Polycarbonate resin composition

Abstract

The present invention provides a polycarbonate-based coating resin composition which exhibits high adhesiveness.　The above are achieved by means of a polycarbonate resin composition which contains (A) a polycarbonate resin that contains a constituent unit represented by general formula (1) and a terminal structure represented by general formula (2) and (B) a polyisocyanate compound, wherein 0.1% by mass or more of the polyisocyanate compound (B) is contained on the basis of the total mass of the polycarbonate resin (A) and the polyisocyanate compound (B). (In formula (1) and formula (2), R1 to R3, X, m and n are as defined in the description.)

Description

[Technical field]

[0001] The present invention relates to a polycarbonate resin composition and the like, and more particularly to a polycarbonate resin composition that can be used for a polycarbonate coating resin solution and the like that has excellent adhesion to a substrate. [Background technology]

[0002] Polycarbonate resins are excellent in transparency and moldability, and also have excellent mechanical properties such as impact resistance, and are therefore used in electrical products, automobiles, and other mechanical products. Among these, polycarbonate resin solutions are known for obtaining functional thin films and for coating articles (Patent Document 1).

[0003] Although the coating film obtained from the polycarbonate resin solution has excellent durability such as impact resistance, it has poor adhesion, and it is known that it is used for easily peelable nail polish by utilizing this property (Patent Document 2). Therefore, there is room for improvement in the adhesion between these coating films and the substrate.

[0004] As a resin composition in which a polycarbonate resin is blended with another resin, for example, a blended resin composition of a polycarbonate resin and a polyphenylene ether resin is known, but this blended resin composition does not improve adhesion (Patent Document 3). Therefore, there is still a demand for the development of a polycarbonate resin composition that can improve the adhesion between a coating film and a substrate. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 4-268365 [Patent Document 2] JP 2014-024789 A [Patent Document 3] Patent No. 6340811 Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention provides a blend resin composition of a polycarbonate resin and another resin, which can improve the adhesion between a coating film and a substrate. [Means for solving the problem]

[0007] As a result of extensive investigations, the present inventors have found that a blend resin composition of a specific polycarbonate resin and a polyisocyanate compound can be used in a solution that forms a strong coating film having high adhesion to a substrate, and have thus completed the present invention.

[0008] That is, the present invention includes the following aspects.

[0009] <1> A polycarbonate resin (A) containing a structural unit represented by the following general formula (1) and a terminal structure represented by the following general formula (2): A polyisocyanate compound (B), A polycarbonate resin composition containing 0.1 mass % or more of the polyisocyanate compound (B) based on the total mass of the polycarbonate resin (A) and the polyisocyanate compound (B). [ka] [ka] (In formula (1), R1 and R2 each independently represent an alkyl group having 1 to 4 carbon atoms; and n each independently represents an integer of 0 to 4, provided that no n is 0; X is -O-, -S-, -SO-, -SO2-, -CO-, or a divalent group represented by any one of the following general formulas (3) to (8). (In formula (2), R3 each independently represents an alkyl group having 1 to 8 carbon atoms which may be substituted by a hydroxyl group, m is an integer from 0 to 5. [ka] (In general formula (3), R8~R 17 each independently represents hydrogen or an alkyl group having 1 to 3 carbon atoms; R to R 17 at least one of the groups represents an alkyl group having 1 to 3 carbon atoms; In general formulas (4) to (8), R 18 and R 19 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, an aralkyl group having 7 to 17 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms which may have a substituent, R 18 and R 19 are bonded to each other to form a carbocyclic ring having 3 to 20 carbon atoms or a heterocyclic ring having 1 to 20 carbon atoms; R 20 represents an alkylene group having 1 to 9 carbon atoms which may have a substituent, c represents an integer from 0 to 20; d represents an integer from 1 to 500.

[0010] <2> R1 and R2 in the general formula (1) are methyl groups, n is 1 in each case, the above <1> 10. The polycarbonate resin composition according to claim 9 .

[0011] <3> R in the general formula (4) 18 and R 19 is a methyl group and c is 1, <2> 10. The polycarbonate resin composition according to claim 9 .

[0012] <4> In the polycarbonate resin (A), the structural unit represented by the general formula (1) is contained in an amount of 40 mol % or more based on the number of moles of all structural units. <1> ~ <3> 10. The polycarbonate resin composition according to claim 9,

[0013] <5> The above, wherein R3 in the general formula (2), which is a terminal group of the polycarbonate resin (A), is an alkyl group having 1 to 4 carbon atoms which may be substituted with one hydroxyl group. <1> ~ <4> 10. The polycarbonate resin composition according to claim 9,

[0014] <6> The viscosity average molecular weight (Mv) of the polycarbonate resin is 10,000 to 60,000. <1> ~ <5> 10. The polycarbonate resin composition according to claim 9,

[0015] <7> The above-mentioned is a mixture of the polycarbonate resin (A) and the polyisocyanate compound (B). <1> ~ <6> 10. The polycarbonate resin composition according to claim 9,

[0016] <8> The polyisocyanate compound (B) contains at least one of hexamethylene diisocyanate and xylylene diisocyanate. <1> ~ <7> 10. The polycarbonate resin composition according to claim 9,

[0017] <9> the above <1> ~ <8> A resin solution comprising the polycarbonate resin composition according to any one of claims 1 to 5 and an organic solvent.

[0018] <10> The organic solvent includes at least one of a non-halogen-based solvent, an ester-based solvent, an ether-based solvent, a carbonate-based solvent, and a ketone-based solvent. <9> The resin solution according to claim 1.

[0019] <11> the above <9> or <10> A printing ink using the resin solution described in the above as a binder resin solution.

[0020] <12> the above <11> A substrate film coated with the printing ink described in 1.

[0021] <13> the above <1> ~ <8> 2. A film or coating comprising the polycarbonate resin composition according to claim 1.

[0022] <14> The film comprises a film laminate. <13> 2. The film or coating according to claim 1. Effect of the Invention

[0023] A resin film obtained from a resin solution containing the resin composition of the present invention has the advantage of being stronger in adhesion to a substrate and less likely to peel off than conventional polycarbonate resin films. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0024] The present invention relates to a polycarbonate resin composition containing a specific polycarbonate resin and a polyisocyanate compound, a resin solution containing the polycarbonate resin composition, a printing ink containing the resin solution, a substrate film coated with the printing ink, and a film or coating containing the polycarbonate resin composition. Each of these objects of the present invention will be described below.

[0025] 1. Polycarbonate resin composition As described above, the polycarbonate resin composition of the present invention contains the polycarbonate resin (A) and the polyisocyanate compound (B). The polycarbonate resin composition preferably contains the polycarbonate resin (A) and the polyisocyanate compound (B) as a mixture. As described above, the polycarbonate resin composition of the present invention contains 0.1 mass% or more of the polyisocyanate compound (B) based on the total mass of the polycarbonate resin (A) and the polyisocyanate compound (B). In one embodiment of the present invention, the amount of the polyisocyanate compound (B) in the above total mass is 1.0 mass% or more, preferably 3.0 mass% or more, more preferably 5.0 mass% or more, even more preferably 6.5 mass% or more, particularly preferably 8.0 mass% or more, for example, more than 10 mass%. In one embodiment of the present invention, the amount of the polyisocyanate compound (B) contained in the polycarbonate resin composition may be 0.1 part by mass or more, preferably 1.0 part by mass or more, more preferably 3.0 parts by mass or more, even more preferably 5.0 parts by mass or more, particularly preferably 8.0 parts by mass or more, for example, more than 10 parts by mass, per 100 parts by mass of the polycarbonate resin (A). Even if the polyisocyanate compound (B) is used in excess relative to the polycarbonate resin (A), the adhesive effect can be obtained, so the upper limit of the content of the polyisocyanate compound (B) in the resin composition is not particularly important. However, in one embodiment of the present invention, the amount of the polyisocyanate compound (B) in the above total mass may be, for example, 50 mass% or less, preferably 45 mass% or less, more preferably 40 mass% or less, even more preferably 35 mass% or less, and particularly preferably 30 mass% or less. The amount of the polyisocyanate compound (B) may be, for example, 50 parts by mass or less, preferably 45 parts by mass or less, more preferably 40 parts by mass or less, even more preferably 35 parts by mass or less, and particularly preferably 30 parts by mass or less, relative to 100 parts by mass of the polycarbonate resin (A).

[0026] 2. Polycarbonate resin (A) As described above, the polycarbonate resin (A) contained in the polycarbonate resin composition has a structural unit represented by formula (1) (hereinafter also referred to as structural unit (1)) and a terminal structure represented by formula (2) (hereinafter also referred to as terminal structure (2)). The oxygen atom of the terminal structure (2) is bonded to the carbonyl carbon (carbon of the carbonyl group of C=O) of the structural unit at the end of the polymer chain among the structural units represented by formula (1). [ka] [ka] (In formula (1), R1 and R2 each independently represent an alkyl group having 1 to 4 carbon atoms; Each n is independently an integer of 0 to 4, with the proviso that no n is 0, and X is -O-, -S-, -SO-, -SO2-, -CO-, or a divalent group represented by any one of the following general formulas (3) to (8). (In formula (2), R3 each independently represents an alkyl group having 1 to 8 carbon atoms which may be substituted by a hydroxyl group, m is an integer from 0 to 5. [ka] (In general formula (3), R8~R 17 each independently represents hydrogen or an alkyl group having 1 to 3 carbon atoms; R to R 17 at least one of the groups represents an alkyl group having 1 to 3 carbon atoms; In general formulas (4) to (8), R 18 and R 19 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, an aralkyl group having 7 to 17 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms which may have a substituent, R 18 and R 19 are bonded to each other to form a carbocyclic ring having 3 to 20 carbon atoms or a heterocyclic ring having 1 to 20 carbon atoms; R 20 represents an alkylene group having 1 to 9 carbon atoms which may have a substituent, c represents an integer from 0 to 20; d represents an integer from 1 to 500.

[0027] In one embodiment of the present invention, the terminal structure (2) may be contained in an amount of 0.5 mol % or more and 12 mol % or less, preferably 1.0 mol % or more and 10 mol % or less, and more preferably 1.5 mol % or more and 8 mol % or less, based on the total number of moles of the structural unit (1) and the terminal structure (2).

[0028] (i) Structural unit (1) In one embodiment of the present invention, in the structural unit (1), R1 and R2 are each independently an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms, and particularly preferably a methyl group. In the structural unit (1), the value of n, which indicates the number of R1 and R2, is each independently an integer of 0 to 4, with the proviso that neither n is 0. The values ​​of n are preferably each independently an integer of 1 to 4, more preferably each independently an integer of 1 to 3, more preferably each independently an integer of 1 or 2, and even more preferably both are 1.

[0029] In one embodiment of the present invention, in the structural unit (1), X is -O-, -S-, -SO-, -SO2-, -CO-, or a divalent group represented by any one of the following general formulas (3) to (8). [ka] (In general formula (3), R8~R 17 each independently represents hydrogen or an alkyl group having 1 to 3 carbon atoms, R8~R 17 at least one of the groups represents an alkyl group having 1 to 3 carbon atoms; In general formulas (4) to (8), R 18 and R 19 each independently represents hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, an aralkyl group having 7 to 17 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms which may have a substituent, R 18 and R 19 are bonded to each other to form a carbocyclic ring having 3 to 20 carbon atoms or a heterocyclic ring having 1 to 20 carbon atoms; R 20 represents an alkylene group having 1 to 9 carbon atoms which may have a substituent, c represents an integer from 0 to 20; d represents an integer from 1 to 500.

[0030] In one embodiment of the present invention, in the structural unit (1), when X is a divalent group represented by the above general formula (3), R 17 each independently represents hydrogen or an alkyl group having 1 to 3 carbon atoms, preferably hydrogen or a methyl group, and R to R 17 At least one of these represents an alkyl group having 1 to 3 carbon atoms. In one embodiment of the present invention, R to R 17 may each independently be hydrogen, methyl, ethyl, n-propyl, or isopropyl, and R to R 17 At least one of is methyl, ethyl, n-propyl, or isopropyl.

[0031] In one embodiment of the present invention, in the structural unit (1), when X is a divalent group represented by the above general formulas (4) to (8), R 18 and R 19 each independently represents hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, an aralkyl group having 7 to 17 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms which may have a substituent, and is preferably hydrogen, halogen, an alkyl group having 1 to 10 carbon atoms which may have a substituent, an alkoxy group having 1 to 3 carbon atoms which may have a substituent, an aryl group having 6 to 8 carbon atoms which may have a substituent, an aralkyl group having 7 to 12 carbon atoms which may have a substituent, or an alkenyl group having 2 to 5 carbon atoms which may have a substituent. In another embodiment of the present invention, R 18 and R 19 may be bonded to each other to form a carbocyclic ring having 3 to 20 carbon atoms or a heterocyclic ring having 1 to 20 carbon atoms, preferably a carbocyclic ring having 3 to 12 carbon atoms or a heterocyclic ring having 1 to 12 carbon atoms. In a preferred embodiment of the present invention, R 18 and R 19 may be bonded to each other to form a carbon ring having 3 to 12 carbon atoms. In one embodiment of the present invention, in the structural unit (1), when X is a divalent group represented by the above general formula (8), R 20 is an alkylene group having 1 to 9 carbons which may have a substituent, and is preferably an alkylene group having 1 to 5 carbons which may have a substituent. In one embodiment of the present invention, in the structural unit (1), when X is a divalent group represented by the above general formulas (4) to (8), c may represent an integer of 0 to 20, and d may represent an integer of 1 to 500, preferably c may represent an integer of 0 to 12, and d may represent an integer of 1 to 300, more preferably c may represent an integer of 1 to 6, and particularly preferably c is 1. In addition, d may represent an integer of 1 to 100.

[0032] In one embodiment of the present invention, in the structural unit (1), X may be -O-, -S-, or a divalent group represented by any one of the above general formulas (3) to (4), and is preferably a divalent group represented by the above general formula (4). Examples of the substituent contained in the structural unit (1) include halogen, a cyano group, and an alkenyl group having, for example, 5 or less carbon atoms. The number of carbon atoms mentioned above is the total number of carbon atoms including the number of carbon atoms of the substituent.

[0033] In one embodiment of the present invention, the structural unit (1) may be derived from a bisphenol compound. Examples of bisphenol compounds forming the structural unit (1) include bisphenol C (2,2-bis(3-methyl-4-hydroxyphenyl)propane; BPC), 1,1-bis(4-hydroxy-3-methylphenyl)-1-phenylethane), 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-methylphenyl)ethane, and bis(4-hydroxy-3-methylphenyl)methane. Among these specific examples of bisphenol compounds, bisphenol C (2,2-bis(3-methyl-4-hydroxyphenyl)propane) is preferred. That is, the structural unit (1) is preferably derived only from bisphenol C (BPC) or from a bisphenol compound containing BPC as the main component.

[0034] In one embodiment of the present invention, the polycarbonate resin (A) may contain a structural unit other than the structural unit (1). The structural unit other than the structural unit (1) may also be derived from a bisphenol compound. Examples of bisphenol compounds that form structural units other than the structural unit (1) include the following. For example, 4,4'-biphenyldiol, bis(4-hydroxyphenyl)methane (bisphenol F; BPF), bis(2-hydroxyphenyl)methane, 2,4'-dihydroxydiphenylmethane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenylsulfone, bis(2-hydroxyphenyl)sulfone, bis(4-hydroxy-3-methylphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)ketone, 1,1-bis(4-hydroxyphenyl)ethane (bisphenol E; BPE), 1,1-bis( 4-hydroxyphenyl)-1-phenylethane (bisphenol AP; BPAP), bis(4-hydroxyphenyl)diphenylmethane (bisphenol BP; BPBP), 2,2-bis(4-hydroxyphenyl)propane (bisphenol A; BPA), 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxy-3-methylphenyl)ethane, bis(4-hydroxy-3-methylphenyl)methane, 2,2-bis(4-hydroxy-3-t-butylphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane (bisphenol B; BPB), 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z;BPZ), 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cycloundecane, 1,1-bis(4-hydroxyphenyl)cyclododecane (bisphenol CD), 2,2-bis(4-hydroxy-3-allylphenyl)propane, 3,3,5-trimethyl-1,1-bis(4-hydroxyphenyl)cyclohexane, 9,9-bis(4-hydroxy-3-ethylphenyl)fluorene , 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxyphenyl)fluorene, α,ω-bis[3-(o-hydroxyphenyl)propyl]polydimethyldiphenyl random copolymer siloxane, α,ω-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane, 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisphenol, 4,4'-[1,3-phenylenebis(1 -methylethylidene)]bisphenol, 2,2-bis(4-hydroxy-3-isopropylphenyl)propane (bisphenol G), 1,1-bis(4-hydroxyphenyl)-2-ethylhexane (bisphenol IOTD), 1,1-bis(4-hydroxyphenyl)-2-methylpropane (bisphenol IBTD), 1,1-bis(4-hydroxyphenyl)-2-methylpentane (bisphenol MIBK), 5,5'-(1-methylethylidene)-bis[1,1'-(bisphenyl)-2-ol]propane (bisphenol PH), 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol TMC), 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 1,1-bis(4-hydroxyphenyl)decane, 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane, and the like. These may be used alone or in combination of two or more kinds. Among these, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A; BPA), bisphenol AP, bisphenol Z, bisphenol CD, bisphenol TMC, bisphenol IOTD, bisphenol IBTD, and bisphenol MIBK are particularly preferred, with bisphenol A being more preferred.

[0035] That is, in one embodiment of the present invention, the structural unit (1) is preferably a structural unit derived from BPC represented by the following formula (9), and in the polycarbonate resin (A), in addition to the structural unit (1), a structural unit derived from BPA represented by the following formula (10), and one or more structural units selected from the group of structural units represented by the formulas (11) to (21) may be used in combination. [ka] [ka] [ka]

[0036] In one embodiment of the present invention, the structural unit (1) is preferably contained in an amount of 40 mol % or more based on the number of moles of all structural units contained in the polycarbonate resin (A). In the polycarbonate resin (A), the structural unit (1) is contained in an amount of preferably 50 mol % or more, further preferably 55 mol % or more, and particularly preferably 60 mol % or more, based on all structural units. The polycarbonate resin (A) may be composed only of the structural unit (1). Thus, although the upper limit for the proportion of the structural unit (1) in the polycarbonate resin (A) is not particularly important, for example, the proportion of the structural unit (1) in the polycarbonate resin (A) is 98 mol % or less, 97 mol % or less, or 95 mol % or less based on all structural units.

[0037] (ii) Terminal structure (2) In one embodiment of the present invention, in formula (2) representing the terminal structure of the polycarbonate resin (A), R3 is an alkyl group having 1 to 8 carbon atoms, and the alkyl group of R3 may have a substituent such as a hydroxyl group, but preferably has no substituent. [ka] In one embodiment of the present invention, in structural formula (2), R3 is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms which may be substituted with a hydroxyl group.

[0038] In one embodiment of the present invention, in structural formula (2), the value of m indicating the number of substituents R3 is an integer of 0 to 5, and the value of m is preferably an integer of 0 to 4, more preferably an integer of 1 to 3, even more preferably 1 or 2, and particularly preferably 1. In addition, the same polycarbonate molecule contains multiple terminal structures represented by formula (2), and R3 and m are determined independently for each terminal.

[0039] In one embodiment of the present invention, examples of monohydric phenols that induce structure (2) at the molecular end include, but are not limited to, phenol, p-tert-butylphenol (PTBP), p-cumylphenol, octylphenol, long-chain alkyl-substituted phenols, p-hydroxyphenethyl alcohol (=tyrosol), m-hydroxyphenethyl alcohol, o-hydroxyphenethyl alcohol, o-hydroxybenzyl alcohol (=salicyl alcohol), p-hydroxybenzyl alcohol, m-hydroxybenzyl alcohol, vanillyl alcohol, homovanillyl alcohol, 3-(4-hydroxy-3-methoxyphenyl)-1-propanol, sinapyl alcohol, coniferyl alcohol, and p-coumaryl alcohol. Among these, p-tert-butylphenol (PTBP), p-hydroxyphenethyl alcohol (PHEP), and p-hydroxybenzyl alcohol are preferred from the viewpoint of reactivity, and p-tert-butylphenol (PTBP) and p-hydroxyphenethyl alcohol are more preferred.

[0040] In one embodiment of the present invention, the terminal structure represented by structural formula (2) can be derived from either p-tert-butylphenol (PTBP) or p-hydroxyphenethyl alcohol (PHEP).

[0041] In one embodiment of the present invention, the proportion of the terminal structure (2) in the number of moles of all structural units contained in the polycarbonate resin (A) is preferably 12 mol% or less, more preferably 10 mol% or less, and particularly preferably 8.0 mol% or less. The proportion of the number of moles of the terminal structure (2) in the number of moles of all structural units contained in the polycarbonate resin (A) is, for example, 0.1 mol% or more, preferably 0.3 mol% or more, and more preferably 0.5 mol% or more.

[0042] (iii) Production of polycarbonate resin (A) The polycarbonate resin (A) used in the present invention can be produced by a conventional method, for example, as follows.

[0043] The polycarbonate resin used in the coating resin solution of the present invention can be produced by reacting a monohydric phenol that derives the terminal structure (2), a bisphenol that derives the structural unit (1), and a carbonate ester-forming compound. A known method used in producing a polycarbonate derived from bisphenol A, such as a direct reaction of a bisphenol with phosgene (phosgene method) or a transesterification reaction of a bisphenol with a bisarylcarbonate (transesterification method) can be used.

[0044] In the phosgene method, bisphenol, a monohydric phenol which induces the terminal structural formula (2), and phosgene are reacted in the presence of an acid binder and a solvent. As the acid binder, for example, pyridine, or an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is used, and as the solvent, for example, methylene chloride or chloroform is used. Furthermore, in order to promote the condensation polymerization reaction, it is preferable to use a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt such as benzyltriethylammonium chloride. The monohydric phenol that induces the terminal structure (2) functions as a polymerization degree regulator, but it is also possible to use other monohydric phenols such as phenol, pt-butylphenol, p-cumylphenol, and long-chain alkyl-substituted phenols in an amount of less than 50% by mass relative to the monohydric phenol that induces the terminal structure (2). If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfite, or a branching agent such as phloroglucin or isatin bisphenol may be added. The reaction is usually carried out at 0 to 150°C, preferably at 5 to 40°C. The reaction time depends on the reaction temperature, but is usually 0.5 minutes to 10 hours, preferably 1 minute to 2 hours. During the reaction, it is desirable to maintain the pH of the reaction system at 10 or higher.

[0045] On the other hand, in the transesterification method, bisphenol, a monohydric phenol which induces the terminal structure (2), and a bisaryl carbonate are mixed and reacted at high temperature under reduced pressure. Examples of bisaryl carbonate include bisaryl carbonates such as diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, and dinaphthyl carbonate. Two or more of these compounds can be used in combination. The reaction is usually carried out at a temperature in the range of 150 to 350°C, preferably 200 to 300°C, and the final pressure reduction is preferably 1 mmHg or less to distill off phenols derived from the bisaryl carbonate produced by the transesterification reaction. The reaction time depends on the reaction temperature and the pressure reduction, but is usually about 1 to 24 hours. The reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon. If desired, a small amount of a molecular weight regulator other than the monohydric phenol that induces the terminal structure (2) may be used in combination, or an antioxidant or a branching agent may be added to carry out the reaction.

[0046] The polycarbonate resin used in the present invention preferably maintains a good balance of the solvent solubility, coatability, adhesion, scratch resistance, impact resistance, etc., required for a film-forming resin for a coating resin solution. If the intrinsic viscosity of the resin is too low, the scratch resistance and impact resistance strength are insufficient, and if the intrinsic viscosity is too high, the solvent solubility decreases and the solution viscosity increases, resulting in a decrease in coatability. The desirable range of the intrinsic viscosity is preferably in the range of 0.3 to 2.0 dl / g, and more preferably in the range of 0.35 to 1.5 dl / g.

[0047] 3. Polyisocyanate compound (B) In the present invention, the polycarbonate resin composition contains the polyisocyanate compound (B) as described above. The polyisocyanate compound contained in the polycarbonate resin composition is preferably a compound having two or more isocyanate groups in one molecule. By using a compound having two or more isocyanate groups in the molecule as the polyisocyanate compound, a crosslinked structure can be partially formed in the polycarbonate resin composition, and the polycarbonate resin composition can be made into a crosslinked composition in which at least a part of the polycarbonate resin composition is crosslinked.

[0048] Examples of polyisocyanate compounds that can be used in the present invention include, but are not limited to, aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates.

[0049] Examples of the aliphatic polyisocyanate include 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,2'-diethyl ether diisocyanate, dimer acid diisocyanate, and the like. Of these, hexamethylene diisocyanate is preferred, but the polyisocyanate is not limited to these.

[0050] Examples of alicyclic polyisocyanates include, but are not limited to, 1,4-cyclohexane diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, 1,4-bis(isocyanatemethyl)cyclohexane, 3-isocyanatemethyl-3,3,5-trimethylcyclohexane (IPDI, isophorone diisocyanate), bis-(4-isocyanatecyclohexyl)methane (hydrogenated MDI), hydrogenated (1,3- or 1,4-)xylylene diisocyanate, and norbornane diisocyanate.

[0051] Examples of aromatic polyisocyanates include, but are not limited to, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 3,3'-dimethyl-4,4'-diisocyanate biphenyl, 3,3'-dimethyl-4,4'-diisocyanate diphenylmethane, 1,5-naphthylene diisocyanate, 4,4'-diphenyl ether diisocyanate, and tetrachlorophenylene diisocyanate.

[0052] Examples of the aromatic aliphatic polyisocyanate include xylylene diisocyanates such as 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, (α,α,α',α'-tetramethylxylylene diisocyanate, and 3,3'-methylene d-tolylene-4,4'-diisocyanate, but are not limited to these.

[0053] These polyisocyanate compounds can be used alone or in combination of two or more.

[0054] In one embodiment of the present invention, the polyisocyanate compound may be, for example, a diisocyanate compound having two isocyanate groups in one molecule, or may be a diisocyanate prepolymerized by reacting a diisocyanate with a diol, a diamine, or the like. In addition, a diisocyanate compound partly oligomerized to a trifunctional or higher isocyanate compound may also be used. A known method can be used for oligomerizing a diisocyanate compound, and examples of oligomerization of a diisocyanate compound include isocyanurate, allophanate, biuret, and urethanization or urea with a polyfunctional alcohol or a polyfunctional amine. In one embodiment of the present invention, the polyisocyanate compound may be a polyisocyanate having three or more isocyanate groups, such as triphenylmethane triisocyanate.

[0055] In one embodiment of the present invention, the polyisocyanate compound may be, for example, a diisocyanate compound having two isocyanate groups in one molecule. Examples of the diisocyanate compound that can be used in the present invention include Aromatic diisocyanate compounds such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), phenylene diisocyanate, naphthylene diisocyanate (NDI); Aliphatic diisocyanate compounds such as 1,6-hexamethylene diisocyanate (HDI) and tetramethylene diisocyanate; Alicyclic diisocyanate compounds such as 2,4-diisocyanate-1-methylcyclohexane, isophorone diisocyanate (IPDI), cyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, norbornane diisocyanate (NBDI), nuclear hydrogenated XDI (H6-XDI), and nuclear hydrogenated MDI (H12-MDI); Aromatic and aliphatic diisocyanate compounds such as xylylene diisocyanate (XDI) and tetramethylxylylene diisocyanate (TMXDI); In a preferred embodiment of the present invention, the polyisocyanate compound may be 1,6-hexamethylene diisocyanate (HDI) in terms of market availability and price.

[0056] 4. Other components in polycarbonate resin composition The polycarbonate resin composition may contain components other than the polycarbonate resin (A) and the polyisocyanate compound (B), such as thermoplastic resins other than the polycarbonate resin (A), additives such as antioxidants and ultraviolet absorbers, inorganic fillers, conductive fillers, etc. From the viewpoint of simplifying the constituent components, the content of the thermoplastic resin other than the polycarbonate resin (A) contained in the polycarbonate resin composition is preferably 20 mass% or less, more preferably 15 mass% or less, even more preferably 10 mass% or less, still more preferably 8 mass% or less, and particularly preferably 5 mass% or less, based on the total weight of the polycarbonate resin composition. Also, preferably, the polycarbonate resin composition does not contain any thermoplastic resin other than the polycarbonate resin (A).

[0057] 5. Resin solution containing a polycarbonate resin composition The coating resin solution of the present invention is a solution in which the above-mentioned polycarbonate resin composition is dissolved in an organic solvent, such as a solvent containing a non-halogenated solvent, and in this state, it becomes a coating film generally called a clear color. Furthermore, a desired dye or pigment can be dissolved or dispersed to make a colored coating film.

[0058] As described above, the solvent for the coating resin solution of the present invention is an organic solvent, and the organic solvent is preferably a solvent containing a non-halogenated solvent, and more preferably a solvent containing a non-halogenated organic solvent as the main solvent. The non-halogen-based organic solvent that can be used as a solvent for the coating resin solution of the present invention may include one or more solvents selected from the group consisting of ester-based solvents, ether-based solvents, carbonate-based solvents, and ketone-based solvents. The solvent of the coating resin solution of the present invention is, that is, mainly composed of a solvent generally used in paints, etc., and specifically includes ester solvents such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-ethoxyethyl acetate, 2-methoxy-1-methylethyl acetate, ethyl lactate, etc., ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, etc., carbonate ester solvents such as dimethyl carbonate, ethyl methyl carbonate, etc., ether solvents such as tetrahydrofuran, 1,4-dioxane, diethyl ether, dimethoxymethane, ethyl cellosolve, anisole, etc., aromatic hydrocarbon solvents such as toluene, ethylbenzene, xylene, pseudocumene, mesitylene, etc. Furthermore, a small amount of an alcohol poor solvent such as ethanol, isopropyl alcohol, etc., or a hydrocarbon poor solvent such as n-heptane, cyclohexane, mineral spirits, etc. may be used in combination. Among these, it is preferable to dissolve the compound in an ester solvent such as propyl acetate or butyl acetate, a ketone solvent such as methyl ethyl ketone or cyclohexanone, or an ether solvent such as tetrahydrofuran or dimethoxymethane, which are inexpensive, easy to work with, and relatively safe, and methyl ethyl ketone and propyl acetate are particularly preferable.

[0059] Moreover, since halogen-based solvents such as dichloromethane have a large effect on the coating work environment, it is preferable not to use them as the main solvent of the coating resin solution of the present invention.

[0060] In one embodiment of the present invention, the resin solution contains the polycarbonate resin composition and a non-halogen-based organic solvent. In one embodiment of the present invention, the polycarbonate resin composition may be a crosslinked composition obtained by crosslinking at least a part of the polycarbonate resin composition.

[0061] The viscosity of the coating resin solution of the present invention can be set arbitrarily depending on the desired coating method, but is preferably in the range of 10 to 20,000 mPa / s, more preferably 400 to 20,000 mPa / s for airless spray, brush coating, and roller coating, 100 to 6,000 mPa s for air spray, and 10 to 500 mPa s for dip coating and can spray.

[0062] In order to enhance the color effect, pigments, dyes, colored particles, and particles having optical coherence can be added to the coating resin solution of the present invention. As the pigments and dyes, organic pigments include azo pigments and phthalocyanine pigments, and specific examples thereof include Red No. 104, Red No. 106, Red No. 201, Red No. 202, Red No. 204, Red No. 215, Red No. 220, Orange No. 203, Orange No. 204, Blue No. 1, Blue No. 404, Yellow No. 205, Yellow No. 401, and Yellow No. 405. In addition, in order to produce white, pearl color, metallic color, and glitter, it is also possible to use titanium mica, titanium oxide, iron oxide, tin oxide, zirconium oxide, chromium oxide, bismuth oxychloride, silica, chromium, titanium nitride, titanium, magnesium fluoride, gold, silver, nickel, and the like. Particles having optical coherence are particles that enhance the color effect by reflecting or scattering light, and examples thereof include glass beads, tiny shells, and mica. These are preferably added in the range of 0.0001 to 10.0 mass %, more preferably 0.01 to 5.0 mass %, and even more preferably 0.1 to 3.0 mass %, to the coating as desired.

[0063] Furthermore, if necessary, rust inhibitors, antioxidants, dispersants, ultraviolet absorbers, antifoaming agents, leveling agents, etc. may be added.

[0064] The amount of polycarbonate resin in the coating resin solution of the present invention depends on the intrinsic viscosity and solvent solubility, but is preferably 1 to 50 mass%, more preferably 4 to 30 mass%. When the concentration is within this range, the solvent solubility and coatability are well balanced, and the workability and appearance are improved.

[0065] The film formed after coating with the coating resin solution of the present invention is less susceptible to damage or peeling due to friction, impact, etc. during transportation or use, compared to films formed with conventional polycarbonate coating resin solutions.

[0066] The thickness of the coating film after coating with the coating resin solution of the present invention is preferably in the range of 5 to 200 μm, more preferably 10 to 120 μm, and even more preferably 15 to 60 μm. A thin coating film less than 5 μm is not strong enough and is likely to cause scratches that reach the substrate, while a coating film that is too thick, exceeding 200 μm, is likely to peel off due to shrinkage, and is economically disadvantageous when considering the use of the coating film that will ultimately be peeled off and discarded.

[0067] 6. Printing ink containing resin solution The above resin solution can be used as a binder resin solution to make a printing ink. Such a printing ink of the present invention can be used, for example, for decorative printing. In general, a printing ink for decorative printing is mainly composed of a solvent, a dye / pigment, and a binder resin. Examples of the dye / pigment used in the above printing ink include, but are not limited to, anthraquinone-based and naphthoquinone-based dyes, inorganic pigments such as titanium oxide, car pump rack, calcium carbonate, and metal particles, and organic pigments such as azo pigments and phthalocyanine pigments. These dyes / pigments are present in the ink together with the binder resin in a dissolved or dispersed state. A printing ink using the resin solution of the present invention as a binder resin solution has excellent adhesion.

[0068] In addition to the binder resin and the dye or pigment, the printing ink may contain organic fine particles, inorganic fine particles, a release agent, an antioxidant, a plasticizer, a dispersant, an infrared absorber, an antistatic agent, an ultraviolet absorber, an antifoaming agent, a leveling agent, etc., as necessary.

[0069] The amount of binder resin in the ink depends on the intrinsic viscosity and solvent solubility, but is preferably 1 to 70% by mass, more preferably 5 to 50% by mass. When the concentration of the binder resin is within this range, the solvent solubility and ink coatability are well balanced, improving workability.

[0070] 7. Base film The substrate film of the present invention is coated with the above-mentioned printing ink. After decorative printing on the substrate film before coating with the printing ink, the solvent is removed by drying, and the dye / pigment is fixed to the binder resin while the film and the binder resin are adhered to each other, thereby obtaining a decoratively printed film, i.e., a substrate film coated with the above-mentioned printing ink. The method for coating the substrate with the printing ink can be a conventional method, such as screen printing, gravure printing, flexographic printing, etc., but is not limited thereto.

[0071] 8. Films or Coatings The film or coating of the present invention contains the above-mentioned polycarbonate resin composition. In one embodiment, a film or coating is provided that contains the above-mentioned polycarbonate resin composition or a crosslinked composition obtained by crosslinking at least a portion of the above-mentioned polycarbonate resin composition.

[0072] In one embodiment of the present invention, the above-mentioned film or coating can be obtained by applying the coating resin solution or printing ink of the present invention to a substrate, followed by heating or drying. In one embodiment of the present invention, the above-mentioned film or coating can be a single layer or a multi-layer laminate.

[0073] 9. Physical properties of polycarbonate resin composition and coating resin solution (i) Viscosity average molecular weight (Mv) In one embodiment of the present invention, the viscosity average molecular weight (Mv) of the polycarbonate resin composition may be 10,000 to 60,000. In the present invention, the viscosity average molecular weight (Mv) of the polycarbonate resin composition may be preferably 14,000 to 55,000, more preferably 16,000 to 50,000, and even more preferably 18,000 to 45,000. In a preferred embodiment of the present invention, the viscosity average molecular weight (Mv) of the polycarbonate resin composition may be 20,000 to 40,000.

[0074] <Viscosity average molecular weight (Mv) measurement method> In the present invention, the viscosity average molecular weight was measured as follows. Measuring instrument: Ubbelohde capillary viscometer Solvent: Dichloromethane Resin solution concentration: 0.5 grams / dl Measurement temperature: 25℃ Measurement was performed under the above conditions, and the intrinsic viscosity [η] deciliters / gram was determined with a Huggins constant of 0.45, and calculated using the following formula. η = 1.23 × 10 -4 ×Mv 0.83

[0075] (ii) Mass average molecular weight (Mw) The present inventors have found that when a coating resin solution containing a polycarbonate resin composition is prepared, coated, air-dried, and then subjected to a heat drying treatment, the weight average molecular weight (Mw) increases. That is, it is believed that the above-mentioned treatment forms a crosslinked composition in which at least a part of the polycarbonate resin composition is crosslinked. As described above, in the present invention, a compound having two or more isocyanate groups in one molecule is used as the polyisocyanate compound, which is believed to contribute to the formation of a crosslinked composition. For example, a compound having two or more isocyanate groups in one molecule may be used to produce a polycarbonate resin composition containing a partial crosslinked structure, which has a mass average molecular weight (Mw) value (mass average molecular weight calculated as polycarbonate (PC)) that is about 100 to 10,000 or about 500 to 5,000 larger than that when the compound is not used.

[0076] <Gel Permeation Chromatography (GPC) Analysis Measurement Conditions> The mass average molecular weight (Mw) of the polycarbonate resin of the present invention and the cured polycarbonate resin composition was measured by gel permeation chromatography analysis under the conditions shown below. Equipment used: Alliance HPLC system manufactured by Waters Column: 2 Shodex 805L columns manufactured by Showa Denko K.K. Eluent: Chloroform Flow rate: 1.0ml / min Sample: 0.25w / v% chloroform solution sample Detection: UV detection at 254 nm The weight average molecular weight (Mw) in terms of polystyrene (PS) and polycarbonate (PC) were determined. That is, the Mw value in terms of PC was calculated from the Mw value in terms of PS obtained by the above-mentioned GPC analysis using the following formula as a conversion formula. Mw (PC conversion) = 0.4782×Mw (PS conversion) 1.014706

[0077] (iii) Peel durability (adhesion) The coating resin solution of the present invention was applied, air-dried, and then subjected to a heat-drying treatment, after which the peel durability (adhesion) was tested by the following cross-cut method.

[0078] <Cross-cut method> Adhesion tests were conducted using a 24mm wide adhesive tape (adhesive strength 4.01N / 10mm) manufactured by Nichiban Co., Ltd., conforming to the JIS K5600-5-6 cross-cut method (1mm intervals). Based on the JIS classification index, the results were classified into a range of 0 (no peeling) to 5 (almost complete peeling), which was used as an index of peel durability. EXAMPLES

[0079] <Example 1> In 600 ml of 9 w / w% aqueous sodium hydroxide solution and 200 ml of pure water, 100.6 g (0.39 mol) of 2,2-bis(4-hydroxy-3-methylphenyl)propane (hereinafter referred to as "BPC": manufactured by Honshu Chemical Industry Co., Ltd.), 1.39 g (0.009 mol, terminal structure content 2.4 mol%) of PTBP, and 0.3 g of hydrosulfite were dissolved. 200 ml of methylene chloride was added to the mixture, and while stirring, 0.08 g of benzyltriethylammonium chloride (hereinafter abbreviated as "TEBAC") was added. While maintaining the temperature at 15 to 20°C, 55.1 g of phosgene was then blown in over about 30 minutes. After the phosgene injection was completed, 100 ml of a 9 w / w% aqueous sodium hydroxide solution was added and the reaction liquid was emulsified by vigorously stirring, after which 0.5 ml of triethylamine was added as a polymerization catalyst and the mixture was polymerized by stirring at 20 to 30°C for about 40 minutes. After the polymerization was completed, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and repeatedly washed with water until the electrical conductivity of the washing liquid (aqueous phase) was 10 μS / cm or less. The obtained polymer solution was dropped into warm water kept at 60°C, and the solvent was evaporated and removed to obtain a white powdery precipitate. The obtained precipitate was filtered and dried at 105°C for 24 hours to obtain a polymer powder. The resulting polycarbonate resin (hereinafter abbreviated as "PC-1") had an Mv of 32,400. A resin composition of PC-1 (10 parts by mass) and 1 part by mass of hexamethylene diisocyanate (hereinafter abbreviated as "HDI") (10 parts by mass per 100 parts by mass of polycarbonate resin) was dissolved in 55 parts by mass of toluene to prepare a coating solution (resin solution). The coating solution was applied (coated) onto a stainless steel plate, air-dried, and then dried at 110°C for 5 hours to obtain a test piece. It is considered that the drying process also produced crosslinks due to the reaction between hydroxyl groups of compounds contained as impurities in the resin composition and isocyanate groups of HDI. According to JIS K5600-5-6, the cross-cut method was performed on the test piece and the result was 1.

[0080] <Example 2> The evaluation was carried out in the same manner as in Example 1, except that the coating solution was prepared using xylylene diisocyanate (hereinafter abbreviated as "XDI") instead of HDI.

[0081] <Example 3> The amount of BPC used was changed to 65.3 g (0.26 mol), the amount of PTBP used was changed to 2.01 g (0.013 mol, 3.0 mol% as the terminal structure content), and 43.5 g (0.19 mol) of 2,2-bis(4-hydroxyphenyl)propane (hereinafter abbreviated as "BPA": manufactured by Mitsubishi Chemical Corporation) was used at the same time. Except for this, polymerization was carried out in the same manner as in Example 1 to obtain a polycarbonate resin (Mv 26,000, hereinafter abbreviated as "PC-2"). A coating solution was prepared by dissolving PC-2 (10 parts by mass) and 1 part by mass of HDI (10 parts by mass per 100 parts by mass of polycarbonate resin) in 55 parts by mass of toluene.

[0082] <Example 4> The evaluation was carried out in the same manner as in Example 3, except that a coating solution was prepared using tolylene diisocyanate (hereinafter abbreviated as "TDI") instead of HDI.

[0083] <Example 5> Polymerization was carried out in the same manner as in Example 3, except that the amount of PTBP used was changed to 0.86 g (0.006 mol, 1.3 mol% as the terminal structure content), to obtain a polycarbonate resin (Mv 51,400, hereinafter abbreviated as "PC-3"). A coating solution was prepared by dissolving PC-3 (10 parts by mass) and 1 part by mass of HDI (10 parts by mass per 100 parts by mass of polycarbonate resin) in 55 parts by mass of toluene.

[0084] <Example 6> A coating solution was prepared and evaluated in the same manner as in Example 1, except that the HDI was changed to 3 parts by mass (30 parts by mass per 100 parts by mass of the polycarbonate resin).

[0085] <Example 7> In 600 ml of 9 w / w% aqueous sodium hydroxide solution and 200 ml of pure water, 65.3 g (0.26 mol) of 2,2-bis(4-hydroxy-3-methylphenyl)propane (hereinafter abbreviated as "BPC": manufactured by Honshu Chemical Industry Co., Ltd.), 43.5 g (0.19 mol) of 2,2-bis(4-hydroxyphenyl)propane (hereinafter abbreviated as "BPA": manufactured by Mitsubishi Chemical Corporation), 3.06 g (0.022 mol, terminal structure content 5.0 mol%) of PHEP, and 0.3 g of hydrosulfite were dissolved.

[0086] 200 ml of methylene chloride was added to the mixture, and while stirring, 0.08 g of benzyltriethylammonium chloride (hereinafter abbreviated as "TEBAC") was added. While maintaining the temperature at 15 to 20°C, 46.9 g of phosgene was then blown in over about 30 minutes.

[0087] After the phosgene injection was completed, 100 ml of a 9 w / w% aqueous sodium hydroxide solution was added and the reaction liquid was emulsified by vigorously stirring. After emulsification, 0.5 ml of triethylamine was added and the mixture was stirred at 20 to 30° C. for about 1 hour to polymerize.

[0088] After the polymerization was completed, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and repeatedly washed with water until the electrical conductivity of the washing liquid (aqueous phase) was 10 μS / cm or less. The obtained polymer solution was dropped into warm water kept at 60°C, and the solvent was evaporated and removed to obtain a white powdery precipitate.

[0089] The resulting precipitate was filtered and dried at 105° C. for 24 hours to obtain a polymer powder.

[0090] The obtained polycarbonate resin (hereinafter abbreviated as "PC-4") had an Mv of 25,500 and an Mw of 57,000 (PS equivalent) and 32,000 (PC equivalent). PC-4 (10 parts by mass) and 1 part by mass of HDI (10 parts by mass per 100 parts by mass of polycarbonate resin) were dissolved in 55 parts by mass of toluene to prepare a coating solution, which was evaluated in the same manner as in Example 1. The Mw of the polycarbonate resin composition after drying was 65,700 (PS equivalent) and 37,000 (PC equivalent). In addition, the drying process caused a crosslinked body to be generated by the reaction between the terminal hydroxyl group derived from PHEP in the resin composition and the isocyanate group of HDI.

[0091] <Example 8> A coating solution was prepared by dissolving PC-4 (10 parts by mass) and 0.01 parts by mass of HDI (0.1 parts by mass per 100 parts by mass of polycarbonate resin) in 55 parts by mass of toluene, and evaluation was performed in the same manner as in Example 1. The Mw of the polycarbonate resin composition after drying was 58,400 (PS equivalent) and 32,800 (PC equivalent).

[0092] <Example 9> A coating solution was prepared and evaluated in the same manner as in Example 3, except that the amount of HDI used was changed to 0.8 parts by mass (8 parts by mass per 100 parts by mass of polycarbonate resin).

[0093] <Comparative Example 1> The evaluation was carried out in the same manner as in Example 1, except that the coating solution was prepared without using HDI.

[0094] <Comparative Example 2> The evaluation was carried out in the same manner as in Example 3, except that the coating solution was prepared without using HDI.

[0095] <Comparative Example 3> Polymerization was carried out in the same manner as in Example 1, except that 100.3 g (0.35 mol) of 1,1-bis(4-hydroxyphenyl)-1-phenylethane (hereinafter abbreviated as "BPAP": manufactured by Honshu Chemical Industry Co., Ltd.) was used instead of BPC, and the amount of PTBP used was changed to 2.01 g (0.013 mol, 3.9 mol% as the terminal structure content), to obtain a polycarbonate resin (Mv20,000, hereinafter abbreviated as "PC-5"). PC-5 (10 parts by mass) and 1 part by mass of HDI (10 parts by mass relative to 100 parts by mass of polycarbonate resin) were dissolved in 55 parts by mass of toluene to prepare a coating solution, which was evaluated in the same manner as in Example 1.

[0096] <Comparative Example 4> A coating solution was prepared and evaluated in the same manner as in Comparative Example 3, except that the amount of HDI used was changed to 3 parts by mass (30 parts by mass per 100 parts by mass of the polycarbonate resin).

[0097] <Comparative Example 5> Polymerization was carried out in the same manner as in Example 1, except that 100.5 g (0.38 mol) of 1,1-bis(4-hydroxyphenyl)cyclohexane (hereinafter abbreviated as "BPZ": manufactured by Honshu Chemical Industry Co., Ltd.) was used instead of BPC, and the amount of PTBP used was changed to 1.13 g (0.008 mol, 2.0 mol% as the terminal structure content), to obtain a polycarbonate resin (Mv32,500, hereinafter abbreviated as "PC-6"). A coating solution was prepared and evaluated in the same manner as in Example 4, except that PC-6 was used instead of PC-2.

[0098] <Comparative Example 6> Polymerization was carried out in the same manner as in Example 1 to obtain a polycarbonate resin (Mv 50,000, hereinafter abbreviated as "PC-7"), except that 90.3 g (0.33 mol) of 2,2-bis(4-hydroxyphenyl)-4-methylpentane (hereinafter abbreviated as "MIBK": manufactured by Honshu Chemical Industry Co., Ltd.) was used instead of BPC, and the amount of PTBP used was changed to 0.63 g (0.004 mol, 1.3 mol% as the terminal structure content). A coating solution was prepared and evaluated in the same manner as in Example 1, except that PC-7 was used instead of PC-1.

[0099] The following table shows the compositions of the coating solutions of the above examples and comparative examples, and the measured results of peel durability.

[0100] [Table 1]

[0101] As described above, it has been demonstrated that the resin composition of the present invention can improve the adhesion between a coating film and a substrate, and is useful as a blend resin composition of a polycarbonate resin and another resin. [Industrial Applicability]

[0102] The resin composition of the present invention can be used as a coating resin solution for protecting articles, and is particularly suitable for coatings in fields where durability is required in daily life, such as IC cards and security cards.

Claims

1. A polycarbonate resin (A) containing a structural unit represented by the following general formula (1) and a terminal structure represented by the following general formula (2): A polycarbonate resin composition containing a polyisocyanate compound (B), The polyisocyanate compound (B) is contained in an amount of 6.5 mass% or more and 50 mass% or less based on the total mass of the polycarbonate resin (A) and the polyisocyanate compound (B), The polycarbonate resin composition contains a polycarbonate resin (A) and a polyisocyanate compound (B) as a mixture, and is capable of forming a crosslinked structure. 【Chemistry 1】 【Chemistry 2】 (In formula (1), R １ and R ２ are each independently an alkyl group having 1 to 4 carbon atoms, each n is independently an integer from 0 to 4, provided that no n is 0; X is -O-, -S-, -SO-, -SO ２ -, -CO-, or a divalent group represented by any one of the following general formulas (3) to (8). (In formula (2), R ３ each independently represents an alkyl group having 1 to 8 carbon atoms which may be substituted by a hydroxyl group, m is an integer from 0 to 5. 【Chemistry 3】 (In general formula (3), R ８ ~R １７ each independently represents hydrogen or an alkyl group having 1 to 3 carbon atoms; R ８ ~R １７ at least one of the above represents an alkyl group having 1 to 3 carbon atoms; In general formulas (4) to (8), R １８ and R １９ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, an aralkyl group having 7 to 17 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms which may have a substituent, R １８ and R １９ are bonded to each other to form a carbocyclic ring having 3 to 20 carbon atoms or a heterocyclic ring having 1 to 20 carbon atoms; R ２０ represents an alkylene group having a carbon number of 1 to 9 which may have a substituent, c represents an integer of 0 to 20; d represents an integer of 1 to 500.

2. R in the general formula (1) １ and R ２ is a methyl group, n is 1 in each case; The polycarbonate resin composition according to claim 1 .

3. R in the general formula (4) １８ and R １９ The polycarbonate resin composition according to claim 2 , wherein is a methyl group and c is 1.

4. The polycarbonate resin composition according to any one of claims 1 to 3, wherein the polycarbonate resin (A) contains the structural unit represented by the general formula (1) in an amount of 40 mol% or more based on the number of moles of all structural units.

5. R of general formula (2), which is the terminal group of the polycarbonate resin (A), ３ The polycarbonate resin composition according to any one of claims 1 to 4, wherein is an alkyl group having 1 to 4 carbon atoms which may be substituted with one hydroxyl group.

6. The polycarbonate resin composition according to any one of claims 1 to 5, wherein the terminal structure represented by the general formula (2) is derived from p-tert-butylphenol (PTBP), p-hydroxyphenethyl alcohol (PHEP), or p-hydroxybenzyl alcohol.

7. The polycarbonate resin composition according to any one of claims 1 to 6, wherein the proportion of the terminal structure represented by the general formula (2) contained in the number of moles of all structural units of the polycarbonate resin (A) is 0.1 mol % or more and 12 mol % or less.

8. The polycarbonate resin composition according to any one of claims 1 to 7, wherein the viscosity average molecular weight (Mv) of the polycarbonate resin is 10,000 to 60,000.

9. The polycarbonate resin composition according to any one of claims 1 to 8, which is a mixture of the polycarbonate resin (A) and the polyisocyanate compound (B).

10. The polycarbonate resin composition according to any one of claims 1 to 9, wherein the polyisocyanate compound (B) contains at least one of hexamethylene diisocyanate and xylylene diisocyanate.

11. A resin solution comprising the polycarbonate resin composition according to any one of claims 1 to 10 and an organic solvent.

12. The resin solution according to claim 11, wherein the organic solvent includes at least one of a non-halogen-based solvent, an ester-based solvent, an ether-based solvent, a carbonate-based solvent, and a ketone-based solvent.

13. A printing ink comprising the resin solution according to claim 11 or 12 as a binder resin solution.

14. A substrate film coated with the printing ink according to claim 13.

15. A film or coating comprising the polycarbonate resin composition according to any one of claims 1 to 10.

16. 16. The film or coating of claim 15, wherein the film comprises a film laminate.

Images