Resin composition and molded article

Abstract

To provide a resin composition containing a polycarbonate resin, capable of providing a molding having excellent oil and water repellency in a balanced manner; and a molding of the resin composition.SOLUTION: A resin composition contains a polycarbonate resin, a fluorinated polymer, and a water repellency improver. The fluorinated polymer contains a fluorine atom and a constitutional unit derived from a compound F containing CH2=CH-C(=O)- or CH2=C(CH3)-C(=O)-. Relative to total mass of the polycarbonate resin and the fluorinated polymer, the fluorinated polymer is 0.1-5.0 mass%.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to resin compositions and molded articles. [Background technology]

[0002] Techniques for applying fluorine treatment to the surface of molded products to impart water-repellent and oil-repellent properties have been known for some time, and examples include immersion treatment and coating treatment of the surface of molded products. However, the method of applying a fluorine treatment to the surface of molded products had the problem that the water-repellent and oil-repellent functions did not last long, and the water-repellent and oil-repellent functions deteriorated with repeated use. Therefore, as a method for imparting water-repellent and oil-repellent properties, the incorporation of a fluorine-containing polymer into a thermoplastic resin is being considered (Patent Documents 1 and 2). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2006-037085 [Patent Document 2] Japanese Patent Publication No. 2020-100780 [Overview of the project] [Problems that the invention aims to solve]

[0004] The inventors' investigations revealed that when a resin composition is made by blending a fluorine-containing polymer with polycarbonate resin, while oil repellency improves depending on the type of fluorine-containing polymer used, water repellency may decrease. Furthermore, it was found that the transparency of molded products obtained from this resin composition may be poor. The present invention aims to solve the aforementioned problems and provides a resin composition containing a polycarbonate resin that is excellent in a good balance of oil repellency and water repellency and can provide a transparent molded article, and a molded article obtained from the said resin composition.

Means for Solving the Problem

[0005] Based on the above problems, as a result of the inventor's study, it was found that the above problems can be solved by using a specific fluoropolymer and a water repellency improver in combination. Specifically, the above problems were solved by the following means. <1>A resin composition comprising a polycarbonate resin, a fluoropolymer, and a water repellency improver, wherein the fluoropolymer contains a structural unit derived from a compound F containing a fluorine atom and CH2=CH-C(=O)- or CH2=C(CH3)-C(=O)-, and the fluoropolymer is contained in an amount of 0.1 to 5.0% by mass based on the total mass of the polycarbonate resin and the fluoropolymer. <2>The resin composition according to <1>, wherein the polycarbonate resin contains 0 to 90 mol% of the structural unit represented by the formula (1) and 100 to 10 mol% of the structural unit represented by the formula (2) based on all the structural units. Formula (1)

Chemical Formula

Chemical Formula

Chemical Formula

Chemical Formula

[0006] The present invention provides a resin composition containing a polycarbonate resin that exhibits a good balance of oil repellency and water repellency, and that can provide a transparent molded article, as well as a molded article obtained from the said resin composition. [Modes for carrying out the invention]

[0007] The following describes in detail embodiments for carrying out the present invention (hereinafter simply referred to as "this embodiment"). Note that the following embodiment is illustrative for explaining the present invention, and the present invention is not limited to this embodiment. In this specification, "~" is used to mean that the numbers before and after it are included as the lower and upper limits, respectively. In this specification, all physical properties and characteristic values ​​shall be those at 23°C unless otherwise specified. If the standards described herein differ in measurement methods, etc., from year to year, unless otherwise specified, the standards as of January 1, 2021 shall apply.

[0008] The resin composition of this embodiment is a resin composition comprising a polycarbonate resin, a fluorine-containing polymer, and a water-repellent modifier, wherein the fluorine-containing polymer comprises a fluorine atom and a constituent unit derived from compound F containing CH2=CH-C(=O)- or CH2=C(CH3)-C(=O)-, and is characterized in that the fluorine-containing polymer is present in an amount of 0.1 to 5.0% by mass relative to the total mass of the polycarbonate resin and the fluorine-containing polymer. By adopting this configuration, it becomes possible to provide molded articles formed from a composition containing polycarbonate resin that exhibit a good balance of oil repellency and water repellency, as well as excellent transparency.

[0009] <Polycarbonate resin> The resin composition of this embodiment includes a polycarbonate resin. The polycarbonate resin used in this embodiment is not particularly limited as long as it contains a carbonate ester bond-containing -[OR-OC(=O)]- unit in the molecular main chain (where R is a hydrocarbon group, specifically an aliphatic group, an aromatic group, or a group containing both an aliphatic and an aromatic group, and furthermore, a linear or branched structure). In this embodiment, an aromatic polycarbonate resin is preferred, and a polycarbonate resin having a bisphenol skeleton is more preferred. By using such a polycarbonate resin, better heat resistance and toughness can be achieved. In this embodiment, it is preferable that 90 mol% or more of the total constituent units of the polycarbonate resin having a bisphenol skeleton are constituent units.

[0010] In this embodiment, the polycarbonate resin preferably contains 0 to 90 mol% of the constituent units represented by formula (1) and 100 to 10 mol% of the constituent units represented by formula (2). By including the structural unit represented by formula (1), the impact resistance and heat resistance of the resin composition can be improved. Further, by including the structural unit represented by formula (2), the transparency and surface hardness of the molded product can be improved. Formula (1)

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0011] <<Structural unit represented by formula (1)>> The polycarbonate resin used in this embodiment preferably contains a structural unit represented by formula (1). Formula (1)

Chemical formula

Chemical formula

[0012] Examples of alicyclic hydrocarbons formed by the bonding of Z with C include cycloalkylidene groups such as cyclohexylidene, cycloheptylidene, cyclododecylidene, adamantylidene, and cyclododecylidene. Examples of alicyclic hydrocarbons having substituents formed by the bonding of Z with C include methyl-substituted and ethyl-substituted derivatives of the above-mentioned alicyclic hydrocarbon groups. Among these, cyclohexylidene, methyl-substituted derivatives of cyclohexylidene (preferably 3,3,5-trimethyl-substituted derivatives), and cyclododecylidene are preferred.

[0013] In formula (1), X 1 teeth, [ka] If R 3 and R 4 Preferably, at least one of them is a methyl group, and more preferably, both are methyl groups. Also X 1 but, [ka] In this case, Z bonds with the carbon C bonded to the two phenyl groups in formula (1) above to form a divalent alicyclic hydrocarbon group having 6 to 12 carbon atoms. Examples of divalent alicyclic hydrocarbon groups include cycloalkylidene groups such as cyclohexylidene, cycloheptylidene, cyclododecylidene, adamantylidene, and cyclododecylidene. Substituted forms include those having methyl substituents and ethyl substituents. Among these, cyclohexylidene, methyl-substituted cyclohexylidene (preferably 3,3,5-trimethyl-substituted), and cyclododecylidene are preferred. In formula (1), X 1 The following structure is preferred. [ka]

[0014] A preferred specific example of the constituent unit represented by formula (1) above is a constituent unit (carbonate constituent unit) composed of 2,2-bis(4-hydroxyphenyl)propane, i.e., bisphenol A.

[0015] In this embodiment, the polycarbonate resin may not contain any of the constituent units represented by formula (1), may contain only one type, or may contain two or more types.

[0016] <<Constituent units represented by equation (2)>> The polycarbonate resin used in this embodiment preferably contains the constituent unit represented by formula (2). Formula (2) [ka] (In formula (2), R 1 represents a methyl group, R 2 X represents a hydrogen atom or a methyl group. 2 This represents one of the following expressions: [ka] R 3 and R 4 Each of these independently represents either a hydrogen atom or a methyl group, and Z represents a group that, when bonded to C, forms an alicyclic hydrocarbon with 6 to 12 carbon atoms, which may have substituents. The two R's in equation (2) 2 These may be the same or different, but are preferably the same. 2 It is preferable that it is a hydrogen atom.

[0017] In formula (2), X 2 teeth, [ka] If R 3 and R 4 Preferably, at least one of them is a methyl group, and more preferably, both are methyl groups. Also X 2 but, [ka] In this case, Z bonds with the carbon C bonded to the two phenyl groups in formula (2) above to form a divalent alicyclic hydrocarbon group having 6 to 12 carbon atoms. Examples of divalent alicyclic hydrocarbon groups include cycloalkylidene groups such as cyclohexylidene, cycloheptylidene, cyclododecylidene, adamantylidene, and cyclododecylidene. Substituted forms include those having methyl substituents and ethyl substituents. Among these, cyclohexylidene, methyl-substituted cyclohexylidene (preferably 3,3,5-trimethyl-substituted), and cyclododecylidene are preferred. In formula (2), X 2 The following structure is preferred. [ka]

[0018] In this embodiment, the polycarbonate resin may contain only one type of constituent unit represented by formula (2), or it may contain two or more types.

[0019] In this embodiment, the polycarbonate resin may contain other structural units besides those represented by formula (1) and formula (2). Examples of other structural units include those derived from the dihydroxy compounds shown below.

[0020] Bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3-(1-methylethyl)phenyl)propane, 2,2-bis(4-hydroxy-3-tert-butylphenyl)propane, 2,2-bis(4-hydroxy-3-(1-methylpropyl)phenyl)propane, 2,2-bis(4-hydroxy-3-cyclohexylphenyl)propane, 2,2-bis(4-hydroxy-3-phenylphenyl)propane, 1,1-bis(4-hydroxyphenyl)decane, 1,1-bis(4-hydroxyphenyl) Cyclohexane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)phenylmethane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-(1-methylethyl)phenyl)cyclohexane, 1,1-bis(4-hydroxy-3-tert-butylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-(1-methylpropyl)phenyl)cyclohexane, 1,1-bis(4-hydroxy-3-cyclohexylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-phenylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-methylphenyl)-1-phenylethane, 1,1-bis(4-hydroxy-3 ,5-dimethylphenyl)-1-phenylethane, 1,1-bis(4-hydroxy-3-(1-methylethyl)phenyl)-1-phenylethane, 1,1-bis(4-hydroxy-3-tert-butylphenyl)-1-phenylethane, 1,1-bis(4-hydroxy-3-(1-methylpropyl)phenyl)-1-phenylethane, 1,1-bis(4-hydroxy-3-cyclohexylphenyl)-1-phenylethane, 1,1-bis(4-hydroxy-3-phenylphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl Phenyl)cyclooctane, 4,4'-(1,3-phenylenediisopropylidene)bisphenol, 4,4'-(1,4-phenylenediisopropylidene)bisphenol, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxyphenyl ether, 4,4'-dihydroxybiphenyl, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxy-6-methyl-3-tert-butylphenyl)butane.

[0021] Furthermore, as another embodiment of the constituent unit, reference can be made to the constituent unit represented by formula (2) described in paragraph 0008 of International Publication No. 2017 / 099226, the descriptions in paragraphs 0043 to 0052 of International Publication No. 2017 / 099226, and the descriptions in Japanese Patent Application Publication No. 2011-046769, the contents of which are incorporated herein by reference.

[0022] Furthermore, the polycarbonate resin used in this embodiment preferably contains 0 to 90 mol% of the constituent units represented by formula (1) and 100 to 10 mol% of the constituent units represented by formula (2). The proportion of the constituent unit represented by formula (1) in all the constituent units is more preferably 10 mol% or more, even more preferably 20 mol% or more, even more preferably 30 mol% or more, and even more preferably 40 mol% or more. The upper limit of the proportion of the constituent unit represented by formula (1) in all the constituent units is more preferably 80 mol% or less, even more preferably 70 mol% or less, and even more preferably 60 mol% or less. Furthermore, the proportion of the constituent unit represented by formula (2) in all the constituent units is preferably 20 mol% or more, more preferably 30 mol% or more, and even more preferably 40 mol% or more. Furthermore, the lower limit of the proportion of the constituent unit represented by formula (2) in all the constituent units is more preferably 90 mol% or less, even more preferably 80 mol% or less, even more preferably 70 mol% or less, and even more preferably 60 mol% or less.

[0023] In the polycarbonate resin used in this embodiment, the sum of the constituent units represented by formula (1) and formula (2) is preferably 90 mol% or more of the total constituent units, more preferably 95 mol% or more, and even more preferably 97 mol% or more. The upper limit of the sum is 100 mol% or less.

[0024] The polycarbonate resin used in this embodiment is preferably in the following forms. In this embodiment, (A1) or (A2) is preferred, and (A1) is more preferred. (A1) A blend of polycarbonate resin containing the constituent units represented by formula (1) and polycarbonate resin containing the constituent units represented by formula (2). (A2) Polycarbonate resin containing the constituent units represented by formula (1) and the constituent units represented by formula (2) (A3) A polycarbonate resin containing the constituent units represented by formula (1), and a blend of polycarbonate resins containing the constituent units represented by formula (1) and the constituent units represented by formula (2). (A4) A blend of polycarbonate resin containing the constituent units represented by formula (2) and polycarbonate resin containing the constituent units represented by formula (1) and the constituent units represented by formula (2). (A5) A blend of polycarbonate resin containing the constituent units represented by formula (1), polycarbonate resin containing the constituent units represented by formula (2), and polycarbonate resin containing the constituent units represented by formula (1) and the constituent units represented by formula (2). (A6) In (A1) to (A5) above, the polycarbonate resin constituting the polycarbonate resin or its blend contains other constituent units other than the constituent units represented by formula (1) and the constituent units represented by formula (2). (A7) A blend of polycarbonate resin consisting of the polycarbonate resins or blends described in (A1) to (A6) above and other constituent units.

[0025] The viscosity-average molecular weight (Mv) of the polycarbonate resin used in this embodiment is preferably 5,000 or more, more preferably 8,000 or more, even more preferably 10,000 or more, and even more preferably 12,000 or more. The upper limit of Mv is preferably 32,000 or less, more preferably 30,000 or less, even more preferably 29,000 or less, even more preferably 27,000 or less, and even more preferably 25,000 or less. If two or more types of polycarbonate resins are included, the sum of the values ​​obtained by multiplying the viscosity-average molecular weight of each polycarbonate resin by its mass fraction shall be used. By setting the viscosity-average molecular weight above the lower limit, moldability is improved and molded products with high mechanical strength can be obtained. Furthermore, by setting it below the upper limit, the fluidity of the molded product is improved, and thin-walled molded products can be manufactured efficiently. In particular, the viscosity-average molecular weight of the polycarbonate resin containing the constituent unit represented by formula (1) is preferably 20,000 to 30,000, and more preferably 20,000 to 25,000. Furthermore, the viscosity-average molecular weight of the polycarbonate resin containing the constituent unit represented by formula (2) is preferably 12,000 to 28,000, and more preferably 18,000 to 27,000. The viscosity-average molecular weight (Mv) is measured according to the method described in the examples below.

[0026] The polycarbonate resin used in this embodiment (a total polycarbonate resin including the constituent units represented by formula (1) and formula (2)) is exemplified by having a pencil hardness of 3B to 2H, measured according to ISO-15184, with 2B to 2H being preferred. The pencil hardness is measured according to the method described in the examples below. In particular, the pencil hardness of polycarbonate resin containing the constituent unit represented by formula (1) is preferably 2B to HB, and the pencil hardness of polycarbonate resin containing the constituent unit represented by formula (2) is preferably H to 2H.

[0027] The method for producing the polycarbonate resin used in this embodiment is not particularly limited, but for example, paragraphs 0027 to 0043 and the examples of Japanese Patent Application Publication No. 2014-065901 can be referenced, and the contents of these are incorporated herein.

[0028] The polycarbonate resin content in the resin composition of this embodiment is preferably 80% by mass or more, more preferably 85% by mass or more, even more preferably 90% by mass or more, and even more preferably 93% by mass or more. Setting it above the lower limit tends to further improve the impact strength and heat resistance of molded articles formed from the resin composition. It is also preferable that it be 99% by mass or less. Setting it below the upper limit tends to improve the fluidity of the resin composition.

[0029] <Fluorine-containing polymer> The resin composition of this embodiment contains a fluorine-containing polymer. The fluorine-containing polymer contains a fluorine atom and a constituent unit derived from compound F containing CH2=CH-C(=O)- or CH2=C(CH3)-C(=O)-. By including such a fluorine-containing polymer, it is possible to achieve oil repellency while maintaining the high transparency inherent in polycarbonate resin. This is because, by using a polymer formed by the polymerization of CH2=CH-C(=O)- or CH2=C(CH3)-C(=O)-, the heat resistance of the fluorine-containing polymer is improved, and it is thought that the decomposition of the fluorine-containing polymer can be suppressed even during the molding of the polycarbonate resin. Therefore, it is presumed that compatibility with the polycarbonate resin can be maintained and clouding can be effectively suppressed. Furthermore, it is presumed that oil repellency can be effectively achieved by ensuring that fluorine atoms are evenly distributed in the side chains of the fluorine-containing polymer.

[0030] The fluorine-containing polymer used in this embodiment preferably has a cyclic structure, and more preferably contains an aromatic ring. The inclusion of a cyclic structure improves compatibility with the polycarbonate resin, and tends to further improve the transparency of the resulting molded article. This effect is particularly pronounced when an aromatic polycarbonate resin is used as the polycarbonate resin. The aforementioned cyclic structure is a monoring of a 5-membered ring or a 6-membered ring, or a fused ring formed by the fusion of two or more (preferably two or three, more preferably two) monorings of a 5-membered ring or a 6-membered ring, with a monoring of a 6-membered ring being preferred. Specifically, a cyclohexane ring and a benzene ring are preferred, with a benzene ring being more preferred.

[0031] In this embodiment, the compound F preferably contains a fluorine-containing group, and more preferably has a C1-C6 polyfluoroalkyl group and / or a C1-C6 polyfluoroether group. Such a fluorine-containing group disperses well in the polycarbonate resin and does not easily impair the water repellency of the resulting molded article, while effectively achieving oil repellency.

[0032] In this embodiment, the compound F is preferably represented by formula (F). Formula (F) X f -L f -Ar-L f -R f (In formula (F), X f CH2=CH-C(=O)- or CH2=C(CH3)-C(=O)-, L f Each of these is independently a divalent linking group, Ar is an aromatic ring, and R f (This is a polyfluoroalkyl group having 1 to 6 carbon atoms or a polyfluoroether group having 1 to 6 carbon atoms.) L f It is preferable that the group consists of a heteroatom, a C1-C6 alkylene group which may be substituted with a fluorine atom, or a combination thereof. Furthermore, it is preferable that Ar is a benzene ring. The molecular weight of compound F is preferably between 200 and 500.

[0033] The proportion of constituent units derived from compound F in the fluorine-containing polymer used in this embodiment is, for example, 50% by mass or more, and may also be 90% by mass or more, of the total constituent units.

[0034] In this embodiment, the content of the fluorine-containing polymer is 0.1 to 5.0% by mass relative to the total mass of the polycarbonate resin and the fluorine-containing polymer. Setting it above the lower limit improves oil repellency. Setting it below the upper limit maintains the transparency of the polycarbonate. The lower limit is preferably 0.2% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.4% by mass or more. The upper limit is preferably 4.0% by mass or less, more preferably 3.0% by mass or less, even more preferably 2.0% by mass or less, even more preferably 1.5% by mass or less, even more preferably 1.0% by mass or less, and even more preferably 0.8% by mass or less. The resin composition of this embodiment may contain only one fluorine-containing polymer or two or more. When two or more are included, it is preferable that the total amount is within the above range.

[0035] <Water-repellent agent> The resin composition of this embodiment contains a water-repellency modifier. By including the water-repellency modifier, the water repellency of the resulting molded product can be improved. Examples of water-repellent modifiers used in this embodiment include silicones, higher aliphatic hydrocarbons, and fluorine-based additives, with silicones and higher aliphatic hydrocarbons being preferred, and silicones being more preferred.

[0036] Polyorganosiloxanes are preferred as the silicone. The polyorganosiloxane used in this embodiment preferably has a molecular weight distribution (Mw / Mn) of 1.01 to 1.40. The upper limit of the molecular weight distribution is preferably 1.35, more preferably 1.30, even more preferably 1.25, and particularly preferably 1.20. The lower limit is preferably 1.02, more preferably 1.03, even more preferably 1.04, and particularly preferably 1.05. Setting the molecular weight distribution below the above upper limit is preferable because it reduces the amount of low molecular weight volatile components and improves moldability. Furthermore, setting the molecular weight distribution below the above upper limit is preferable because it reduces the amount of high molecular weight components that have poor compatibility with polycarbonate resin. Moreover, setting the molecular weight distribution below the above upper limit is preferable because it reduces the proportion of high molecular weight components that are less likely to segregate on the surface, and the surface performance modification effect, such as the water contact angle, is more effectively exhibited. Furthermore, setting the molecular weight distribution above the above lower limit is preferable because it reduces the cost of purifying the polyorganosiloxane.

[0037] The number-average molecular weight (Mn) of the polyorganosiloxane used in this embodiment is not particularly limited, but is preferably 500 or more, more preferably 600 or more, even more preferably 700 or more, and even more preferably 750 or more. It is also preferably 2000 or less, more preferably 1800 or less, even more preferably 1600 or less, even more preferably 1100 or less, and even more preferably 1000 or less. Setting the number-average molecular weight above the lower limit reduces the amount of volatile components, improves retention and moldability, and more effectively suppresses the reduction of components that affect the water contact angle on the surface, which is preferable. Setting the number-average molecular weight below the upper limit reduces the viscosity of the polyorganosiloxane, making it easier to segregate on the surface in the molded article, and as a result, the water contact angle tends to improve, which is preferable.

[0038] The weight-average molecular weight (Mw) of the polyorganosiloxane used in this embodiment is not particularly limited, but is preferably 500 or more, more preferably 600 or more, even more preferably 700 or more, and particularly preferably 800 or more. It may also be preferably 2000 or less, more preferably 1800 or less, even more preferably 1700 or less, even more preferably 1600 or less, and even more preferably 1100 or less. Setting the weight-average molecular weight above the lower limit reduces the amount of volatile components, improves moldability, and more effectively suppresses the reduction of components that affect the water contact angle on the surface, which is preferable. Setting the weight-average molecular weight below the upper limit reduces the viscosity of the polyorganosiloxane, making it easier to segregate on the surface in the molded article, which tends to improve the water contact angle, and is therefore preferable. Furthermore, setting the weight-average molecular weight below the upper limit improves the compatibility of the polyorganosiloxane with (A) polycarbonate resin, making it easier to obtain a more transparent resin composition, which is preferable. For other polyorganosiloxanes, refer to paragraphs 0032 to 0054 of Japanese Patent Publication No. 2021-038305, which are incorporated herein by reference.

[0039] As the higher aliphatic hydrocarbon, paraffin wax is preferred. Examples of paraffin waxes include substances whose main component is a saturated aliphatic hydrocarbon such as n-paraffin and / or i-paraffin, or low molecular weight polyethylene having hydroxyl groups at its ends and having a waxy appearance. The molecular weight of the paraffin wax, as measured by GPC, is preferably 300 to 1500, more preferably 300 to 1000. The paraffin wax can be easily produced by conventional organic reactions, or a commercially available product can be used.

[0040] The water-repellent improving agent content in the resin composition of this embodiment is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, even more preferably 1.0 part by mass or more, even more preferably 1.5 parts by mass or more, and even more preferably 2.5 parts by mass or more, per 100 parts by mass of polycarbonate resin. Setting the content above the lower limit tends to more effectively exhibit water repellency in the molded product. Furthermore, the upper limit of the water-repellent improving agent content is preferably 15.0 parts by mass or less, more preferably 10.0 parts by mass or less, even more preferably 8.0 parts by mass or less, even more preferably 5.0 parts by mass or less, and even more preferably 4.0 parts by mass or less, per 100 parts by mass of polycarbonate resin. Setting the content below the upper limit tends to further improve the transparency of the resulting molded product. The resin composition of this embodiment may contain only one water-repellent modifier or two or more. When two or more are included, it is preferable that the total amount is within the above range.

[0041] In this embodiment, the resin composition preferably has a mass ratio of fluorine-containing polymer to water-repellent modifier (water-repellent modifier / fluorine-containing polymer) of 3.0 or higher, more preferably 3.5 or higher, more preferably 7.0 or lower, and more preferably 6.5 or lower. By keeping the ratio within this range, a better balance between water repellency and oil-repellent properties tends to be achieved.

[0042] <Other ingredients> The resin composition of this embodiment may contain other components as needed, as long as they do not significantly impair the desired physical properties. Examples of other components include thermoplastic resins other than the polycarbonate resin described above (e.g., acrylic resins, etc.), and various resin additives. Examples of resin additives include stabilizers (heat stabilizers, antioxidants, etc.), UV absorbers, antistatic agents, flame retardants, flame retardant enhancers, dyes, pigments, antifogging agents, antiblocking agents, flow improvers, plasticizers, dispersants, and antibacterial agents. The resin may contain only one type of additive, or two or more types in any combination and ratio. For antistatic agents, refer to paragraphs 0063 to 0067 of Japanese Patent Publication No. 2016-216534, and these contents are incorporated herein by reference. For flame retardants, refer to paragraphs 0068 to 0075 of Japanese Patent Publication No. 2016-216534, and these contents are incorporated herein by reference.

[0043] <<Stabilizer>> Examples of stabilizers include heat stabilizers and antioxidants. Examples of stabilizers include phenolic stabilizers, amine stabilizers, phosphorus stabilizers, and thioether stabilizers. Among these, phosphorus stabilizers and phenolic stabilizers are preferred in this embodiment. Any known phosphorus-based stabilizer can be used. Specific examples include phosphorus oxoacids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphate; acidic pyrophosphate metal salts such as sodium acidic pyrophosphate, potassium acidic pyrophosphate, and calcium acidic pyrophosphate; phosphates of Group 1 or Group 2B metals such as potassium phosphate, sodium phosphate, cesium phosphate, and zinc phosphate; and organic phosphate compounds, organic phosphite compounds, and organic phosphonite compounds, with organic phosphite compounds being particularly preferred.

[0044] Examples of organic phosphite compounds include triphenyl phosphite, tris(mononylphenyl) phosphite, tris(mononyl / dinonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, monooctyldiphenyl phosphite, dioctylmonophenyl phosphite, monodecyldiphenyl phosphite, didecylmonophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, and 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite. Examples of such organic phosphite compounds include, for example, "ADEKA Stab (registered trademark; hereinafter the same) 1178," "ADEKA Stab 2112," and "ADEKA Stab HP-10" manufactured by ADEKA Corporation, "JP-351," "JP-360," and "JP-3CP" manufactured by Johoku Chemical Industry Co., Ltd., and "Irgaphos (registered trademark; hereinafter the same) 168" manufactured by BASF.

[0045] As a phenolic stabilizer, a hindered phenolic stabilizer is preferably used. Specific examples of hindered phenol stabilizers include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphate, and 3,3',3'',5,5',5''-hexa-tert-butyl-a,a',a''-(methylpentadecyl) (2,4,6-triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl) Examples include -4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazine-2-ylamino)phenol, and 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate.

[0046] Among these, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate are preferred. Specific examples of such hindered phenol-based stabilizers include, for example, BASF's "Irganox (registered trademark; hereinafter the same) 1010" and "Irganox 1076," and ADEKA's "ADEKA Stab AO-50" and "ADEKA Stab AO-60."

[0047] The stabilizer content in the resin composition of this embodiment is typically 0.001 parts by mass or more, preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, and typically 1 part by mass or less, preferably 0.5 parts by mass or less, more preferably 0.3 parts by mass or less, per 100 parts by mass of polycarbonate resin. By setting the stabilizer content within the above range, the effect of adding the stabilizer is more effectively exerted. The resin composition of this embodiment may contain only one stabilizer or two or more stabilizers. When two or more stabilizers are included, it is preferable that the total amount is within the above range.

[0048] The resin composition of this embodiment is prepared so that the total amount of polycarbonate resin, fluorine-containing polymer, water-repellent modifier, and other components added as needed is 100% by mass. In this embodiment, the resin composition preferably contains a total of 95% by mass or more of the polycarbonate resin, fluorine-containing polymer, and water-repellent modifier, and more preferably 98% by mass or more. The upper limit may be 100% by mass. In this embodiment, the resin composition preferably contains a total of 96% by mass or more of the polycarbonate resin, fluorine-containing polymer, water-repellent modifier, and stabilizer, and more preferably 99% by mass or more. The upper limit may be 100% by mass.

[0049] <Physical properties of resin compositions> The resin composition of this embodiment preferably exhibits excellent transparency. Specifically, the haze of a 2 mm thick test piece formed from the resin composition, measured according to JIS K-7105, is preferably 50.0% or less, more preferably 40.0% or less, even more preferably 30.0% or less, even more preferably 20.0% or less, even more preferably 10.0% or less, even more preferably 8.0% or less, and in order of preference, 6.0% or less, 4.0% or less, and 3.5% or less. The lower limit of the haze is ideally 0%, but 0.1% or more is practical. Furthermore, it is preferable that the total light transmittance of a 2 mm thick test piece formed from the resin composition, as measured according to JIS K-7105, be 70% or higher, more preferably 76% or higher, more preferably 82% or higher, even more preferably 84% or higher, even more preferably 85% or higher, and even more preferably 87% or higher. The upper limit of the total light transmittance is ideally 100%, but 99% or less is practical. Such high transparency can be achieved, for example, by using polycarbonate resin, using a specific fluorine-containing polymer, or by adjusting the blending ratio of the specific fluorine-containing polymer or other components.

[0050] The molded article obtained using the resin composition of this embodiment preferably has a large water contact angle. When the resin composition is molded into a 2 mm thick flat plate, the water contact angle is more preferably 88° or higher, even more preferably 89° or higher, even more preferably 90° or higher, and even more preferably 91° or higher. There is no particular upper limit to the water contact angle, but it can be 105° or lower, 100° or lower, or 98° or lower. Such a high water contact angle is achieved by incorporating a water-repellent modifier. In particular, in the resin composition of this embodiment, the water-repellent modifier can exert its function without being affected by other components such as fluorine-containing polymers. The molded article obtained using the resin composition of this embodiment preferably has a large oil contact angle. When the resin composition is molded into a 2 mm thick flat plate, the oil contact angle is preferably greater than 11°, more preferably 12° or greater, even more preferably 15° or greater, and most preferably 17° or greater. There is no particular upper limit to the oil contact angle, but it can be 40° or less, or 33° or less. Such a high oil contact angle is achieved by using a predetermined amount of a specific fluorine-containing polymer.

[0051] The aforementioned physical properties are measured according to the examples described later. The resin composition of this embodiment preferably satisfies at least two of the above physical properties, more preferably satisfies at least three, and even more preferably satisfies all of the above physical properties.

[0052] <Method for producing resin compositions> There are no limitations on the manufacturing method of the resin composition of this embodiment, and a wide range of known methods for manufacturing resin compositions can be used. For example, a method may involve pre-mixing polycarbonate resin, a fluorine-containing polymer, a water-repellent modifier, and other components as needed using various mixers such as a tumbler or Henschel mixer, and then melt-kneading them using a mixer such as a Banbury mixer, roll mixer, braver, single-screw extruder, twin-screw extruder, or kneader. The melt-kneading temperature is not particularly limited, but is usually in the range of 240 to 320°C.

[0053] <Molded products> The resin composition described above (for example, pellets) is molded into a molded product by various molding methods. That is, the molded product of this embodiment is molded from the resin composition of this embodiment. There are no particular restrictions on the shape of the molded product, and it can be appropriately selected according to the use and purpose of the molded product. Examples include film-shaped, rod-shaped, cylindrical, annular, circular, elliptical, polygonal, irregularly shaped, hollow, frame-shaped, box-shaped, panel-shaped, and button-shaped products. Among these, film-shaped, frame-shaped, panel-shaped, and button-shaped products are preferred, and the thickness is, for example, about 1 mm to 5 mm in the case of frame-shaped and panel-shaped products.

[0054] The method for molding the molded product is not particularly limited, and conventionally known molding methods can be employed. Examples include injection molding, injection compression molding, extrusion molding, shape extrusion, transfer molding, hollow molding, gas-assisted hollow molding, blow molding, extrusion blow molding, IMC (in-mold coating) molding, rotational molding, multilayer molding, two-color molding, insert molding, sandwich molding, foam molding, and pressure molding. In particular, the resin composition of this embodiment is suitable for molded products obtained by injection molding, injection compression molding, and extrusion molding. However, it goes without saying that the resin composition of this embodiment is not limited to molded products obtained by these methods.

[0055] The molded articles of this embodiment are suitably used in electrical and electronic equipment, office automation equipment, personal digital assistants, machine parts, home appliances, vehicle parts, various containers, lighting equipment, displays, and other components. Among these, they are particularly suitable for use as display components, personal digital assistant components, household electrical appliance components, or interior furnishing components, and are more preferably used as display components. Examples of display components include those for automotive interiors and smartphones. [Examples]

[0056] The present invention will be described in more detail below with reference to examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate, as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. If the measuring instruments used in the examples are difficult to obtain due to discontinuation or other reasons, measurements can be taken using other instruments with equivalent performance.

[0057] 1. Raw materials The raw materials shown in Tables 1 and 2 below were used. [Table 1] [Table 2]

[0058] <Manufacturing Example 1> 26.14 moles (6.75 kg) of bisphenol C (BPC) and 26.79 moles (5.74 kg) of diphenyl carbonate were placed in an aluminum (SUS) reactor (internal volume 10 liters) equipped with a stirrer and a distillation condenser. After replacing the reactor with nitrogen gas, the temperature was raised to 220°C over 30 minutes under a nitrogen gas atmosphere. Next, the reaction mixture in the reactor is stirred, and cesium carbonate (Cs2CO3) is added to the molten reaction mixture as a transesterification catalyst at a rate of 1.5 × 10⁻¹⁶ per mole of BPC. -6 The mixture was added to form moles, and the reaction mixture was stirred and matured at 220°C for 30 minutes under a nitrogen gas atmosphere. Next, the pressure in the reactor was reduced to 100 Torr over 40 minutes at the same temperature, and the reaction was continued for another 100 minutes to distill off the phenol. Next, the temperature inside the reactor was raised to 284°C over 60 minutes, and the pressure was reduced to 3 Torr, allowing almost the entire theoretical amount of phenol to be distilled off. Then, the pressure inside the reactor was maintained at less than 1 Torr at the same temperature, and the reaction was continued for another 60 minutes to complete the polycondensation reaction. At this time, the stirring speed of the stirrer was 38 revolutions per minute, the reaction solution temperature just before the end of the reaction was 289°C, and the stirring power was 0.60 kW. Next, the molten reaction mixture was fed into a twin-screw extruder, and 4 times the molar amount of butyl p-toluenesulfonate relative to cesium carbonate was supplied from the first feed port of the twin-screw extruder and mixed with the reaction mixture. Then, the reaction mixture was extruded in strand form through the die of the twin-screw extruder and cut with a cutter to obtain pellets of polycarbonate resin A1.

[0059] <Measurement of viscosity-average molecular weight (Mv) of polycarbonate resin> The viscosity-average molecular weight (Mv) of polycarbonate resin was calculated using Schnell's viscosity formula, after determining the intrinsic viscosity (η) (unit: dL / g) at 20°C using an Ubbelohde viscometer with methylene chloride as the solvent. η = 1.23 × 10 -4 Mv 0.83

[0060] <Measurement of pencil hardness of polycarbonate resin> After drying polycarbonate resin pellets at 100°C for 5 hours, a flat test piece (90mm x 50mm x 2mm thick) was injection molded using an injection molding machine (Japan Steel Works Ltd. "J55-60H") with a cylinder temperature set to 280°C, a mold temperature of 80°C, a screw rotation speed of 100 rpm, and an injection speed of 100 mm / s. The flat test specimens (90 mm × 50 mm × 2 mm thick) obtained as described above were measured using a pencil hardness tester in accordance with ISO-15184, with a load of 750 g, to determine their pencil hardness. The pencil hardness tester used was manufactured by Toyo Seiki Co., Ltd.

[0061] Examples 1-4, Comparative Examples 1-10 <Manufacturing of resin composition pellets> Each component listed in Table 1 or Table 2 above was blended in the proportions (expressed in parts by mass) shown in Tables 3 to 5 below, and then uniformly mixed in a tumbler mixer. One vent was then supplied to a twin-screw extruder (Shibaura Machinery Co., Ltd., TEM26SX) from the upstream feeder, and melt-kneaded at a cylinder temperature of 260°C, a screw rotation speed of 250 rpm, and a discharge rate of 25 kg / hr to obtain resin composition pellets.

[0062] <HAZE (General Mold, 80 °C) and Total Light Transmittance> After drying the resin composition pellets obtained above at 100 °C for 5 hours, using an injection molding machine ("J55-60H" manufactured by Japan Steel Works, Ltd.), under the conditions of a cylinder set temperature of 280 °C, a mold temperature of 80 °C, a screw rotation speed of 100 rpm, and an injection speed of 100 mm / s, a flat test piece (90 mm × 50 mm × 2 mm thick) was injection molded. For the flat test piece obtained above, in accordance with JIS K-7105, using a haze meter, the HAZE (haze) and total light transmittance at 23 °C were measured. As the haze meter, an NDH-2000 type haze meter manufactured by Nippon Denshoku Industries Co., Ltd. was used. The units of HAZE and total light transmittance were shown in %.

[0063] <Water Repellency> After drying the resin composition pellets above at 100 °C for 5 hours, using an injection molding machine ("J55-60H" manufactured by Japan Steel Works, Ltd.), under the conditions of a cylinder set temperature of 280 °C, a mold temperature of 70 °C, a screw rotation speed of 100 rpm, and an injection speed of 25 mm / s, a three-stage plate (90 mm × 50 mm × thickness 3 mm (length 20 mm), 2 mm (length 45 mm), 1 mm (length 25 mm) from the gate side) was injection molded. For the 2 mm thick part of the obtained three-stage plate, after removing static electricity and adjusting the surface temperature to 23 °C, using a microsyringe, ion-exchanged water with a droplet diameter of 1.0 mm was dropped, and the contact angle (water contact angle) (unit: degree) was measured. As the measuring device, a solid-liquid interface analysis device DropMaster 300 manufactured by Kyowa Interface Science was used.

[0064] <Oil Repellency> After drying polycarbonate resin pellets at 100°C for 5 hours, a three-stage plate (90mm x 50mm x thicknesses of 3mm (length 20mm), 2mm (length 45mm), and 1mm (length 25mm) from the gate side) was injection molded using an injection molding machine (Japan Steel Works Ltd. "J55-60H") with a cylinder temperature set to 280°C, a mold temperature of 70°C, a screw rotation speed of 100 rpm, and an injection speed of 25 mm / s. After removing static electricity from the 2 mm thick three-tiered plate, oleic acid (manufactured by Tokyo Chemical Industry Co., Ltd., product code: O0180) with a droplet diameter of 0.5 mm was dropped onto the plate using a microsyringe, and the contact angle (in degrees) was measured. The measurement device used was the DropMaster 300 solid-liquid interface analyzer manufactured by Kyowa Interface Science. Samples with an oil contact angle of 5 degrees or less were indicated as unmeasurable.

[0065] [Table 3]

[0066] [Table 4]

[0067] [Table 5]

[0068] As is clear from the above results, the molded articles formed from the resin compositions of the present invention (Examples 1-4) exhibited a good balance of excellent oil repellency and water repellency. Furthermore, these molded articles also exhibited excellent transparency.

Claims

1. Polycarbonate resin and Fluorine-containing polymers and A resin composition comprising a water-repellent modifier, The aforementioned fluorine-containing polymer contains fluorine atoms and CH ２ =CH-C(=O)- or CH ２ = C(CH ３ It contains a constituent unit derived from compound F which includes )-C(=O)-, The aforementioned water-repellent improving agent contains paraffin wax, A resin composition (excluding resin compositions containing organopolysiloxane as a water-repellent modifier) ​​comprising 0.1 to 5.0% by mass of the fluorine-containing polymer relative to the total mass of the polycarbonate resin and the fluorine-containing polymer.

2. The resin composition according to claim 1, wherein the polycarbonate resin contains 0 to 90 mol% of the total constituent units of the constituent units represented by formula (1) and 100 to 10 mol% of the total constituent units of the constituent units represented by formula (2). Formula (1) 【Chemistry 1】 (In formula (1), X １ This represents one of the following expressions: 【Chemistry 2】 R 3 and R 4 Each of these independently represents a hydrogen atom or a methyl group, and Z represents a group that, when bonded to C, forms an alicyclic hydrocarbon having 6 to 12 carbon atoms, which may have substituents. Formula (2) 【Transformation 3】 (In formula (2), R 1 represents a methyl group, R 2 represents a hydrogen atom or a methyl group, X ２ represents any of the following formulas, 【Chemistry 4】 R 3 and R 4 Each of these independently represents a hydrogen atom or a methyl group, and Z represents a group that, when bonded to C, forms an alicyclic hydrocarbon having 6 to 12 carbon atoms, which may have substituents.

3. The resin composition according to claim 1 or 2, wherein the fluorine-containing polymer further has a cyclic structure.

4. The resin composition according to claim 3, wherein the cyclic structure includes an aromatic ring.

5. The resin composition according to any one of claims 1 to 4, wherein the compound F has a polyfluoroalkyl group having 1 to 6 carbon atoms and / or a polyfluoroether group having 1 to 6 carbon atoms.

6. A molded article formed from the resin composition according to any one of claims 1 to 5.

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