Polycarbonate resin composition

Abstract

The present application provides a resin composition containing a polycarbonate resin and capable of improving adhesion, and the like. The above technical problem is solved by a polycarbonate resin composition containing: a polycarbonate resin (A) having a structural unit represented by the following general formula (1); and a silane coupling agent (B) represented by the following general formula (2), containing the above silane coupling agent (B) 0.06 parts by mass or more with respect to 100 parts by mass of the polycarbonate resin (A). [In formulae (1) and (2), R 21 ~R 23 , X, Y, m are as described in the specification.]

Description

TECHNICAL FIELD

[0001] The present application relates to a polycarbonate resin composition and the like, and more particularly, to a polycarbonate resin composition which can be used for a polycarbonate coating resin solution and the like having excellent adhesion to a substrate. BACKGROUND

[0002] A polycarbonate resin is used for electrical products, mechanical products such as automobiles, and the like, because of excellent mechanical properties such as transparency, moldability, and impact resistance. Among them, a polycarbonate resin solution for obtaining a functional film and for performing coating of an article is known (Patent Literature 1).

[0003] A coating film obtained from a polycarbonate resin solution has excellent durability such as impact resistance, but has poor adhesion, and on the contrary, a nail coating use utilizing the easy peelability of this property is known (Patent Literature 2). Therefore, the adhesion of these coating films to a substrate still has room for improvement.

[0004] As a resin composition obtained by blending a polycarbonate resin and another resin, a blended resin composition of a polycarbonate resin and a polyphenylene ether resin is known, but this blended resin composition is not a product for improving adhesion (Patent Literature 3). Therefore, development of a polycarbonate resin composition capable of improving the adhesion of a coating film to a substrate is still desired.

[0005] PRIOR ART DOCUMENTS

[0006] PATENT LITERATURE

[0007] Patent Literature 1: Japanese Patent Application Laid-Open No. 4-268365

[0008] Patent Literature 2: Japanese Patent Application Laid-Open No. 2014-024789

[0009] Patent Literature 3: Japanese Patent No. 6340811 SUMMARY

[0010] PROBLEMS TO BE SOLVED BY THE INVENTION

[0011] The present application provides a blended resin composition of a polycarbonate resin and another component and the like which can improve the adhesion of a coating film to a substrate.

[0012] MEANS FOR SOLVING THE PROBLEMS

[0013] The present inventors have intensively studied, and as a result, have found that a blended resin composition of a specific polycarbonate resin and a silane coupling agent can be used for a solution for forming a firm coating film having high adhesion to a substrate, thereby completing the present application. The substrate includes, for example, a substrate formed of a wide range of materials such as metals represented by stainless steel and glass.

[0014] That is, the present application includes the following modes.

[0015] <1> A polycarbonate resin composition comprising: a polycarbonate resin (A) having a structural unit represented by the following general formula (1); and a silane coupling agent (B) represented by the following general formula (2), the polycarbonate resin composition containing the silane coupling agent (B) 0.06 parts by mass or more per 100 parts by mass of the polycarbonate resin (A).

[0016]

[0017] In formula (1), R1 to R4 are each independently hydrogen, fluorine, chlorine, bromine, iodine, or 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 can have a substituent,

[0018] X is a single bond, -O-, -S-, -SO-, -SO2-, -CO-, or a divalent group represented by any one of the following general formulas (4) to (9).

[0019]

[0020] In general formula (4), R8 to R 17 each independently represent hydrogen or an alkyl group having 1 to 3 carbon atoms, R8 to R 17 at least one of which represents an alkyl group having 1 to 3 carbon atoms,

[0021] In general formulas (5) to (9), R 18 and R 19 each independently represent hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which can have a substituent, an alkoxy group having 1 to 5 carbon atoms which can have a substituent, an aryl group having 6 to 12 carbon atoms which can have a substituent, an aralkyl group having 7 to 17 carbon atoms which can have a substituent, or an alkenyl group having 2 to 15 carbon atoms which can have a substituent, or 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,

[0022] R 20 is an alkylene group having 1 to 9 carbon atoms which can have a substituent, c represents an integer of 0 to 20, and d represents an integer of 1 to 500.

[0023]

[0024] In general formula (2), R 21 represents an alkylene group having 1 to 4 carbon atoms or a phenylene group, and R22 R represents alkyl groups having 1 to 4 carbon atoms, each independently. 23 Each can be independently represented by a hydroxyl group or an alkyl group having 1 to 4 carbon atoms.

[0025] Y represents an active group containing an epoxy group, isocyanate group, vinyl group, styrene group, acryloyl group, urea group, isocyanurate group, or mercapto group.

[0026] m can represent integers from 1 to 3 independently.

[0027] <2> As mentioned above <1> The polycarbonate resin composition wherein the end structure of the polycarbonate resin (A) is represented by the following general formula (3).

[0028]

[0029] In general formula (3), R5 is an alkyl group with 1 to 8 carbon atoms that can be replaced by a hydroxyl group, and n is an integer from 0 to 5.

[0030] <3> As mentioned above <1> or <2> The polycarbonate resin composition wherein, in the above general formula (1), X is represented by -O-, -S-, or the above general formula (4) or (5).

[0031] <4> As mentioned above <1> ~ <3> The polycarbonate resin composition according to any one of the following statements, wherein the above general formula (1) is represented by one or more formulas selected from (10) to (22) below.

[0032]

[0033] <5> As mentioned above <1> ~ <4> The polycarbonate resin composition according to any one of the above-mentioned general formula (2) wherein the active group represented by Y has at least one of epoxy group, isocyanate group and vinyl group.

[0034] <6> As mentioned above <1> ~ <4> The polycarbonate resin composition described in any one of the above-mentioned general formulas (2) contains any one of the following formulas (i) to (ix).

[0035]

[0036] In general formulas (i) to (ix), * denotes R in general formula (2) above. 21 The bonding point.

[0037] <7> As mentioned above <1> ~ <6> The polycarbonate resin composition according to any one of the following methods, wherein the viscosity-average molecular weight of the polycarbonate resin (A) is 10,000 to 60,000.

[0038] <8> The polycarbonate resin composition according to any one of <1> to <7>, wherein the silane coupling agent (B) is contained in an amount of 10 parts by mass or less, relative to 100 parts by mass of the polycarbonate resin (A).

[0039] <9> A film or a coating film comprising the polycarbonate resin composition according to any one of <1> to <8>.

[0040] <10> A coating composition comprising the polycarbonate resin composition according to any one of <1> to <8>.

[0041] <11> The coating composition according to <10>, further comprising a solvent component.

[0042] <12> A resin solution comprising the resin composition according to any one of <1> to <8> and a non-halogen organic solvent.

[0043] <13> A coating solution comprising the resin composition according to any one of <1> to <8>.

[0044] <14> A printing ink comprising the resin composition according to any one of <1> to <8>.

[0045] <15> An electroconductive paste comprising the resin composition according to any one of <1> to <8>.

[0046] <16> An adhesion-cured resin composition comprising the polycarbonate resin composition according to any one of <1> to <8>, and not containing a solvent.

[0047] Effects of the Invention

[0048] A resin coating film obtained from a resin solution containing the resin composition of the present application has the advantage of strong adhesion to a substrate and difficulty in peeling, compared with a conventional polycarbonate resin coating film. Furthermore, the resin composition according to the present application can improve adhesion to a wide variety of substrates. DETAILED DESCRIPTION

[0049] The present application relates to a polycarbonate resin composition containing a specific polycarbonate resin and a silane coupling agent, a film or a coating film each containing the polycarbonate resin composition, a resin solution, a coating solution, a printing ink, an electroconductive paste, a coating composition, and an adhesion-cured resin composition. These objects of the present application are described below.

[0050] 1. Polycarbonate resin composition

[0051] As described above, the polycarbonate resin composition of the present application contains a polycarbonate resin (A) and a silane coupling agent (B). In the polycarbonate resin composition, it is preferable to contain the polycarbonate resin (A) and the silane coupling agent (B) in the form of a mixture.

[0052] The polycarbonate resin composition of the present application contains 0.06 parts by mass or more of the silane coupling agent (B) with respect to 100 parts by mass of the polycarbonate resin (A). That is, the polycarbonate resin composition of the present application contains 0.06% by mass or more (600 parts by mass or more) of the silane coupling agent (B) with respect to the total mass of the polycarbonate resin (A) and the silane coupling agent (B).

[0053] In one embodiment of the present application, the polycarbonate resin composition contains 0.07 parts by mass or more, more preferably 0.08 parts by mass or more, particularly preferably 0.09 parts by mass or more, or 0.1 parts by mass or more of the silane coupling agent (B) with respect to 100 parts by mass of the polycarbonate resin (A). Thus, the amount of the silane coupling agent (B) with respect to the total mass of the polycarbonate resin (A) and the silane coupling agent (B) in the polycarbonate resin composition is preferably 0.07% by mass or more, more preferably 0.08% by mass or more, particularly preferably 0.09% by mass or more, or 0.1% by mass or more.

[0054] Even if the silane coupling agent (B) is used in excess with respect to the polycarbonate resin (A), it is highly likely that the effect of adhesion is obtained. Therefore, the upper limit of the content of the silane coupling agent (B) in the resin composition is not so important, but in one embodiment of the present application, the polycarbonate resin composition preferably contains 10 parts by mass or less, more preferably 8 parts by mass or less, further preferably 6 parts by mass or less, particularly preferably 5 parts by mass or less, for example, 2 parts by mass or less of the silane coupling agent (B) with respect to 100 parts by mass of the polycarbonate resin (A). Thus, the amount of the silane coupling agent (B) with respect to the total mass of the polycarbonate resin (A) and the silane coupling agent (B) in the polycarbonate resin composition can be about 10 parts by mass or less, more preferably about 8 parts by mass or less, further preferably about 6 parts by mass or less, particularly preferably about 5 parts by mass or less, for example, can be about 2 parts by mass or less.

[0055] 2. Polycarbonate resin (A)

[0056] 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)).

[0057]

[0058] In formula (1), R1to R4are each independently hydrogen, fluorine, chlorine, bromine, iodine, or 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 can have a substituent. R1to R4may each independently be an alkyl group having 1 to 12, 1 to 8, or 1 to 4 carbon atoms, an aryl group having 6 to 12, 6 to 10, or 6 or 7 carbon atoms, an alkenyl group having 2 to 12, 2 to 8, 2 to 6, or 2 to 4 carbon atoms, an alkoxy group having 1 to 5, 1 to 3, or 1 or 2 carbon atoms, or an aralkyl group having 7 to 17, 7 to 12, 7 to 10, or 7 or 8 carbon atoms.

[0059] Note that R1to R4each represent four groups bonded to the benzene ring in formula (1), and can be the same as or different from each other.

[0060] R1to R4are preferably hydrogen or an alkyl group having 1 to 10 carbon atoms, more preferably hydrogen or an alkyl group having 1 to 5 carbon atoms, and particularly preferably hydrogen or an alkyl group such as methyl group or ethyl group.

[0061] X in formula (1) is a single bond, -O-, -S-, -SO-, -SO2-, -CO-, or a divalent group represented by any one of the following general formulae (4) to (9).

[0062]

[0063] In general formula (4), R8to R 17 each independently represent hydrogen or an alkyl group having 1 to 3 carbon atoms, and at least one of R8to R 17 represents an alkyl group having 1 to 3 carbon atoms.

[0064] In general formulae (5) to (9), R 18 and R 19 each independently represent hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which can have a substituent, an alkoxy group having 1 to 5 carbon atoms which can have a substituent, an aryl group having 6 to 12 carbon atoms which can have a substituent, an aralkyl group having 7 to 17 carbon atoms which can have a substituent, or an alkenyl group having 2 to 15 carbon atoms which can have a substituent, or 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.

[0065] R 20 is an alkylene group having 1 to 9 carbon atoms which can have a substituent. Note that two R 20 in formula (9) are each independently selected from an alkylene group having 1 to 9 carbon atoms which can have a substituent, and the two R 20The same or different alkylene groups can be used.

[0066] In General Formula (5), c represents an integer of 0 to 20, and in General Formula (9), d represents an integer of 1 to 500.

[0067] In one embodiment of the present application, in the case where X is a divalent group represented by General Formula (4) in Structural Unit (1), R8to R 17 independently represent hydrogen or an alkyl group having 1 to 3 carbon atoms, and preferably hydrogen or a methyl group, and at least one of R8to R 17 independently represent hydrogen or an alkyl group having 1 to 3 carbon atoms, and preferably hydrogen or a methyl group, and at least one of R8to R

[0068] In one embodiment of the present application, in the case where X is a divalent group represented by General Formula (9) in Structural Unit (1), R 17 independently represent hydrogen, a methyl group, an ethyl group, a n-propyl group or an iso-propyl group, and at least one of R8to R 17 independently represent hydrogen, a methyl group, an ethyl group, a n-propyl group or an iso-propyl group, and at least one of R8to R

[0069] In one embodiment of the present application, in the case where X is a divalent group represented by General Formula (5) to (9) in Structural Unit (1), R 18 and R 19 independently represent hydrogen, a halogen, an alkyl group having 1 to 20 carbon atoms which can have a substituent, an alkoxy group having 1 to 5 carbon atoms which can have a substituent, an aryl group having 6 to 12 carbon atoms which can have a substituent, an aralkyl group having 7 to 17 carbon atoms which can have a substituent, or an alkenyl group having 2 to 15 carbon atoms which can have a substituent, and preferably represent hydrogen, a halogen, an alkyl group having 1 to 10 carbon atoms which can have a substituent, an alkoxy group having 1 to 3 carbon atoms which can have a substituent, an aryl group having 6 to 8 carbon atoms which can have a substituent, an aralkyl group having 7 to 12 carbon atoms which can have a substituent, or an alkenyl group having 2 to 5 carbon atoms which can have a substituent.

[0070] In another embodiment of the present application, 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, and preferably a carbocyclic ring having 3 to 12 carbon atoms or a heterocyclic ring having 1 to 12 carbon atoms.

[0071] In one preferred embodiment of the present application, R 18 and R 19 may be bonded to each other to form a carbocyclic ring having 3 to 12 carbon atoms.

[0072] In one embodiment of the present application, in the case where X is a divalent group represented by General Formula (9) in Structural Unit (1), R 20The alkylene group of 1 to 9 which can have a substituent is preferably an alkylene group of 1 to 5 which can have a substituent.

[0073] In one embodiment of the present application, in the structural unit (1), when X is a divalent group represented by the general formula (5) or (9) described above, it is preferable that c represents an integer of 0 to 12 and d represents an integer of 1 to 300, more preferably c represents an integer of 1 to 6, and particularly preferably c is 1. In addition, d can represent an integer of 1 to 100.

[0074] In one embodiment of the present application, in the structural unit (1), X can be a single bond, -0-, -S-, or a divalent group represented by any one of the general formulae (4) and (5) described above, and is preferably a divalent group represented by the general formula (5) described above.

[0075] In addition, as the substituent contained in the structural unit (1), a halogen, a cyano group, an alkenyl group having a carbon number of, for example, 5 or less, or the like can be given. In addition, the carbon number described above is the total carbon number including the carbon number of the substituent.

[0076] In one embodiment of the present application, the structural unit (1) can be a structural unit derived from a bisphenol compound. As the bisphenol compound forming the structural unit (1), 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, bis(4-hydroxy-3-methylphenyl)methane, 4,4'-diphenyldiol, 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), 1,1-bis(4-hydroxyphenyl)cyclododecane (bisphenol CD; BPCD), 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-tert-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, 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]polydimethylphenyl random copoly 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), 2,2-bis(4-hydroxyphenyl)-4-methylpentane (bisphenol MIBK;MIBK), 5,5'-(1-methylethylidene)-bis[1,1'-(diphenyl)-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, but are not limited to these. These can be used singly or in combination of two or more.

[0077] In addition, among the specific examples of these bisphenol compounds, 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), 1,1-bis(4-hydroxyphenyl)-1-phenylethane (bisphenol AP; BPAP), 1,1-bis(4-hydroxyphenyl)cyclododecane (bisphenol CD; BPCD), 2,2-bis(4-hydroxy-3-methylphenyl)propane (bisphenol C; BPC), 2,2-bis(4-hydroxyphenyl)propane (bisphenol A; BPA), 2,2-bis(4-hydroxyphenyl)-4-methylpentane (bisphenol MIBK; MIBK), 2-bis(4-hydroxyphenyl)hexafluoropropane (BPAF), and the like can be given. Note that in the case where 2,2-bis(4-hydroxyphenyl)propane (bisphenol A; BPA) is used alone, the solubility in non-halogen-based organic solvents decreases. Therefore, in the present application, it is preferable that 2,2-bis(4-hydroxyphenyl)propane not be used alone, and a polycarbonate resin having a structural unit derived from BPA and a structural unit derived from a bisphenol compound other than BPA is preferably used.

[0078] Further, in one embodiment of the present application, the polycarbonate resin (A) can contain a structural unit other than the structural unit (1). The structural unit other than the structural unit (1) can also be derived from a bisphenol compound.

[0079] In one embodiment of the present application, the structural unit (1) is preferably one or more selected from the group consisting of the structural units represented by the following formulae (10) to (22).

[0080]

[0081] In one embodiment of the present application, it is preferable that the polycarbonate resin (A) contain 40 mol% or more of the structural unit (1), based on the total number of moles of all the structural units contained in the polycarbonate resin (A).

[0082] In the polycarbonate resin (A), it is more preferable that 50 mol% or more, further preferably 55 mol% or more, particularly preferably 60 mol% or more of the structural unit (1) be contained, based on all the structural units.

[0083] Further, the polycarbonate resin (A) can be composed only of the structural unit (1). Therefore, the upper limit value of the proportion of the structural unit (1) in the polycarbonate resin (A) is not particularly important, but 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 the structural units.

[0084] (ii) End structure

[0085] As described above, the polycarbonate resin composition contained in the polycarbonate resin (A) preferably has a terminal structure represented by General Formula (3) (hereinafter also referred to as terminal structure (3)).

[0086]

[0087] In General Formula (3), R5is each independently an alkyl group having 1 to 8 carbon atoms which can be substituted with a hydroxyl group. In one embodiment of the present application, R5in General Formula (3) is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms which can be substituted with a hydroxyl group.

[0088] Further, via the bond line on the left side of the O atom in General Formula (3), the terminal structure is bonded to the carbonyl carbon (carbon of the carbonyl group of C=O) of the structural unit located at the terminal of the polymer chain of the polycarbonate (A).

[0089] As specific examples of the terminal structure represented by General Formula (3), there can be mentioned terminal structures having an aromatic ring (benzene ring) of an alkyl group having 2 to 4 carbon atoms which can contain 1 hydroxyl group, such as the structures represented by the following Formulas (3-1) and (3-2). In Formulas (3-1) and (3-2), the symbol * indicates the site bonded to the carbonyl group of C=O at the terminal of the main chain of the polycarbonate resin (A).

[0090]

[0091] In General Formula (3), n is an integer of 0 to 5, preferably an integer of 0 to 4, more preferably an integer of 1 to 3, further preferably 1 or 2, and particularly preferably 1.

[0092] Further, as to the alkyl group R5having 1 to 8 carbon atoms contained in the terminal unit (3), as a substituent, in addition to the above hydroxyl group, a halogen, a cyano group, an alkenyl group having a carbon number of, for example, 5 or less, or the like can be contained. Further, the carbon number of the above R5is the total carbon number including the carbon number of the substituent.

[0093] Note that in the same polycarbonate molecule, a plurality of terminal structures represented by Formula (3) are contained, but the values of R5and n can be determined independently for each terminal.

[0094] In one embodiment of the present application, the proportion of the terminal structure (3) in the molecules of the polycarbonate resin is 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 moles of the structural unit (1) and the terminal structure (3).

[0095] In one embodiment of the present application, the terminal structure (3) is derived to the polycarbonate resin from, for example, a monohydric phenol. As the monohydric phenol from which the terminal structure (3) is derived to the molecular terminal of the polycarbonate, for example, there can be mentioned phenol, para-tert-butylphenol (PTBP) and the like, para-cumylphenol and the like, octylphenol, long-chain alkyl-substituted phenol, para-hydroxyphenethyl alcohol (= tyrosol), meta-hydroxyphenethyl alcohol, ortho-hydroxyphenethyl alcohol, ortho-hydroxybenzyl alcohol (= salicyl alcohol), para-hydroxybenzyl alcohol, meta-hydroxybenzyl alcohol, vanillyl alcohol, vanillyl alcohol such as coniferyl alcohol, and the like, but not limited to these.

[0096] Among these specific examples, from the viewpoint of reactivity, para-tert-butylphenol (PTBP), para-hydroxyphenethyl alcohol (PHEP), and para-hydroxybenzyl alcohol are preferred, and para-tert-butylphenol (PTBP) and para-hydroxyphenethyl alcohol (PHEP) are more preferred.

[0097] In one embodiment of the present application, the terminal structure represented by the structural formula (3) can be derived from either of para-tert-butylphenol (PTBP) and para-hydroxyphenethyl alcohol (PHEP). PTBP forms the terminal structure of the above formula (3-1), and PHEP forms the terminal structure of the above formula (3-2).

[0098] In one embodiment of the present application, the proportion of the terminal structure (3) in the total moles of all the 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. In addition, the proportion of the moles of the terminal structure (3) contained in the total moles of all the 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.

[0099] (iii) Production of the polycarbonate resin (A)

[0100] The polycarbonate resin (A) used in the present application can be produced by a conventional method. For example, as follows.

[0101] The polycarbonate resin used in the coating resin solution of the present application can be produced by reacting a monohydric phenol that derives the terminal structure (3), a bisphenol that derives the structural unit (1), and a carbonate-forming compound, and known methods used when producing polycarbonate derived from bisphenol A, such as direct reaction of bisphenol with phosgene (phosgene method) or transesterification of bisphenol with diaryl carbonate (transesterification method), and the like can be employed.

[0102] In the phosgene method, the bisphenol, the monohydric phenol that derives the terminal structure (3), and phosgene are generally reacted in the presence of an acid-binding agent and a solvent. As the acid-binding agent, for example, pyridine, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and the like can be used, and as the solvent, for example, dichloromethane, chloroform, and the like can be used. Furthermore, in order to promote the polycondensation reaction, a tertiary amine such as triethylamine or a quaternary ammonium salt such as benzyltriethylammonium chloride, and the like can be used as a catalyst.

[0103] The monohydric phenol that derives the terminal structure (3) functions as a degree of polymerization adjuster, and in addition to the monohydric phenol that derives the terminal structure (3), a monohydric phenol such as phenol, p-t-butylphenol, p-cumylphenol, and long-chain alkyl-substituted phenol can be used in combination in an amount of less than 50% by mass. Furthermore, an antioxidant such as sodium sulfite and sodium hydrosulfite, a branching agent such as phloroglucinol and indigo bisphenol can be added in a small amount as needed. The reaction temperature is generally in the range of 0 to 150°C, and preferably 5 to 40°C. The reaction time depends on the reaction temperature, and is generally 0.5 minutes to 10 hours, and preferably 1 minute to 2 hours. In addition, during the reaction, the pH of the reaction system is preferably maintained at 10 or higher.

[0104] On the other hand, in the transesterification method, the bisphenol, the monohydric phenol that derives the terminal structure (3), and a diaryl carbonate are mixed and reacted under reduced pressure and at a high temperature. As examples of the diaryl carbonate, diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, dinaphthyl carbonate, and the like can be given. Two or more of these compounds can be used in combination. The reaction is generally carried out at a temperature in the range of 150 to 350°C, and preferably 200 to 300°C, and the degree of reduction is preferably 1 mmHg or lower at the end, and the phenol derived from the diaryl carbonate produced by the transesterification reaction is distilled and removed from the system. The reaction time depends on the reaction temperature and the degree of reduction, and the like, and is generally about 1 to 24 hours. The reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen and argon, and in addition, a molecular weight adjuster other than the monohydric phenol that derives the terminal structure (3) can be used in a small amount as needed, or an antioxidant and a branching agent can be added and reacted.

[0105] The polycarbonate resin used in the present application preferably maintains a good balance of solvent solubility, coatability, adhesion, scratch resistance, impact resistance and the like required as a film forming resin for a coating resin solution. When the intrinsic viscosity of the resin is too low, the scratch resistance and impact strength are insufficient, and when the intrinsic viscosity is too high, there is a case where the solvent solubility decreases and the solution viscosity increases, and the coatability decreases. As a desired intrinsic viscosity range, 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.

[0106] 3. Silane coupling agent (B)

[0107] In the present application, the polycarbonate resin composition contains a silane coupling agent (B) as described above.

[0108] The silane coupling agent (B) is represented by General Formula (2).

[0109]

[0110] In General Formula (2), R 21 is a linear or branched alkylene group having 1 to 4 carbon atoms, or a phenylene group, for example, a phenylene group having 6 to 12 carbon atoms, R 21 is preferably a linear or branched alkylene group having 1 to 4 carbon atoms, more preferably a linear alkylene group having 1 to 3 carbon atoms, and further preferably an alkylene group having 1 or 2 carbon atoms. Among the alkylene groups represented by R 21 may contain an ether bond.

[0111] In General Formula (2), R 22 are each independently an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably an alkyl group having 1 or 2 carbon atoms (i.e., a methyl group or an ethyl group).

[0112] In General Formula (2), R 23 each independently represent a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably an alkyl group having 1 or 2 carbon atoms (i.e., a methyl group or an ethyl group).

[0113] In General Formula (2), m is an integer of 1 to 3.

[0114] As specific examples of the active group Y in the silane coupling agent (B) of General Formula (2), an epoxy group, an isocyanate group, a vinyl group, a styryl group, an acryloyl group, a urea group, an isocyanurate group, or a mercapto group can be given, and the active group Y can be represented by, for example, the following Formulas (i) to (ix).

[0115] In Formulas (i) to (ix), the symbol * indicates a bonding point with R 21 in General Formula (2).

[0116]

[0117] In formulae (i) to (ix), the hydrogen atoms represented by H of CH2, NH, N-H can be independently substituted by the above R 18 , for example, one H (hydrogen atom) in CH2of general formula (iv) or (v) can be substituted by R 18 .

[0118] As the active group Y of an epoxy group, for example, represented by the above formula (i) or (ii), an alkyl group having 1 to 5 carbon atoms, for example, 1 to 3 carbon atoms can be further included. In addition, an alicyclic structure having 4 to 8 carbon atoms can be further included.

[0119] As the active group Y of an isocyanate group, for example, represented by the above formula (iii), an alkylene group having 1 to 5 carbon atoms, for example, 1 to 3 carbon atoms bonded to N can be further included.

[0120] As the active group Y of a vinyl group, for example, represented by the above formula (iv), an alkyl group having 1 to 5 carbon atoms, for example, 1 to 3 carbon atoms can be further included. In addition, an aromatic ring having 6 to 10 carbon atoms can be further included.

[0121] As the active group Y of a styryl group, for example, represented by the above formula (v), an alkyl group having 1 to 5 carbon atoms, for example, 1 to 3 carbon atoms can be further included. In addition, as a specific example of the silane coupling agent (B) containing a styryl group as the active group Y, a compound of the following formula (2-5) can be mentioned.

[0122] As the active group Y of a ureido group, for example, represented by the above formula (vi), an alkyl group having 1 to 5 carbon atoms, for example, 1 to 3 carbon atoms can be further included.

[0123] As the active group Y of an isocyanurate group, for example, represented by the above formula (vii), one or two of the three bonding points (symbol *) of R 21 in general formula (2) can be independently substituted by a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, for example, 1 to 3 carbon atoms.

[0124] As the active group Y of a mercapto group, for example, represented by the above formula (viii), a plurality of mercapto groups can be included in the same molecule of the silane coupling agent (B).

[0125] The acryloyl group as the active group Y is represented by the above formula (ix), for example, and can also have an alkyl group having 1 to 5 carbon atoms, for example, 1 to 3 carbon atoms, preferably excluding a methacryloyl group. In addition, as a specific example of the silane coupling agent (B) containing an acryloyl group as the active group Y, a compound of the following formula (2-6) can be given.

[0126] As a specific example of the silane coupling agent (B), a compound represented by the following formulae (2-1) to (2-6) can be given.

[0127]

[0128] The active group represented by Y in the formula (2) reacts with the terminal hydroxyl group or the like of the polycarbonate resin (A) or the active site of an organic compound in the substrate to form a bond, or interacts with each other without forming a bond such as a hydrogen bond.

[0129] The polycarbonate resin composition containing the silane coupling agent having such an active group can improve the adhesion of the resin layer to a wide variety of substrates as will be described later. For example, not only high adhesion of the resin layer to a metal substrate such as stainless steel as the substrate can be achieved, but also high adhesion of the resin layer to a glass substrate can be achieved.

[0130] Note that, in the polycarbonate resin composition, a single kind of silane coupling agent (B) can be used, or two or more kinds of silane coupling agents (B) can be used.

[0131] 4. Other components in polycarbonate resin composition

[0132] The polycarbonate resin composition can further contain components other than the polycarbonate resin (A) and the silane coupling agent (B). For example, a thermoplastic resin other than the polycarbonate resin (A), an additive such as an antioxidant and an ultraviolet absorber, an inorganic filler, an electrically conductive filler, and the like.

[0133] However, since the polycarbonate resin composition does not need to be curable, for example, photocurable or thermally curable, a photopolymerization initiator, a polymerization precursor that polymerizes at a prescribed efficiency, and the like do not need to be added.

[0134] In the polycarbonate resin composition, the content of the components other than the polycarbonate resin (A) and the silane coupling agent (B) is preferably 10% by mass or less, more preferably 8% by mass or less, further preferably 6% by mass or less, particularly preferably 4% by mass or less, for example, 2% by mass or less, based on the total mass of the polycarbonate resin composition.

[0135] Further, from the viewpoint of simplification of the constituent components, the content of the thermoplastic resin other than the polycarbonate resin (A) contained in the polycarbonate resin composition is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, more further preferably 8% by mass or less, particularly preferably 5% by mass or less, based on the total mass of the polycarbonate resin composition. In addition, it is preferable that the polycarbonate resin composition does not contain the thermoplastic resin other than the polycarbonate resin (A).

[0136] 5. Film or coating film (coating layer)

[0137] The film or coating film of the present application contains the above-described polycarbonate resin composition. In one embodiment, it is possible to provide a film or coating film containing the above-described polycarbonate resin composition or a crosslinked body composition obtained by crosslinking at least a part of the above-described polycarbonate resin composition.

[0138] In one embodiment of the present application, the above-described film or coating film can be obtained by applying the coating resin solution or printing ink of the present application to a substrate and then performing heating or drying. In one embodiment of the present application, the above-described film or coating film can be a single layer or a multilayered laminate.

[0139] In addition, the film can also be obtained by applying the printing ink of the present application as described later. For example, after performing decorative printing on a film of a substrate before applying the printing ink, the dye and / or pigment can be fixed to the binder resin by removing the solvent by drying, and at the same time, the film can be made to adhere to the binder resin, thereby obtaining a film subjected to decorative printing, that is, a film of a substrate to which the above-described printing ink is applied. As the method of applying the printing ink to the substrate, a conventional method can be used, and for example, screen printing, gravure printing, flexographic printing, and the like can be mentioned, but the present application is not limited thereto.

[0140] 6. Coating composition

[0141] The coating composition of the present application contains the above-described polycarbonate resin composition. In one embodiment, the coating composition contains the following substances in addition to the polycarbonate resin composition of the present application. That is, the coating composition can contain: other resin components including an epoxy resin, a polyester resin, an acrylic resin, a polyurethane resin, a fluororesin, a silicone resin, and the like; pigment components including inorganic pigments such as titanium oxide, carbon black, calcium carbonate, metal particles, and the like, organic pigments such as azo pigments, phthalocyanine pigments, and the like; solvent components including alcohols, ketones, aliphatic hydrocarbons, aromatic hydrocarbons, esters, ethers, and the like; and the like.

[0142] In the coating composition, the content of the polycarbonate resin composition is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, further preferably 10 to 30% by mass, based on the total mass of the coating composition.

[0143] In addition, in the coating composition, the content of the other resin component is preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less.

[0144] In addition, in the coating composition, the pigment component preferably contains 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less.

[0145] In addition, in the coating composition, the solvent component preferably contains 10 to 80% by mass, more preferably 20 to 70% by mass, and further preferably 30 to 60% by mass.

[0146] The resin other than the polycarbonate resin can be used as the main component, and the polycarbonate resin can be used as an additive, or the polycarbonate resin can be used as the main component, and the resin other than the polycarbonate resin can be used as an additive, but the latter is preferred.

[0147] 7. Resin solution (coating solution) containing polycarbonate resin composition

[0148] The resin solution of the present application, for example, a coating solution, is a solution obtained by dissolving the above-described polycarbonate resin composition in a solvent containing an organic solvent, for example, a non-halogen-based solvent, and forming a film thereof in a state generally called a transparent color. A film colored by further dissolving or dispersing a desired dye and / or pigment can also be obtained.

[0149] As the solvent of the resin solution and the coating solution of the present application, as described above, an organic solvent is used, and the organic solvent is preferably a solvent containing a non-halogen-based solvent, and more preferably a solvent containing a non-halogen-based organic solvent as a main solvent.

[0150] As the non-halogen-based organic solvent that can be used as the solvent of the resin solution and the coating solution of the present application, one or more kinds of solvents selected from the group consisting of an ester-based solvent, an ether-based solvent, a carbonate-based solvent, and a ketone-based solvent can be contained.

[0151] As the solvent of the resin solution and the coating solution of the present application, that is, a solvent generally used for paints and the like as a main component, ester-based solvents such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-ethoxyethyl acetate, 2-methoxy-1-methylethyl acetate, and ethyl lactate; ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and isophorone; carbonate-based solvents such as dimethyl carbonate and ethyl methyl carbonate; ether-based solvents such as tetrahydrofuran, 1,4-dioxane, diethyl ether, dimethoxy methane, ethyl cellosolve, and anisole; and aromatic hydrocarbon-based solvents such as toluene, ethylbenzene, xylene, pseudocumene, and mesitylene can be specifically mentioned. A small amount of alcohol-based poor solvents such as ethanol and isopropanol, and hydrocarbon-based poor solvents such as n-heptane, cyclohexane, and mineral spirit can also be used.

[0152] Among them, it is preferable to dissolve in ester-based solvents such as propyl acetate, butyl acetate, which are inexpensive, easy to handle, and have high safety, ketone-based solvents such as methyl ethyl ketone, cyclohexanone, ether-based solvents such as tetrahydrofuran, dimethoxymethane, and particularly preferable to methyl ethyl ketone, propyl acetate.

[0153] Furthermore, since halogen-based solvents such as dichloromethane have a large influence on the coating operation environment, it is preferable not to be used as the main solvent of the coating resin solution of the present application.

[0154] In one embodiment of the present application, the resin solution contains the above-mentioned polycarbonate resin composition and a non-halogen-based organic solvent. In one embodiment of the present application, the above-mentioned polycarbonate resin composition can be a crosslinked body composition in which at least a part thereof is crosslinked.

[0155] The viscosity of the coating resin solution of the present application can be arbitrarily set by the desired coating method, and is preferably in the range of 10 to 20,000 mPa / s. In the case of airless spraying, brushing, and roll coating, it is preferably in the range of 400 to 20,000 mPa / s; in the case of air spraying, it is in the range of 100 to 6,000 mPa / s; and in the case of dip coating and cup spraying, it is in the range of 10 to 500 mPa / s.

[0156] In order to enhance the color effect, pigments, dyes, colored particles, particles having light interference can be added to the resin solution of the present application, such as the coating resin solution. Among the pigments and dyes, as organic pigments, azo pigments, phthalocyanine pigments, etc. can be cited, and specifically, for example, 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, Yellow No. 405, etc. can be cited. In addition, in order to express white, pearl color, metallic color, gold and silver line feeling, mica titanium, titanium oxide, iron oxide, tin oxide, zirconium oxide, chromium oxide, bismuth oxychloride, silicon dioxide, chromium, titanium nitride, titanium, magnesium fluoride, gold, silver, nickel, etc. can also be used. The particles having light interference are particles that enhance the color effect by reflection or scattering of light, and as examples, glass beads, small shells, mica, etc. can be cited. These additives are preferably added in the range of 0.0001 to 10.0% by mass, more preferably in the range of 0.01 to 5.0% by mass, and further preferably in the range of 0.1 to 3.0% by mass, based on the total mass of the solution, as needed.

[0157] Furthermore, as needed, rust preventive, antioxidant, dispersant, ultraviolet absorber, defoaming agent, leveling agent, etc. can also be added.

[0158] The blending amount of the polycarbonate resin in the coating resin solution of the present application is preferably 1 to 50 mass%, more preferably 4 to 30 mass% based on the total mass of the solution, depending on the intrinsic viscosity and solvent solubility. When the concentration is within this range, the balance between the solvent solubility and the coatability is good, and the workability and appearance are improved.

[0159] The film formed after coating the coating resin solution of the present application is less likely to be scratched or peeled due to transportation, rubbing, impact, and the like during use, compared to the film of the conventional polycarbonate coating resin solution.

[0160] The thickness of the film formed after coating the coating resin solution of the present application is preferably in the range of 5 to 200 μm, particularly preferably 10 to 120 μm, and further preferably 15 to 60 μm. A thin film having a thickness of less than 5 μm is insufficient in strength, and scratches easily reach the substrate. When the thickness exceeds 200 μm, the film is too thick, and is likely to be peeled due to shrinkage of the film. Considering the use of the film which is finally peeled and discarded, it is also economically disadvantageous.

[0161] 8. Printing ink containing resin solution

[0162] The above resin solution can be used as an adhesive resin solution to obtain a printing ink. Such a printing ink of the present application can be used for, for example, decorative printing. Generally, a printing ink for decorative printing is composed of a solvent, a dye and / or a pigment, and an adhesive resin as main components. As the dye and pigment used in the above printing ink, for example, anthraquinone-based, naphthoquinone-based, and the like, inorganic pigments such as titanium oxide, carbon black, calcium carbonate, and metal particles, organic pigments such as azo pigments and phthalocyanine pigments, and the like can be mentioned, but are not limited to these. These dyes and pigments coexist with the adhesive resin in a state of being dissolved or dispersed in the ink. The adhesion of the printing ink using the resin solution of the present application as the adhesive resin solution is excellent.

[0163] In the above printing ink, in addition to the adhesive resin and the dye and / or pigment, organic and 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, and the like can be added as needed.

[0164] In addition, the blending amount of the adhesive resin in the ink depends on the intrinsic viscosity, solvent solubility, and the like, but is preferably 1 to 70 mass%, more preferably 5 to 50 mass% based on the total mass of the adhesive resin. When the concentration of the adhesive resin is within this range, the balance between the solvent solubility and the coatability of the ink is good, and the workability is improved.

[0165] The blending amount of the polycarbonate resin in the printing ink of the present application is, for example, 1 to 50 mass%, preferably 4 to 30 mass% based on the total mass of the printing ink.

[0166] 9. Conductive paste

[0167] The conductive paste of the present application contains the polycarbonate resin composition. In one embodiment, the conductive paste contains, in addition to the polycarbonate resin composition of the present application, a resin component containing silver, nickel, copper, graphite, carbon nanotube, or the like conductive substance, an epoxy resin, a polyurethane resin, a phenol resin, or the like. Further, in the conductive paste, a solvent component such as butyl carbitol acetate can be contained, or the solvent component can not be contained.

[0168] In the conductive paste, the polycarbonate resin composition is preferably contained at 1 to 40% by mass, more preferably at 3 to 30% by mass, and further preferably at 5 to 20% by mass, based on the total mass of the conductive paste.

[0169] In the conductive paste, the content of the conductive substance is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more.

[0170] Further, in the conductive paste, the content of the resin component is preferably 1 to 40% by mass, more preferably 3 to 30% by mass, and further preferably 5 to 20% by mass.

[0171] Further, in the conductive paste, the content of the solvent component is preferably 1 to 50% by mass, more preferably 3 to 45% by mass, and further preferably 5 to 40% by mass.

[0172] 10. Adhesion-cured resin composition

[0173] The adhesion-cured resin composition of the present application contains the polycarbonate resin composition, but does not contain a solvent component. In one embodiment, the adhesion-cured resin composition contains a curable monomer or the like component.

[0174] As the curable monomer, a monomer that is liquid by itself and can dissolve the polycarbonate resin, such as an epoxy compound, styrene, methyl methacrylate, or the like can be cited. Further, these curable monomers are also useful in that a composite resin composition with the polycarbonate resin (A) can be formed by a curing reaction.

[0175] In the adhesion-cured resin composition, the polycarbonate resin composition is preferably contained at 1% by mass or more, more preferably at 5% by mass or more, and further preferably at 10% by mass or more, based on the total mass of the adhesion-cured resin composition.

[0176] Further, in the adhesion-cured resin composition, the content of the curable monomer is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more.

[0177] 11. Base material

[0178] As the base material to which the polycarbonate resin composition according to the present application can be applied, in addition to the base material represented by stainless steel, there can be mentioned a base material formed of a metal, a glass base material, a resin (plastic) base material, a rubber base material, a flexible substrate (FPC), and a glass fiber composite base material (including an epoxy resin) that can be used as an electronic substrate, and the like.

[0179] 12. Physical properties of polycarbonate resin composition and (coating) resin solution

[0180] (i) Viscosity-average molecular weight (Mv)

[0181] In one embodiment of the present application, the viscosity average molecular weight (Mv) of the polycarbonate resin and the polycarbonate resin composition can be 10,000 to 60,000. In the present application, the viscosity average molecular weight (Mv) of the polycarbonate resin and the polycarbonate resin composition is preferably 14,000 to 55,000, more preferably 16,000 to 50,000, further preferably 18,000 to 45,000. In a preferred embodiment of the present application, the viscosity average molecular weight (Mv) of the polycarbonate resin and the polycarbonate resin composition can be 20,000 to 40,000.

[0182] (ii) Weight-average molecular weight (Mw)

[0183] When a coating resin solution containing the polycarbonate resin composition is prepared, coated and air-dried, and then subjected to a heat drying treatment, the weight average molecular weight (Mw) is increased. That is, it is considered that by subjecting to the treatment as described above, a crosslinked body composition in which at least a part of the polycarbonate resin composition is crosslinked (for example, Examples 12, 13 and the like described below) is formed. As described above, it is considered that in the present application, the use of the silane coupling agent (B) as a technical means contributes to the formation of the crosslinked body composition. For example, a chemical bond is formed between the active group of the silane coupling agent and the terminal group or the like present in the polycarbonate resin (A) portion, whereby the molecular weight (Mw) can be increased.

[0184] Examples

[0185] The following describes Examples and Comparative Examples. The properties of the resin compositions of the Examples and Comparative Examples were measured as shown below.

[0186] <Viscosity average molecular weight (Mv)>

[0187] The viscosity average molecular weight of the resin was measured as follows.

[0188] Measuring instrument: Ubbelohde capillary viscometer

[0189] Solvent: dichloromethane

[0190] Resin solution concentration: 0.5 g / dL

[0191] Measurement temperature: 25°C

[0192] The measurement was performed under the above conditions, and the intrinsic viscosity [η] dL / g was obtained at a Huggins constant of 0.45, and was calculated from the following equation.

[0193] η = 1.23 x 10 ﹣4 x Mv 0.83

[0194] <Substrate adhesion>

[0195] The polycarbonate resin composition was coated on a stainless steel plate and a glass substrate (coating thickness 60 μm), and after air-drying, drying was performed at a temperature of 140°C for 12 hours, to produce a laminate having a coating film formed of the polycarbonate resin composition laminated thereon.

[0196] The adhesion test was performed using a cross-cut test standard 24 mm wide CELLOTAPE (registered trademark) (adhesion 4.01 N / 10 mm) manufactured by NICHIBAN Corporation, by the cross-cut method (1 mm interval) based on JIS K5600-5-6, and the substrate adhesion was evaluated by classification according to the JIS classification index, with a value of 0 (no peeling) to 5 (almost completely peeled).

[0197] <Stability of molecular weight>

[0198] The Mw of the dried resin composition was measured by drying the polycarbonate resin composition at a temperature of 140°C for 12 hours on a PFA culture dish (a culture dish made of tetrafluoroethylene-perfluoroalkoxyethylene copolymer resin). Based on the Mw of the polycarbonate resin used in the resin composition and the Mw of the dried resin composition, a product in which the Mw after drying decreased by 3,000 or more was regarded as a defective product, and a product in which the Mw decreased by less than 3,000 was regarded as a good product.

[0199] In addition, the Mw was measured as follows.

[0200] <Weight average molecular weight (Mw)>

[0201] Gel permeation chromatography (GPC) analysis measurement conditions

[0202] The weight average molecular weight (Mw) of the polycarbonate resin and the polycarbonate resin composition was measured by gel permeation chromatography analysis under the following conditions.

[0203] Apparatus used: Alliance HPLC system manufactured by Waters Corporation

[0204] Column: Shodex 805L column 2 manufactured by Showa Denko K.K.

[0205] Eluent: chloroform

[0206] Flow rate: 1.0 ml / min

[0207] Sample: 0.25 w / v% chloroform solution sample

[0208] Detection: UV detection at 254 nm

[0209] From the above GPC analysis, the weight average molecular weight (Mw) value in polystyrene (PS) conversion can be obtained.

[0210] <Example of synthesis of polycarbonate resin>

[0211] (Synthesis of polycarbonate resin (A-1))

[0212] In 9 w / w% sodium hydroxide aqueous solution 530 ml, pure water 200 ml, dissolved 1,1-bis(4-hydroxyphenyl)cyclohexane (hereinafter referred to as "BPZ": manufactured by Hokoku Corporation) 90 g (0.34 mol), PTBP (p-tert-butylphenol) 1.65 g (0.011 mol) and sodium hydrosulfite 0.3 g.

[0213] To this, added dichloromethane 300 ml, under stirring, and at a temperature of 15 to 20°C, phosgene 46.5 g was blown for about 30 minutes.

[0214] After completion of phosgene blowing, added 9 w / w% sodium hydroxide aqueous solution 100 ml, emulsified the reaction liquid by vigorous stirring, then added 0.5 ml of triethylamine as a polymerization catalyst, stirred at a temperature of 20 to 30°C for about 40 minutes, and polymerization was performed.

[0215] After completion of polymerization, the reaction liquid 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 conductivity of the wash liquid (aqueous phase) was 10 μS / cm or less. The obtained polymer solution was added dropwise to hot water maintained at 60°C, and the solvent was evaporated to obtain a white powder precipitate. The obtained precipitate was filtered and dried at a temperature of 105°C for 24 hours to obtain polycarbonate resin (A-1), which was used.

[0216]

[0217] (Synthesis of polycarbonate resin (A-2))

[0218] Using the same method as polycarbonate resin (A-1), except that PTBP was changed to 0.51 g, polycarbonate resin (A-2) was obtained, which was used.

[0219] (Synthesis of polycarbonate resin (A-3))

[0220] Using 1,1-bis(4-hydroxyphenyl)-1-phenylethane (hereinafter referred to as "BPAP": manufactured by Shinnichi Chemical Industry Co., Ltd.) 97 g instead of BPZ, changing PTBP to 1.93 g, and except for this, the same method as in the polycarbonate resin (A-1) was adopted to obtain the polycarbonate resin (A-3), and this polycarbonate resin (A-3) was used.

[0221]

[0222] (Synthesis of polycarbonate resin (A-4))

[0223] Using 1,1-bis(4-hydroxyphenyl)cyclododecane (hereinafter referred to as "BPCD": manufactured by Shinnichi Chemical Industry Co., Ltd.) 118 g instead of BPZ, changing PTBP to 1.42 g, and except for this, the same method as in the polycarbonate resin (A-1) was adopted to obtain the polycarbonate resin (A-3), and this polycarbonate resin (A-3) was used.

[0224]

[0225] (Synthesis of polycarbonate resin (A-5))

[0226] In 9 w / w% sodium hydroxide aqueous solution 530 ml, pure water 200 ml, 2,2-bis(4-hydroxy-3-methylphenyl)propane (hereinafter referred to as "BPC": manufactured by Shinnichi Chemical Industry Co., Ltd.) 51.5 g (0.20 mol), 2,2-bis(4-hydroxyphenyl)propane (hereinafter referred to as "BPA": manufactured by Mitsubishi Chemical Corporation) 30.5 g (0.13 mol), PTBP 1.56 g (0.010 mol), and sodium hydrosulfite 0.3 g were dissolved.

[0227] To this, dichloromethane 200 ml was added, 0.08 g of benzyltriethylammonium chloride (hereinafter referred to as "TEBAC") was added with stirring, and phosgene 46.5 g was blown for about 30 minutes while maintaining the temperature at 15 to 20°C.

[0228] After the phosgene blowing was completed, 9 w / w% sodium hydroxide aqueous solution 100 ml was added, the reaction liquid was emulsified by vigorous stirring, and then 0.5 ml of triethylamine as a polymerization catalyst was added, and the polymerization was carried out by stirring for about 40 minutes at a temperature of 20 to 30°C.

[0229] After completion of the polymerization, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and water washing was repeated until the conductivity of the washing liquid (aqueous phase) was 10 μS / cm or less. The obtained polymer solution was added dropwise to hot water maintained at 60°C, and the solvent was evaporated to obtain a white powdery precipitate. The obtained precipitate was filtered and dried at a temperature of 105°C for 24 hours to obtain a polycarbonate resin (A-5), which was used.

[0230]

[0231] (Synthesis of polycarbonate resin (A-6))

[0232] Using 48.7 g of BPAP and 45.3 g (0.17 mol) of 2,2-bis(4-hydroxyphenyl)-4- methylpentane (hereinafter referred to as "MIBK": manufactured by Hokoku Corporation) instead of BPZ, changing PTBP to 1.68 g, and otherwise using the same method as in the polycarbonate resin (A-1), a polycarbonate resin (A-6) was obtained, which was used.

[0233]

[0234] (Synthesis of polycarbonate resin (A-7))

[0235] Changing BPC to 50.8 g, changing BPA to 30.2 g, and using p-hydroxyphenylethanol (hereinafter referred to as "PHEP": manufactured by Takachi Chemical Industry Co., Ltd.) 2.03 g (0.20 mol) while not using PTBP, and otherwise using the same method as in the polycarbonate resin (A-5), a polycarbonate resin (A-7) was obtained, which was used.

[0236] (Synthesis of polycarbonate resin (A-8))

[0237] Using 2,2-bis(4-hydroxyphenyl)hexafluoropropane (hereinafter referred to as "BPAF": manufactured by Central Glass Co., Ltd.) 78.6 g (0.23 mol) instead of BPC, changing BPA to 22.9 g, and changing PHEP to 0.92 g, and otherwise using the same method as in the polycarbonate resin (A-7), a polycarbonate resin (A-8) was obtained, which was used.

[0238] The composition and physical property values of the polycarbonate resins (A-1) to (A-8) are shown in Table 1.

[0239] [Table 1]

[0240]

[0241] <Example 1>

[0242] A solution of the polycarbonate resin composition was prepared by dissolving 10 parts by mass of the polycarbonate resin (A-1) and 0.05 parts by mass of the silane coupling agent (B-1) (0.5 parts by mass relative to 100 parts by mass of the polycarbonate resin) in 55 parts by mass of toluene.

[0243] <Examples 2 to 15, Comparative Examples 1 to 5>

[0244] A solution of the polycarbonate resin composition was prepared by changing the kind of the polycarbonate resin or the parts by mass of the silane coupling agent as shown in Table 2, and otherwise in the same manner as in Example 1.

[0245] The composition and the evaluation results of the polycarbonate resin compositions of Examples 1 to 15 and Comparative Examples 1 to 5 are shown in Table 2.

[0246] [Table 2]

[0247]

[0248] The abbreviations of B-1 to B-5 in Table 2 have the following meanings.

[0249] B-1: 3-glycidyloxypropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0250] B-2: 3-(triethoxysilyl)propyl isocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0251] B-3: Vinyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0252] B-4: Methyl methacrylate-3-(trimethoxysilyl)propyl ester (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0253] B-5: 3-Aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0254] As described above, the resin composition of the present application is shown to be useful as a blended resin composition of a polycarbonate resin and other resins, and to improve the adhesion between a coated film and a substrate.

[0255] Industrial applicability

[0256] The resin composition of the present application can be used as a coating resin solution for protecting an article. In particular, it is suitable for use in a field requiring durability in daily life such as IC cards, security cards, and the like.

Claims

1. A polycarbonate resin composition, characterized in that: It contains: a polycarbonate resin (A) having a structural unit shown in general formula (1); and a silane coupling agent (B) shown in general formula (2). The silane coupling agent (B) is present in a concentration of 0.06 parts by weight or more relative to 100 parts by weight of the polycarbonate resin (A). The end structure of the polycarbonate resin (A) is represented by the following general formula (3). In the polycarbonate resin (A), based on the total molar number of the structural unit (1) shown in the general formula (1) and the end structure (3) shown in the general formula (3), the content of the end structure (3) is more than 0.5 mol% and less than 12 mol%. In equation (1), R1 to R4 are independently hydrogen, fluorine, chlorine, bromine, or iodine, or can be alkyl groups with 1 to 20 carbon atoms, aryl groups with 6 to 12 carbon atoms, alkenyl groups with 2 to 12 carbon atoms, alkoxy groups with 1 to 5 carbon atoms, or aralkyl groups with 7 to 17 carbon atoms, which may have substituents. X is a single bond, -O-, -S-, -SO-, -SO2-, -CO-, or a divalent group represented by any of the following general formulas (4) to (9). In general formula (4), R8~R 17 Each of the following can be independently represented by hydrogen or an alkyl group having 1 to 3 carbon atoms, R8 to R9. 17 At least one of them represents an alkyl group having 1 to 3 carbon atoms. In general formulas (5) to (9), R 18 and R 19 Each of the following can independently represent hydrogen, halogen, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkoxy groups having 1 to 5 carbon atoms that may have substituents, aryl groups having 6 to 12 carbon atoms that may have substituents, aralkyl groups having 7 to 17 carbon atoms that may have substituents, or alkenyl groups having 2 to 15 carbon atoms that may have substituents, or... R 18 and R 19 They bond with each other to form carbon rings with 3 to 20 carbon atoms or heterocycles with 1 to 20 carbon atoms. R 20 It can be an alkylene group having 1 to 9 carbon atoms that can have substituents. c represents an integer from 0 to 20. d represents an integer from 1 to 500. In general formula (2), R 21 Indicates alkylene or phenylene with 1 to 4 carbon atoms. R 22 Each alkyl group, having 1 to 4 carbon atoms, is independently represented. R 23 Each can be independently represented by a hydroxyl group or an alkyl group having 1 to 4 carbon atoms. Y represents an active group containing an epoxy group, isocyanate group, vinyl group, styrene group, acryloyl group, urea group, isocyanurate group, or mercapto group. m represents an integer from 1 to 3 independently. In general formula (3), R5 are alkyl groups with 1 to 8 carbon atoms that can be substituted by hydroxyl groups. n is an integer from 0 to 5.

2. The polycarbonate resin composition according to claim 1, characterized in that: In general formula (3), R5 are alkyl groups with 1 to 6 carbon atoms that can be substituted by hydroxyl groups.

3. The polycarbonate resin composition according to claim 1 or 2, characterized in that: In the general formula (1), X is represented by -O-, -S-, the general formula (4) or (5).

4. The polycarbonate resin composition according to claim 1 or 2, characterized in that: The general formula (1) is represented by one or more formulas selected from (10) to (22) below.

5. The polycarbonate resin composition according to claim 1 or 2, characterized in that: The active group represented by Y in general formula (2) has at least one of epoxy group, isocyanate group and vinyl group.

6. The polycarbonate resin composition according to claim 1 or 2, characterized in that: The active group represented by Y in general formula (2) contains any one of the following formulas (i) to (ix). In general formulas (i) to (ix), * represents R in general formula (2). 21 The bonding point.

7. The polycarbonate resin composition according to claim 1 or 2, characterized in that: The polycarbonate resin (A) has a viscosity-average molecular weight of 10,000 to 60,000.

8. The polycarbonate resin composition according to claim 1 or 2, characterized in that: The silane coupling agent (B) is contained in 10 parts by mass or less relative to 100 parts by mass of the polycarbonate resin (A).

9. A membrane or coating, characterized in that: A polycarbonate resin composition comprising any one of claims 1 to 8.

10. A coating composition, characterized in that: A polycarbonate resin composition comprising any one of claims 1 to 8.

11. The coating composition according to claim 10, characterized in that: It also contains solvent components.

12. A resin solution, characterized in that: The resin composition comprising any one of claims 1 to 8 and the nonhalogenated organic solvent.

13. A coating solution, characterized in that: A resin composition comprising any one of claims 1 to 8.

14. A printing ink, characterized in that: A resin composition comprising any one of claims 1 to 8.

15. A conductive paste, characterized in that: A resin composition comprising any one of claims 1 to 8.

16. A sealing and curing resin composition, characterized in that: The composition contains the polycarbonate resin composition according to any one of claims 1 to 8, and is solvent-free.

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