Molded products

Abstract

To provide a fingerprint-resistant molded article which is formed from a resin component containing polycarbonate-polyorganosiloxane copolymer.SOLUTION: A fingerprint-resistant molded article is formed from a resin component containing a polycarbonate-polyorganosiloxane copolymer (A) containing a polycarbonate block (A-1) and a polyorganosiloxane block (A-2), wherein the content of the polyorganosiloxane block in the resin component is 6.0-20.0 wt.%, and the contact angle of the oleic acid of the surface of the molded article is 40° .SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a fingerprint-resistant molded article formed from a resin component. [Background technology]

[0002] Polycarbonate, with its high transparency and excellent heat resistance, is widely used in optical components, electrical and electronic equipment, and automotive applications. Furthermore, to address the recent expansion of application fields, development of copolymer polycarbonates, in which various copolymerizable monomer units are introduced into common monomer raw materials such as bisphenol A (hereinafter abbreviated as BPA), is underway. In particular, polycarbonate-polyorganosiloxane copolymers composed of BPA and polyorganosiloxane comonomers are known to combine high levels of transparency, heat resistance, and impact resistance, and many publications have described them (Patent Documents 1 to 9). On the other hand, many thermoplastic resins, including polycarbonate resin, have a high affinity for fingerprints, which are primarily composed of oleic acid, due to their high lipophilicity, making them prone to fingerprints. Therefore, in applications where fingerprints need to be avoided, a countermeasure is taken by applying an anti-fingerprint coating to the surface of thermoplastic resin molded products. However, the additional process steps and reduced yields associated with coatings lead to increased costs. Therefore, there is a demand for a thermoplastic resin molded article that exhibits fingerprint resistance without the need for a coating, but no polycarbonate resin molded article that has fingerprint resistance and meets this requirement has yet been provided. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2021-031500 [Patent Document 2] Japanese Patent Publication No. 2020-122073 [Patent Document 3] Japanese Patent Application Laid-Open No. 2016-102219 [Patent Document 4] Japanese Patent Application Laid-Open No. 2015-137308 [Patent Document 5] Japanese Patent Application Laid-Open No. 2015-137307 [Patent Document 6] Japanese Patent Application Laid-Open No. 2015-034191 [Patent Document 7] Japanese Patent Application Laid-Open No. 2014-105276 [Patent Document 8] Japanese Patent Application Laid-Open No. 2012-246390 [Patent Document 9] Japanese Patent Application Laid-Open No. 2012-153824 Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present invention is to provide a fingerprint-resistant molded article formed from a resin component containing a polycarbonate-polyorganosiloxane copolymer. [Means for solving the problem]

[0005] As a result of extensive research conducted by the present inventors to achieve this object, they discovered that the above problems can be solved by the following constitution, and arrived at the present invention.

[0006] (Configuration 1) A fingerprint-resistant molded article formed from a resin component containing a polycarbonate-polyorganosiloxane copolymer (A) including a polycarbonate block (A-1) and a polyorganosiloxane block (A-2), wherein the content of the polyorganosiloxane block in the resin component is 6.0 to 20.0% by weight, and the contact angle of oleic acid on the surface of the molded article is 40° or more. (Configuration 2) 2. The molded article according to claim 1, wherein the polycarbonate block (A-1) is represented by the following general formula [1]:

[0007] [ka]

[0008] [(In the above general formula [1], R 1 and R 2 each independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group; when there are multiple of each, they may be the same or different; e and f each represent an integer of 1 to 4; and W represents a single bond or at least one group selected from the group consisting of groups represented by the following general formula [2]:

[0009] [ka]

[0010] (In the above general formula [2], R 11 ,R 12 ,R 13 ,R 14 ,R 15 ,R 16 ,R 17 and R 18 each independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms; R 19 and R 20each independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group; when there are a plurality of groups, they may be the same or different, g is an integer of 1 to 10, and h is an integer of 4 to 7.)

[0011] (Configuration 3) 3. The molded article according to claim 1, wherein the polyorganosiloxane block (A-2) is represented by the following general formula [3]:

[0012] [ka]

[0013] (In the above general formula [3], R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and R 9 and R 10 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, p is a natural number, q is 0 or a natural number, and the average chain length p+q is a natural number from 30 to 100. X is a divalent aliphatic group having 2 to 8 carbon atoms.

[0014] (Configuration 4) 4. The molded article according to claim 3, wherein the average chain length p+q in the general formula [3] is 30 to 70. (Configuration 5) The molded article according to the structure 3 or 4, wherein the polyorganosiloxane block represented by the general formula [3] is derived from a (2-allylphenol)-terminated polyorganosiloxane or a (2-methoxy-4-allylphenol)-terminated polyorganosiloxane. (Configuration 6) In general formula [3], R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is a methyl group. (Configuration 7) 3. The molded article according to claim 2, wherein the polycarbonate block represented by the general formula [1] is derived from 2,2-bis(4-hydroxyphenyl)propane. (Configuration 8) 8. The molded article according to any one of claims 1 to 7, wherein the content of the polyorganosiloxane block in the resin component is 13.0 to 18.0% by weight. (Configuration 9) 9. The molded article according to any one of aspects 1 to 8, wherein the contact angle of oleic acid on the surface of the molded article is 48° or more. (Configuration 10) 10. The molded article according to any one of configurations 1 to 9, wherein the viscosity average molecular weight of the resin component is 14,500 to 30,000. (Configuration 11) 11. The molded article according to any one of configurations 1 to 10, wherein a molded piece having a thickness of 2 mm obtained by injection molding using the resin component has a haze value of 2.0 or less. (Configuration 12) 12. The molded article according to any one of claims 1 to 11, wherein a molded piece having a thickness of 2 mm obtained by injection molding using the resin component is subjected to a high-speed surface impact test according to ISO 6603, and the fracture mode is ductile fracture. (Configuration 13) 13. The molded article according to any one of Configurations 1 to 12, wherein the pellets obtained by melt-kneading the resin component are dried with hot air at 100°C for 5 hours, and then the shear viscosity is measured in accordance with ISO 11443 (JIS K 7199) using a capillary rheometer (Capillograph 1D manufactured by Toyo Seiki Seisaku-sho, Ltd.) with a capillary model EF (diameter: 1.0 mm, length: 10.0 mm, L / D: 10) manufactured by Toyo Seiki Seisaku-sho, Ltd. at a furnace temperature of 300°C and a shear rate of 1220 sec-1, where the shear viscosity is 750 Pa·S or less. (Configuration 14) 14. The molded article according to any one of configurations 1 to 13, wherein the fingerprint adhesion area rate in the following fingerprint adhesion test using the molded article is 2.0% or less. A fake fingerprint sticker (Dipper ID fake fingerprint sticker, manufactured by A-Team Design Co., Ltd.) is dipped in artificial dirt (as specified in JIS C9606), and the fake fingerprint sticker is pressed against four stacked tissues with a 1kg load for one second, repeated 10 times. After that, the fake fingerprint sticker is pressed against four stacked tissues with a 1kg load for 30 seconds, repeated five times. The fake fingerprint sticker is then pressed against the surface of a molded product with a 500g load for five seconds to leave a fake fingerprint. A 50x magnified image of the area with the fake fingerprint is then photographed, and the fingerprint-deposited area rate is calculated from the ratio of the field of view area to the fake fingerprint-deposited area. Fingerprint adhesion area rate (%) = pseudo fingerprint adhesion area / viewing area x 100 (Configuration 15) 15. The molded article according to any one of aspects 1 to 14, wherein the fingerprint area ratio is 1.5 or less. (Configuration 16) 16. The molded article according to any one of configurations 1 to 15, wherein the molded article is any one of an automobile-related part, a railway-related part, an aircraft-related part, a household electrical appliance part, an electric / electronic appliance part, a housing equipment part, an office automation equipment part, a play equipment part, and an eyeglass part. (Configuration 17) The molded article is an automobile-related part selected from steering switches, ignition switches, cup holders, console boxes, displays, instrument panels, center clusters, windows, and interior decorative parts; a railway-related or aircraft-related part selected from switches and touch panel displays; a home appliance part selected from humidifiers, heaters, air purifiers, vacuum cleaners, clothes dryers, hair dryers, refrigerators, rice cookers, washing machines, televisions, television remote controls, and audio players; a digital camera, video camera, web camera, smart watch, earphones, wireless earphones, wireless earphone cases, headphones, neck speakers, and electric appliances. 17. The molded article according to claim 16, which is an electric / electronic device part selected from a musical instrument, a personal computer, a personal computer keyboard, a mouse, a numeric keypad, a mobile information terminal, a mobile information terminal protective cover, a game machine, a controller, a drone housing, and a touch panel for commercial facilities; a home appliance part selected from a toilet seat switch, a light switch, tableware, and a partition; an office automation equipment part selected from a copier, a projector, a POS, a scanner, a facsimile, and a telephone; a play equipment part selected from a pachinko handle, an arcade controller, and a toy; or an eyeglass part selected from an eyeglass frame, sunglasses, safety glasses, medical goggles, ski goggles, and swimming goggles. [Effects of the Invention]

[0015] The molded article of the present invention has excellent fingerprint resistance, transparency and impact resistance, and therefore has exceptional industrial effects. DETAILED DESCRIPTION OF THE INVENTION

[0016] The present invention will be described in more detail below. The molded article of the present invention is formed from a resin component containing a polycarbonate-polyorganosiloxane copolymer (A) including a polycarbonate block (A-1) and a polyorganosiloxane block (A-2), wherein the content of the polyorganosiloxane block in the resin component is 6.0 to 20.0 wt % and the contact angle of oleic acid is 40° or greater.

[0017] <<Polycarbonate-polyorganosiloxane copolymer (A)>> In the present invention, the polycarbonate-polyorganosiloxane copolymer (hereinafter sometimes abbreviated as PC-POS copolymer) (A) comprises a polycarbonate block (A-1) and a polyorganosiloxane block (A-2), and preferably the polycarbonate block (A-1) is represented by the following formula [1] and the polyorganosiloxane block (A-2) is represented by the following formula [3].

[0018] <Polycarbonate block (A-1)> In the present invention, the polycarbonate block (A-1) is a polycarbonate-based portion contained in the PC-POS copolymer, and the type thereof is not particularly limited. For example, such a polycarbonate-based portion may be an aromatic polycarbonate-based portion. For example, the polycarbonate block (A-1) is represented by the following formula [1].

[0019] [ka]

[0020] In the above formula [1], R 1 and R 2R each independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. 1 and R 2 When there are a plurality of each of the above, they may be the same or different.

[0021] Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

[0022] Examples of the alkyl group having 1 to 18 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, and a tetradecyl group. An alkyl group having 1 to 6 carbon atoms is preferred.

[0023] Examples of the alkoxy group having 1 to 18 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexoxy group, an octoxy group, etc. An alkoxy group having 1 to 6 carbon atoms is preferred.

[0024] Examples of the cycloalkyl group having 6 to 20 carbon atoms include a cyclohexyl group, a cyclooctyl group, etc. A cycloalkyl group having 6 to 12 carbon atoms is preferred.

[0025] Preferred examples of the cycloalkoxy group having 6 to 20 carbon atoms include a cyclohexyloxy group, a cyclooctyloxy group, etc. A cycloalkyl group having 6 to 12 carbon atoms is preferred.

[0026] Examples of the alkenyl group having 2 to 10 carbon atoms include a methenyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, etc. An alkyl group having 1 to 6 carbon atoms is preferred.

[0027] Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group, a naphthyl group, etc. Examples of the aryloxy group having 6 to 14 carbon atoms include a phenyloxy group, a naphthyloxy group, etc.

[0028] Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group, a phenylethyl group, etc. Examples of the aralkyloxy group having 7 to 20 carbon atoms include a benzyloxy group, a phenylethyloxy group, etc. e and f each independently represent an integer of 1 to 4. W is a single bond or at least one group selected from the group consisting of groups represented by the following formula [2]:

[0029] [ka]

[0030] In the above formula [2], R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 each independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms.

[0031] Examples of the alkyl group having 1 to 18 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a dodecyl group. An alkyl group having 1 to 6 carbon atoms is preferred.

[0032] Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group and a naphthyl group. These may be substituted. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group.

[0033] Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group and a phenylethyl group.

[0034] R 19 and R 20 each independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. When there are multiple groups, they may be the same or different.

[0035] Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

[0036] Examples of the alkyl group having 1 to 18 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, and a tetradecyl group. An alkyl group having 1 to 6 carbon atoms is preferred.

[0037] Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, etc. An alkyl group having 1 to 6 carbon atoms is preferred.

[0038] Examples of the cycloalkyl group having 6 to 20 carbon atoms include a cyclohexyl group, a cyclooctyl group, etc. A cycloalkyl group having 6 to 12 carbon atoms is preferred.

[0039] Examples of the cycloalkoxy group having 6 to 20 carbon atoms include a cyclohexyloxy group, a cyclooctyl group, etc. A cycloalkyl group having 6 to 12 carbon atoms is preferred.

[0040] Examples of the alkenyl group having 2 to 10 carbon atoms include a methenyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, etc. An alkyl group having 1 to 6 carbon atoms is preferred.

[0041] Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group and a naphthyl group.

[0042] Examples of the aryloxy group having 6 to 14 carbon atoms include a phenyloxy group and a naphthyloxy group.

[0043] Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group and a phenylethyl group.

[0044] Examples of the aralkyloxy group having 7 to 20 carbon atoms include a benzyloxy group and a phenylethyloxy group.

[0045] g is an integer of 1 to 10, preferably an integer of 1 to 6. h is an integer of 4 to 7, preferably an integer of 4 to 5.

[0046] The polycarbonate block represented by the above formula [1] is selected from the group consisting of 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-allyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4-biphenol, 4,4'-sulfonyldiphenol, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 9,9-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane ... Preferred are 2,2-bis(4-hydroxyphenyl)fluorene, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene, etc., more preferred are 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), 4,4-biphenol, 4,4'-sulfonyldiphenol, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, and particularly preferred are blocks derived from 2,2-bis(4-hydroxyphenyl)propane.

[0047] The length of the polycarbonate block (A-1) is preferably 10 to 100, more preferably 30 to 100, and even more preferably 50 to 70, in terms of the average number of repeating units of the formula [1].

[0048] The content of the polycarbonate block (A-1), particularly the content of the polycarbonate block represented by formula [1], is preferably 70.0 to 94.0% by weight, more preferably 74.0 to 92.0% by weight, even more preferably 78.0 to 92.0% by weight, still more preferably 80.0 to 90.0% by weight, particularly preferably 80.0 to 87.0% by weight, and most preferably 82.0 to 87.0% by weight, based on the total weight of the copolymer.

[0049] <Polyorganosiloxane block (A-2)> In the present invention, the polyorganosiloxane block (A-2) is a polyorganosiloxane-based portion contained in the PC-POS copolymer, and the type thereof is not particularly limited. For example, the polyorganosiloxane block is represented by the following formula [3]:

[0050] [ka]

[0051] In the above formula [3], R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms.

[0052] Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, etc. Preferred are alkyl groups having 1 to 6 carbon atoms.

[0053] Examples of the substituted or unsubstituted aryl group having 6 to 12 carbon atoms include a phenyl group, a naphthyl group, etc. Examples of the substituent include an alkyl group having 1 to 12 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.

[0054] R 3 , R 4 , R 5 , R 6 , R 7 , R 8 is preferably a phenyl group, a propyl group, an ethyl group, or a methyl group, and more preferably a methyl group.

[0055] R 9 and R 10 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.

[0056] Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

[0057] Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, etc. Preferred are alkyl groups having 1 to 6 carbon atoms.

[0058] Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexoxy group, a heptoxy group, an octoxy group, etc. An alkoxy group having 1 to 6 carbon atoms is preferred.

[0059] R 9 and R 10 is preferably a hydrogen atom, a methoxy group, or an ethoxy group, more preferably a hydrogen atom or a methoxy group, and even more preferably a hydrogen atom.

[0060] p is a natural number, preferably 20 to 100, more preferably 30 to 90, and even more preferably 35 to 70.

[0061] q is 0 or a natural number, preferably 0 to 80, and more preferably 0 to 50.

[0062] The average chain length p+q is 30 to 100, preferably 30 to 90, and more preferably 30 to 70. Within the above range, sufficient impact resistance is obtained, and furthermore, the appearance (color unevenness, peeling failure) is improved.

[0063] X is a divalent aliphatic group having 2 to 8 carbon atoms. Examples of the divalent aliphatic group include alkylene groups having 2 to 8 carbon atoms. Examples of the alkylene group include an ethylene group, a trimethylene group, and a tetramethylene group, with a trimethylene group being preferred.

[0064] The polyorganosiloxane block represented by the above formula [3] is preferably a block derived from an alkenylphenol-terminated polyorganosiloxane, more preferably a block derived from an allylphenol-terminated polyorganosiloxane, and even more preferably a block derived from a (2-allylphenol)-terminated polyorganosiloxane or a (2-methoxy-4-allylphenol)-terminated polyorganosiloxane. That is, in formula [3], X is a trimethylene group and R 9 and R 10 is a hydrogen atom, or X is a trimethylene group and R 9 and R 10 is preferably a methoxy group.

[0065] The content of the polyorganosiloxane block in the PC-POS copolymer (A) used in the present invention is preferably 6.0 to 30.0 wt %, more preferably 8.0 to 26.0 wt %, even more preferably 8.0 to 22.0 wt %, still more preferably 10.0 to 20.0 wt %, particularly preferably 13.0 to 20.0 wt %, and most preferably 13.0 to 18.0 wt % based on the total weight of the PC-POS copolymer. Within the above ranges, sufficient fingerprint resistance, transparency, and impact resistance can be obtained, and the appearance (color unevenness, peeling failure) can also be improved.

[0066] The viscosity-average molecular weight of the PC-POS copolymer (A) used in the present invention is 14,500 to 30,000, preferably 14,500 to 25,000, and more preferably 14,500 to 22,000. Within the above range, sufficient mechanical strength for practical use can be obtained. Furthermore, separation ability in the water washing step is high, and high productivity can be achieved.

[0067] <<Resin component containing polycarbonate-polyorganosiloxane copolymer (A)>> In the present invention, the resin component containing the polycarbonate-polyorganosiloxane copolymer (A) is a component for producing a resin molded article, and may be composed of only the copolymer, a blend, or a resin composition.

[0068] The content of the polyorganosiloxane block in the resin component of the present invention is 6.0 to 20.0 wt%, preferably 8.0 to 20.0 wt%, more preferably 10.0 to 20.0 wt%, even more preferably 13.0 to 20.0 wt%, particularly preferably 13.0 to 18.0 wt%, and most preferably 16.0 to 18.0 wt%, based on the total weight of the PC-POS copolymer. Within the above ranges, sufficient fingerprint resistance, transparency, and impact resistance are obtained, and further, the appearance (color unevenness, peeling failure) is improved.

[0069] The viscosity average molecular weight of the resin component in the present invention is preferably 14,500 to 30,000, more preferably 14,500 to 25,000, and even more preferably 14,500 to 22,000. Within the above range, sufficient mechanical strength for practical use can be obtained. Furthermore, separation ability in the water washing step is high, and high productivity can be achieved.

[0070] <<Molded article formed from a resin component containing polycarbonate-polyorganosiloxane copolymer (A)>> The molded article of the present invention is formed from a resin component containing the polycarbonate-polyorganosiloxane copolymer (A).

[0071] <Raw materials for polycarbonate-polyorganosiloxane copolymer (A)> (Dihydroxy Compound Component of Polycarbonate Block (A-1)) The dihydroxy compound serving as the raw material for the polycarbonate block (A-1) may be derived mainly from a dihydric phenol (I) represented by the following general formula [4].

[0072] [ka]

[0073] (In the formula, R 1 , R 2 , e, f and W are the same as in formula [1] above.) Examples of the dihydric phenol include 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxy-3,3'-biphenyl)propane, 2,2-bis(4-hydroxy- 2,2-bis(3-isopropylphenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl) 1,1-bis(4-hydroxyphenyl)methane, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'-dimethyl -4,4'-Sulfonyldiphenol, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfide, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,Examples include 4-bis(4-hydroxyphenyl)cyclohexane, 1,3-bis(4-hydroxyphenyl)cyclohexane, 4,8-bis(4-hydroxyphenyl)tricyclo[5.2.1.02,6]decane, 4,4'-(1,3-adamantanediyl)diphenol, and 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane.

[0074] Among these, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-sulfonyldiphenol, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, and 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene are preferred, and 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), 4,4'-sulfonyldiphenol, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene are particularly preferred. Among these, 2,2-bis(4-hydroxyphenyl)propane is the most suitable due to its excellent strength and durability. These may be used alone or in combination of two or more.

[0075] (Dihydroxy Compound Component of Polyorganosiloxane Block (A-2)) The dihydroxy compound used as the raw material for the polyorganosiloxane block (A-2) is a polyorganosiloxane having a specific average chain length. Specifically, a raw material represented by the following general formula [5], hydroxyaryl-terminated polyorganosiloxane (II), is used.

[0076] [ka]

[0077] (In the formula, R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , p, q and X are the same as those in the general formula [3] above.) In the general formula [5], the average chain length p+q is preferably 30 to 100, more preferably 30 to 90, and even more preferably 30 to 70. If it is less than 30, sufficient impact resistance is not achieved, and if it is greater than the upper limit, the appearance deteriorates (color unevenness, poor peeling). To satisfy this specific chain length range, two or more different hydroxyaryl-terminated polyorganosiloxane (II) raw materials having average chain lengths p+q may be mixed to prepare the polyorganosiloxane. In this case, polyorganosiloxane (B-1) having an average chain length p+q of 1 or more but less than 60 and polyorganosiloxane (B-2) having an average chain length p+q of 60 or more but less than 200 are used as raw materials. The polyorganosiloxane raw material can be prepared by mixing appropriate hydroxyaryl-terminated polyorganosiloxane raw materials together, or by premixing polyorganosiloxane precursors having an appropriate average chain length before the end is hydroxyaryl-modified, and then modifying the end with hydroxyaryl. The average chain length (p + q) of the polyorganosiloxane blocks in the PC-POS copolymer obtained by reacting the polyorganosiloxane raw material with a dihydric phenol and a polycarbonate precursor is, as described above, preferably 30 to 100, more preferably 30 to 90, and even more preferably 30 to 70. The average chain length (p + q) is calculated by nuclear magnetic resonance (NMR) measurement.

[0078] When the polyorganosiloxane (B-1) and the polyorganosiloxane (B-2) are mixed, the weight ratio of (B-1):(B-2) is preferably 1:99 to 99:1, and more preferably 10:90 to 90:10.

[0079] It is more preferable to use, as the polyorganosiloxane raw material, polyorganosiloxane (C) obtained by previously blending the above-mentioned polyorganosiloxanes (B-1) and (B-2). The blending ratio is preferably 1:99 to 99:1 by weight, similar to the above-mentioned (B-1):(B-2) weight ratio, and more preferably 10:90 to 90:10.

[0080] When blended in advance, the lower limit of the average chain length p + q of the polyorganosiloxane (B-1) is preferably 1 or more, more preferably 20 or more, and even more preferably 30 or more, and the upper limit is preferably less than 60, more preferably less than 50, and even more preferably less than 45. The lower limit of the average chain length p + q of the polyorganosiloxane (B-2) is preferably 60 or more, more preferably 70 or more, and even more preferably 90 or more, and the upper limit is preferably 200 or less, more preferably 100 or less. As the hydroxyaryl-terminated polyorganosiloxane (II) represented by the general formula [5], for example, the following compounds are preferably used.

[0081] [ka]

[0082] The hydroxyaryl-terminated polyorganosiloxane (II) is a phenol having an olefinic unsaturated carbon-carbon bond, and is preferably vinylphenol, 2-allylphenol, isopropenylphenol, or 2-methoxy-4-allylphenol, and is easily produced by subjecting the end of a polyorganosiloxane chain having a predetermined degree of polymerization to a hydrosilylation reaction. Among these, (2-allylphenol)-terminated polyorganosiloxane and (2-methoxy-4-allylphenol)-terminated polyorganosiloxane are preferred, and (2-allylphenol)-terminated polydimethylsiloxane and (2-methoxy-4-allylphenol)-terminated polydimethylsiloxane are particularly preferred.

[0083] <Method for producing polycarbonate-polyorganosiloxane copolymer> The polycarbonate-polyorganosiloxane copolymer of the present invention can be produced by the following steps. (PC-POS copolymer manufacturing process) The process is a process of reacting a dihydric phenol (I) represented by the above formula [4] with phosgene in a mixed solution of a water-insoluble organic solvent and an alkaline aqueous solution to prepare a solution containing a carbonate oligomer having a terminal chloroformate group.

[0084] As described above, the method for producing the PC-POS copolymer used in the present invention uses a polyorganosiloxane having a specific average chain length as a raw material, and the hydroxyaryl-terminated polyorganosiloxane (II) may be one type or two or more types. Specifically, a raw material represented by the hydroxyaryl-terminated polyorganosiloxane (II) represented by the general formula [5] and having an average chain length p + q of 30 to 100 is used. In addition, two or more different types of hydroxyaryl-terminated polyorganosiloxane (II) raw materials having an average chain length p + q may be mixed and used to satisfy such a specific chain length range. In this case, it can be prepared using a polyorganosiloxane (B-1) having an average chain length p + q of 1 or more and less than 60 and a polyorganosiloxane (B-2) having an average chain length p + q of 60 or more and 200 or less as raw materials, or it can be prepared by pre-mixing polyorganosiloxane precursors having an appropriate average chain length before the terminals are hydroxyaryl-modified, and then using a raw material obtained by modifying the terminals with hydroxyaryl. Furthermore, before reacting with the carbonate precursor and the dihydric phenol, the polyorganosiloxane (B-1) and the polyorganosiloxane (B-2) can be pre-blended, or they can be added to the reaction solution in parallel without being pre-blended, or (B-1) and (B-2) can be divided and added sequentially to the reaction solution to react with the carbonate precursor and the dihydric phenol. More preferably, the polyorganosiloxane (B-1) is added to the reaction solution, and then the polyorganosiloxane (B-2) is added to the reaction solution to react with the carbonate precursor and dihydric phenol. This is desirable from the viewpoint of efficiency and cost effectiveness due to simplified manufacturing process equipment. The weight ratio of the polyorganosiloxanes (B-1) and (B-2) used as raw materials is as described above, and the carbonate precursor and dihydric phenol will be described later.

[0085] In the interfacial polycondensation method for obtaining the PC-POS copolymer used in the present invention, the amount of the water-insoluble organic solvent per mole of the total amount of the dihydric phenols represented by the general formulas [4] and [5] is preferably 8 moles or more and less than 16 moles. Here, the total amount of dihydric phenols means the total amount of bisphenols and polyorganosiloxane monomers, which are raw materials for polycarbonate.

[0086] The amount of the insoluble organic solvent is the total amount used up to the point at which the catalyst is added and the polycondensation reaction is started, and is the total amount of the amount used in producing the polycarbonate oligomer, the amount used to dissolve the polyorganosiloxane monomer and the terminal terminator, and the amount added to adjust the emulsified state during the interfacial polycondensation reaction.

[0087] In the interfacial polycondensation method for obtaining the PC-POS copolymer used in the present invention, if the amount of water-insoluble organic solvent per mole of the total amount of dihydric phenols represented by general formulas [4] and [5] is less than the lower limit, the polymer quality will deteriorate due to poor emulsion during polymerization, and productivity will decrease due to excessively high solution viscosity. If the amount exceeds the upper limit, the poor emulsion state makes it difficult to introduce polyorganosiloxane blocks into the copolymer, resulting in poor appearance. Furthermore, a water-insoluble organic solvent may be added immediately after the reaction between the carbonate precursor, dihydric phenol, and polyorganosiloxane proceeds. Specifically, when the proportion of unreacted polyorganosiloxane in the reaction solution reaches 10% or less of the polyorganosiloxane used, it is desirable to add at least 2 moles of water-insoluble organic solvent per mole of the total amount of dihydric phenols represented by general formulas [4] and [5]. This ensures sufficient reaction progress while also reducing the risk of precipitation of polymer components due to high concentration.

[0088] In addition, other comonomers than the dihydric phenol (I) and hydroxyaryl-terminated polyorganosiloxane (II) can be used in combination in an amount of up to 10% by weight based on the total weight of the copolymer, provided that this does not interfere with the production method of the present invention.

[0089] In the production method of the present invention, a mixed solution containing an oligomer having a terminal chloroformate group is prepared in advance by reacting a dihydric phenol (I) with a carbonate ester-forming compound in a mixed solution of a water-insoluble organic solvent and an alkaline aqueous solution.

[0090] In producing an oligomer of the dihydric phenol (I), the entire amount of the dihydric phenol (I) used in the method of the present invention may be converted into an oligomer at once, or a part of the oligomer may be added as a post-added monomer as a reaction raw material to the interfacial polycondensation reaction in the subsequent stage. The post-added monomer is added to rapidly proceed with the polycondensation reaction in the subsequent stage, and there is no need to add it if it is not necessary. The method for this oligomer formation reaction is not particularly limited, but it is usually preferable to carry out the reaction in a solvent in the presence of an acid binder.

[0091] The proportion of the carbonate ester-forming compound used may be adjusted appropriately in consideration of the stoichiometric ratio (equivalents) of the reaction. When a gaseous carbonate ester-forming compound such as phosgene is used, it is preferable to blow it into the reaction system.

[0092] Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures of these.

[0093] The proportion of the acid binder used may be determined appropriately in consideration of the stoichiometric ratio (equivalents) of the reaction, as described above. Specifically, it is preferable to use 2 equivalents or a slight excess of the acid binder relative to the number of moles of the dihydric phenol (I) used to form the oligomer (usually 1 mole corresponds to 2 equivalents).

[0094] The solvent may be any of various inert solvents used in the production of known polycarbonates, either singly or in combination. Typical examples include hydrocarbon solvents such as xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. Halogenated hydrocarbon solvents such as methylene chloride are particularly preferred.

[0095] The reaction pressure for oligomer formation is not particularly limited and may be normal, elevated, or reduced pressure, but it is usually advantageous to carry out the reaction under normal pressure. The reaction temperature is selected from the range of -20 to 50°C, and since heat is often generated during polymerization, water or ice cooling is desirable. The reaction time depends on other conditions and cannot be specified in general, but is usually 0.2 to 10 hours. The pH range of the oligomer formation reaction is the same as that of known interfacial reactions, and the pH is always adjusted to 10 or higher.

[0096] In the present invention, after obtaining a mixed solution containing an oligomer of a dihydric phenol (I) having terminal chloroformate groups, the hydroxyaryl-terminated polyorganosiloxane (II) is added to the dihydric phenol (I) while stirring the mixed solution, and the hydroxyaryl-terminated polyorganosiloxane (II) and the oligomer are subjected to interfacial polycondensation to obtain a polycarbonate-polyorganosiloxane copolymer.

[0097] When carrying out the interfacial polycondensation reaction, an acid binder may be added appropriately taking into account the stoichiometric ratio (equivalent) of the reaction. Examples of acid binders include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. Specifically, when the hydroxyaryl-terminated polyorganosiloxane (II) used or a portion of the dihydric phenol (I) as described above is added as a post-added monomer to this reaction stage, it is preferable to use 2 equivalents or more of alkali relative to the total moles of the post-added dihydric phenol (I) and hydroxyaryl-terminated polyorganosiloxane (II) (usually 1 mole corresponds to 2 equivalents).

[0098] The polycondensation by interfacial polycondensation reaction between the oligomer of the dihydric phenol (I) and the hydroxyaryl-terminated polyorganosiloxane (II) is carried out by vigorously stirring the above mixture.

[0099] In such polymerization reactions, a terminal terminator or a molecular weight modifier is usually used. Examples of terminal terminators include compounds having a monovalent phenolic hydroxyl group, such as ordinary phenol, p-tert-butylphenol, p-cumylphenol, tribromophenol, etc., as well as long-chain alkylphenols, aliphatic carboxylic acid chlorides, aliphatic carboxylic acids, hydroxybenzoic acid alkyl esters, hydroxyphenyl alkyl acid esters, and alkyl ether phenols. The amount used is in the range of 100 to 0.5 mol, preferably 50 to 2 mol, per 100 mol of the total dihydric phenol compounds used, and it is of course possible to use two or more compounds in combination.

[0100] To accelerate the polycondensation reaction, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt may be added.

[0101] The reaction time for this polymerization reaction must be relatively long to reduce unreacted polyorganosiloxane blocks. It is preferably 30 minutes or more, more preferably 50 minutes or more. On the other hand, since prolonged stirring of the reaction solution can cause polymer precipitation, it is preferably 180 minutes or less, more preferably 90 minutes or less. If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added.

[0102] The PC-POS copolymer used in the present invention can be converted into a branched polycarbonate by using a branching agent in combination with the above-mentioned dihydric phenol compound. Examples of trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucin, phloroglucside, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2,2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-[4-[1,1-bis(4- Examples of the 4-hydroxyphenyl ether include trisphenols such as {4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and acid chlorides thereof. Among these, 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

[0103] The reaction pressure can be reduced, normal, or increased, but is usually preferably normal pressure or the inherent pressure of the reaction system. The reaction temperature is selected from the range of -20 to 50°C, and in many cases, water or ice cooling is desirable because heat is generated during polymerization. The reaction time cannot be generally determined because it varies depending on other conditions such as the reaction temperature, but is usually 0.5 to 10 hours.

[0104] In some cases, the obtained polycarbonate copolymer may be subjected to a suitable physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, crosslinking treatment, partial decomposition treatment, etc.) to obtain a desired reduced viscosity [η SP It can also be obtained as a polycarbonate copolymer of [(2-hydroxybenzoyl)-2-propanol / c].

[0105] The resulting reaction product (crude product) can be subjected to various post-treatments such as known separation and purification methods, and recovered as a polycarbonate-polyorganosiloxane copolymer of the desired purity (degree of purification).

[0106] Furthermore, the polycarbonate-polyorganosiloxane copolymer used in the present invention can be blended with various flame retardants, reinforcing fillers, and additives that are usually blended with polycarbonate resins, as long as the effects of the present invention are not impaired.

[0107] The resin component containing the polycarbonate-polyorganosiloxane copolymer of the present invention can be pelletized by melt-kneading using an extruder such as a single-screw extruder or a twin-screw extruder.

[0108] Furthermore, the resin component of the present invention may further contain other thermoplastic resins (e.g., polyarylate resins, fluororesins, polyester resins, etc.), antioxidants (e.g., hindered phenol compounds, etc.), impact modifiers, ultraviolet absorbers, light stabilizers, mold release agents, lubricants, colorants, inorganic fillers (talc, mica, wollastonite, kaolin, etc.), etc., within the scope of the present invention.

[0109] The molded articles of the present invention can be produced by injection molding the pellets produced as described above. Furthermore, it is also possible to directly produce sheets, films, profile extrusion molded articles, direct blow molded articles, and injection molded articles from the resin components melt-kneaded in an extruder without going through the pelletizing process.

[0110] Injection molding can be used to obtain resin parts for display materials using not only conventional molding methods but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including injection of supercritical fluids), insert molding, in-mold coating molding, heat-insulating mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high-speed injection molding, depending on the purpose. The advantages of these various molding methods are already widely known. Furthermore, molding can be performed using either a cold runner system or a hot runner system.

[0111] The molded article of the present invention may be used in the form of various profile extrusion molded articles, sheets, films, etc. by extrusion molding. Sheets and films can also be molded using inflation, calendaring, casting, etc. Furthermore, by subjecting the material to a specific stretching operation, it can also be molded into heat-shrinkable tubing. The molded article of the present invention can also be obtained by rotational molding, blow molding, etc.

[0112] Furthermore, in the present invention, molded articles made of polycarbonate-polyorganosiloxane copolymers can be subjected to various surface treatments. Surface treatments here refer to the formation of a new layer on the surface of a resin molded article, such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot-dip plating, etc.), painting, coating, and printing, and methods commonly used for polycarbonate resins can be applied. Specific examples of surface treatments include hard coating, water-repellent and oil-repellent coating, ultraviolet-absorbing coating, infrared-absorbing coating, and metallizing (vapor deposition, etc.).

[0113] <<Property values ​​of resin components containing polycarbonate-polyorganosiloxane copolymer (A) and molded products formed from the resin components>> (contact angle of oleic acid) The contact angle of oleic acid on the surface of the molded article of the present invention is 40° or more, preferably 43° or more, more preferably 45° or more, even more preferably 46° or more, particularly preferably 48° or more, and most preferably 51° or more. If the contact angle is within the above range, the molded article can be applied to resin parts that require fingerprint resistance.

[0114] (transparency) The resin component used in the present invention preferably has a haze value of 2.0 or less in a molded piece having a thickness of 2 mm obtained by injection molding, more preferably 1.6 or less, even more preferably 1.2 or less, particularly preferably 1.0 or less, and most preferably 0.8 or less. If the transparency is within the above range, the resin component has excellent colorability when blended with a coloring agent, and can be applied to resin parts that require high appearance.

[0115] (shock resistance) The resin component used in the present invention exhibits ductile fracture in a high-speed surface impact test performed on a 2 mm thick injection-molded piece in accordance with JIS K7211-2. Ductile fracture is suitable for use in resin parts, as the material is less susceptible to breakage due to a drop impact.

[0116] (Liquidity) The resin component used in the present invention is melt-kneaded to obtain pellets, which are then dried in hot air at 100°C for 5 hours. The shear viscosity is preferably 750 Pa·S or less, more preferably 550 Pa·S or less, even more preferably 350 Pa·S or less, and particularly preferably 250 Pa·S or less, at a furnace temperature of 300°C and a shear rate of 1220 sec-1, as measured in accordance with ISO 11443 (JIS K 7199) using a capillary rheometer (Capillograph 1D, manufactured by Toyo Seiki Seisaku-sho, Ltd.) and a Toyo Seiki Seisaku-sho Capillary Model EF (diameter: 1.0 mm, length: 10.0 mm, L / D: 10). The shear viscosity is preferably 750 Pa·S or less, more preferably 550 Pa·S or less, even more preferably 350 Pa·S or less, and particularly preferably 250 Pa·S or less. If the fluidity is within the above range, the resin component can be used for thin-walled and large resin parts.

[0117] (Fingerprint resistance) When the molded article of the present invention is subjected to the following fingerprint adhesion test, the fingerprint adhesion area ratio is 2.0% or less, preferably 1.8% or less, more preferably 1.7% or less, even more preferably 1.6% or less, particularly preferably 1.5% or less, and most preferably 1.3% or less. If the fingerprint adhesion area ratio is within the above range, the molded article can be applied to resin parts that require fingerprint resistance.

[0118] (Fingerprint adhesion test method) A fake fingerprint sticker (Dipper ID fake fingerprint sticker, manufactured by A-Team Design Co., Ltd.) is dipped in artificial dirt (as specified in JIS C9606), and the fake fingerprint sticker is pressed against four stacked tissues with a 1kg load for one second, repeated 10 times, and then another four stacked tissues are pressed against the sticker with a 1kg load for 30 seconds, repeated five times, and the fake fingerprint sticker is then pressed against the surface of a molded product with a 500g load for five seconds to leave a fake fingerprint. A 50x magnified image of the area with the fake fingerprint is taken, and the fingerprint area rate is calculated from the ratio of the field of view area to the fake fingerprint area. Fingerprint adhesion area rate (%) = pseudo fingerprint adhesion area / viewing area x 100

[0119] <<Uses of molded articles formed from resin components containing polycarbonate-polyorganosiloxane copolymer (A)>> The molded article of the present invention can be used as parts for, for example, automobile-related parts, railway-related parts, aircraft-related parts, household electrical appliance parts, electric / electronic equipment parts, housing equipment parts, office automation equipment parts, play equipment parts, eyeglass parts, etc.

[0120] Examples of automobile-related parts include steering switches, ignition switches, cup holders, console boxes, displays, instrument panels, center clusters, meter panels, dashboards, door trims, door handles, fuel lids, trunks, windows, interior decorative parts, etc. Among these, steering switches, ignition switches, cup holders, console boxes, displays, instrument panels, center clusters, windows, and interior decorative parts are preferred.

[0121] Examples of railway-related parts include handrails, ticket vending machine touch panel displays, ticket vending machine switches, ticket vending machine trays, etc. Of these, switches and touch panel displays are preferred.

[0122] Examples of aircraft-related parts include switches, touch panel displays, baggage inspection baskets, etc. Among these, switches and touch panel displays are preferred.

[0123] Examples of household electrical appliance parts include humidifiers, heaters, air purifiers, vacuum cleaners, clothes dryers, hair dryers, refrigerators, rice cookers, washing machines, televisions, television remote controls, audio players, electric fans, dehumidifiers, oven ranges, microwave ovens, etc. Among these, humidifiers, heaters, air purifiers, vacuum cleaners, clothes dryers, hair dryers, refrigerators, rice cookers, washing machines, televisions, television remote controls, and audio players are preferred.

[0124] Examples of electrical and electronic equipment parts include digital cameras, video cameras, web cameras, smart watches, camera lenses, earphones, wireless earphones, wireless earphone cases, headphones, wireless LAN routers, neck speakers, electronic musical instruments, personal computers, computer keyboards, mice, numeric keypads, mobile phones, smartphones, smartphone protective covers, tablets, tablet protective covers, game consoles, controllers, drone housings, and touch panels for commercial facilities. Of these, digital cameras, video cameras, web cameras, smart watches, earphones, wireless earphones, wireless earphone cases, headphones, neck speakers, electronic musical instruments, personal computers, computer keyboards, mice, numeric keypads, personal digital assistants, personal digital assistant protective covers, game consoles, controllers, drone housings, and touch panels for commercial facilities are preferred.

[0125] Examples of household equipment parts include toilet seats, toilet seat switches, doors, doorknobs, stair railings, light switches, tableware, partitions, etc. Of these, toilet seat switches, light switches, tableware, and partitions are preferred.

[0126] Examples of office automation equipment parts include home appliance parts selected from a copier, a copier touch panel, a projector, a POS, a scanner, a facsimile, and a telephone, and examples thereof include a copier, a projector, a POS, a scanner, a facsimile, and a telephone, with a copier, a projector, a POS, a scanner, a facsimile, and a telephone being preferred.

[0127] Examples of plaything parts include pachinko handles, arcade controllers, and toys.

[0128] Examples of eyeglass parts include eyeglass frames, eyeglass lenses, sunglasses, safety glasses, medical goggles, ski goggles, and swimming goggles, of which eyeglass frames, sunglasses, safety glasses, medical goggles, ski goggles, and swimming goggles are preferred.

[0129] More preferred are center clusters, touch panel displays, rice cookers, televisions, television remote controls, audio players, digital cameras, video cameras, web cameras, wireless earphones, headphones, neck speakers, electronic musical instruments, personal computers, computer keyboards, mice, numeric keypads, personal digital assistants, protective covers for personal digital assistants, game consoles, controllers, touch panels for commercial facilities, light switches, partitions, projectors, POS systems, toys, eyeglass frames, sunglasses, safety glasses, and medical goggles. [Example]

[0130] The present invention will be described in more detail below with reference to examples, but these examples are not intended to limit the scope of the present invention. Unless otherwise specified, parts in the examples are parts by weight and % is % by weight. Evaluations were made according to the following methods.

[0131] (1) Viscosity average molecular weight (Mv) The specific viscosity (ηSP) calculated by the following formula was measured using an Ostwald viscometer from a solution prepared by dissolving 0.7 g of PC-POS copolymer or resin component in 100 ml of methylene chloride at 20°C. Specific viscosity (ηSP)=(t-t0) / t0 [t0 is the number of seconds that methylene chloride falls, and t is the number of seconds that the sample solution falls] The viscosity average molecular weight Mv is calculated from the determined specific viscosity (ηSP) using the following formula. ηSP / c=[η]+0.45×[η] 2 c (where [η] is the intrinsic viscosity) [η]=1.23×10 -4 Mv 0.83 c=0.7

[0132] (2) Polyorganosiloxane block content and average polyorganosiloxane repeat number (p + q) The H-NMR spectrum of the polycarbonate-polyorganosiloxane copolymer was measured using a JEOL NMR JNM-AL400, and the average chain length p + q was calculated by comparing the integral ratio of the peak derived from the dihydric phenol (I) with the integral ratio of the peak derived from the hydroxyaryl-terminated polyorganosiloxane (II). Similarly, the average chain length p + q was calculated by comparing the integral ratio of the peak derived from the hydroxyaryl-terminated peak with the integral ratio of the peak derived from the polyorganosiloxane.

[0133] The content of the polyorganosiloxane block in the resin component was calculated as the sum of the values ​​obtained by multiplying the content of the polyorganosiloxane block in each polycarbonate resin applied by the blending ratio.

[0134] (3) Contact angle of oleic acid The pellets were dried with hot air at 100°C for 5 hours, and then a three-stage plate was produced using an injection molding machine (SE130EV-A, manufactured by Sumitomo Heavy Industries, Ltd.) at a molding temperature of 280°C, a mold temperature of 80°C, and a molding cycle of 40 seconds. The contact angle of the 2.0 mm thick portion of the test piece with oleic acid was measured using a goniometer-type contact angle measuring instrument GI-1000 manufactured by Elma Co., Ltd.

[0135] (4) Transparency evaluation (haze measurement) The resulting pellets were dried with hot air at 100°C for 5 hours, and then a three-layer plate was produced using an injection molding machine (SE130EV-A, manufactured by Sumitomo Heavy Industries, Ltd.) at a molding temperature of 280°C, a mold temperature of 80°C, and a molding cycle of 40 seconds. The haze of a 2.0 mm-thick section of the three-layer plate was measured in accordance with ISO 17482 using a Haze Meter 300A manufactured by Nippon Denshoku Industries Co., Ltd.

[0136] (5) Impact resistance evaluation (high-speed surface impact test) The resulting pellets were dried with hot air at 100°C for 5 hours, and then a three-stage plate was produced using an injection molding machine (SE130EV-A, manufactured by Sumitomo Heavy Industries, Ltd.) at a molding temperature of 280°C, a mold temperature of 80°C, and a molding cycle of 40 seconds. In accordance with JIS K7211-2, a punching test was conducted on a 2.0 mm thick portion of the test piece using a high-speed puncture impact tester "Hydroshot HTM-P10" (manufactured by Shimadzu Corporation) at a punching speed of 7 mm / sec in an environment of 23°C, and the fracture morphology was visually confirmed.

[0137] (6) Fluidity evaluation (shear viscosity measurement) The pellets obtained were dried with hot air at 100°C for 5 hours, and then subjected to shear rate measurement at a furnace temperature of 300°C and a shear rate of 1220 sec-1 in accordance with ISO11443 (JIS K 7199) using a capillary rheometer (Capillograph 1D manufactured by Toyo Seiki Seisaku-sho Co., Ltd.) and a capillary model EF manufactured by Toyo Seiki Seisaku-sho Co., Ltd. (diameter: 1.0 mm, length: 10.0 mm, L / D: 10). -1 The shear viscosity was measured.

[0138] (7) Fingerprint test The resulting pellets were dried with hot air at 100°C for 5 hours and then fabricated into three-layer plates using an injection molding machine (Sumitomo Heavy Industries, Ltd., SE130EV-A) at a molding temperature of 280°C, a mold temperature of 80°C, and a molding cycle of 40 seconds. A pseudo-fingerprint sticker (Dipper ID, manufactured by A-Team Design, Inc.) was immersed in artificial dirt (JIS C9606 specifications) and pressed against four stacked tissues with a 1 kg load for 1 second, repeated 10 times. Then, another four stacked tissues were pressed against the surface of the three-layer plate with a 500 g load for 5 seconds to deposit a pseudo-fingerprint. Images of the pseudo-fingerprint-covered area were photographed at 50x magnification, and the fingerprint coverage was calculated from the ratio of the visual area to the pseudo-fingerprint-covered area. Fingerprint adhesion area rate (%) = pseudo fingerprint adhesion area / viewing area x 100

[0139] [Both-end phenol-modified polyorganosiloxane] In the examples and comparative examples, a polyorganosiloxane compound having the following structure was used as the dihydric phenol (II) having a polyorganosiloxane structure. (II): p + q = 37 (KF-2201 manufactured by Shin-Etsu Chemical Co., Ltd.) The average repeating number p+q of the dimethylsiloxane unit was evaluated by 1H-NMR measurement.

[0140] [Production of polycarbonate-polyorganosiloxane copolymer] (PC-POS-1 manufacturing method) A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 17,890 parts of ion-exchanged water and 7,003 parts of a 25% aqueous sodium hydroxide solution, and 3,812 parts of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) as the dihydric phenol (I) represented by the general formula [4] and 7.5 parts of hydrosulfite were dissolved therein. Then, 14,310 parts of methylene chloride was added, and 1,900 parts of phosgene was blown in over 70 minutes at 22 to 30°C with stirring. 7150 parts of methylene chloride was added, and a solution of 1347 parts of 25% aqueous sodium hydroxide and 149 parts of p-tert-butylphenol dissolved in 850 parts of methylene chloride was added. While stirring, a solution of 428 parts of the above KF-2201 (as dihydric phenol (II) represented by the general formula [5]) dissolved in 800 parts of methylene chloride (0.55 molar equivalents relative to the total amount of dihydric phenol) was added at a rate of 0.0008 molar equivalents / min relative to the dihydric phenol (I) to emulsify, and then vigorously stirred again. With stirring, 4.3 parts of triethylamine was added when the reaction solution was at 26 ° C., and the reaction was continued by stirring at a temperature of 26 to 31 ° C. for 1 hour to complete the reaction. After the reaction was complete, the organic phase was separated, diluted with methylene chloride, washed with water, and then acidified with hydrochloric acid and washed again. When the conductivity of the aqueous phase reached nearly the same level as that of ion-exchanged water, the mixture was placed in a kneader filled with warm water and the methylene chloride was evaporated while stirring to obtain a polycarbonate-polyorganosiloxane copolymer powder. After dehydration, the mixture was dried at 100°C for 12 hours in a hot air circulating dryer. The resulting polycarbonate-polyorganosiloxane copolymer had a viscosity-average molecular weight of 16,000 and a polyorganosiloxane block content of 8.4 wt%.

[0141] (PC-POS-2 manufacturing method) The same production method as for PC-POS-1 was used, except that the amount of p-tert-butylphenol was changed to 109 parts. The viscosity average molecular weight of the obtained polycarbonate-polyorganosiloxane copolymer was 20,000, and the polyorganosiloxane block content was 8.4 wt%.

[0142] (PC-POS-3 manufacturing method) The production method was the same as for PC-POS-1, except that the amount of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) was changed to 3796 parts, the amount of p-tert-butylphenol to 149 parts, and the amount of KF-2201 to 648 parts. The viscosity average molecular weight of the resulting polycarbonate-polyorganosiloxane copolymer was 15,500, and the polyorganosiloxane block content was 12.0 wt%.

[0143] (PC-POS-4 manufacturing method) The production method was the same as for PC-POS-1, except that the amount of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) was changed to 3796 parts, the amount of p-tert-butylphenol to 121 parts, and the amount of KF-2201 to 648 parts. The viscosity average molecular weight of the resulting polycarbonate-polyorganosiloxane copolymer was 18,000, and the polyorganosiloxane block content was 12.0 wt%.

[0144] (PC-POS-5 manufacturing method) The production method was the same as for PC-POS-1, except that the amount of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) was changed to 3786 parts, the amount of p-tert-butylphenol to 149 parts, and the amount of KF-2201 to 776 parts. The viscosity average molecular weight of the resulting polycarbonate-polyorganosiloxane copolymer was 15,500, and the polyorganosiloxane block content was 14.0 wt%.

[0145] (PC-POS-6 manufacturing method) The production method was the same as for PC-POS-1, except that the amount of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) was changed to 3786 parts, the amount of p-tert-butylphenol to 121 parts, and the amount of KF-2201 to 776 parts. The viscosity average molecular weight of the resulting polycarbonate-polyorganosiloxane copolymer was 18,000, and the polyorganosiloxane block content was 14.0 wt%.

[0146] (PC-POS-7 manufacturing method) The production method was the same as for PC-POS-1, except that the amount of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) was changed to 3788 parts, the amount of p-tert-butylphenol to 78 parts, and the amount of KF-2201 to 751 parts. The viscosity average molecular weight of the resulting polycarbonate-polyorganosiloxane copolymer was 25,000, and the polyorganosiloxane block content was 14.0 wt%.

[0147] (PC-POS-8 manufacturing method) The production method was the same as for PC-POS-1, except that the amount of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) was changed to 3774 parts, the amount of p-tert-butylphenol to 149 parts, and the amount of KF-2201 to 945 parts. The viscosity average molecular weight of the resulting polycarbonate-polyorganosiloxane copolymer was 15,500, and the polyorganosiloxane block content was 17.0 wt%.

[0148] (PC-POS-9 manufacturing method) The production method was the same as for PC-POS-1, except that the amount of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) was changed to 3774 parts, the amount of p-tert-butylphenol to 121 parts, and the amount of KF-2201 to 945 parts. The viscosity average molecular weight of the resulting polycarbonate-polyorganosiloxane copolymer was 18,000, and the polyorganosiloxane block content was 17.0 wt%.

[0149] (PC-POS-10 manufacturing method) The production method was the same as for PC-POS-1, except that the amount of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) was changed to 3739 parts, the amount of p-tert-butylphenol to 126 parts, and the amount of KF-2201 to 1402 parts. The viscosity average molecular weight of the resulting polycarbonate-polyorganosiloxane copolymer was 18,000, and the polyorganosiloxane block content was 25.0 wt%.

[0150] (PC-1) A linear aromatic polycarbonate resin powder (Panlite, manufactured by Teijin Limited) with a solution viscosity of 17,000 and a molecular weight of 17,000, which has a repeating skeleton of 2,2-bis(4-hydroxyphenyl)propane.

[0151] [Production of polycarbonate resin composition containing PC-POS copolymer] [Examples 1 to 12 and Comparative Examples 1 to 4] The PC-POS and PC obtained in the above Production Examples were blended in the proportions shown in the table, and then melt-kneaded and pelletized using a vented twin-screw extruder (The Japan Steel Works, Ltd., TEX30α-31.5BV-2V) at a discharge rate of 20 kg / h, a screw rotation speed of 150 rpm, and an extrusion temperature of 270 °C from the first feed port to the die, to obtain a resin component. The resulting pellets were then dried with hot air at 100 °C for 5 hours, and then molded specimens for various evaluations were obtained using an injection molding machine (Sumitomo Heavy Industries, Ltd., SE130EV-A). The polyorganosiloxane block content, viscosity average molecular weight Mv, oleic acid contact angle, haze, fingerprint area ratio, high-speed surface impact test failure morphology, and shear viscosity of the test specimens were evaluated. The evaluation results are shown in Table 1.

[0152] [Table 1]

[0153] As shown in Table 1, Comparative Examples 1 to 3 have a lower polyorganosiloxane block content than the Examples, and therefore are inferior in fingerprint resistance compared to the Examples. Comparative Example 4 has a higher polyorganosiloxane block content than the Examples, and therefore, poor appearance occurred during molding, and a molded product suitable for fingerprint resistance evaluation could not be obtained.

[0154] It has been found that molded articles made using the resin composition of the present invention exhibit excellent fingerprint resistance, transparency and impact resistance. [Industrial Applicability]

[0155] The molded article of the present invention has excellent fingerprint resistance, transparency, and impact resistance, and is therefore highly practical for use as automobile-related parts, railway-related parts, aircraft-related parts, household electrical appliance parts, electrical and electronic equipment parts, housing equipment parts, office automation equipment parts, play equipment parts, and eyeglass parts.

Claims

1. A molded article formed from a resin component containing a polycarbonate-polyorganosiloxane copolymer (A) including a polycarbonate block (A-1) and a polyorganosiloxane block (A-2), wherein the content of the polyorganosiloxane block in the resin component is 10.0 to 20.0% by weight, and the molded article has a surface with a contact angle of oleic acid of 40° or more, wherein the polycarbonate block (A-1) is derived from 2,2-bis(4-hydroxyphenyl)propane, and the polyorganosiloxane block (A-2) is represented by the following general formula [3]: 【Chemistry 1】 (In the above general formula [3], R 3 , R 4 , R 5 , R 6 , R 7 and R 8 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms; R 9 and R 10 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; p is a natural number; q is 0 or a natural number; the average chain length (p+q) is a natural number from 30 to 70; and X is a divalent aliphatic group having 2 to 8 carbon atoms.)

2. The molded article according to claim 1, wherein the polyorganosiloxane block represented by the general formula [3] is derived from a (2-allylphenol)-terminated polyorganosiloxane or a (2-methoxy-4-allylphenol)-terminated polyorganosiloxane.

3. In general formula [3], R ３ , R ４ , R ５ , R ６ , R ７ and R ８ The molded article according to claim 1 or 2, wherein is a methyl group.

4. The molded article according to any one of claims 1 to 3, wherein the content of the polyorganosiloxane block in the resin component is 13.0 to 18.0% by weight.

5. The molded article according to any one of claims 1 to 4, wherein the contact angle of oleic acid on the surface of the molded article is 48° or more.

6. The molded article according to any one of claims 1 to 5, wherein the viscosity average molecular weight of the resin component is 14,500 to 30,000.

7. The molded article according to any one of claims 1 to 6, wherein a haze value of a molded piece having a thickness of 2 mm obtained by injection molding using the resin component is 2.0 or less.

8. The molded article according to any one of claims 1 to 7, wherein the fracture morphology in a high-speed surface impact test measured in accordance with ISO 6603 of a molded piece having a thickness of 2 mm obtained by injection molding using the resin component is ductile fracture.

9. A molded article according to any one of claims 1 to 8, which is formed from the resin component, wherein the resin component is melt-kneaded to obtain pellets, which are then dried with hot air at 100°C for 5 hours, and then rated in accordance with ISO 11443 (JIS K 7199) using a capillary rheometer (Capillograph 1D manufactured by Toyo Seiki Seisaku-sho, Ltd.) with a capillary model EF (diameter: 1.0 mm, length: 10.0 mm, L / D: 10) manufactured by Toyo Seiki Seisaku-sho, Ltd., at a furnace temperature of 300°C and a shear rate of 1220 sec-1 to give a shear viscosity of 750 Pa·S or less.

10. The molded article according to any one of claims 1 to 9, wherein the fingerprint adhesion area rate in the following fingerprint adhesion test using the molded article is 2.0% or less. A pseudo fingerprint sticker (Dipper ID pseudo fingerprint sticker, manufactured by A-Team Design Co., Ltd.) is immersed in artificial dirt (described in JIS C9606), and the pseudo fingerprint sticker is pressed against four stacked tissues with a load of 1 kg for one second, repeated 10 times. After that, the pseudo fingerprint sticker is pressed against four stacked tissues with a load of 1 kg for 30 seconds, repeated five times. The pseudo fingerprint sticker is then pressed against the surface of a molded product with a load of 500 g for five seconds to adhere the pseudo fingerprint. A 50x magnified image of the area with the pseudo fingerprint attached is photographed, and the fingerprint-adhered area rate is calculated from the ratio of the field of view area to the pseudo fingerprint-adhered area. Fingerprint adhesion area rate (%) = pseudo fingerprint adhesion area / viewing area x 100

11. The molded article according to claim 10, wherein the fingerprint area ratio is 1.5 or less.

12. The molded article according to any one of claims 1 to 11, wherein the molded article is an automobile-related part, a railway-related part, an aircraft-related part, a household electrical appliance part, an electric / electronic device part, a housing equipment part, an office automation equipment part, a plaything part, or an eyeglass part.

13. The molded article is an automobile-related part selected from steering switches, ignition switches, cup holders, console boxes, displays, instrument panels, center clusters, windows, and interior decorative parts; a railway-related or aircraft-related part selected from switches and touch panel displays; a home appliance part selected from humidifiers, heaters, air purifiers, vacuum cleaners, clothes dryers, hair dryers, refrigerators, rice cookers, washing machines, televisions, television remote controls, and audio players; a digital camera, video camera, web camera, smart watch, earphones, wireless earphones, wireless earphone cases, headphones, neck speakers, electronics The molded product according to claim 12 is any one of an electrical / electronic device part selected from a musical instrument, a personal computer, a personal computer keyboard, a mouse, a numeric keypad, a mobile information terminal, a mobile information terminal protective cover, a game console, a controller, a drone housing, and a touch panel for a commercial facility; a housing equipment part selected from a toilet seat switch, a light switch, tableware, and a partition; an office automation device part selected from a copier, a projector, a POS, a scanner, a facsimile, and a telephone; a play equipment part selected from a pachinko handle, an arcade controller, and a toy; and an eyeglass part selected from an eyeglass frame, sunglasses, safety glasses, medical goggles, ski goggles, and swimming goggles.

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