Polycarbonate resin composition, coating solution, and coating film

Abstract

There has been a need for a polycarbonate resin composition which provides high flexibility and the like and also exhibits excellent color hue.　The foregoing problem can be solved by the following resin composition.　This resin composition contains a polycarbonate resin (A) and a condensed phosphoric acid ester (B). The polycarbonate resin (A) contains a constituent unit derived from a monomer represented by general formula (1). In general formula (1), R1 to R5 and R5 to R8 each independently denote hydrogen, fluorine, chlorine, bromine, iodine, or an optionally substituted alkyl group having 1-20 carbon atoms, aryl group having 6-12 carbon atoms, alkenyl group having 2-12 carbon atoms, alkoxy group having 1-5 carbon atoms or aralkyl group having 7-17 carbon atoms, and X is as defined in the description of the present application.

Description

Polycarbonate resin composition, coating solution and coating film

[0001] The present invention relates to a polycarbonate resin composition, a coating solution, and the like, and particularly to a polycarbonate resin composition containing a predetermined compound together with a polycarbonate resin, and the like.

[0002] Polycarbonate resins are generally known to have excellent mechanical properties, transparency, moldability, etc. Such polycarbonate resins are widely used in fields such as the formation of functional thin films and the coating of articles, as well as in mechanical products such as electrical appliances and automobiles. Furthermore, resins such as polycarbonate resins are often used as resin compositions containing various additives and other components depending on the application (e.g., Patent Documents 1 and 2 listed below).

[0003] Patent Document 1: WO2018 / 047693 Patent Document 2: JP 2004-352807 A

[0004] In resin-containing compositions, when additives are used to improve specific performance of the resin, there are cases where other properties are impaired. For example, when an additive to improve flexibility is added to a polycarbonate resin, a problem occurs in that the color is reduced. Therefore, there has been a demand for a polycarbonate resin composition that has high flexibility and excellent color.

[0005] The present invention provides the following polycarbonate resin composition, etc.: [1] A resin composition containing a polycarbonate resin (A) and a condensed phosphate ester (B), wherein the polycarbonate resin (A) contains a structural unit derived from a monomer represented by the following general formula (1): (In general formula (1), R １ ~R ４ and R ５ ~R ８each independently represents hydrogen, fluorine, chlorine, bromine, or 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 may have a substituent; X is a single bond or is represented by any of the following formulas (i) to (ix): Here, R ９ and R １０ each independently represents hydrogen, fluorine, chlorine, bromine, or iodine, or an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aryl group having 6 to 12 carbon atoms, each of which may have a substituent; R ９ and R １０ and R are bonded to form a carbocyclic ring having 5 to 20 carbon atoms or a heterocyclic ring having 5 to 12 atoms (provided that R ９ and R １０ and R are methyl groups, １１ and R １２ each independently represents hydrogen, fluorine, chlorine, bromine, or iodine, or an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, each of which may have a substituent, and c represents an integer of 0 to 20. [2] The polycarbonate resin composition according to the above [1], which contains 1 to 80 mass% of the condensed phosphate ester (B) based on the total mass of the polycarbonate resin (A) and the condensed phosphate ester (B). [3] In the formula (1), R １ ~R ４ and R ５ ~R ８ are each independently selected from hydrogen, an alkyl group having 1 to 6 carbon atoms which may have a substituent, and an aryl group having 6 to 8 carbon atoms which may have a substituent, X is a single bond or is represented by the formula (i), and R ９ and R １０ are each independently selected from hydrogen, an alkyl group having 1 to 10 carbon atoms which may have a substituent, and an aryl group having 6 to 10 carbon atoms which may have a substituent, or R ９ and R １０and (3) are each a group bonded to form a carbon ring having 5 to 20 carbon atoms. [4] The polycarbonate resin composition according to any one of [1] to [3] above, for example [3] above, wherein the monomer represented by general formula (1) includes at least one selected from the group consisting of the following formulae (2) to (7): [5] The polycarbonate resin composition according to any one of the above [1] to [4], for example, the above [1], wherein the condensed phosphate ester (B) comprises an aromatic condensed phosphate ester having 12 to 80 carbon atoms. [6] The polycarbonate resin composition according to any one of the above [1] to [5], for example, the above [5], wherein the condensed phosphate ester (B) is represented by at least one of the following formulas (8) and (9): (In general formulas (8) and (9), n is each independently selected from an integer of 0 to 3.) [7] A polycarbonate resin composition according to any one of the above [1] to [6], for example, the above [1], which is substantially free of solid content. [8] A polycarbonate resin composition according to any one of the above [1] to [7], for example, the above [1], in which the polycarbonate resin (A) contains less than 5 mol% of structural units derived from a monomer having a fluorene moiety represented by formula (vii).

[0006] [9] A resin composition comprising a polycarbonate resin (A) and a condensed phosphate ester (B), wherein the polycarbonate resin (A) comprises a structural unit derived from a monomer represented by the following general formula (1) (excluding polycarbonate resins whose structural units are constituted only by 2,2-bis(4-hydroxyphenyl)propane): (In general formula (1), R １ ~R ４ and R ５ ~R ８each independently represents hydrogen, fluorine, chlorine, bromine, or 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 may have a substituent; X is a single bond or is represented by any of the following formulas (i) to (ix): Here, R ９ and R １０ each independently represents hydrogen, fluorine, chlorine, bromine, or iodine, or an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aryl group having 6 to 12 carbon atoms, each of which may have a substituent; R ９ and R １０ and R represent a group that combine to form a carbocyclic ring having 5 to 20 carbon atoms or a heterocyclic ring having 5 to 12 atoms; １１ and R １２ each independently represents hydrogen, fluorine, chlorine, bromine, or iodine, or an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, each of which may have a substituent; and c represents an integer of 0 to 20.

[0007]

[10] A coating solution comprising the polycarbonate resin composition according to any one of [1] to [9] above, for example, the polycarbonate resin composition according to [1] above.

[11] A coating film comprising the polycarbonate resin composition according to any one of [1] to [9] above, for example, the polycarbonate resin composition according to [1] above.

[0008] The polycarbonate resin composition of the present invention contains a polycarbonate resin and has excellent flexibility that contributes to, for example, adhesion to a substrate and thermocompression bonding, as well as excellent color, such as high transparency, that is observed in polycarbonate resins. Furthermore, according to the present invention, it is also possible to provide a coating solution, a coating film, and the like that contain the polycarbonate resin composition having excellent properties.

[0009] The polycarbonate resin composition of the present invention contains at least a polycarbonate resin (A) and a condensed phosphate ester (B). Preferred embodiments of the present invention will be described in detail below.

[0010] 1. Polycarbonate Resin (A) 1-1. Structural Units of Polycarbonate Resin The polycarbonate resin (A) contained in the polycarbonate resin composition contains at least a structural unit derived from a monomer represented by general formula (1). In general formula (1), R １ ~R ４ and R ５ ~R ８ each independently represents hydrogen, fluorine, chlorine, bromine, or 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 may have a substituent.

[0011] R in formula (1) １ ~R ４ and R ５ ~R ８ are preferably each independently hydrogen, or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, each of which may have a substituent; more preferably hydrogen, or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, each of which may have a substituent; and even more preferably hydrogen, or an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 8 carbon atoms, or an alkoxy group having 1 to 2 carbon atoms, each of which may have a substituent.

[0012] X in the general formula (1) is a single bond or is represented by any one of the following formulas (i) to (ix).

[0013] R in formula (i) ９ and R １０ each independently represents hydrogen, fluorine, chlorine, bromine, or iodine, or an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aryl group having 6 to 12 carbon atoms, each of which may have a substituent; R ９ and R １０ and represent a group that combines to form a carbocyclic ring having 5 to 20 carbon atoms or a heterocyclic ring having 5 to 12 atoms.９ and R １０ It is preferable that none of R in formula (i) is a methyl group. ９ and R １０ In this way, the polycarbonate resin may contain a structural unit derived from a compound in which both R and R are methyl groups, such as bisphenol A, bisphenol C, etc. ９ and R １０ is not a methyl group, R ９ and R １０ may include a form in which all of the groups represented by the general formula (1) are methyl groups. Furthermore, among the monomers represented by the general formula (1), polycarbonate resins whose structural units are composed solely of bisphenol A (2,2-bis(4-hydroxyphenyl)propane) may be excluded from the components of the polycarbonate resin composition. In other words, it is preferable that the polycarbonate resin (A) does not contain a polycarbonate resin whose structural units are composed solely of bisphenol A. However, the polycarbonate resin (A) may contain a polycarbonate resin whose structural units are composed solely of bisphenol A.

[0014] R in formula (i) ９ and R １０ are preferably each independently hydrogen, or an alkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aryl group having 6 to 12 carbon atoms, each of which may have a substituent, or R ９ and R １０ and bond to form a carbon ring having 5 to 20 carbon atoms. ９ and R １０ is more preferably hydrogen, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, each of which may have a substituent; or R ９ and R １０ and bond to form a carbon ring having 5 to 12 carbon atoms. ９ and R １０ is more preferably hydrogen, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 8 carbon atoms, each of which may have a substituent, or R ９ and R１０ and bond to form a carbon ring having 5 to 10 carbon atoms, and particularly preferably R ９ and R １０ is hydrogen, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 8 carbon atoms, each of which may have a substituent; or R ９ and R １０ and bond to form a carbon ring having 6 to 8 carbon atoms. ９ and R １０ and are both methyl groups, R １ ~R ４ and R ５ ~R ８ In formula (i), it is preferable that any one of R is a group other than hydrogen from the above options, for example, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, an alkenyl group having 2 to 12 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, or an aralkyl group having 7 to 17 carbon atoms which may have a substituent. ９ and R １０ and are both methyl groups, R １ ~R ４ and R ５ ~R ８ It is more preferable that one or more of the above groups are alkyl groups having 1 to 20 carbon atoms which may have a substituent, even more preferable that they are alkyl groups having 1 to 10 carbon atoms which may have a substituent, and particularly preferable that they are alkyl groups having 1 to 4 carbon atoms which may have a substituent, such as a methyl group or an ethyl group.

[0015] In formula (iii), c is an integer of 0 to 20. In formula (iii), c is preferably an integer of 0 to 10 or 1 to 10, more preferably an integer of 0 to 5 or 1 to 5, and even more preferably an integer of 0 to 3 or 1 to 3, for example, 1 or 2.

[0016] R in formulas (vii) to (ix) １１ and R １２each independently represents hydrogen, fluorine, chlorine, bromine, or iodine, or an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, each of which may have a substituent. １１ and R １２ are preferably each independently hydrogen, or an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms, each of which may have a substituent; and more preferably are each independently hydrogen, or an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an aryl group having 6 to 8 carbon atoms, each of which may have a substituent.

[0017] The above-mentioned substituents contained in the structural units of the polycarbonate resin derived from the monomer of formula (1) are each independently selected from halogen, a hydroxyl group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, etc., and when an alkyl group, an alkenyl group, or an aryl group is contained as a substituent, the above-mentioned number of carbon atoms is the number of carbon atoms including the carbon of the substituent.

[0018] Specific preferred examples of the monomer represented by the general formula (1) above include those represented by the following formulas (2) to (7), namely, bisphenol C, 1,1-bis(4-hydroxyphenyl)-1-phenylethane (BPAP), 2,2-bis(4-hydroxyphenyl)-4-methylpentane (MIBK), 2,2-bis(4-hydroxyphenyl)hexafluoropropane (BPAF), 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), dihydroxydiphenylmethane (bisphenol F (BPF or BPF-SG)), and the like.

[0019] The polycarbonate resin may be a random copolymer or a block copolymer containing structural units derived from a plurality of different monomers represented by formula (1), or may be a homopolymer containing only structural units derived from a single type of monomer represented by formula (1). Furthermore, the polycarbonate resin contained in the polycarbonate resin composition may be a mixture of different resins.

[0020] For example, a polycarbonate resin having both a structural unit derived from bisphenol C represented by formula (2) and a structural unit derived from bisphenol A may be used as a component of the composition. In such a polycarbonate resin, for example, the proportion of the structural units derived from bisphenol C is preferably 20 to 90 mass% based on the total mass of the structural units derived from bisphenol C and the structural units derived from bisphenol A. Furthermore, the proportion of the structural units derived from bisphenol C based on the total mass of the structural units derived from bisphenol C and the structural units derived from bisphenol A is more preferably 30 to 80 mass%, even more preferably 40 to 75 mass%, and particularly preferably 45 to 70 mass%.

[0021] In polycarbonate resins, for example, the proportion of structural units derived from bisphenol C is preferably 20 to 90 mass%, more preferably 30 to 80 mass%, even more preferably 40 to 75 mass%, and particularly preferably 45 to 70 mass%, based on the total mass. Also, in polycarbonate resins in which bisphenol C and bisphenol A can be used in combination, for example, the proportion of structural units derived from bisphenol A is, for example, 10 to 80 mass%, preferably 20 to 70 mass%, more preferably 25 to 60 mass%, and even more preferably 30 to 55 mass%, based on the total mass.

[0022] Thus, although various structural units may be contained in the polycarbonate resin, the proportion of structural units derived from the monomer having the fluorene moiety represented by formula (vii) is preferably less than 5 mol% based on the number of moles of all structural units in the polycarbonate resin. In the polycarbonate resin, the proportion of structural units derived from the monomer having the fluorene moiety represented by formula (vii) is more preferably less than 3 mol%, and even more preferably less than 2 mol% or less than 1 mol%, based on the number of moles of all structural units in the polycarbonate resin.

[0023] 1-2. Structural Units That May Be Included in Polycarbonate Resins Polycarbonate resins may contain structural units other than structural units derived from the monomer of formula (1) described above (hereinafter also referred to as structural units of formula (1)). In polycarbonate resins, the proportion of structural units of formula (1) based on the total number of moles of all structural units is, for example, 5 mol% or more, preferably 10 mol% or more, more preferably 15 mol% or more, and even more preferably 20 mol% or more or 25 mol% or more, and the proportion of structural units of formula (1) may be even higher. For example, the proportion of structural units of formula (1) based on the above-mentioned total number of moles may be 30 mol% or more or 40 mol% or more. Furthermore, in polycarbonate resins, substantially all structural units may be derived from monomers of formula (1). In polycarbonate resins, the proportion of structural units of formula (1) based on the total number of moles of all structural units may be 80 mol% or less, 70 mol% or less, 60 mol% or less, or even lower. For example, the proportion of the structural units of formula (1) based on the total number of moles described above may be 50 mol % or less, or 40 mol % or less, or 30 mol % or less, or 20 mol % or less.

[0024] 1-3. Method for Producing Polycarbonate Resin The polycarbonate resin contained in the polycarbonate resin composition can be produced by a conventional method. For example, the method is as follows. The polycarbonate resin can be produced, for example, by reacting a bisphenol that derives the structural unit (1), a compound such as a monohydric phenol that derives a terminal structure, and a carbonate ester-forming compound. Known methods can be used, such as the direct reaction of a bisphenol with phosgene (phosgene method) or the transesterification of a bisphenol with a bisarylcarbonate (transesterification method).

[0025] In the phosgene method, for example, a compound such as a bisphenol that induces the structural unit (1) or a monohydric phenol that induces a terminal structure is reacted with phosgene in the presence of a typical acid binder and a solvent. Examples of acid binders that can be used include pyridine and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and solvents such as dichloromethane and chloroform. Furthermore, in order to promote the condensation polymerization reaction, it is preferable to use a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt such as benzyltriethylammonium chloride.

[0026] Compounds such as monohydric phenols that induce terminal structures function as polymerization degree regulators, but it is also possible to use other monohydric phenols such as phenol, p-t-butylphenol, p-cumylphenol, and long-chain alkyl-substituted phenols in combination in an amount of less than 50% by mass relative to the monohydric phenol that induces terminal structures. If desired, small amounts of antioxidants such as sodium sulfite and hydrosulfite, or branching agents such as phloroglucin and isatin bisphenol, may also be added. The polymerization reaction is typically carried out at a temperature in the range of 0 to 150°C, preferably 5 to 40°C. The reaction time varies depending on the reaction temperature, but is typically 0.5 minutes to 10 hours, preferably 1 minute to 2 hours. It is also desirable to maintain the pH of the reaction system at 10 or higher during the reaction.

[0027] On the other hand, in the transesterification method, for example, a bisphenol that derives the structural unit (1), a compound such as a dihydric phenol that derives the terminal structure, and a bisaryl carbonate are mixed and reacted, typically at a high temperature under reduced pressure. Examples of bisaryl carbonates include diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, and dinaphthyl carbonate. Two or more of these compounds can also be used in combination. The polymerization reaction is typically carried out at a temperature ranging from 150 to 350°C, preferably from 200 to 300°C, and the final pressure reduction is preferably 1 mmHg or less, allowing phenols derived from the bisaryl carbonate produced by the transesterification reaction to be distilled out of the system. The reaction time varies depending on the reaction temperature and the degree of vacuum, but is typically about 1 to 24 hours. The polymerization reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon. If desired, the reaction may be carried out in the presence of a small amount of a molecular weight regulator other than a compound such as a dihydric phenol that induces a terminal structure, or by adding an antioxidant or a branching agent.

[0028] 1-4. Properties of Polycarbonate Resin When a polycarbonate resin is used as the main component of a composition to form a coating, it is preferable to maintain a good balance of the necessary solvent solubility, coatability, adhesion, scratch resistance, impact resistance, and other properties. If the intrinsic viscosity of the polycarbonate resin solution is too low, scratch resistance and impact strength may be insufficient. Furthermore, if the intrinsic viscosity is too high, reduced solvent solubility and increased solution viscosity may be observed, potentially resulting in reduced coatability of the resulting coating. Therefore, the intrinsic viscosity of a polycarbonate resin solution with a concentration of 0.5 g / dl in dichloromethane as the solvent, measured under conditions described in detail below, is, for example, in the range of 0.1 to 2.0 dl / g, preferably in the range of 0.2 to 1.6 dl / g, more preferably in the range of 0.3 to 1.4 dl / g, and even more preferably in the range of 0.4 to 1.2 dl / g.

[0029] <2. Condensed Phosphate Ester (B)> The type of condensed phosphate ester (B) contained in the polycarbonate resin composition is not particularly limited, and for example, an aromatic condensed phosphate ester or the like may be used. As the condensed phosphate ester (B), for example, an aromatic condensed phosphate ester having 12 to 80 carbon atoms which may have a substituent may be used. The condensed phosphate ester (B) is preferably an aromatic condensed phosphate ester having 15 to 60 carbon atoms which may have a substituent, and more preferably an aromatic condensed phosphate ester having 20 to 50 carbon atoms. As the aromatic condensed phosphate ester, those represented by the following formula (8) or (9) are preferred. In general formulas (8) and (9), n is each independently selected from an integer of 0 to 3, preferably selected from an integer of 0 to 2, and more preferably 1. The aromatic condensed phosphate ester of formula (8) may be a mixture of multiple types, and the aromatic condensed phosphate ester of formula (9) may also be a mixture of multiple types.

[0030] Furthermore, aromatic condensed phosphate esters that can be used as condensed phosphate esters also include, for example, those represented by the following formula (a):

[0031] In formula (a), A represents a divalent aromatic group which may have a substituent, or a divalent aromatic hydrocarbon group which may have a substituent. In formula (a), A is preferably an aromatic group or aromatic hydrocarbon group having 6 to 24 carbon atoms, and more preferably an aromatic group having 6 to 18 carbon atoms. In formula (a), X each independently represents an alkyl group having 1 to 14 carbon atoms, an aryl group having 6 to 18 carbon atoms, an oxyalkyl group having 1 to 8 carbon atoms, or an oxyaryl group having 6 to 18 carbon atoms. In formula (a), X is preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 8 carbon atoms. In formula (a), y represents an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 or 1. Furthermore, the aromatic condensed phosphate ester of formula (a) may be a mixture of two or more types.

[0032] Specific examples of the aromatic condensed phosphate ester of formula (a) include 1,3-phenylene-bis(diphenyl phosphate), 1,4-naphthylene-bis(diphenyl phosphate), 4,4'-biphenylene-bis(diphenyl phosphate), 4,4"-p-terphenylene-bis(diphenyl phosphate), 4,4'-(methylenediphenyl)-bis(diphenyl phosphate), 4,4'-( ... tetra(2-t-butylphenyl)4,4'-isopropylidene diphenyl diphosphate, tetra(2,4-di-t-butylphenyl)4,4'-isopropylidene diphenyl diphosphate, 4,4'-[isopropylidene-di(2-t-butyl-5-methylphenyl)]-bis(diphenyl phosphate), and the like.

[0033] Other examples of the condensed phosphate ester (B) include those represented by the following formula (b). In formula (b), R １ , R ２ , R ３ and R ４ R each independently represents an alkyl group having 1 to 6 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent. １ , R ２ , R ３ and R ４ is preferably a phenyl group, naphthyl group, or the like which may have a substituent. In formula (b), p, q, r, and s each independently represent 0 or 1, preferably 1. In formula (b), t represents an integer of 1 to 5, preferably an integer of 1 to 3, more preferably an integer of 1 or 2, and even more preferably 1. In formula (b), X represents an arylene group which may have a substituent, and is preferably a phenylene group, naphthylene group, or the like.

[0034] Specific examples of the condensed phosphate ester of formula (b) include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, tricresyl phenyl phosphate, octyldiphenyl phosphate, diisopropylphenyl phosphate, tris(chloroethyl)phosphate, tris(dichloropropyl)phosphate, tris(chloropropyl)phosphate, bis(2,3-dibromopropyl)phosphate, bis(2,3-dibromo Examples of the condensed phosphate ester of formula (b) include various phosphate esters such as bis(propyl)-2,3-dichlorophosphate, bis(chloropropyl)monoctyl phosphate, bisphenol A tetraphenyl phosphate, bisphenol A tetracresyl diphosphate, bisphenol A tetraxylyl diphosphate, hydroquinone tetraphenyl diphosphate, hydroquinone tetracresyl phosphate, hydroquinone tetraxylyl diphosphate, resorcinol tetraphenyl phosphate, resorcinol tetra-2,6-xylenol phosphate, and resorcinol bisdixylenyl phosphate. A mixture of multiple types of condensed phosphate esters of formula (b) may also be used.

[0035] The above-mentioned substituents contained in the condensed phosphate ester (B) are each independently selected from halogen, hydroxyl group, cyano group, alkyl group having 1 to 20 carbon atoms, alkenyl group having 1 to 20 carbon atoms, aryl group having 6 to 12 carbon atoms, etc., and when an alkyl group, alkenyl group, or aryl group is contained as a substituent, the above-mentioned number of carbon atoms is the number of carbon atoms including the carbon atoms of the substituent. Furthermore, the condensed phosphate ester (B) may be a mixture of multiple types represented by the above general formula.

[0036] <3. Resin Composition> 3-1. Components of the Resin Composition The resin composition of the present invention contains at least a polycarbonate resin (A) and a condensed phosphate ester (B). In the resin composition, the proportion of the condensed phosphate ester (B) is preferably 1 to 80 mass% based on the total mass of the polycarbonate resin (A) and the condensed phosphate ester (B). Furthermore, the proportion of the condensed phosphate ester (B) based on the total mass of the polycarbonate resin (A) and the condensed phosphate ester (B) is more preferably 10 to 70 mass%, even more preferably 15 to 65 mass%, and particularly preferably 20 to 60 mass%.

[0037] In the resin composition, the proportion of the polycarbonate resin (A) based on the total mass of the components excluding the solvent is preferably 1 to 80 mass%, more preferably 10 to 70 mass%, even more preferably 15 to 65 mass%, and particularly preferably 20 to 60 mass%. Also, in the resin composition, the proportion of the condensed phosphate ester (B) based on the total mass of the components excluding the solvent is preferably 1 to 80 mass%, 10 to 70 mass%, etc., more preferably 15 to 70 mass%, 20 to 65 mass%, etc., even more preferably 30 to 70 mass% or 40 to 65 mass%, and particularly preferably 50 to 65 mass%, 55 to 65 mass%, or 55 to 60 mass%.

[0038] The resin composition may contain components other than the polycarbonate resin (A) and the condensed phosphate ester (B). For example, these may include thermoplastic resins other than the polycarbonate resin (A), additives such as antioxidants, ultraviolet absorbers, and flame retardants, and fillers. However, from the viewpoint of simplifying the constituent components, it is preferable that the resin composition does not contain flame retardants such as silicone-based flame retardants, solids such as inorganic fillers, and the like. In a resin composition that is substantially or completely free of solids, it is easy to maintain the respective components uniformly.

[0039] The content of components other than the polycarbonate resin (A) and the condensed phosphate ester (B) contained in the polycarbonate resin composition is preferably 20 mass% or less, more preferably 15 mass% or less, even more preferably 10 mass% or less, still more preferably 8 mass% or less, and particularly preferably 5 mass% or less, based on the total weight of the polycarbonate resin composition. Also, preferably, the polycarbonate resin composition does not contain any components other than the polycarbonate resin (A) and the condensed phosphate ester (B).

[0040] 3-2. Properties of Resin Composition The turbidity (color difference meter measurement value (%)) of the resin composition, as an index of transparency, measured under conditions described in detail below, is preferably 10.0 or less, more preferably 5.0 or less, even more preferably 2.0 or less, and particularly preferably 1.0 or less. Furthermore, the resin composition preferably has a color that is colorless and transparent when visually confirmed by a method described in detail below.

[0041] In the resin composition, the durometer reading, which is an index of flexibility and is measured by a method described in detail below, is preferably 100 or less. The durometer reading is more preferably 90 or less, even more preferably 85 or less, and particularly preferably 80 or less or 75 or less. In this way, a resin composition with a low durometer reading can be said to have high flexibility, and is excellent in adhesion to a substrate such as a resin substrate, thermocompression bondability, etc.

[0042] 3-3. Method for Producing Resin Composition The resin composition of the present invention can be produced by mixing the above-mentioned polycarbonate resin (A), condensed phosphate ester (B), and other components by a known method.

[0043] 4. Coating Solution Comprising Polycarbonate Resin Composition The coating solution of the present invention comprises the polycarbonate resin composition described above. The coating solution further comprises a solvent and the like. The solvent is not particularly limited as long as it can dissolve the polycarbonate resin composition. For example, a halogen-based solvent, a (meth)acrylate compound having a (meth)acrylate group, or an aromatic compound having an aromatic ring can be used as the solvent.

[0044] Examples of halogen-based solvents include dichloromethane and trichloromethane. The (meth)acrylate compound as the solvent preferably contains at least a (meth)acrylate ester. The (meth)acrylate ester is not particularly limited, but is preferably a mono- or di(meth)acrylate ester having a total of 4 to 20 carbon atoms, more preferably a mono- or di(meth)acrylate ester having a total of 5 to 15 carbon atoms, and even more preferably a mono- or di(meth)acrylate ester having a total of 5 to 10, 5 to 12, 6 to 10, or 6 to 12 carbon atoms. Preferred specific examples of the (meth)acrylate ester include methyl acrylate, methyl methacrylate (MMA), tetrahydrofurfuryl acrylate (THF-A), tetrahydrofurfuryl methacrylate (THF-M), phenyl acrylate, hydroxyphenyl acrylate, benzyl acrylate (BZA), phenoxymethyl acrylate, phenoxyethyl acrylate, 1,6-hexanediol diacrylate, etc. Among these, tetrahydrofurfuryl acrylate (THF-A), tetrahydrofurfuryl methacrylate (THF-M), benzyl acrylate (BZA), phenoxyethyl acrylate, and 1,6-hexanediol diacrylate are suitable as solvents, and particularly preferred specific examples include THF-M, etc. Examples of aromatic compounds that can be used as solvents include styrene, toluene, xylene, ethylbenzene, cumene, phenol, cresol, benzyl alcohol, anisole, benzaldehyde, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, and toluidine. Among these, styrene, toluene, and xylene are particularly suitable as solvents. The solvents contained in the coating solution are preferably those described above, and more preferably, halogenated solvents are used.

[0045] The above-mentioned compounds used as solvents for (meth)acrylate esters and the like have excellent compatibility with polycarbonate resins, and polycarbonate resins exhibit good solubility in polycarbonate resin solutions containing (meth)acrylate esters and the like as solvents. Furthermore, polycarbonate resin solutions containing the above-mentioned solvents can promote crosslinking reactions in solution. Furthermore, the use of such polycarbonate resin solutions has been shown to improve the color of the cured product obtained by polymerizing the polycarbonate resin. Specifically, when polycarbonate resins contained in polycarbonate resin solutions are cured using (meth)acrylate esters containing THF-M and the like as solvents, clouding is prevented, resulting in transparent cured products or molded articles.

[0046] Although the concentration of the polycarbonate resin composition in the coating solution is not particularly limited, the concentration of the polycarbonate resin composition is, for example, 1 to 50 mass% based on the total mass of the coating solution (resin solution). The concentration of the polycarbonate resin composition based on the total mass of the coating solution (resin solution) is preferably 1 to 30 mass% or 1 to 40 mass%. The concentration of the polycarbonate resin composition in the coating solution (resin solution) is more preferably 5 to 35 mass% or 10 to 40 mass%, even more preferably 10 to 35 mass% or 15 to 40 mass%, and particularly preferably 15 to 30 mass%, 20 to 30 mass%, or 25 to 30 mass%. The concentration of the polycarbonate resin (A) based on the total mass of the coating solution (resin solution) is, for example, 1 to 30 mass%, more preferably 3 to 25 mass% or 5 to 30 mass%, even more preferably 5 to 25 mass% or 10 to 30 mass%, and particularly preferably 10 to 25 mass% or 12 to 20 mass%. The coating solution (resin solution) can be easily produced by mixing a solid component such as a polycarbonate resin with a solvent according to a conventional method.

[0047] 5. Coating film containing polycarbonate resin composition The coating film of the present invention can be obtained, for example, by drying the coating solution described above. Alternatively, the coating film can be formed by causing a crosslinking reaction between polycarbonate resin molecules contained in the coating solution containing reactive groups.

[0048] 6. Molded Articles Comprising Polycarbonate Resin Compositions The polycarbonate resin composition of the present invention may contain, for example, a crosslinked polycarbonate resin. Using such a polycarbonate resin composition, molded articles, such as cast molded articles, can be produced by crosslinking various coatings and binder resin applications. Specific examples of molded articles include films such as substrate films formed on substrates, coatings (coatings); binder resins for electrophotographic photoreceptors, conductive pastes, and the like; adhesives, resin modifiers, and UV inks. The substrate film is formed on, for example, a PVB (polybutyral resin) substrate or a PET (polyethylene terephthalate resin) substrate, and the crosslinked film formed on these substrates exhibits particularly excellent adhesion to the substrate. Thus, the coating obtained by coating a resin solution and curing it by heating is less susceptible to scratches or peeling due to friction, impact, and the like during transportation and use, compared to coatings made from conventional resin solutions.

[0049] The substrate film as a molded article can be produced, for example, by removing the solvent from the coating solution and irradiating or heating the residual resin with energy rays. That is, a coating is formed by crosslinking or polymerization of the polycarbonate resin by irradiation with energy rays such as ultraviolet rays or by heating. When a heating step is used, the heating temperature is preferably 50 to 150°C, more preferably 70 to 130°C, and even more preferably 80 to 120°C.

[0050] The thickness of the substrate film is preferably in the range of 5 to 200 μm, particularly 10 to 120 μm, and more preferably 15 to 60 μm. A thin coating less than 5 μm is not strong enough and scratches are likely to reach the substrate, while a coating that is too thick, exceeding 200 μm, is prone to peeling due to shrinkage, which is economically disadvantageous considering the use of the coating, which will ultimately be peeled and discarded.

[0051] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. 1. Synthesis Example 1 40.0 parts by mass of 2,2-bis(4-hydroxyphenyl)propane (hereinafter abbreviated as "BPA": manufactured by Mitsubishi Chemical Corporation), 60.0 parts by mass of 2,2-bis(4-hydroxy-3-methylphenyl)propane (hereinafter abbreviated as "BPC": manufactured by Honshu Chemical Industry Co., Ltd.), and 0.5 parts by mass of hydrosulfite were dissolved in 590 parts by mass of a 5 wt % aqueous sodium hydroxide solution. Furthermore, 0.05 parts by mass of benzyltriethylammonium chloride (manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.) was dissolved in the solution as a phase transfer catalyst. 770 parts by mass of dichloromethane was added to the resulting aqueous solution, and while stirring, the mixture was further maintained at 15°C. Then, 60 parts by mass of phosgene was blown in over 40 minutes. After the phosgene injection was completed, 1.86 parts by mass of 4-t-butylphenol (hereinafter abbreviated as "PTBP": manufactured by Dainippon Ink and Chemicals, Inc.) as a molecular weight modifier was added to the suspension, and the reaction liquid was emulsified by vigorously stirring. After the emulsification, 0.5 parts by mass of triethylamine was added, and the mixture was stirred at 20 to 25°C for about 1 hour to allow polymerization.

[0052] 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 conductivity of the washings (aqueous phase) was 10 μS / cm or less. The polymer solution, which was the organic phase thus obtained, was added dropwise to warm water maintained at 50°C, and the solvent was evaporated to obtain a white powdery precipitate. The obtained precipitate was filtered and dried at 110°C for 24 hours to obtain a polymer powder. The intrinsic viscosity of a 0.5 g / dl solution of this polymer in dichloromethane at 20°C was 0.54 dl / g. The obtained polymer was analyzed by infrared absorption spectroscopy, and the intrinsic viscosity was 1770 cm －１Absorption due to carbonyl groups at a position near 1240 cm －１ Absorption due to ether bonds was observed in the vicinity, and it was confirmed that the resin was a polycarbonate resin having carbonate bonds (hereinafter abbreviated as "PC-1").

[0053] 2. Synthesis Example 2 Polymerization was carried out in the same manner as in Synthesis Example 1, except that 50.4 parts by mass of 2,2-bis(4-hydroxyphenyl)-4-methylpentane (hereinafter abbreviated as "MIBK": manufactured by Honshu Chemical Industry Co., Ltd.) was used instead of BPA, 54.1 parts by mass of 1,1-bis(4-hydroxyphenyl)-1-phenylethane (hereinafter abbreviated as "BPAP": manufactured by Honshu Chemical Industry Co., Ltd.) was used instead of BPC, and the amount of PTBP was changed to 1.87 parts by mass, to obtain a polycarbonate resin (intrinsic viscosity: 0.49 dl / g, hereinafter abbreviated as "PC-2").

[0054] 3. Synthesis Example 3 Polymerization was carried out in the same manner as in Example 1, except that the amount of BPA was changed to 70.0 parts by mass, 30.0 parts by mass of 1,1-bis(4-hydroxyphenyl)cyclohexane (hereinafter abbreviated as "BPZ": manufactured by Honshu Chemical Industry Co., Ltd.) was used instead of BPC, and the amount of PTBP was changed to 0.72 parts by mass, to obtain a polycarbonate resin (intrinsic viscosity: 1.00 dl / g, hereinafter abbreviated as "PC-3").

[0055] 4. Synthesis Example 4 Polymerization was carried out in the same manner as in Example 1, except that 100.0 parts by mass of BPZ was used instead of BPA and BPC, and the amount of PTBP was changed to 1.84 parts by mass, to obtain a polycarbonate resin (intrinsic viscosity: 0.45 dl / g, hereinafter abbreviated as "PC-4").

[0056] 5. Synthesis Example 5 Polymerization was carried out in the same manner as in Example 1, except that the amount of BPA was changed to 60.6 parts by mass, 15.2 parts by mass of 2,2-bis(4-hydroxyphenyl)hexafluoropropane (hereinafter abbreviated as "BPAF": manufactured by Central Glass Co., Ltd.) was used instead of BPC, and 24.2 parts by mass of dihydroxydiphenylmethane (hereinafter abbreviated as "BPF-SG": manufactured by Gunei Chemical Industry Co., Ltd.) was used, and the amount of PTBP was changed to 1.81 parts by mass, to obtain a polycarbonate resin (intrinsic viscosity: 0.55 dl / g, hydroxyl value: 2 mg-KOH / g, hereinafter abbreviated as "PC-5").

[0057] The types of monomers used in the polycarbonate resins obtained in each synthesis example and in the polycarbonate resin ("PC-6") in the comparative examples described below are as follows:

[0058] <Method for Measuring Intrinsic Viscosity> The intrinsic viscosity [η] deciliters / gram of the polycarbonate resin obtained in the above Synthesis Examples was determined as follows: That is, in accordance with JIS K7367-1, the drip time of a 0.5 gram / dL dichloromethane solution of the polycarbonate resin was measured at 25°C using an Ubbelohde capillary viscometer, and the intrinsic viscosity was determined using a Huggins constant of 0.45.

[0059] <Transparency (Measurement by Colorimeter)> The resin solutions obtained in the examples described below were used as coating solutions to evaluate transparency. Specifically, transparency (turbidity) was measured using a colorimeter as follows, in accordance with JIS K 7136 (Plastics - Determination of haze for transparent materials). First, the coating solution was applied to a glass substrate using a cast coater to a thickness of 400 μm, and then air-dried for 48 hours to form a coating film on the glass substrate. The resulting coating film was used to measure turbidity using a colorimeter. The measurement conditions are as follows: Apparatus: Colorimeter COH770 manufactured by Nippon Denshoku Co., Ltd. Measurement conditions: Viewing angle 10°, light source D65 used Measurement method: After starting the apparatus, wait for the light source to stabilize, and then perform standardization using only the glass substrate. The prepared coating film was then measured together with the glass substrate, and the turbidity was evaluated.

[0060] <Flexibility and Transparency (Visual Inspection)> Resin solutions obtained in the examples described below were air-dried for 120 hours to obtain sample pieces. The sample pieces were stacked to a thickness of 6 mm to obtain a test sample. The flexibility of the test sample was measured using a durometer in accordance with JIS K 7215. The measurement conditions are as follows: Apparatus: Teclock Rubber / Plastic Hardness Tester GS-706N. Measurement conditions: Spring load value 539-8379 mN, probe size 0.79 mm, 35 mm truncated cone, height 2.54 mm. Measurement method: The hardness tester was pressed against the sample at a constant speed in an upright position to bring it into close contact with the sample. The maximum value within 1 second of contact with the sample was recorded. Measurement point: 12 mm inside from the edge of the sample.

[0061] Example 1 24 g of the polycarbonate resin (PC-1) obtained in Synthesis Example 1 and 6 g of a phosphate ester (a condensed phosphate ester compound manufactured by ADEKA Corporation; Adekastab FP-600) were dissolved in 160 g of dichloromethane to obtain a resin composition (resin solution / coating solution).

[0062] (Examples 2 to 17) Resin compositions (resin solutions) were obtained in the same manner as in Example 1 using the compositions shown in Table 2 below. In Table 2, FP-900L represents a phosphate ester (a condensed phosphate ester compound manufactured by ADEKA Corporation; Adekastab FP-900L). (Comparative Examples 1 to 8) Resin compositions (resin solutions) were obtained in the same manner as in Example 1 using the compositions shown in Table 2.

[0063] Although the color difference meter measurements were not taken for Comparative Examples 1 to 4, they were transparent when observed visually. However, Comparative Examples 1 to 4 showed results of poor flexibility. Furthermore, Comparative Example 6 showed a relatively low color difference meter measurement result, but was visually confirmed to be cloudy. Therefore, Comparative Example 6 could not be said to have shown good results, similar to Comparative Examples 7 and 8.

[0064] As is clear from the above results, it was confirmed that the polycarbonate resin compositions of the Examples containing the polycarbonate resin (A) having structural units derived from the monomer of formula (1) and the condensed phosphate ester (B) have excellent flexibility and high transparency compared to the Comparative Examples. Thus, the polycarbonate resin composition of the present invention has excellent adhesion to substrates and thermocompression bondability, and also exhibits good transparency despite containing a predetermined amount or more of the condensed phosphate ester (B) as an additive.

[0065] Although the preferred embodiments of the present invention have been described in detail above, the present invention is not limited to these examples. It is clear that a person skilled in the art to which the present invention pertains can conceive of various modifications and alterations within the scope of the technical ideas set forth in the claims, and it is understood that these also naturally fall within the technical scope of the present invention.

Claims

1. A resin composition comprising a polycarbonate resin (A) and a condensed phosphate ester (B), wherein the polycarbonate resin (A) comprises a structural unit derived from a monomer represented by the following general formula (1): (In general formula (1), R １ ~R ４ and R ５ ~R ８ each independently represents hydrogen, fluorine, chlorine, bromine, or 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 may have a substituent; X is a single bond or is represented by any of the following formulas (i) to (ix): Here, R ９ and R １０ each independently represents hydrogen, fluorine, chlorine, bromine, or iodine, or an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aryl group having 6 to 12 carbon atoms, each of which may have a substituent; R ９ and R １０ and R are bonded to form a carbocyclic ring having 5 to 20 carbon atoms or a heterocyclic ring having 5 to 12 atoms (provided that R ９ and R １０ and R are methyl groups, １１ and R １２ each independently represents hydrogen, fluorine, chlorine, bromine, or iodine, or an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, each of which may have a substituent; and c represents an integer of 0 to 20.

2. The polycarbonate resin composition according to claim 1, which contains 1 to 80 mass% of the condensed phosphate ester (B) based on the total mass of the polycarbonate resin (A) and the condensed phosphate ester (B).

3. In the formula (1), R １ ~R ４ and R ５ ~R ８ are each independently selected from hydrogen, an alkyl group having 1 to 6 carbon atoms which may have a substituent, and an aryl group having 6 to 8 carbon atoms which may have a substituent, X is a single bond or is represented by the formula (i), and R ９ and R １０ are each independently selected from hydrogen, an alkyl group having 1 to 10 carbon atoms which may have a substituent, and an aryl group having 6 to 10 carbon atoms which may have a substituent, or R ９ and R １０ and are groups which combine to form a carbon ring having 5 to 20 carbon atoms.

4. The polycarbonate resin composition according to claim 3, wherein the monomer represented by general formula (1) includes at least one monomer selected from the group consisting of the following formulae (2) to (7):

5. The polycarbonate resin composition according to claim 1, wherein the condensed phosphate ester (B) comprises an aromatic condensed phosphate ester having 12 to 80 carbon atoms.

6. The polycarbonate resin composition according to claim 5, wherein the condensed phosphate ester (B) is represented by at least one of the following formulas (8) and (9): (In general formulas (8) and (9), n is independently selected from integers of 0 to 3.) 7. The polycarbonate resin composition of claim 1, which is substantially free of solids.

8. The polycarbonate resin composition according to claim 1, wherein the polycarbonate resin (A) contains less than 5 mol% of structural units derived from a monomer having a fluorene moiety represented by formula (vii).

9. A resin composition comprising a polycarbonate resin (A) and a condensed phosphate ester (B), wherein the polycarbonate resin (A) comprises a structural unit derived from a monomer represented by the following general formula (1) (excluding polycarbonate resins whose structural units are composed solely of 2,2-bis(4-hydroxyphenyl)propane). (In general formula (1), R １ ~R ４ and R ５ ~R ８ each independently represents hydrogen, fluorine, chlorine, bromine, or 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 may have a substituent; X is a single bond or is represented by any of the following formulas (i) to (ix): Here, R ９ and R １０ each independently represents hydrogen, fluorine, chlorine, bromine, or iodine, or an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aryl group having 6 to 12 carbon atoms, each of which may have a substituent; R ９ and R １０ and R represent a group that combine to form a carbocyclic ring having 5 to 20 carbon atoms or a heterocyclic ring having 5 to 12 atoms; １１ and R １２ each independently represents hydrogen, fluorine, chlorine, bromine, or iodine, or an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, each of which may have a substituent; and c represents an integer of 0 to 20.

10. A coating solution comprising the polycarbonate resin composition of claim 1.

11. A coating film comprising the polycarbonate resin composition according to claim 1.

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