diphenyl carbonate, and a substituted diphenyl carbonate, and more preferably comprises at least one of phosgene and diphenyl carbonate.

[0129] In one embodiment, the monohydric phenol endblocker represented by formula (5) used in the third polycarbonate resin is selected from the group consisting of methyl parahydroxybenzoate, ethyl parahydroxybenzoate, propyl parahydroxybenzoate, butyl parahydroxybenzoate, amyl parahydroxybenzoate, hexyl parahydroxybenzoate, heptyl parahydroxybenzoate, decyl parahydroxybenzoate, dodecyl parahydroxybenzoate, tetradecyl parahydroxybenzoate, and hexadecyl parahydroxybenzoate (parahydroxybenzoate). Preferably, the hydroxybenzoic acid ester contains at least one selected from the group consisting of parahydroxybenzoic acid tetradecyl ester, parahydroxybenzoic acid hexadecyl ester (parahydroxybenzoic acid cetyl), parahydroxybenzoic acid 2-hexyldecyl ester, and parahydroxybenzoic acid octadecyl ester, more preferably at least one selected from the group consisting of parahydroxybenzoic acid tetradecyl ester, parahydroxybenzoic acid hexadecyl ester (parahydroxybenzoic acid cetyl), parahydroxybenzoic acid 2-hexyldecyl ester, and parahydroxybenzoic acid octadecyl ester, and even more preferably parahydroxybenzoic acid hexadecyl ester (parahydroxybenzoic acid cetyl).

[0130] In one embodiment, the third polycarbonate resin preferably contains a bisphenol A polycarbonate resin. In this case, the bisphenol A polycarbonate resin is a polycarbonate obtained by reacting bisphenol A, a carbonate binder, and a monohydric phenol end-terminator represented by formula (5). The bisphenol A polycarbonate resin can be further reacted, optionally with bisphenols other than bisphenol A, compounds that derive other structural units, and the like, together with bisphenol A, the carbonate binder, and the monohydric phenol end-terminator represented by formula (5).

[0131] In the third polycarbonate resin, the bisphenol A polycarbonate resin preferably has a terminal structure derived from at least one selected from the group consisting of tetradecyl parahydroxybenzoate, hexadecyl parahydroxybenzoate (cetyl parahydroxybenzoate), 2-hexyldecyl parahydroxybenzoate, and octadecyl parahydroxybenzoate, and more preferably has hexadecyl parahydroxybenzoate (cetyl parahydroxybenzoate).

[0132] In one embodiment, the third polycarbonate resin is a thermoplastic resin, and therefore the molding time can be significantly reduced compared to when a thermosetting resin such as an epoxy resin is used. For example, the molding time for a bisphenol epoxy resin is more than 60 minutes, whereas the molding time for a polycarbonate resin is 60 minutes or less (e.g., 5 to 30 minutes).

[0133] In one embodiment, the third polycarbonate resin has a low molding temperature, thereby reducing production costs. The molding temperature of polycarbonate resins is generally set to 220 to 300°C. This means that the molding temperature of polycarbonate resins is high, which tends to increase production costs. On the other hand, the third polycarbonate resin can be molded at temperatures between 160°C and 200°C, thereby reducing production costs. In addition, when epoxy resins are used as thermosetting resins in conventional carbon fiber reinforced plastics (CFRP), the molding temperature of the main epoxy resin (e.g., so-called 350F-type novolac epoxy resins, which can withstand temperatures of 350°F (approximately 177°C)) is 170 to 180°C. Therefore, when attempting to produce carbon fiber reinforced thermoplastic resins (CFRTP) instead of carbon fiber reinforced plastics (CFRP), using the third polycarbonate resin allows the utilization of existing equipment used for CFRP. This also contributes to reducing production costs.

[0134] In one embodiment, the third polycarbonate resin may be the same as or different from the first polycarbonate resin, but is preferably the same as the first polycarbonate resin from the viewpoints of improving mechanical properties, reducing production costs, etc. In one embodiment, the third polycarbonate resin may be the same as or different from the second polycarbonate resin, but is preferably the same as the second polycarbonate resin from the viewpoints of improving mechanical properties, reducing production costs, etc. In one embodiment, the third polycarbonate resin may be the same as or different from the first polycarbonate resin and the second polycarbonate resin, but is preferably the same as the first polycarbonate resin and the second polycarbonate resin from the viewpoints of improving mechanical properties, reducing production costs, etc.

[0135] [Other Resins and Additives] The other resins and additives may be the same as those used in the first polycarbonate resin layer. In this case, the other resins and additives may be used alone or in combination of two or more.

[0136] [Configuration of Carbon Fiber Reinforced Resin Layer] The carbon fibers contained in the carbon fiber reinforced resin layer are preferably impregnated with the third polycarbonate resin and bonded to the third polycarbonate resin.

[0137] The carbon fiber reinforced resin layer may have a single layer structure or a laminated structure. For example, a carbon fiber reinforced resin layer having a predetermined thickness and a predetermined carbon fiber orientation can be obtained by stacking and fusing carbon fiber reinforced resin layers having a predetermined thickness or a predetermined carbon fiber orientation to each other. In the case of a laminated structure, the carbon fiber reinforced resin layers may be the same or different, but are preferably the same from the viewpoint of improving mechanical properties.

[0138] The shape of the carbon fiber reinforced resin layer is not particularly limited and may be any of a flat plate shape, a curved shape, a circular ring shape (cylindrical shape), etc. The shape of the carbon fiber reinforced resin layer can be appropriately set depending on the use of the laminate, etc.

[0139] The thickness of the carbon fiber reinforced resin layer is not particularly limited, but is preferably 0.1 to 10 mm, more preferably 0.1 to 5 mm, and even more preferably 0.1 to 3 mm, and is preferably 0.2 to 3 mm, 0.2 to 2 mm, 0.2 to 1.9 mm, 0.2 to 1.6 mm, 0.2 to 1.2 mm, 0.2 to 0.8 mm, 0.2 to 0.5 mm, 0.5 to 3 mm, 0.5 to 2 mm. mm, 0.5 to 1.9 mm, 0.5 to 1.6 mm, 0.5 to 1.2 mm, 0.5 to 0.8 mm, 0.8 to 3 mm, 0.8 to 2 mm, 0.8 to 1.9 mm, 0.8 to 1.6 mm, 0.8 to 1.2 mm, 1.2 to 3 mm, 1.2 to 2 mm, 1.2 to 1.9 mm, 1.2 to 1.6 mm, 1.6 to 3 mm, 1.6 to 2 mm, and 1.6 to 1.9 mm are particularly preferred.

[0140] <Configuration of Laminate> The ratio of the thickness of the first unreinforced polycarbonate resin layer to the thickness of the carbon fiber reinforced resin layer (thickness of first unreinforced polycarbonate resin layer / thickness of carbon fiber reinforced resin layer) is 0.05 to 4, preferably 0.1 to 3, more preferably 0.1 to 2, and even more preferably 0.2 to 2.0, 0.2 to 1.5, 0.2 to 1.2, 0.2 to 1.0, 0.2 to 0.4, 0.4 to 2.0, 0.4 to 1.5, 0.4 to 1.2, 0.4 to 1.0, 1.0 to 2.0, 1.0 to 1.5, 1.0 to 1.2, 1.2 to 2.0, 1.2 to 1.5, or 1.5 to 2.0. In a preferred embodiment, from the viewpoint of obtaining higher impact resistance, the ratio of the thickness of the first unreinforced polycarbonate resin layer to the thickness of the carbon fiber reinforced resin layer (thickness of the first unreinforced polycarbonate resin layer / thickness of the carbon fiber reinforced resin layer) is preferably 1.0 to 2.0, 1.0 to 1.5, 1.0 to 1.2, 1.2 to 2.0, 1.2 to 1.5, or 1.5 to 2.0. In a preferred embodiment, from the viewpoint of obtaining higher flexural strength and flexural modulus, the ratio of the thickness of the first unreinforced polycarbonate resin layer to the thickness of the carbon fiber reinforced resin layer (thickness of the first unreinforced polycarbonate resin layer / thickness of the carbon fiber reinforced resin layer) is preferably 0.2 to 1.0, 0.2 to 0.4, or 0.4 to 1.0.

[0141] In one embodiment, the thickness of the second unreinforced polycarbonate resin layer relative to the thickness of the carbon fiber reinforced resin layer (thickness of the second unreinforced polycarbonate resin layer / thickness of the carbon fiber reinforced resin layer) is preferably 0.05 to 4, more preferably 0.1 to 3, still more preferably 0.1 to 2, and particularly preferably 0.2 to 2.0, 0.2 to 1.5, 0.2 to 1.2, 0.2 to 1.0, 0.2 to 0.4, 0.4 to 2.0, 0.4 to 1.5, 0.4 to 1.2, 0.4 to 1.0, 1.0 to 2.0, 1.0 to 1.5, 1.0 to 1.2, 1.2 to 2.0, 1.2 to 1.5, 1.5 to 2.0. In a preferred embodiment, from the viewpoint of obtaining higher impact resistance, the ratio of the thickness of the second unreinforced polycarbonate resin layer to the thickness of the carbon fiber reinforced resin layer (thickness of the second unreinforced polycarbonate resin layer / thickness of the carbon fiber reinforced resin layer) is preferably 1.0 to 2.0, 1.0 to 1.5, 1.0 to 1.2, 1.2 to 2.0, 1.2 to 1.5, or 1.5 to 2.0. In a preferred embodiment, from the viewpoint of obtaining higher flexural strength and flexural modulus, the ratio of the thickness of the second unreinforced polycarbonate resin layer to the thickness of the carbon fiber reinforced resin layer (thickness of the second unreinforced polycarbonate resin layer / thickness of the carbon fiber reinforced resin layer) is preferably 0.2 to 1.0, 0.2 to 0.4, or 0.4 to 1.0.

[0142] In one embodiment, the thickness of the carbon fiber reinforced resin layer is preferably 0.1 to 3 mm, the thickness of the first unreinforced polycarbonate resin layer is preferably 0.05 to 1 mm, and the thickness of the carbon fiber reinforced resin layer is preferably 0.2 to 3 mm, 0.2 to 2 mm, 0.2 to 1.9 mm, 0.2 to 1.6 mm, 0.2 to 1.2 mm, 0.2 to 0.8 mm, 0.2 to 0.5 mm, 0.5 to 3 mm, 0.5 to 2 mm, 0.5 to 1.9 mm, 0.5 to 1.6 mm, 0.5 to 1.2 mm, 0.5 to 0.8 mm, 0.8 to 3 mm, 0.8 to 2 mm, 0.8 to 1.9 mm, 0.8 to 1.6 mm, 0.8 to 1.2 mm, 1.2 to 3 mm, 1.2 and the thickness of the first unreinforced polycarbonate resin layer is preferably 0.05 to 2 mm, 1.2 to 1.9 mm, 1.2 to 1.6 mm, 1.6 to 3 mm, 1.6 to 2 mm, or 1.6 to 1.9 mm, and the thickness of the first unreinforced polycarbonate resin layer is preferably 0.05 to 0.8 mm, 0.05 to 0.6 mm, 0.05 to 0.4 mm, 0.05 to 0.2 mm, 0.1 to 1 mm, 0.1 to 0.8 mm, 0.1 to 0.6 mm, 0.1 to 0.4 mm, 0.1 to 0.2 mm, 0.2 to 1 mm, 0.2 to 0.8 mm, 0.2 to 0.6 mm, 0.2 to 0.4 mm, 0.4 to 1 mm, 0.4 to 0.8 mm, 0.4 to 0.6 mm, 0.6 to 1 mm, 0.6 to 0.8 mm, or 0.8 to 1 mm. In a preferred embodiment, from the viewpoint of obtaining higher impact resistance, the thickness of the carbon fiber reinforced resin layer is 0.2 to 0.8 mm, 0.2 to 0.5 mm, or 0.5 to 0.8 mm, and the thickness of the first unreinforced polycarbonate resin layer is 0.6 to 1 mm, 0.6 to 0.8 mm, or 0.8 to 1 mm. In a preferred embodiment, from the viewpoint of obtaining higher bending strength and bending modulus, the thickness of the carbon fiber reinforced resin layer is 0.8 to 3 mm, 0.8 to 2 mm, 0.8 to 1.9 mm, 0.8 to 1.6 mm, 0.8 to 1.2 mm, 1.2 to 3 mm, 1.2 to 2 mm, 1.2 to 1.9 mm, 1.2 to 1.6 mm, 1.6 to 3 mm, 1.6 to 2 mm, 1.6 to 1.9 mm, and the thickness of the first unreinforced polycarbonate resin layer is 0.05 to 0.6 mm, 0.05 to 0.4 mm, 0.05 to 0.2 mm, 0.1 to 0.6 mm, 0.1 to 0.4 mm, 0.1 to 0.2 mm, 0.2 to 0.6 mm, 0.2 to 0.4 mm, 0.4 to 0.6 mm.

[0143] In one embodiment, the thickness of the carbon fiber reinforced resin layer is preferably 0.1 to 3 mm, and the thickness of the second unreinforced polycarbonate resin layer is preferably 0.05 to 1 mm. The thickness of the carbon fiber reinforced resin layer is preferably 0.2 to 3 mm, 0.2 to 2 mm, 0.2 to 1.9 mm, 0.2 to 1.6 mm, 0.2 to 1.2 mm, 0.2 to 0.8 mm, 0.2 to 0.5 mm, 0.5 to 3 mm, 0.5 to 2 mm, 0.5 to 1.9 mm, 0.5 to 1.6 mm, 0.5 to 1.2 mm, 0.5 to 0.8 mm, 0.8 to 3 mm, 0.8 to 2 mm, 0.8 to 1.9 mm, 0.8 to 1.6 mm, 0.8 to 1.2 mm, 1.2 to 3 mm, 1.2 and the thickness of the second unreinforced polycarbonate resin layer is preferably 0.05 to 2 mm, 1.2 to 1.9 mm, 1.2 to 1.6 mm, 1.6 to 3 mm, 1.6 to 2 mm, or 1.6 to 1.9 mm, and the thickness of the second unreinforced polycarbonate resin layer is preferably 0.05 to 0.8 mm, 0.05 to 0.6 mm, 0.05 to 0.4 mm, 0.05 to 0.2 mm, 0.1 to 1 mm, 0.1 to 0.8 mm, 0.1 to 0.6 mm, 0.1 to 0.4 mm, 0.1 to 0.2 mm, 0.2 to 1 mm, 0.2 to 0.8 mm, 0.2 to 0.6 mm, 0.2 to 0.4 mm, 0.4 to 1 mm, 0.4 to 0.8 mm, 0.4 to 0.6 mm, 0.6 to 1 mm, 0.6 to 0.8 mm, or 0.8 to 1 mm. In a preferred embodiment, from the viewpoint of obtaining higher impact resistance, the thickness of the carbon fiber reinforced resin layer is 0.2 to 0.8 mm, 0.2 to 0.5 mm, or 0.5 to 0.8 mm, and the thickness of the second unreinforced polycarbonate resin layer is 0.6 to 1 mm, 0.6 to 0.8 mm, or 0.8 to 1 mm. In a preferred embodiment, from the viewpoint of obtaining higher bending strength and bending modulus, the thickness of the carbon fiber reinforced resin layer is 0.8 to 3 mm, 0.8 to 2 mm, 0.8 to 1.9 mm, 0.8 to 1.6 mm, 0.8 to 1.2 mm, 1.2 to 3 mm, 1.2 to 2 mm, 1.2 to 1.9 mm, 1.2 to 1.6 mm, 1.6 to 3 mm, 1.6 to 2 mm, 1.6 to 1.9 mm, and the thickness of the second unreinforced polycarbonate resin layer is 0.05 to 0.6 mm, 0.05 to 0.4 mm, 0.05 to 0.2 mm, 0.1 to 0.6 mm, 0.1 to 0.4 mm, 0.1 to 0.2 mm, 0.2 to 0.6 mm, 0.2 to 0.4 mm, 0.4 to 0.6 mm.

[0144] In one embodiment, the thickness of the carbon fiber reinforced resin layer is 0.1 to 3 mm, the thickness of the first unreinforced polycarbonate resin layer is 0.05 to 1 mm, and the thickness of the second unreinforced polycarbonate resin layer is preferably 0.05 to 1 mm. The thickness of the carbon fiber reinforced resin layer is 0.2 to 3 mm, 0.2 to 2 mm, 0.2 to 1.9 mm, 0.2 to 1.6 mm, 0.2 to 1.2 mm, 0.2 to 0.8 mm, 0.2 to 0.5 mm, 0.5 to 3 mm. mm, 0.5 to 2 mm, 0.5 to 1.9 mm, 0.5 to 1.6 mm, 0.5 to 1.2 mm, 0.5 to 0.8 mm, 0.8 to 3 mm, 0.8 to 2 mm, 0.8 to 1.9 mm, 0.8 to 1.6 mm, 0.8 to 1.2 mm, 1.2 to 3 mm, 1.2 to 2 mm, 1.2 to 1.9 mm, 1.2 to 1.6 mm, 1.6 to 3 mm, 1.6 to 2 mm, 1.6 to 1.9 mm, and the thickness of the first unreinforced polycarbonate resin layer is 0.05 to 0.8 mm, 0 0.05 to 0.6 mm, 0.05 to 0.4 mm, 0.05 to 0.2 mm, 0.1 to 1 mm, 0.1 to 0.8 mm, 0.1 to 0.6 mm, 0.1 to 0.4 mm, 0.1 to 0.2 mm, 0.2 to 1 mm, 0.2 to 0.8 mm, 0.2 to 0.6 mm, 0.2 to 0.4 mm, 0.4 to 1 mm, 0.4 to 0.8 mm, 0.4 to 0.6 mm, 0.6 to 1 mm, 0.6 to 0.8 mm, 0.8 to 1 mm, and the thickness of the second unreinforced polycarbonate resin layer is preferably 0.05 to 0.8 mm, 0.05 to 0.6 mm, 0.05 to 0.4 mm, 0.05 to 0.2 mm, 0.1 to 1 mm, 0.1 to 0.8 mm, 0.1 to 0.6 mm, 0.1 to 0.4 mm, 0.1 to 0.2 mm, 0.2 to 1 mm, 0.2 to 0.8 mm, 0.2 to 0.6 mm, 0.2 to 0.4 mm, 0.4 to 1 mm, 0.4 to 0.8 mm, 0.4 to 0.6 mm, 0.6 to 1 mm, 0.6 to 0.8 mm, or 0.8 to 1 mm. In a preferred embodiment, from the viewpoint of obtaining higher impact resistance, it is preferable that the thickness of the carbon fiber reinforced resin layer is 0.2 to 0.8 mm, 0.2 to 0.5 mm, or 0.5 to 0.8 mm, the thickness of the first unreinforced polycarbonate resin layer is 0.6 to 1 mm, 0.6 to 0.8 mm, or 0.8 to 1 mm, and the thickness of the second unreinforced polycarbonate resin layer is 0.6 to 1 mm, 0.6 to 0.8 mm, or 0.8 to 1 mm.In a preferred embodiment, from the viewpoint of obtaining higher bending strength and bending modulus, the thickness of the carbon fiber reinforced resin layer is 0.8 to 3 mm, 0.8 to 2 mm, 0.8 to 1.9 mm, 0.8 to 1.6 mm, 0.8 to 1.2 mm, 1.2 to 3 mm, 1.2 to 2 mm, 1.2 to 1.9 mm, 1.2 to 1.6 mm, 1.6 to 3 mm, 1.6 to 2 mm, or 1.6 to 1.9 mm, and the thickness of the first unreinforced polycarbonate resin layer is 0.05 to 0.6 mm, 0.05 to 0.6 mm, or 0.4 mm, 0.05 to 0.2 mm, 0.1 to 0.6 mm, 0.1 to 0.4 mm, 0.1 to 0.2 mm, 0.2 to 0.6 mm, 0.2 to 0.4 mm, or 0.4 to 0.6 mm, and the thickness of the second unreinforced polycarbonate resin layer is preferably 0.05 to 0.6 mm, 0.05 to 0.4 mm, 0.05 to 0.2 mm, 0.1 to 0.6 mm, 0.1 to 0.4 mm, 0.1 to 0.2 mm, 0.2 to 0.6 mm, 0.2 to 0.4 mm, or 0.4 to 0.6 mm.

[0145] The laminate according to the present invention may have an additional layer. By including the additional layer, the laminate can have a structure of four or more layers. In this case, examples of the additional layer include a first unreinforced polycarbonate resin layer, a carbon fiber reinforced resin layer, a second unreinforced polycarbonate resin layer, and a functional layer. The functional layer is not particularly limited, but examples thereof include a hard coat layer, an antireflection layer, an antiglare layer, an antistatic layer, a colored layer, an ultraviolet shielding layer, and an infrared shielding layer.

[0146] When the additional layer includes a carbon fiber reinforced resin layer, it is preferable that the laminate is configured so that the carbon fiber reinforced resin layer is not the outermost layer, in order to prevent the carbon fibers contained in the carbon fiber reinforced resin layer from protruding from the surface of the laminate or scattering to the outside due to impact.

[0147] In one embodiment, the laminate preferably comprises a first unreinforced polycarbonate resin layer A, a carbon fiber reinforced resin layer A, a second unreinforced polycarbonate resin layer B, and a third unreinforced polycarbonate resin layer B, arranged in this order. In this case, the carbon fiber reinforced resin layer A and the carbon fiber reinforced resin layer B contain carbon fiber and a third polycarbonate resin. The ratio of the thickness of the first unreinforced polycarbonate resin layer A to the thickness of the carbon fiber reinforced resin layer A (thickness of the first unreinforced polycarbonate resin layer A / thickness of the carbon fiber reinforced resin layer A) is 0.05 to 4. For a preferred range, see the description of the ratio of the thickness of the first unreinforced polycarbonate resin layer to the thickness of the carbon fiber reinforced resin layer (thickness of the first unreinforced polycarbonate resin layer / thickness of the carbon fiber reinforced resin layer) above. According to this embodiment, a laminate with improved impact resistance can be obtained.

[0148] For the ratio of the thickness of the second unreinforced polycarbonate resin layer to the thickness of the carbon fiber reinforced resin layer A (thickness of second unreinforced polycarbonate resin layer / thickness of carbon fiber reinforced resin layer A) and the ratio of the thickness of the second unreinforced polycarbonate resin layer to the thickness of the carbon fiber reinforced resin layer B (thickness of second unreinforced polycarbonate resin layer / thickness of carbon fiber reinforced resin layer B), refer to the description of the ratio of the thickness of the second unreinforced polycarbonate resin layer to the thickness of the carbon fiber reinforced resin layer above (thickness of second unreinforced polycarbonate resin layer / thickness of carbon fiber reinforced resin layer). For the ratio of the thickness of the first unreinforced polycarbonate resin layer B to the thickness of the carbon fiber reinforced resin layer B (thickness of first unreinforced polycarbonate resin layer B / thickness of carbon fiber reinforced resin layer B), refer to the description of the ratio of the thickness of the first unreinforced polycarbonate resin layer to the thickness of the carbon fiber reinforced resin layer (thickness of first unreinforced polycarbonate resin layer / thickness of carbon fiber reinforced resin layer) described above.

[0149] Note that functional layers may be provided between the first unreinforced polycarbonate resin layer A and the carbon fiber reinforced resin layer A, between the carbon fiber reinforced resin layer A and the second unreinforced polycarbonate resin layer, between the second unreinforced polycarbonate resin layer and the carbon fiber reinforced resin layer B, between the carbon fiber reinforced resin layer B and the first unreinforced polycarbonate resin layer B, and on the outermost layer of the laminate (on the first unreinforced polycarbonate resin layer A and / or the first unreinforced polycarbonate resin layer B). In this case, a known configuration may be appropriately adopted as the configuration of the functional layer.

[0150] In another embodiment, the laminate preferably comprises a first unreinforced polycarbonate resin layer A, a carbon fiber reinforced resin layer A, a second unreinforced polycarbonate resin layer A, a carbon fiber reinforced resin layer B, a first unreinforced polycarbonate resin layer B, a carbon fiber reinforced resin layer C, and a second unreinforced polycarbonate resin layer B, arranged in this order. In this case, the carbon fiber reinforced resin layer A, the carbon fiber reinforced resin layer B, and the carbon fiber reinforced resin layer C contain carbon fiber and a third polycarbonate resin. The ratio of the thickness of the first unreinforced polycarbonate resin layer A to the thickness of the carbon fiber reinforced resin layer A (thickness of the first unreinforced polycarbonate resin layer A / thickness of the carbon fiber reinforced resin layer A) is 0.05 to 4, and for a preferred range, see the description of the ratio of the thickness of the first unreinforced polycarbonate resin layer to the thickness of the carbon fiber reinforced resin layer (thickness of the first unreinforced polycarbonate resin layer / thickness of the carbon fiber reinforced resin layer) above. According to this embodiment, a laminate with improved impact resistance can be obtained.

[0151] The configurations of the first unreinforced polycarbonate resin layer A and the first unreinforced polycarbonate resin layer B are the same as those of the first unreinforced polycarbonate resin layer described above. The first unreinforced polycarbonate resin layer A and the first unreinforced polycarbonate resin layer B may have the same or different configurations, but are preferably the same configuration from the viewpoint of improving impact resistance. The configurations of the second unreinforced polycarbonate resin layer A and the second unreinforced polycarbonate resin layer B are the same as those of the second unreinforced polycarbonate resin layer described above. The second unreinforced polycarbonate resin layer A and the second unreinforced polycarbonate resin layer B may have the same or different configurations, but are preferably the same configuration from the viewpoint of improving impact resistance. The configurations of the carbon fiber reinforced resin layer A, the carbon fiber reinforced resin layer B, and the carbon fiber reinforced resin layer C are the same as those of the carbon fiber reinforced resin layer described above. The carbon fiber reinforced resin layer A, the carbon fiber reinforced resin layer B, and the carbon fiber reinforced resin layer C may have the same configuration or different configurations, but from the viewpoint of improving impact resistance, it is preferable that they have the same configuration.

[0152] For the ratio of the thickness of the second unreinforced polycarbonate resin layer A to the thickness of the carbon fiber reinforced resin layer A (thickness of second unreinforced polycarbonate resin layer A / thickness of carbon fiber reinforced resin layer A) and the ratio of the thickness of the second unreinforced polycarbonate resin layer A to the thickness of the carbon fiber reinforced resin layer B (thickness of second unreinforced polycarbonate resin layer A / thickness of carbon fiber reinforced resin layer B), refer to the description of the ratio of the thickness of the second unreinforced polycarbonate resin layer to the thickness of the carbon fiber reinforced resin layer above (thickness of second unreinforced polycarbonate resin layer / thickness of carbon fiber reinforced resin layer). For the ratio of the thickness of the first unreinforced polycarbonate resin layer B to the thickness of the carbon fiber reinforced resin layer B (thickness of first unreinforced polycarbonate resin layer B / thickness of carbon fiber reinforced resin layer B) and the ratio of the thickness of the first unreinforced polycarbonate resin layer B to the thickness of the carbon fiber reinforced resin layer C (thickness of first unreinforced polycarbonate resin layer B / thickness of carbon fiber reinforced resin layer C), refer to the description of the ratio of the thickness of the first unreinforced polycarbonate resin layer to the thickness of the carbon fiber reinforced resin layer above (thickness of first unreinforced polycarbonate resin layer / thickness of carbon fiber reinforced resin layer). The ratio of the thickness of the second unreinforced polycarbonate resin layer B to the thickness of the carbon fiber reinforced resin layer C (thickness of second unreinforced polycarbonate resin layer A / thickness of carbon fiber reinforced resin layer C) is determined by reference to the above-mentioned ratio of the thickness of the second unreinforced polycarbonate resin layer to the thickness of the carbon fiber reinforced resin layer (thickness of second unreinforced polycarbonate resin layer / thickness of carbon fiber reinforced resin layer).

[0153] A functional layer may be provided between the first unreinforced polycarbonate resin layer A and the carbon fiber reinforced resin layer A, between the carbon fiber reinforced resin layer A and the second unreinforced polycarbonate resin layer A, between the second unreinforced polycarbonate resin layer A and the carbon fiber reinforced resin layer B, between the carbon fiber reinforced resin layer B and the first unreinforced polycarbonate resin layer B, between the first unreinforced polycarbonate resin layer B and the carbon fiber reinforced resin layer C, between the carbon fiber reinforced resin layer C and the second unreinforced polycarbonate resin layer B, and on the outermost layer of the laminate (on the first unreinforced polycarbonate resin layer A and / or the second unreinforced polycarbonate resin layer B). In this case, a known configuration may be appropriately adopted as the configuration of the functional layer.

[0154] In another embodiment, the laminate may further include additional layers in the same manner as above. For example, the laminate may have a configuration in which a first unreinforced polycarbonate resin layer A, a carbon fiber reinforced resin layer A, a second unreinforced polycarbonate resin layer A, a carbon fiber reinforced resin layer B, a first unreinforced polycarbonate resin layer B, a carbon fiber reinforced resin layer C, a second unreinforced polycarbonate resin layer B, a carbon fiber reinforced resin layer D, and a first unreinforced polycarbonate resin layer C are arranged in this order.

[0155] The shape of the laminate is not particularly limited and may be any of a flat plate shape, a curved shape, a circular ring shape (cylindrical shape), etc. The laminate according to the present invention is not limited to a flat plate shape, and can be formed into a curved shape, a circular ring shape (cylindrical shape), etc., because the carbon fibers are unlikely to protrude from the surface or scatter to the outside even when a strong impact is applied. Therefore, it can be used for a variety of purposes.

[0156] 2. Method for Producing Laminate According to one aspect of the present invention, there is provided a method for producing the above-described laminate. The method includes a press-molding step of arranging a first unreinforced polycarbonate resin layer, a carbon fiber reinforced resin layer, and a second unreinforced polycarbonate resin layer in this order and integrating them by press-molding. During this press-molding, the press-molding temperature is 160°C or higher but lower than 200°C.

[0157] The first unreinforced polycarbonate resin layer, the carbon fiber reinforced resin layer, and the second unreinforced polycarbonate resin layer can be produced by known methods.

[0158] For example, when each of the first unreinforced polycarbonate resin layer, the carbon fiber reinforced resin layer, and the second unreinforced polycarbonate resin layer is to have a flat plate shape, the flat plate-shaped resin layer can be manufactured by applying a resin solution, drying, stretching, etc. Furthermore, when each of the first unreinforced polycarbonate resin layer, the carbon fiber reinforced resin layer, and the second unreinforced polycarbonate resin layer is to have a circular ring shape (cylindrical shape), the circular ring-shaped (cylindrical shape) resin layer can be manufactured by wrapping a sheet of the resin layer around a mandrel (core metal) that has been heated to 60 to 80°C in advance, and further heating and shaping the resin layer.

[0159] In addition, the shape and directionality of the carbon fibers used in the carbon fiber-reinforced resin layer can be appropriately controlled to obtain a predetermined carbon fiber orientation. For example, by arranging the fiber direction of the unidirectional sheet so that it is parallel to the longitudinal direction of the flat plate shape or the longitudinal direction of the annular (cylindrical) shape, a laminate with high mechanical properties in the longitudinal direction can be produced. Furthermore, by arranging the fiber direction of the unidirectional sheet so that it is perpendicular to the longitudinal direction of the flat plate shape or the longitudinal direction of the annular (cylindrical) shape (i.e., parallel to the transverse direction), a laminate with high mechanical properties in the transverse direction can be produced. Furthermore, by using a fiber sheet laminate in which two unidirectional sheets are stacked at ±45 degrees or a multiaxial carbon fiber stack at ±45 degrees, a laminate with high mechanical properties in multiple directions can be produced.

[0160] A first unreinforced polycarbonate resin layer, a carbon fiber reinforced resin layer, and a second unreinforced polycarbonate resin layer are arranged in this order. In this case, two or more layers can be laminated for each layer in terms of adjusting the thickness, physical properties, etc. For example, by laminating two or more carbon fiber reinforced resin layers, it is possible to adjust the thickness and carbon fiber orientation to a predetermined value.

[0161] The first unreinforced polycarbonate resin layer, the carbon fiber reinforced resin layer, and the second unreinforced polycarbonate resin layer are then integrated by press molding. Since the first unreinforced polycarbonate resin layer, the carbon fiber reinforced resin layer, and the second unreinforced polycarbonate resin layer all contain thermoplastic resins, the layers can be heat-fused together by heating to obtain a laminate. In this case, the mold used for press molding can be appropriately changed depending on the shape of the laminate.

[0162] In addition, when the third polycarbonate resin contained in the carbon fiber reinforced resin layer contains a terminal structure derived from the monohydric phenol terminal blocking agent represented by formula (5), it is possible to obtain effects such as easing the molding conditions and application conditions of the molding device, reducing the energy required for molding, and suppressing overheating during press molding.

[0163] The temperature for press molding is 160°C or higher and lower than 200°C, preferably 160 to 195°C, and more preferably 170 to 180°C. The contact pressure for press molding is preferably 0.2 to 5 MPa, and more preferably 0.3 to 3 MPa. The pressing time is preferably 5 to 60 minutes, and more preferably 5 to 30 minutes.

[0164] Since the third polycarbonate resin according to the present invention is a thermoplastic resin, the molding time can be significantly reduced compared to when a thermosetting resin such as an epoxy resin is used. Furthermore, the third polycarbonate resin according to the present invention can be molded at a temperature of 160°C or higher but lower than 200°C, which reduces production costs.

[0165] The press molding can be carried out in two stages as needed. For example, after the first press molding is carried out at a temperature of 170 to 180°C and a contact pressure of 0.2 to 1 MPa, the second press molding can be carried out at a contact pressure of more than 1 MPa but not more than 5 MPa.

[0166] When the laminate has an additional layer, the laminate can be manufactured by integrating the first unreinforced polycarbonate resin layer, the carbon fiber reinforced resin layer, and the second unreinforced polycarbonate resin layer by a press molding process, and then forming the additional layer. Alternatively, the laminate can be manufactured by integrating the additional layer with the first unreinforced polycarbonate resin layer, the carbon fiber reinforced resin layer, and the second unreinforced polycarbonate resin layer.

[0167] For example, when the laminate has a five-layer structure in which a first unreinforced polycarbonate resin layer A, a carbon fiber reinforced resin layer A, a second unreinforced polycarbonate resin layer, a carbon fiber reinforced resin layer B, and a first unreinforced polycarbonate resin layer B are arranged in this order, a five-layer laminate can be manufactured by arranging these five layers in order and performing a press molding process in which they are integrated by press molding.

[0168] According to one aspect of the present invention, there is provided a molded article including the laminate described above. The laminate according to the present invention is highly safe, as the carbon fibers are unlikely to protrude from the surface or scatter to the outside even when subjected to a strong impact, and can be used in a variety of molded articles.

[0169] Specific examples of molded articles include mobility components (aircraft components, etc.), bicycle components (bicycles, road bikes, bicycle motocross (BMX)), spacecraft components, ship components, civil engineering and construction materials, sporting goods, drones, helmets, prosthetic limbs, etc.

[0170] For example, if the molded article is an aircraft component, it can absorb impact in the event of a crash, and the carbon fibers are unlikely to protrude from the surface of the aircraft component or scatter outside. This can prevent parachutes escaping from being injured by flying debris generated when the aircraft crashes. Furthermore, even if a strong impact is applied while wearing a helmet, the impact can be absorbed, and the carbon fibers are unlikely to protrude from the surface or scatter outside when the helmet is broken, so the helmet wearer can be protected from injury.

[0171] The present invention will be specifically explained below with reference to examples, but the present invention is not limited to these examples.

[0172] Example 1 (1) Production of Carbon Fiber Reinforced Polycarbonate Resin Sheet After producing bisphenol A polycarbonate resin, a carbon fiber reinforced polycarbonate resin sheet was produced by compounding the resin with a carbon fiber fabric.

[0173] The bisphenol A polycarbonate resin was prepared as follows.

[0174] Specifically, 100 g (0.44 mol) of bisphenol A (BPA, manufactured by Mitsubishi Chemical Corporation) and 0.3 g of antioxidant hydrosulfite (sodium hyposulfite) were dissolved in 650 mL of 9 wt% aqueous sodium hydroxide solution. 385 mL of dichloromethane was added to the resulting solution, and while stirring, 60.0 g of phosgene was bubbled in over 40 minutes while maintaining the solution temperature in the range of 15°C to 25°C. After the phosgene bubble was completed, 100 mL of 9 wt% aqueous sodium hydroxide solution and a solution of 6.23 g (0.017 mol) of cetyl parahydroxybenzoate (CEPB, manufactured by Ueno Pharmaceutical Co., Ltd.) dissolved in 100 mL of dichloromethane were added. The resulting mixture was emulsified by vigorously stirring, and then 0.2 mL of triethylamine was added as a polymerization catalyst, followed by polymerization for approximately 40 minutes. The polymerization solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and the resulting solution was repeatedly washed with pure water until the pH of the washings became neutral, thereby obtaining a polycarbonate resin solution having a resin concentration of 15% by mass.

[0175] Next, the carbon fiber fabric was compounded to form a carbon fiber reinforced polycarbonate resin sheet.

[0176] Specifically, a carbon fiber fabric, Torayka Cloth CO6347B (manufactured by Toray Industries, Inc., 3000 filament carbon fiber, carbon fiber single fiber diameter: 7 μm, warp threads: 12.5 threads / 25 mm, weft threads: 12.5 threads / 25 mm, basis weight: 198 g / m ２The sheet was impregnated with the polycarbonate resin solution prepared above, dried in a hot air dryer at 70°C for 1 minute, and then dried in a hot air dryer at 130°C for 30 minutes to obtain a carbon fiber reinforced polycarbonate resin sheet (thickness: 0.2 mm, carbon fiber content: 64% by mass (55% by volume)).

[0177] (2) Production of Laminate (Flat Plate) One Iupilon sheet NF-2000 (polycarbonate resin, thickness: 0.1 mm, manufactured by Mitsubishi Gas Chemical Co., Inc.), nine laminated carbon fiber reinforced polycarbonate resin sheets (thickness of each sheet: 0.2 mm), and one Iupilon sheet NF-2000 were laminated in this order and press molded under the following conditions.

[0178] Contact pressure: 0.5 MPa Press mold temperature: set to 175°C Press time: 15 minutes

[0179] Following press molding, the contact pressure was increased to 2.0 MPa, and the mixture was pressed for an additional 5 minutes. While maintaining the pressure, the mixture was cooled to 80°C and demolded to produce a laminate (plate) including a first unreinforced polycarbonate resin layer, a carbon fiber reinforced resin layer, and a second unreinforced polycarbonate resin layer.

[0180] Examples 2 to 6 By appropriately changing the number of Iupilon Sheet NF-2000 layers, the number of carbon fiber reinforced polycarbonate resin sheets, and the number of Iupilon Sheet NF-2000 layers, laminates (flat plates) with different thicknesses of the first unreinforced polycarbonate resin layer, the carbon fiber reinforced resin layer, and the second unreinforced polycarbonate resin layer were produced.

[0181] Comparative Example 1 A laminate (flat plate) consisting of a carbon fiber reinforced resin layer (B) was produced in the same manner as in Example 1, except that 10 carbon fiber reinforced polycarbonate resin sheets were laminated together and no Iupilon sheet NF-2000 was laminated on either side of the laminate.

[0182] The laminates (flat plates) produced in Examples 1 to 6 and Comparative Example 1 are shown in Table 1 below.

[0183] [Evaluation] The laminates (flat plates) produced in Examples 1 to 6 and Comparative Example 1 were subjected to various evaluations.

[0184] (1) Charpy impact strength Measurements were made in accordance with JIS K 7077:1991. Specific details are as follows: Test item: Charpy impact strength Test piece shape: 80 x 10 x t2 (mm) strip Test conditions: Orientation: flatwise Distance between branches: 62 mm Nominal pendulum energy: 7.5 J Lifting angle: 150 degrees Number of tests: n=10 Test room environment: 23°C ± 2°C, 50% RH ± 10% RH Measuring device: Digital impact tester DG-UB type (manufactured by Toyo Seiki Seisakusho Co., Ltd.)

[0185] (2) Charpy Fracture Mode After measuring the Charpy impact strength in (1) above, the samples were visually observed, observed under an optical microscope, and / or tactilely inspected, and evaluated according to the following criteria.

[0186] A: No fracture. B: Ductile fracture, in which the carbon fibers of the carbon fiber reinforced resin layer (B) do not protrude from the surface of the first unreinforced polycarbonate layer (A) or the second unreinforced polycarbonate layer (C). C: Brittle fracture, in which the carbon fibers of the carbon fiber reinforced resin layer (B) do not protrude from the surface of the first unreinforced polycarbonate layer (A) or the second unreinforced polycarbonate layer (C). D: Brittle fracture, in which the carbon fibers of the carbon fiber reinforced resin layer (B) protrude from the surface of the first unreinforced polycarbonate layer (A) or the second unreinforced polycarbonate layer (C).

[0187] Here, ductile fracture means that fracture occurs with at least 5% or more plastic deformation. In the case of ductile fracture, the sample laminate (flat plate) is broken after absorbing energy and bending (bending loss), so carbon fibers tend not to protrude from the surface of the laminate (flat plate) or scatter from the laminate (flat plate) to the outside. In addition, brittle fracture means that fracture occurs without plastic deformation (plastic deformation less than 5%). In the case of brittle fracture, the sample laminate (flat plate) is broken without absorbing almost any energy (breakage), so carbon fibers tend to protrude from the surface of the laminate (flat plate) or scatter from the laminate (flat plate) to the outside.

[0188] Schematic diagrams of the laminates (flat plates) in Examples 2 to 4 and Comparative Example 1, as well as schematic diagrams and photographs of samples after Charpy impact strength measurement, are shown in Figure 1. Figure 1A shows the results for Example 2, Figure 1B shows the results for Example 3, Figure 1C shows the results for Example 4, and Figure 1D shows the results for Comparative Example 1. Referring to the schematic diagram and photograph in Figure 1D (Comparative Example 1), it can be seen that the sample laminate (flat plate) in Comparative Example 1 breaks, indicating brittle fracture. Furthermore, the schematic diagram and photograph in Figure 1D (Comparative Example 1) reveal that the sample laminate (flat plate) is split into two at the break, with carbon fibers protruding from the surface at the break. On the other hand, referring to the schematic diagrams and photographs in Figure 1A (Example 2) and Figure 1B (Example 3), it can be seen that both show bending damage accompanied by plastic deformation, indicating ductile fracture. Furthermore, it can be seen that protruding carbon fibers are barely observed in the photograph in Figure 1A (Example 2), and even less so in Figure 1B (Example 3). As is clear from the schematic diagram and photograph, Figure 1C (Example 4) shows that the structure is undamaged. If carbon fibers protrude from the surface or scatter to the outside, the protruding or scattered carbon fibers may injure the user (e.g., the helmet wearer if the product is intended for use as a helmet). However, if the protrusion or scattering of carbon fibers can be suppressed or prevented, as in Figures 1A to 1C, injury to the user can be suppressed, providing high safety.

[0189] (3) Flexural strength and flexural modulus Measurements were made in accordance with JIS K 7074:1998. Specific details are as follows: Measurement items: flexural strength, flexural modulus Test piece shape: strip 100 x 15 x t2.0 (mm) Test conditions: Test speed: 5 mm / min Distance between branches: 80 mm Indenter radius R1: 5 mm Support table radius R2: 2 mm Number of measurements: n=5 Test room environment: 23°C ± 2°C, 50% RH ± 10% RH Measuring device: Universal testing machine (Shimadzu Corporation)

[0190] (4) Bending Test Breakdown Mode After measuring the bending strength and bending modulus in (3) above, the samples were visually observed, observed under an optical microscope, and / or touched with fingers, and evaluated according to the following criteria. A: Ductile fracture, the fracture location cannot be identified visually, and the carbon fibers of the carbon fiber reinforced resin layer (B) do not protrude from the surface of the first unreinforced polycarbonate layer (A) or the second unreinforced polycarbonate layer (C). B: Ductile fracture, the fracture location can be identified visually, and the carbon fibers of the carbon fiber reinforced resin layer (B) do not protrude from the surface of the first unreinforced polycarbonate layer (A) or the second unreinforced polycarbonate layer (C). C: Brittle fracture, and the carbon fibers of the carbon fiber reinforced resin layer (B) do not protrude from the surface of the first unreinforced polycarbonate layer (A) or the second unreinforced polycarbonate layer (C). D: Brittle fracture, and the carbon fibers of the carbon fiber reinforced resin layer (B) protrude from the surface of the first unreinforced polycarbonate layer (A) or the second unreinforced polycarbonate layer (C).

[0191] Schematic diagrams of the laminates (flat plates) in Examples 2 to 4 and Comparative Example 1, as well as stress-strain curves during measurement of bending strength and bending modulus, are shown in Figure 2. Figure 2A shows the results for Example 2, Figure 2B shows the results for Example 3, Figure 2C shows the results for Example 4, and Figure 2D shows the results for Comparative Example 1. When stress drops sharply after brittle fracture (breakage), as in the stress-strain curve of Figure 2D (Comparative Example 1), the total amount of bending energy absorbed by the laminate (flat plate) of Comparative Example 1 is small. In the stress-strain curve of Figure 2A (Example 2), the stress drop after brittle fracture (breakage) is suppressed, so the total amount of bending energy absorbed by the laminate (flat plate) of Example 2 is improved compared to Comparative Example 1. In the stress-strain curves of Figure 2B (Example 3) and Figure 2C (Example 4), stress does not drop even after ductile fracture (bending loss), but is maintained or even increased, so the total amount of bending energy absorbed by the laminates (flat plates) of Examples 3 and 4 is high.

[0192] The evaluation results of (1) to (4) above are shown in Table 2 below.

[0193]

[0194] The laminates of Examples 1 to 6 all had a Charpy fracture mode of C or higher, and even at the time of fracture, the carbon fibers did not protrude from the surface layer of the laminate but remained inside the laminate, indicating that they are highly safe.

[0195] Example 7 A laminate (a torus) was produced.

[0196] (1) Formation of a Circular Ring-Shaped First Unreinforced Polycarbonate Layer Figure 3 is a schematic diagram of an apparatus for forming a circular ring-shaped first unreinforced polycarbonate layer. A first unreinforced polycarbonate layer (thickness: 0.7 mm, not shown) consisting of seven Iupilon Sheet NF-2000 sheets (thickness: 0.1 mm) stacked together was placed between a mandrel (core) 1 with an outer diameter of 200 mm, the surface of which was coated with a release agent, and a semi-cylindrical lower mold part 3 connected to a hot plate 2. The heated lower mold part 3 was pressed against the mandrel (core) 1, thereby deforming the first unreinforced polycarbonate layer placed between the mandrel (core) 1 and the lower mold part 3.

[0197] The first unreinforced polycarbonate layer was rotated 45 degrees, and the heated lower mold part 3 was pressed against the mandrel (core metal) 1 again, thereby further deforming the first unreinforced polycarbonate layer. This process was repeated once more to form a circular first unreinforced polycarbonate layer (thickness: 0.7 mm). The end of the circular first unreinforced polycarbonate layer was heat-sealed using a soldering iron after the excess length was cut off.

[0198] (2) Formation of a Circular Carbon Fiber Reinforced Resin Layer A circular carbon fiber reinforced resin layer was formed on a 0.7 mm thick first unreinforced polycarbonate layer formed on the surface of a mandrel (core) with an outer diameter of 200 mm. Specifically, the carbon fiber reinforced polycarbonate resin sheet (thickness: 0.2 mm, carbon fiber content: 64% by mass (55% by volume)) produced in Example 1 was wrapped three times around the first unreinforced polycarbonate layer while applying back tension and heating with a heat gun, to form a circular carbon fiber reinforced resin layer (thickness: 0.6 mm). The excess length of the end of the circular carbon fiber reinforced resin layer was then cut off and heat-sealed using a soldering iron.

[0199] (3) Formation of a Circular Ring-Shaped Third Unreinforced Polycarbonate Layer A circular ring-shaped third unreinforced polycarbonate layer (thickness: 0.7 mm) was formed in the same manner as in the formation of the above-described circular ring-shaped first unreinforced polycarbonate layer, and then the layer was removed from the mandrel (core metal).

[0200] A third unreinforced polycarbonate layer (thickness: 0.7 mm) having a circular ring shape was wound around the surface (carbon fiber reinforced resin layer surface) of a laminate in which a mandrel (core metal), a first unreinforced polycarbonate layer, and a carbon fiber reinforced resin layer were arranged in this order, forming a third unreinforced polycarbonate layer (thickness: 0.7 mm). At this time, the springback force of the third unreinforced polycarbonate layer was utilized to laminate the third unreinforced polycarbonate layer in a state of intimate contact with the carbon fiber reinforced resin layer. The end of the third unreinforced polycarbonate layer was then heat-sealed using a soldering iron after the excess length was cut off.

[0201] (4) Manufacturing of Laminate (Torus) A laminate (torus) was manufactured by integrating a laminate in which a first unreinforced polycarbonate resin layer, a carbon fiber reinforced resin layer, and a second unreinforced polycarbonate resin layer were arranged in this order by press molding.

[0202] FIG. 4 is a schematic diagram of the apparatus used to integrate the laminate. A circular laminate 4, consisting of a first unreinforced polycarbonate layer, a carbon fiber-reinforced resin layer, and a second unreinforced polycarbonate layer arranged in this order, was wound around the surface of a mandrel (core) 1 with an outer diameter of 200 mm. The mandrel (core) 1 around which the circular laminate 4 was wound was placed between a semi-cylindrical lower mold part 3 connected to a hot plate 2 and a semi-cylindrical upper mold part 6 connected to a hot plate 5, and clamped between the lower mold part 3 and the upper mold part 6. At this time, the surface temperature of the lower mold part 3 and the upper mold part 6 was 175°C. After clamping, the mandrel (core) was pressed at 0.5 MPa for 15 minutes, then at 2 MPa for 5 minutes, to form a circular laminate 4. After cooling, the mandrel (core) around which the laminate (circular body) was wound was removed and cooled with liquid nitrogen. The laminate (annular ring) was removed from the mandrel (core metal) whose volume had been shrunk by liquid nitrogen, to obtain a laminate (annular ring). The laminate (annular ring) was a laminate (total thickness: 2 mm) consisting of a first unreinforced polycarbonate layer (thickness: 0.7 mm), a carbon fiber reinforced resin layer (thickness: 0.6 mm), and a third unreinforced polycarbonate layer (thickness: 0.7 mm). The inner diameter (diameter) of the laminate (annular ring) was 200 mm.

[0203] Comparative Example 2 A torus composed of a carbon fiber reinforced resin layer was produced. Specifically, the carbon fiber reinforced polycarbonate resin sheet (thickness: 0.2 mm, carbon fiber content: 64% by mass (55% by volume)) produced in Example 1 was wrapped 10 degrees around the surface of a mandrel (core metal) with an outer diameter of 200 mm while applying back tension and heating with a heat gun, to produce a torus-shaped carbon fiber reinforced resin layer (thickness: 0.6 mm). The excess length of the end of the torus-shaped carbon fiber reinforced resin layer was then cut off and heat-fused using a soldering iron. A torus composed of a carbon fiber reinforced resin layer (thickness: 2 mm) was produced by press molding in the same manner as in Example 7.

[0204] Comparative Example 3: A torus was produced using a carbon fiber reinforced resin layer in which epoxy resin was used instead of polycarbonate resin. Specifically, a carbon fiber woven fabric, Torayka Cloth CO6347B (manufactured by Toray Industries, Inc., 3000 filament carbon fiber, carbon fiber diameter: 7 μm, warp threads: 12.5 / 25 mm, weft threads: 12.5 / 25 mm, basis weight: 198 g / m) was used. ２ ) was impregnated with an epoxy resin solution containing cresol novolac epoxy resin N-673 (epoxy equivalent: 210, manufactured by DIC Corporation), dicyandiamide as an amine curing agent, and 2-ethyl-4-imidazole as an accelerator for the amine curing agent, followed by coating and semi-curing to produce a carbon fiber reinforced resin layer using epoxy resin (thickness: 0.2 mm, resin content: 36% by mass (45% by volume), carbon fiber content: 64% by mass (55% by volume)). A torus made of a carbon fiber reinforced resin layer (thickness: 2 mm) was produced using the carbon fiber reinforced resin layer using the epoxy resin in the same manner as in Comparative Example 2.

[0205] [Evaluation] The toric bodies produced in Example 7 and Comparative Examples 2 and 3 were subjected to various evaluations.

[0206] (1) Preparation of Measurement Samples The torus was cut into a circumferential length of 15 mm and an axial length of 100 mm to prepare curved rectangular measurement samples. The arrow height (height of the arc) of the measurement samples was 0.28 mm.

[0207] The bending strength, bending modulus, and fracture mode of the bending test were evaluated in the same manner as in the evaluation of the laminate (flat plate). The results are shown in Table 3 below.

[0208] The results in Table 3 show that the laminate has a toric shape, the Charpy fracture mode is C or higher, and even at the time of fracture, the carbon fibers do not protrude from the surface layer of the laminate but remain inside the laminate, thereby providing a high level of safety.

[0209] Example 8 A five-layer laminate (flat plate) was produced, specifically a laminate (flat plate) having a first unreinforced polycarbonate resin layer A, a carbon fiber reinforced resin layer A, a second unreinforced polycarbonate resin layer, a carbon fiber reinforced resin layer B, and a first unreinforced polycarbonate resin layer B laminated in this order.

[0210] Seven stacked Iupilon NF-2000 sheets (thickness of each sheet: 0.1 mm) were used as the first unreinforced polycarbonate layer A and the first unreinforced polycarbonate layer B. Seven stacked Iupilon NF-2000 sheets (thickness of each sheet: 0.1 mm) were used as the second unreinforced polycarbonate layer. One carbon fiber reinforced polycarbonate resin sheet (thickness of each sheet: 0.2 mm) produced in Example 1 was used as the carbon fiber reinforced resin layer A and the carbon fiber reinforced resin layer B.

[0211] A laminate (flat plate) was produced by laminating the first unreinforced polycarbonate layer A, the carbon fiber reinforced resin layer A, the second unreinforced polycarbonate layer, the carbon fiber reinforced resin layer B, and the first unreinforced polycarbonate layer B in this order and performing press molding under the same conditions as in Example 1.

[0212] Examples 9 and 10 By appropriately changing the number of Iupilon sheets NF-2000 laminated and the number of carbon fiber reinforced polycarbonate resin sheets laminated, laminates (flat plates) were produced in which the thicknesses of the first unreinforced polycarbonate layer A, the carbon fiber reinforced resin layer A-second unreinforced polycarbonate layer, the carbon fiber reinforced resin layer B, and the first unreinforced polycarbonate layer B were different.

[0213] The five-layer laminates (flat plates) produced in Examples 8 to 10 are shown in Tables 4 and 5 below.

[0214]

[0215]

[0216] [Evaluation] The five-layer laminates (flat plates) of Examples 8 to 10 were evaluated in the same manner as in Examples 1 to 6 and Comparative Example 1. However, the Charpy fracture mode and bending test fracture mode were observed and confirmed for the first unreinforced polycarbonate layer A, the carbon fiber reinforced resin layer A, and the second unreinforced polycarbonate layer. The results are shown in Table 6 below.

[0217] The laminates of Examples 8 to 10 all had a Charpy fracture mode of B or higher, and even at the time of fracture, the carbon fibers did not protrude from the surface layer of the laminate but remained inside the laminate, indicating that they are highly safe.

Claims

1. A laminate comprising a first unreinforced polycarbonate resin layer containing a first polycarbonate resin, a carbon fiber reinforced resin layer, and a second unreinforced polycarbonate resin layer containing a second polycarbonate resin, arranged in this order, wherein the carbon fiber reinforced resin layer contains carbon fiber and a third polycarbonate resin, and the third polycarbonate resin is a polycarbonate resin containing a bisphenol, a carbonate binder, and a carboxylic acid represented by the following formula (5): (In the above formula, R ３ is an alkyl group having 1 to 30 carbon atoms or an alkenyl group having 8 to 30 carbon atoms, R ４ are each independently a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and c is 0 to 4), and a monohydric phenol end-terminator represented by the formula (I), wherein the ratio of the thickness of the first unreinforced polycarbonate resin layer to the thickness of the carbon fiber reinforced resin layer (thickness of the first unreinforced polycarbonate resin layer / thickness of the carbon fiber reinforced resin layer) is 0.05 to 4.

2. The laminate according to claim 1, wherein the ratio of the thickness of the second unreinforced polycarbonate resin layer to the thickness of the carbon fiber reinforced resin layer (thickness of the second unreinforced polycarbonate resin layer / thickness of the carbon fiber reinforced resin layer) is 0.05 to 4.

3. The laminate according to claim 1, wherein the carbon fiber reinforced resin layer has a thickness of 0.1 to 3 mm, and the first unreinforced polycarbonate resin layer has a thickness of 0.05 to 1 mm.

4. The laminate according to claim 3, wherein the thickness of the second unreinforced polycarbonate resin layer is 0.05 to 1 mm.

5. The laminate of claim 1, wherein the bisphenol comprises bisphenol A.

6. The monohydric phenol end-terminator represented by the formula (5) is a monohydric phenol end-terminator represented by the formula (5-1): (In the above formula, R ３ wherein R is an alkyl group having 1 to 30 carbon atoms or an alkenyl group having 8 to 30 carbon atoms.

7. The laminate according to claim 6, wherein the monohydric phenol end-terminator represented by formula (5) includes cetyl parahydroxybenzoate.

8. The laminate of claim 1, which is a torus.

9. A molded article comprising the laminate according to any one of claims 1 to 8.

10. A method for producing the laminate according to any one of claims 1 to 8, comprising a press molding step of arranging a first unreinforced polycarbonate resin layer, a carbon fiber reinforced resin layer, and a second unreinforced polycarbonate resin layer in this order and integrating them by press molding, wherein the press molding temperature is 160°C or higher but lower than 200°C.

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