Polycarbonate resin composition

Abstract

The present invention provides a polycarbonate-based coating resin composition having high adhesiveness, more specifically provides a polycarbonate resin composition that contains not less than 0.1 parts by mass of a polyisocyanate compound and 100 parts by mass of a terminal-modified polycarbonate resin (A) having a structural unit (2) and a terminal structure represented by structural formula (1).　[In formula (1) and formula (2), R1-R7, X, Y, Z, and a are as described in the description.]

Description

[Technical field]

[0001] The present invention relates to a polycarbonate resin composition, and more particularly to a polycarbonate resin composition that can be used for a polycarbonate coating resin solution having 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 blended resin composition of a polycarbonate resin and another resin that can improve 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 polycarbonate resin having a specific molecular end and a polyisocyanate compound can be used in a solution that forms a strong coating film having strong adhesion to a substrate, and have thus completed the present invention.

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

[0009] <1> 100 parts by mass of a terminal-modified polycarbonate resin (A) having a terminal structure represented by the following structural formula (1) and the following structural unit (2), 0.1 parts by mass or more of polyisocyanate compound A polycarbonate resin composition comprising: [ka] (In formula (1), R1 represents an alkylene group having 1 to 20 carbon atoms or an alkenylene group having 2 to 20 carbon atoms, each of which may have a substituent; R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms; Z represents an ether bond, a carbonyl group, an ester bond, or a single bond; a is an integer from 1 to 3; Y represents an ether bond or an ester group. [ka] (In formula (2), R4 to R7 each independently represent hydrogen, fluorine, chlorine, bromine or iodine, or each of which may have a substituent, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms; 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.

[0010] <2> In the structural formula (1), Z represents a single bond, R1 represents an alkylene having 1 to 2 carbon atoms, and R2 and R3 represent hydrogen. <1> 10. The polycarbonate resin composition according to claim 9 .

[0011] <3> In the structural unit (2), X is -O-, -S-, or a divalent group represented by any one of the following general formulas (3) to (4): <1> or <2> 10. The polycarbonate resin composition according to claim 9 .

[0012] <4> The structural unit (2) is at least one selected from the group consisting of the following formulas (9) to (22): <1> ~ <3> 10. The polycarbonate resin composition according to claim 9, [ka] TIFF0007669929000005.tif125170

[0013] <5> The structural unit (2) is derived from a bisphenol compound. <1> ~ <3> 10. The polycarbonate resin composition according to claim 9,

[0014] <6> The bisphenol compound is selected from the group consisting of bisphenol A, bisphenol AP, bisphenol Z, bisphenol CD, bisphenol C, bisphenol IOTD, bisphenol IBTD, bisphenol MIBK, and bisphenol AF. <5> 10. The polycarbonate resin composition according to claim 9 .

[0015] <7> The terminal structure represented by the structural formula (1) is p-hydroxyphenethyl alcohol (PHEP). <1> ~ <6> 10. The polycarbonate resin composition according to claim 9,

[0016] <8> The terminal structure represented by the structural formula (1) is contained in an amount of 0.5 mol % or more relative to the structural unit (2). <1> ~ <7> 10. The polycarbonate resin composition according to claim 9,

[0017] <9> The polyisocyanate compound is an isocyanate compound containing two or more isocyanate groups in one molecule. <1> ~ <8> 10. The polycarbonate resin composition according to claim 9,

[0018] <10> The above, wherein the isocyanate compound is a diisocyanate compound. <9> 10. The polycarbonate resin composition according to claim 9 .

[0019] <11> The viscosity average molecular weight of the polycarbonate resin composition is 10,000 to 60,000. <1> ~ <10> 10. The polycarbonate resin composition according to claim 9,

[0020] <12> the above <1> ~ <11> 2. A crosslinked composition obtained by crosslinking at least a portion of the polycarbonate resin composition according to claim 1.

[0021] <13> the above <1> ~ <11> The polycarbonate resin composition according to any one of the above <12> A resin solution comprising the crosslinked composition according to claim 1 and a non-halogen-based organic solvent.

[0022] <14> the above <13> A printing ink using the resin solution described in the above as a binder resin solution.

[0023] <15> the above <14> A substrate film coated with the printing ink described in 1.

[0024] <16> the above <1> ~ <11> The polycarbonate resin composition according to any one of the above <12> A film or coating comprising the crosslinked composition according to claim 1.

[0025] <17> The non-halogen-based organic solvent includes one or more solvents selected from the group consisting of ester-based solvents, ether-based solvents, carbonate-based solvents, and ketone-based solvents. <13> The resin solution according to claim 1. Effect of the Invention

[0026] 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

[0027] 1. Polycarbonate resin composition The polycarbonate resin composition of the present invention contains a terminal-modified polycarbonate resin (A) having a terminal structure represented by the following structural formula (1) and the following structural unit (2), and a polyisocyanate compound. [ka] (In formula (1), R1 represents an alkylene group having 1 to 20 carbon atoms or an alkenylene group having 2 to 20 carbon atoms, each of which may have a substituent; R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms; Z represents an ether bond, a carbonyl group, an ester bond, or a single bond; a is an integer from 1 to 3; Y represents an ether bond or an ester group. [ka] (In formula (2), R4 to R7 each independently represent hydrogen, fluorine, chlorine, bromine, or iodine, or each optionally has a substituent, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms; 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.

[0028] In one embodiment of the present invention, the polycarbonate resin composition contains 100 parts by mass of a terminal-modified polycarbonate resin (A) having a terminal structure represented by the above structural formula (1) and the above structural unit (2), and 0.1 parts by mass or more of a polyisocyanate compound. In one embodiment of the present invention, the amount of the polyisocyanate compound contained in the polycarbonate resin composition may be 0.1 parts by mass or more, preferably 1.0 parts by mass or more, more preferably 3.0 parts by mass or more, even more preferably 5.0 parts by mass or more, and particularly preferably 8.0 parts by mass or more, based on 100 parts by mass of the terminal-modified polycarbonate resin (A).

[0029] 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) 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).

[0030] 2. Terminally modified polycarbonate resin (A) In the present invention, the terminally modified polycarbonate resin (A) contained in the polycarbonate resin composition has a terminal structure represented by the following structural formula (1) and the following structural unit (2), as described above. [ka] (In formula (1), R1 represents an alkylene group having 1 to 20 carbon atoms or an alkenylene group having 2 to 20 carbon atoms, each of which may have a substituent; R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms; Z represents an ether bond, a carbonyl group, an ester bond, or a single bond; a is an integer from 1 to 3; Y represents an ether bond or an ester group. [ka] (In formula (2), R4 to R7 each independently represent hydrogen, fluorine, chlorine, bromine, or iodine, or each optionally has a substituent, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms; 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.

[0031] In one embodiment of the present invention, the terminal structure represented by the structural formula (1) 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, relative to the structural unit (2).

[0032] (i) A terminal structure represented by structural formula (1) In one embodiment of the present invention, in structural formula (1), R1 represents an alkylene group having 1 to 20 carbon atoms or an alkenylene group having 2 to 20 carbon atoms, which may have a substituent. In one embodiment of the present invention, in structural formula (1), R1 may be an alkylene group having 1 to 20 carbon atoms, which may have a substituent, preferably an alkylene group having 1 to 15 carbon atoms, which may have a substituent, more preferably an alkylene group having 1 to 10 carbon atoms, which may have a substituent, even more preferably an alkylene group having 1 to 5 carbon atoms, which may have a substituent, and even more preferably an alkylene group having 1 to 2 carbon atoms, which may have a substituent. In a preferred embodiment of the present invention, in structural formula (1), R1 may be an alkylene group having 1 to 2 carbon atoms.

[0033] In one embodiment of the present invention, in structural formula (1), R2 and R3 each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms. In one embodiment of the present invention, in structural formula (1), R2 and R3 each independently represent preferably hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and more preferably hydrogen, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or an aryl group having 6 to 8 carbon atoms. In a preferred embodiment of the present invention, in structural formula (1), R2 and R3 may be hydrogen.

[0034] In one embodiment of the present invention, in structural formula (1), Z represents an ether bond, a carbonyl group, an ester bond, or a single bond. In one embodiment of the present invention, in structural formula (1), Z may be an ether bond. In another embodiment of the present invention, in structural formula (1), Z may be a carbonyl group. In yet another embodiment of the present invention, in structural formula (1), Z may be an ester bond. In yet another embodiment of the present invention, in structural formula (1), Z may be a single bond. In a preferred embodiment of the present invention, in structural formula (1), Z may be a single bond.

[0035] In one embodiment of the present invention, in structural formula (1), a is an integer of 1 to 3. In one embodiment of the present invention, in structural formula (1), a may be 1, 2, or 3.

[0036] In one embodiment of the present invention, in the structural formula (1), Y represents an ether bond or an ester group. In one embodiment of the present invention, in the structural formula (1), Y may be an ether bond. In one embodiment of the present invention, in the structural formula (1), Y may be an ester group.

[0037] In a preferred embodiment of the present invention, in structural formula (1), Z represents a single bond, R1 is alkylene having 1 to 2 carbon atoms, and R2 and R3 may be hydrogen.

[0038] In one embodiment of the present invention, examples of monohydric phenols that induce structural formula (1) at the molecular end include, but are not limited to, 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, p-coumaryl alcohol, etc. Among these, p-hydroxyphenethyl alcohol and p-hydroxybenzyl alcohol are preferred from the viewpoint of reactivity, and p-hydroxyphenethyl alcohol is more preferred.

[0039] In one embodiment of the present invention, the terminal structure represented by structural formula (1) can be derived from p-hydroxyphenethyl alcohol (PHEP).

[0040] (ii) Structural unit (2) In one embodiment of the present invention, in the structural unit (2), R4 to R7 each independently represent hydrogen, fluorine, chlorine, bromine, iodine, or an optionally substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms. In one embodiment of the present invention, in the structural unit (2), R4 to R7 are each independently preferably hydrogen, fluorine, chlorine, bromine, or iodine, or may be an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 15 carbon atoms, each of which may have a substituent, and more preferably hydrogen, fluorine, chlorine, bromine, or iodine, or may be an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, each of which may have a substituent. In a preferred embodiment of the present invention, R4 to R7 are each independently hydrogen or a methyl group.

[0041] In one embodiment of the present invention, in the structural unit (2), X is -O-, -S-, -SO-, -SO2-, -CO-, or a divalent group represented by any one of the following general formulae (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 19each 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.

[0042] In one embodiment of the present invention, in the structural unit (2), 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 R8 to R9 represents an alkyl group having 1 to 3 carbon atoms. 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.

[0043] In one embodiment of the present invention, in the structural unit (2), when X is a divalent group represented by the above general formulas (4) to (8), R 18 and R 19each 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 (2), when X is a divalent group represented by the above general formula (8), R 20 may be an alkylene group of 1 to 9 which may have a substituent, and preferably an alkylene group of 1 to 5 which may have a substituent. In one embodiment of the present invention, in the structural unit (2), 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, and more preferably c may represent an integer of 0 to 6 and d may represent an integer of 1 to 100.

[0044] In one embodiment of the present invention, in the structural unit (2), X may be -O-, -S-, or a divalent group represented by any one of the above general formulas (3) to (4).

[0045] In one embodiment of the present invention, examples of the diol from which the structural unit (2) is derived include 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)ether, and the like. 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, 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-hydroxyphenyl)fluorene, Bisphenol C; BPC, 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, 2,2-bis(4-hydroxyphenyl)hexafluoropropane (bisphenol AF;BPAF), but are not limited thereto. These may be used alone or in combination of two or more. Among these, bisphenol A, bisphenol AP, bisphenol Z, bisphenol CD, bisphenol TMC, bisphenol C, bisphenol IOTD, bisphenol IBTD, bisphenol MIBK, and bisphenol AF are particularly preferred. Furthermore, it is preferred to use 2,2-bis(4-hydroxy-3-methylphenyl)propane (bisphenol C; BPC) or 2,2-bis(4-hydroxyphenyl)hexafluoropropane (bisphenol AF; BPAF) as the main component. When 2,2-bis(4-hydroxyphenyl)propane (bisphenol A; BPA) is used alone, it has low solubility in non-halogen organic solvents, so it is preferred not to use 2,2-bis(4-hydroxyphenyl)propane alone in the present invention.;

[0046] In one embodiment of the present invention, the structural unit (2) may be one or more types selected from the group consisting of the following formulas (9) to (22), but is not limited thereto. [ka] TIFF0007669929000014.tif125170

[0047] In one embodiment of the present invention, the structural unit (2) may be derived from a bisphenol compound. In one embodiment of the present invention, the bisphenol compound may be selected from the group consisting of bisphenol A (2,2-bis(4-hydroxyphenyl)propane), bisphenol AP (1,1-bis(4-hydroxyphenyl)-1-phenylethane), bisphenol Z (1,1-bis(4-hydroxyphenyl)cyclohexane), bisphenol CD (1,1-bis(4-hydroxyphenyl)cyclododecane), bisphenol C (2,2-bis(3-methyl-4-hydroxyphenyl)propane), bisphenol IOTD (1,1-bis(4-hydroxyphenyl)-2-ethylhexane), bisphenol IBTD (1,1-bis(4-hydroxyphenyl)-2-methylpropane), bisphenol MIBK (1,1-bis(4-hydroxyphenyl)-2-methylpentane), and bisphenol AF (2,2-bis(4-hydroxyphenyl)hexafluoropropane), but is not limited thereto.

[0048] (iii) Production of terminally modified polycarbonate resin (A) The terminally modified polycarbonate resin (A) of the present invention can be produced by a conventional method.

[0049] The polycarbonate resin used in the coating resin solution of the present invention can be produced by reacting a monohydric phenol that derives structural formula (1) at the molecular end, a bisphenol that derives structural unit (2), and a carbonate-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.

[0050] In the phosgene method, bisphenol and a monohydric phenol which induces structural formula (1) are reacted with phosgene in the presence of an acid binder and a solvent. Examples of the acid binder include pyridine and hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, and examples of the solvent include methylene chloride and chloroform. In addition, in order to promote the polycondensation 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 which induces structural formula (1) 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 phenol in an amount of less than 50% by mass relative to the monohydric phenol which induces structural formula (1). 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 a temperature of 0 to 150°C, preferably 5 to 40°C. The reaction time varies depending 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.

[0051] On the other hand, in the transesterification method, bisphenol, a monohydric phenol which induces the structural formula (1), and a bisaryl carbonate are mixed and reacted at a high temperature under reduced pressure. Examples of the 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 degree of reduced pressure is preferably 1 mmHg or less, and phenols derived from the bisaryl carbonate produced by the transesterification reaction are distilled out of the system. The reaction time depends on the reaction temperature and the degree of reduced pressure, 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, the reaction may be carried out using a small amount of a molecular weight regulator other than the monohydric phenol which induces the structural formula (1), or by adding an antioxidant or a branching agent.

[0052] The polycarbonate resin of 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.

[0053] 3. Polyisocyanate compounds In the present invention, the polycarbonate resin composition contains 0.1 parts by mass or more of a polyisocyanate compound per 100 parts by mass of the above-mentioned terminally modified polycarbonate resin (A). 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 a molecule as the polyisocyanate compound, a crosslinked structure is formed in the polycarbonate resin composition, and the polycarbonate resin composition can be made into a crosslinked composition.

[0054] 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.

[0055] Examples of aliphatic polyisocyanates include, but are not limited to, 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, and dimer acid diisocyanate.

[0056] 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.

[0057] 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.

[0058] Examples of the aralkyl polyisocyanate include, but are not limited to, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, (α,α,α',α'-tetramethylxylylene diisocyanate, 3,3'-methylene d-tolylene-4,4'-diisocyanate, and the like.

[0059] These polyisocyanate compounds can be used alone or in combination of two or more.

[0060] 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.

[0061] 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.

[0062] 4. 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 a solvent containing a non-halogen-based 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.

[0063] As described above, the solvent of the coating resin solution of the present invention is a solvent containing a non-halogenated solvent, and preferably a solvent containing a non-halogenated organic solvent as the main solvent. The non-halogenated organic solvent that can be used as the solvent of the coating resin solution of the present invention may contain one or more solvents selected from the group consisting of ester solvents, ether solvents, carbonate ester solvents, and ketone solvents. The solvent of the coating resin solution of the present invention is mainly composed of a solvent generally used in paints, and specifically includes ester solvents such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-ethoxyethyl acetate, 2-methoxy-1-methylethyl acetate, and ethyl lactate, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and isophorone, carbonate ester solvents such as dimethyl carbonate and ethyl methyl carbonate, ether solvents such as tetrahydrofuran, 1,4-dioxane, diethyl ether, dimethoxymethane, ethyl cellosolve, and anisole, and aromatic hydrocarbon solvents such as toluene, ethylbenzene, xylene, pseudocumene, and mesitylene. Furthermore, a small amount of an alcohol-based poor solvent such as ethanol or isopropyl alcohol, or a hydrocarbon-based poor solvent such as n-heptane, cyclohexane, mineral spirits, etc. may be used in combination. Among these, it is preferable to dissolve in an ester-based solvent such as propyl acetate or butyl acetate, a ketone-based solvent such as methyl ethyl ketone or cyclohexanone, or an ether-based 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.

[0064] Furthermore, halogen-based solvents such as dichloromethane have a large effect on the coating work environment, and therefore are not used as the main solvent for the coating resin solution of the present invention.

[0065] 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.

[0066] 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.

[0067] 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% by mass in the coating as desired.

[0068] Furthermore, if necessary, rust inhibitors, antioxidants, dispersants, ultraviolet absorbers, antifoaming agents, leveling agents, etc. may be added.

[0069] The amount of the 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.

[0070] 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.

[0071] 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.

[0072] In one embodiment of the present invention, the resin solution can be used as a binder resin solution to make a printing ink. Such a printing ink can be used, for example, as a printing ink 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 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.

[0073] In addition to the binder resin and dye / pigment, the printing ink may contain organic fine particles, inorganic fine particles, release agents, antioxidants, plasticizers, dispersants, infrared absorbers, antistatic agents, ultraviolet absorbers, defoamers, leveling agents, etc., as necessary.

[0074] 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.

[0075] In one embodiment of the present invention, the above-mentioned printing ink is printed on a base film for decorative printing, and then the solvent is removed by drying, and the dye / pigment is fixed to the binder resin and the film and the binder resin are adhered to each other at the same time, so that a decoratively printed film, i.e., a base film coated with the above-mentioned printing ink, can be obtained. A conventional method can be used as a method for applying the printing ink to a base film, and examples of the method include, but are not limited to, screen printing, gravure printing, and flexographic printing.

[0076] In one embodiment of the present invention, there is provided a film or coating comprising the above-mentioned polycarbonate resin composition or a crosslinked composition obtained by crosslinking at least a portion of the above-mentioned polycarbonate resin composition.

[0077] 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 multilayer.

[0078] 5. 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 18,000 to 45,000.

[0079] <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

[0080] (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.

[0081] <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 mass average molecular weight (Mw) converted into polystyrene (PS) and polycarbonate (PC) were calculated using the following conversion formula: Mw (PC conversion) = 0.4782×Mw (PS conversion) 1.014706

[0082] <Method for measuring hydroxyl value> The hydroxyl value of the polycarbonate resin used in the present invention was measured under the following conditions. Test method: Compliant with JIS K0070 (potentiometric titration method) Measuring device: Potentiometric titrator Electrode: Composite glass electrode

[0083] (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.

[0084] <Cross-cut method> Adhesion tests were conducted using the JIS K5600-5-6 cross-cut method (1mm intervals) using 24mm wide cellophane tape (adhesive strength 4.01N / 10mm) manufactured by Nichiban Co., Ltd., which is compliant with the cross-cut test method. 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

[0085] EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.

[0086] <Example 1> In 600 ml of 9 w / w% aqueous sodium hydroxide solution and 200 ml of pure water, 108 g (0.37 mol) of 1,1-bis(4-hydroxyphenyl)-1-phenylethane (hereinafter abbreviated as "BPAP": manufactured by Honshu Chemical Industry Co., Ltd.), 2.88 g (0.021 mol, terminal structure content 5.6 mol%) of p-hydroxyphenethyl alcohol (hereinafter abbreviated as "PHEP": manufactured by Otsuka Chemical Co., Ltd.) and 0.3 g of hydrosulfite were dissolved.

[0087] 200 ml of methylene chloride was added thereto, and while stirring, 51.6 g of phosgene was blown in over about 30 minutes while maintaining the temperature at 15 to 20°C.

[0088] 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.

[0089] 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.

[0090] The resulting polycarbonate resin (hereinafter abbreviated as "PC-1") had an Mv of 19,700, an Mw of 54,000 (PS equivalent) and 30,300 (PC equivalent), and a hydroxyl value of 11 mgKOH / g.

[0091] A resin composition containing 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, heated to 110°C, and dried for 5 hours to obtain a test piece. The Mw of the polycarbonate resin composition (crosslinked body) after drying was 58,900 (PS equivalent) and 33,100 (PC equivalent). When the test piece was subjected to the cross-cut method in accordance with JIS K5600-5-6, the result was 0.

[0092] <Example 2> Instead of BPAP, 1,1-bis(4-hydroxyphenyl)cyclohexane (hereinafter abbreviated as "BPZ": manufactured by Honshu Chemical Industry Co., Ltd.) 103.8g (0.39mol) was used, and PHEP was changed to 1.53g (0.011mol, terminal structure content 2.9mol%). Polymerization was performed in the same manner as in Example 1 to obtain a polycarbonate resin (Mv: 30,600, Mw: 89,100 (PS equivalent), 50,400 (PC equivalent), hydroxyl value: 5mgKOH / g, hereinafter abbreviated as "PC-2"). PC-2 (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. The Mw of the polycarbonate resin composition after drying was 95,900 (PS equivalent) and 54,300 (PC equivalent).

[0093] <Example 3> Polymerization was carried out in the same manner as in Example 1, except that 101.7 g (0.38 mol) of 2,2-bis(4-hydroxyphenyl)-4-methylpentane (hereinafter abbreviated as "MIBK": manufactured by Honshu Chemical Industry Co., Ltd.) was used instead of BPAP, and 0.79 g (0.006 mol, terminal structure content 1.5 mol%) of PHEP was changed to 0.79 g (0.006 mol). A polycarbonate resin (Mv 43,500, Mw: 124,200 (PS equivalent), 70,600 (PC equivalent), hydroxyl value: 3 mgKOH / g, hereinafter abbreviated as "PC-3") was obtained. PC-3 (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. The Mw of the polycarbonate resin composition after drying was 130,300 (PS equivalent) and 74,100 (PC equivalent).

[0094] <Example 4> 48.0 g (0.19 mol) of 2,2-bis(4-hydroxy-3-methylphenyl)propane (hereinafter abbreviated as "BPC": manufactured by Honshu Chemical Industry Co., Ltd.), 32.0 g (0.14 mol) of 2,2-bis(4-hydroxyphenyl)propane (hereinafter abbreviated as "BPA": manufactured by Mitsubishi Chemical Corporation), 2.25 g (0.016 mol, terminal structure content 4.7 mol%) of PHEP, and 0.3 g of hydrosulfite were dissolved in 600 ml of 9 w / w% aqueous sodium hydroxide solution and 200 ml of pure water.

[0095] 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.

[0096] 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.

[0097] 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.

[0098] The resulting precipitate was filtered and dried at 105° C. for 24 hours to obtain a polymer powder.

[0099] The obtained polycarbonate resin (hereinafter abbreviated as "PC-4") had an Mv of 25,500, an Mw of 57,000 (PS equivalent) and 32,000 (PC equivalent), and a hydroxyl value of 8 mgKOH / g. PC-4 (10 parts by mass) and 1 part by mass of xylylene diisocyanate (XDI) (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).

[0100] <Example 5> 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).

[0101] <Example 6> A coating solution was prepared by dissolving 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) 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 69,900 (PS equivalent) and 39,400 (PC equivalent).

[0102] <Example 7> Instead of BPC, 71.4 g (0.21 mol) of 2,2-bis(4-hydroxyphenyl)hexafluoropropane (hereinafter abbreviated as "BPAF": manufactured by Central Glass Co., Ltd.) was used, and BPA was changed to 20.4 g (0.09 mol) and PHEP to 0.833 g (0.006 mol, terminal structure content 2.0 mol%). Except for this, polymerization was carried out in the same manner as in Example 4 to obtain a polycarbonate resin (Mv: 27,300, Mw: 84,200 (PS equivalent), 47,600 (PC equivalent), hydroxyl value: 6 mgKOH / g, hereinafter abbreviated as "PC-A"). PC-A (10 parts by mass) and 0.25 parts by mass of HDI (2.5 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. The Mw of the polycarbonate resin composition after drying was 91,700 (PS equivalent) and 51,900 (PC equivalent).

[0103] <Comparative Example 1> Polymerization was carried out in the same manner as in Example 1, except that 2.21 g (0.015 mol, terminal structure content 4.0 mol%) of PTBP was used instead of PHEP, to obtain a polycarbonate resin (Mv 20,000, Mw: 56,600 (PS equivalent), 31,800 (PC equivalent), hydroxyl value: 0 mgKOH / g, hereinafter abbreviated as "PC-5"). A coating solution was prepared and evaluated in the same manner as in Example 1, except that no HDI was used and PC-5 was used instead of PC-1. The Mw of the polycarbonate resin composition after drying was 56,600 (PS equivalent) and 31,800 (PC equivalent).

[0104] <Comparative Example 2> Except for using PC-5 instead of PC-1, a coating solution was prepared and evaluated in the same manner as in Example 1. The Mw of the polycarbonate resin composition after drying was 56,600 (PS equivalent) and 31,800 (PC equivalent).

[0105] <Comparative Example 3> Except for using PC-5 instead of PC-1 and changing HDI to 3 parts by mass (30 parts by mass per 100 parts by mass of polycarbonate resin), a coating solution was prepared and evaluated in the same manner as in Example 1. The Mw of the polycarbonate resin composition after drying was 56,600 (PS equivalent) and 31,800 (PC equivalent).

[0106] <Comparative Example 4> Polymerization was carried out in the same manner as in Example 2, except that PHEP was replaced with 1.17 g (0.008 mol, terminal structure content 2.0 mol%) of PTBP, to obtain a polycarbonate resin (Mv 32,500, Mw: 98,900 (PS equivalent), 56,000 (PC equivalent), hydroxyl value: 0 mgKOH / g, hereinafter abbreviated as "PC-6"). A coating solution was prepared and evaluated in the same manner as in Example 2, except that PC-6 was used instead of PC-2. The Mw of the polycarbonate resin composition after drying was 98,900 (PS equivalent) and 56,000 (PC equivalent).

[0107] <Comparative Example 5> Polymerization was carried out in the same manner as in Example 3, except that PHEP was replaced with 0.71 g (0.005 mol, terminal structure content 1.3 mol%) of PTBP, to obtain a polycarbonate resin (Mv 50,000, Mw: 149,900 (PS equivalent), 85,400 (PC equivalent), hydroxyl value: 0 mgKOH / g, hereinafter abbreviated as "PC-7"). A coating solution was prepared and evaluated in the same manner as in Example 3, except that PC-7 was used instead of PC-3. The Mw of the polycarbonate resin composition after drying was 149,900 (PS equivalent) and 85,400 (PC equivalent).

[0108] <Comparative Example 6> Polymerization was carried out in the same manner as in Example 4, except that 1.47 g (0.013 mol, terminal structure content 3.0 mol%) of PTBP was used instead of PHEP, to obtain a polycarbonate resin (Mv 26,000, Mw: 61,500 (PS equivalent), 34,600 (PC equivalent), hydroxyl value: 0 mgKOH / g, hereinafter abbreviated as "PC-8"). A coating solution was prepared and evaluated in the same manner as in Example 4, except that no HDI was used and PC-8 was used instead of PC-4. The Mw of the polycarbonate resin composition after drying was 61,500 (PS equivalent) and 34,600 (PC equivalent).

[0109] <Comparative Example 7> Except for not using HDI, a coating solution was prepared and evaluated in the same manner as in Example 1. The Mw of the polycarbonate resin composition after drying was 54,000 (PS equivalent) and 30,300 (PC equivalent).

[0110] <Comparative Example 8> Except for not using HDI, a coating solution was prepared and evaluated in the same manner as in Example 2. The Mw of the polycarbonate resin composition after drying was 89,100 (PS equivalent) and 50,400 (PC equivalent).

[0111] <Comparative Example 9> Except for not using HDI, a coating solution was prepared and evaluated in the same manner as in Example 4. The Mw of the polycarbonate resin composition after drying was 57,000 (PS equivalent) and 32,000 (PC equivalent).

[0112] The following table shows the results of the peel durability measured for the coating solutions of the above Examples and Comparative Examples.

[0113] [Table 1]

[0114] The polycarbonate resins used in the above examples and comparative examples are as shown in the table below.

[0115] [Table 2]

[0116] As described above, it has been demonstrated that the resin composition of the present invention is useful as a blend resin composition of a polycarbonate resin and another resin, which can improve the adhesion between a coating film and a substrate.

[0117] 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. 100 parts by mass of a terminal-modified polycarbonate resin (A) having a terminal structure represented by the following structural formula (1) and the following structural unit (2), 0.1 parts by mass or more of a polyisocyanate compound or a crosslinked composition obtained by crosslinking at least a part of the polycarbonate resin composition, A non-halogenated organic solvent; A resin solution comprising: 【Chemistry 1】 (In formula (1), R １ represents an alkylene group having 1 to 20 carbon atoms or an alkenylene group having 2 to 20 carbon atoms, each of which may have a substituent; R ２ and R ３ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms; Z represents an ether bond, a carbonyl group, an ester bond, or a single bond; a is an integer from 1 to 3; Y represents an ether bond or an ester group. 【Chemistry 2】 (In formula (2), R ４ ~R ７ each independently represents hydrogen, fluorine, chlorine, bromine or iodine, or represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, each of which may have a substituent; X is -O-, -S-, -SO-, -SO ２ -, -CO-, or a divalent group represented by any one of the following general formulas (3) to (8). 【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. However, When the structural unit (2) is derived from a bisphenol compound, except for when bisphenol A is used alone as the bisphenol compound, Except when the polyisocyanate compound is 4,4'-ethylidene diphenyl diisocyanate, Resin solution.

2. In the structural formula (1), Z represents a single bond, R １ is an alkylene having 1 to 2 carbon atoms, and R ２ ~R ３ The resin solution of claim 1 , wherein is hydrogen.

3. The resin solution according to claim 1 or 2, wherein in the structural unit (2), X is -O-, -S-, or a divalent group represented by any one of the following general formulas (3) to (4).

4. The resin solution according to any one of claims 1 to 3, wherein the structural unit (2) is at least one selected from the group consisting of the following formulas (9) to (22): 【Chemistry 4】 【change】

5. The resin solution according to any one of claims 1 to 3, wherein the structural unit (2) is derived from a bisphenol compound.

6. 6. The resin solution of claim 5, wherein the bisphenol compound is selected from the group consisting of bisphenol A, bisphenol AP, bisphenol Z, bisphenol CD, bisphenol C, bisphenol IOTD, bisphenol IBTD, bisphenol MIBK, and bisphenol AF.

7. The resin solution according to any one of claims 1 to 6, wherein the terminal structure represented by the structural formula (1) is p-hydroxyphenethyl alcohol (PHEP).

8. The resin solution according to any one of claims 1 to 7, wherein the terminal structure represented by the structural formula (1) is contained in an amount of 0.5 mol% or more relative to the structural unit (2).

9. The resin solution according to any one of claims 1 to 8, wherein the polyisocyanate compound is an isocyanate compound containing two or more isocyanate groups in one molecule.

10. The resin solution according to claim 9 , wherein the isocyanate compound is a diisocyanate compound.

11. The resin solution according to any one of claims 1 to 10, wherein the viscosity average molecular weight of the polycarbonate resin composition is 10,000 to 60,000.

12. A resin solution described in any one of claims 1 to 11, comprising the crosslinked composition and a non-halogenated organic solvent.

13. The resin solution according to claim 1, comprising the polycarbonate resin composition and a non-halogenated organic solvent.

14. A printing ink comprising the resin solution according to any one of claims 1 to 13 as a binder resin solution.

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

16. A film or coating comprising the resin solution according to any one of claims 1 to 13.

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