Resin composition, flat plate-shaped molded body, multilayer body, and method for manufacturing molded article

Abstract

The objective of this invention is to provide a resin composition for manufacturing polycarbonate resin films or sheets, and a method for manufacturing flat molded bodies, multilayers, and molded articles using the above-mentioned resin composition, wherein the polycarbonate resin film or sheet does not spring back even when hot-bent together with an acrylic resin layer, and can provide multilayers with excellent resistance to damp heat. The solution is a resin composition comprising: 70-99 parts by weight of an aromatic polycarbonate resin having the end structure shown in formula (1); 1-12 parts by weight of a phosphate ester; and 0-29 parts by weight of another thermoplastic resin other than the aromatic polycarbonate resin having the end structure shown in formula (1). In formula (1), R... 1 It refers to an alkyl group with 8 to 36 carbon atoms or an alkenyl group with 8 to 30 carbon atoms.

Description

Technical Field

[0001] This invention relates to a method for manufacturing resin compositions, flat molded articles, multilayers, and molded articles. Background Technology

[0002] Polycarbonate resin not only has excellent transparency, but also superior processability and impact resistance compared to glass. Furthermore, unlike other plastic materials, it does not produce toxic gases. Therefore, it is widely used in various fields and is also used as a thermoforming material for vacuum forming, air compression forming, and other processes.

[0003] On the other hand, since polycarbonate resin generally has low surface hardness, the surface of molded articles formed from polycarbonate resin is prone to damage. Therefore, when polycarbonate resin is made into a film, solutions have been explored to form a layer or hard coating (protective layer) containing acrylic resin on the surface to avoid damage to the surface of the article.

[0004] For example, Patent Document 1 discloses a molding resin sheet, which is a laminated sheet having a coating layer with an acrylic resin (B) as the main component on one side of a substrate layer. The substrate layer has a polycarbonate resin composition (A) composed of a polymer alloy of aromatic polycarbonate (A1) and other resins (A2) as the main component. The molding resin sheet is characterized in that the absolute value of the difference between the glass transition temperature of the polycarbonate resin composition (A) and the acrylic resin (B) is within 30°C.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2009-196153 Summary of the Invention

[0008] The technical problem that the invention aims to solve

[0009] As described above, when forming a multilayer consisting of an acrylic resin layer and a hard coating on a film or sheet made of polycarbonate resin, the acrylic resin typically has a lower glass transition temperature than the polycarbonate resin. Therefore, during thermoforming, especially when using a mold with a small radius of curvature, the acrylic resin layer elongates excessively, and the hard coating cannot keep up with the deformation, sometimes resulting in cracks in the hard coating. To eliminate this phenomenon, a scheme to suppress the deformation of the acrylic resin by thermoforming at low temperatures has been considered. However, when hot bending the multilayer at low temperatures, a phenomenon occurs where the hot-bent multilayer returns to its original shape (springback). Furthermore, it is known that changes in appearance sometimes occur during the damp heat resistance test of the aforementioned multilayer.

[0010] The purpose of this invention is to solve the above-mentioned technical problems and provide a resin composition for manufacturing polycarbonate resin films or sheets, as well as a method for manufacturing flat molded bodies, multilayer bodies, and molded articles using the above-mentioned resin composition. The polycarbonate resin film or sheet does not spring back even when hot-bent together with an acrylic resin layer, and can provide a multilayer body with excellent resistance to damp heat.

[0011] Technical solutions for solving technical problems

[0012] The inventors of this invention explored the above-mentioned technical problems and found that the above-mentioned technical problems could be solved by using a resin composition containing an aromatic polycarbonate resin and a phosphate ester having a defined end structure.

[0013] Specifically, the above-mentioned technical problems were solved through the following technical solutions.

[0014] <1> A resin composition comprising: 70 to 99 parts by weight of an aromatic polycarbonate resin having the end structure shown in formula (1); 1 to 12 parts by weight of a phosphate ester; and 0 to 29 parts by weight of a thermoplastic resin other than the aromatic polycarbonate resin having the end structure shown in formula (1).

[0015]

[0016] (In equation (1), R) 1 Represents an alkyl group with 8 to 36 carbon atoms or an alkenyl group with 8 to 30 carbon atoms. R 2 Each of these groups independently represents a halogen atom, an alkyl group with 1 to 20 carbon atoms, or an aryl group with 6 to 12 carbon atoms. n represents an integer from 0 to 4. * indicates a bonding site with other sites.

[0017] <2> The resin composition as described in <1>, wherein the other thermoplastic resins described above comprise an aromatic polycarbonate resin having the end structure shown in formula (2).

[0018]

[0019] (In equation (2), R) 2 Each of these groups independently represents a halogen atom, an alkyl group with 1 to 20 carbon atoms, or an aryl group with 6 to 12 carbon atoms. t-Bu represents a tert-butyl group. n represents an integer from 0 to 4. * indicates a bonding site with other sites.

[0020] <3> The resin composition as described in <1> or <2>, wherein the glass transition temperature of the resin composition, as determined by differential scanning calorimetry, is below 120°C.

[0021] <4> The resin composition as described in any one of <1> to <3>, wherein the glass transition temperature of the resin composition, as determined by differential scanning calorimetry, is 100°C or higher.

[0022] <5> The resin composition as described in any one of <1> to <4>, wherein the phosphate ester contains an aromatic ring.

[0023] <6> The resin composition as described in any one of <1> to <5>, wherein the resin composition is molded into a flat plate with a thickness of 100 μm, and the haze after being treated at 85°C and 85% relative humidity for 200 hours is less than 20%.

[0024] <7> The resin composition as described in any one of <1> to <6>, wherein when the resin composition is treated at 85°C and 85% relative humidity for 200 hours, the difference in weight-average molecular weight (Mw) before and after treatment is 10,000 or less.

[0025] <8> A flat molded body formed from any one of <1> to <7>.

[0026] <9> The plate-shaped molded body as described in <8> has a thickness of 10 to 5,000 μm.

[0027] <10> A multilayer body having a flat molded body as described in <8> or <9> and a layer containing acrylic resin.

[0028] <11> The multilayer body as described in <10>, wherein the total thickness of the multilayer body is 10 to 10,000 μm.

[0029] <12> The multilayer body as described in <10> or <11> further has a hard coating layer, wherein the hard coating layer is stacked in the order of a flat molded body, an acrylic resin-containing layer, and a hard coating layer.

[0030] <13> A molded article formed from any one of <10> to <12>, having a portion having a radius of curvature of 50 mmR or less.

[0031] <14> A method for manufacturing a molded article, comprising the step of hot bending a multilayer body as described in any one of <10> to <12> at 105 to 117°C.

[0032] <15> A method for manufacturing a molded article as described in <14>, wherein the molded article has a portion having a radius of curvature of 50 mmR or less.

[0033] Invention Effects

[0034] The present invention provides a resin composition for manufacturing polycarbonate resin films or sheets, as well as a method for manufacturing flat molded bodies, multilayers, and molded articles using the above-mentioned resin composition. The polycarbonate resin films or sheets do not spring back even when hot-bent together with acrylic resin layers, and multilayers with excellent resistance to damp heat can be provided. Attached Figure Description

[0035] Figure 1 This is a schematic diagram illustrating the layer structure of the multilayer body of the present invention.

[0036] Symbol Explanation

[0037] 1: Multilayer body; 2: Flat molded body (polycarbonate resin film or sheet); 3: Acrylic resin layer; 4: Hard coating. Detailed Implementation

[0038] The following describes in detail specific embodiments of the present invention (hereinafter referred to as "this embodiment"). These embodiments are merely examples used to illustrate the present invention, and the present invention is not limited to these embodiments.

[0039] Furthermore, in this specification, “~” is used to mean that the values ​​recorded before and after it are included as lower and upper limits.

[0040] Unless otherwise specified, all physical property values ​​and characteristic values ​​in this manual are values ​​at 23°C.

[0041] In this specification, the terms "flat molded body" and "multilayer body" each include cases where the body is formed into a film or sheet. "Film" and "sheet" each refer to a molded body that is thin and generally flat relative to its length and width. There is no explicit distinction between "film" and "sheet"; generally, a thickness of 250 μm or less is referred to as a "film," and a thickness of 250 μm or more is referred to as a "sheet." Furthermore, in this specification, "film" and "sheet" can be single-layered or multilayered.

[0042] In addition, "parts by mass" in this specification indicates the relative amount of the ingredient; "% by mass" indicates the absolute amount of the ingredient.

[0043] In this specification, "(meth)acrylic acid" means either or both of acrylic acid and methacrylic acid.

[0044] Furthermore, in this specification, the flat molded body formed from the resin composition of this embodiment is sometimes referred to as a "polycarbonate resin film" or "polycarbonate resin sheet"; and the layer containing acrylic resin is referred to as an "acrylic resin layer".

[0045] Unless otherwise specified, the standard measurement methods shown in this specification are based on the standard at the time of application, unless otherwise specified.

[0046] The resin composition of this embodiment is characterized by containing: 70 to 99 parts by mass of an aromatic polycarbonate resin having the end structure shown in Formula (1); 1 to 12 parts by mass of a phosphate ester; and 0 to 29 parts by mass of other thermoplastic resins besides the aromatic polycarbonate resin having the end structure shown in Formula (1). With this configuration, a multilayer polycarbonate resin film or sheet that does not rebound and provides excellent resistance to damp heat can be provided. Furthermore, a polycarbonate resin film or sheet with low initial haze and low haze after damp heat testing, and with minimal molecular weight change after damp heat testing, can be obtained. In addition, when the acrylic resin layer and the above-mentioned polycarbonate resin film or sheet are formed into a multilayer, flow marks and foreign matter formation can be suppressed, and cracking after hot bending can be suppressed.

[0047]

[0048] (In equation (1), R) 1 Represents an alkyl group with 8 to 36 carbon atoms or an alkenyl group with 8 to 30 carbon atoms. R 2 Each of these groups independently represents a halogen atom, an alkyl group with 1 to 20 carbon atoms, or an aryl group with 6 to 12 carbon atoms. n represents an integer from 0 to 4. * indicates a bonding site with other sites.

[0049] The reasoning is that by using an aromatic polycarbonate resin with a defined end structure and incorporating a phosphate ester, the glass transition temperature of the resin composition can be lowered, and it is less likely to affect other properties. Furthermore, as a result, thermal degradation of the resin composition after damp heat testing can be suppressed. It is further speculated that when forming a multilayer of polycarbonate resin film or sheet and acrylic resin layer, the difference in glass transition temperature between the polycarbonate resin film or sheet and the acrylic resin layer becomes smaller, thus resulting in a multilayer with excellent thermal bending properties.

[0050] While incorporating additives into resins lowers the glass transition temperature, it often negatively impacts other properties. For example, phosphites readily react with peroxides in the resin. In this embodiment, various studies were conducted as additives, and phosphate esters were found to be suitable.

[0051] <Aromatic polycarbonate resin>

[0052] The resin composition of this embodiment contains an aromatic polycarbonate resin having the end structure shown in Formula (1). By using an aromatic polycarbonate resin having the end structure shown in Formula (1), the glass transition temperature of the polycarbonate resin can be lowered.

[0053]

[0054] (In equation (1), R) 1 Represents an alkyl group with 8 to 36 carbon atoms or an alkenyl group with 8 to 30 carbon atoms. R 2 Each of these groups independently represents a halogen atom, an alkyl group with 1 to 20 carbon atoms, or an aryl group with 6 to 12 carbon atoms. n represents an integer from 0 to 4. * indicates a bonding site with other sites.

[0055] R 1 The resin is represented by an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 30 carbon atoms, preferably an alkyl or alkenyl group having 10 or more carbon atoms, more preferably an alkyl or alkenyl group having 12 or more carbon atoms, and even more preferably an alkyl or alkenyl group having 14 or more carbon atoms. This lowers the glass transition temperature of the resin and improves the thermal flexibility of the multilayer. Additionally, R... 1 Preferably, the alkyl or alkenyl group has 22 or fewer carbon atoms, and more preferably, it has 18 or fewer alkyl or alkenyl groups. This improves compatibility with other resins. 1 Alkyl groups are preferred. Alkyl and alkenyl groups are preferably straight-chain or branched alkyl or alkenyl groups, more preferably straight-chain alkyl or alkenyl groups.

[0056] In this embodiment, R 1 Hexadecyl is particularly preferred.

[0057] Additionally, R 1 It can be located in any position among intermediate, opposite, and adjacent positions, preferably in intermediate or opposite positions, and more preferably in opposite positions.

[0058] R 2 Each of the following can be independently represented: a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms, preferably a fluorine atom, a chlorine atom, a methyl group, an ethyl group, or a phenyl group, more preferably a fluorine atom, a chlorine atom, or a methyl group.

[0059] n represents an integer from 0 to 4, preferably an integer from 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0060] By using end-capping agents such as hexadecyl p-hydroxybenzoate, the end structure shown in formula (1) can be added to polycarbonate resin. For details, please refer to paragraphs 0022 to 0030 of Japanese Patent Application Publication No. 2019-002023, and these contents are incorporated herein by reference.

[0061] Regarding the aromatic polycarbonate resin with the end structure shown in Formula (1) in this embodiment, the end structure shown in Formula (1) can be one type or two or more types.

[0062] In this embodiment, the aromatic polycarbonate resin having the end structure shown in Formula (1) is preferably a bisphenol type polycarbonate resin, and more preferably a bisphenol A type polycarbonate resin. In addition, it is preferable that 50 mol% or more of the bisphenol type polycarbonate resin has at least one end structure shown in Formula (1).

[0063] Bisphenol A type polycarbonate resins may also have structural units other than the carbonate structural units of bisphenol A and its derivatives. Examples of dihydroxy compounds constituting such other structural units include, for instance, the aromatic dihydroxy compounds described in paragraph 0014 of Japanese Patent Application Publication No. 2018-154819, and these contents are incorporated herein by reference.

[0064] In the bisphenol-type polycarbonate resin of this embodiment, the carbonate structural units from bisphenol A and its derivatives preferably account for 90% or more by mass of all structural units excluding end structures, more preferably 95% or more by mass, and even more preferably 97% or more by mass.

[0065] There are no particular limitations on the manufacturing method of bisphenol A type polycarbonate resin; any method can be used. Examples include interfacial polymerization, melt transesterification, pyridine polymerization, ring-opening polymerization of cyclic carbonate compounds, and solid-phase transesterification of prepolymers.

[0066] The weight-average molecular weight of the aromatic polycarbonate resin having the end structure shown in Formula (1) is not particularly limited, but is preferably 10,000 or more, more preferably 20,000 or more, even more preferably 30,000 or more, even more preferably 40,000 or more, and even more preferably 50,000 or more. By setting it to the lower limit or above, the impact resistance of the multilayer and the suppression of flow marks during molding tend to be further improved. In addition, the weight-average molecular weight of the aromatic polycarbonate resin having the end structure shown in Formula (1) is preferably 200,000 or less, more preferably 150,000 or less, even more preferably 100,000 or less, even more preferably 80,000 or less, and even more preferably 60,000 or less. By setting it to the upper limit or below, the moldability of the multilayer tends to be improved.

[0067] The glass transition temperature of the aromatic polycarbonate resin with the end structure shown in Formula (1) used in this embodiment is preferably 145°C or lower, more preferably 140°C or lower, even more preferably 135°C or lower, even more preferably 130°C or lower, and even more preferably 125°C or lower. By setting it to the upper limit value or lower, the thermal bending formability of the multilayer tends to be further improved. In addition, the glass transition temperature of the aromatic polycarbonate resin with the end structure shown in Formula (1) used in this embodiment is preferably 121°C or higher, more preferably 122°C or higher, and even more preferably 123°C or higher. By setting it to the lower limit value or higher, the durability of environmental resistance tests such as damp heat test and high temperature test tends to be further improved.

[0068] <Other thermoplastic resins>

[0069] The resin composition of this embodiment may also contain other thermoplastic resins besides aromatic polycarbonate resins having the end structure shown in formula (1). By containing other thermoplastic resins, there is a tendency to adjust the glass transition temperature of the resin and improve its durability in environmental tests such as damp heat test and high temperature test.

[0070] Other thermoplastic resins are not particularly limited as long as they are thermoplastic resins that can be melt-blended with aromatic polycarbonate resins having the end structure shown in formula (1), and known thermoplastic resins can be used.

[0071] Other thermoplastic resins may be exemplified as polycarbonate resins other than aromatic polycarbonate resins having the end structure shown in formula (1), polyester resins (preferably aromatic polyester resins), acrylic resins (preferably aromatic acrylic resins), and preferably other polycarbonate resins other than aromatic polycarbonate resins having the end structure shown in formula (1).

[0072] As for the other polycarbonate resins mentioned above, aromatic polycarbonate resins are preferred, and bisphenol A type polycarbonate resins are more preferred.

[0073] The other polycarbonate resins mentioned above are preferably aromatic polycarbonate resins having the end structure shown in formula (2). By using such aromatic polycarbonate resins, in addition to the effects described above, there is a tendency to further improve the transparency of the flat molded articles.

[0074]

[0075] (In equation (2), R) 2Each of these groups independently represents a halogen atom, an alkyl group with 1 to 20 carbon atoms, or an aryl group with 6 to 12 carbon atoms. t-Bu represents a tert-butyl group. n represents an integer from 0 to 4. * indicates a bonding site with other sites.

[0076] In equation (2), R 2 The meanings of and n are respectively the same as R in equation (1). 2 The range of preferred values ​​is the same as that of n.

[0077] Regarding the aromatic polycarbonate resin with the end structure shown in formula (2) in this embodiment, the end structure shown in formula (2) can be one type or two or more types.

[0078] In this embodiment, the aromatic polycarbonate resin having the end structure shown in formula (2) is preferably a bisphenol A type polycarbonate resin. Furthermore, it is preferable that 50 mol% or more of the bisphenol A type polycarbonate resin has at least one end structure shown in formula (2).

[0079] Bisphenol A type polycarbonate resins may also contain structural units other than those derived from bisphenol A and its derivatives. Examples of dihydroxy compounds constituting such other structural units include, for instance, the aromatic dihydroxy compounds described in paragraph 0014 of Japanese Patent Application Publication No. 2018-154819, and these contents are incorporated herein by reference.

[0080] In this embodiment, the carbonate structural units derived from bisphenol A and its derivatives of the bisphenol-type polycarbonate resin preferably account for 90% or more by mass of all structural units excluding end structures, more preferably 95% or more by mass, and even more preferably 97% or more by mass.

[0081] The weight-average molecular weight of other thermoplastic resins (preferably aromatic polycarbonate resins having the end structure shown in formula (2)) is not particularly limited, but is preferably 10,000 or more, more preferably 20,000 or more, further preferably 30,000 or more, even more preferably 40,000 or more, and even more preferably 50,000 or more. By setting the weight-average molecular weight to the lower limit or above, the impact resistance of the multilayer and the suppression of flow marks during molding tend to be further improved. In addition, the weight-average molecular weight of other thermoplastic resins (preferably aromatic polycarbonate resins having the end structure shown in formula (2)) is preferably 200,000 or less, more preferably 150,000 or less, further preferably 100,000 or less, even more preferably 80,000 or less, and even more preferably 60,000 or less. By setting the weight-average molecular weight to the upper limit or below, there is a tendency to improve compatibility with aromatic polycarbonate resins having the end structure shown in formula (1) and further improve the transparency of the molded article.

[0082] The glass transition temperature of the other thermoplastic resins used in this embodiment (preferably aromatic polycarbonate resins having the end structure shown in formula (2)) is preferably 155°C or lower, more preferably 154°C or lower, even more preferably 153°C or lower, even more preferably 152°C or lower, and even more preferably 151°C or lower. By setting it to the upper limit value or lower, there is a tendency to further improve the hot bending formability of the multilayer. In addition, the glass transition temperature of the other thermoplastic resins used in this embodiment (preferably aromatic polycarbonate resins having the end structure shown in formula (2)) is preferably 145°C or higher. By setting it to the lower limit value or higher, there is a tendency to further improve the durability in environmental tests such as damp heat tests and high temperature tests.

[0083] <Phosphate>

[0084] The resin composition of this embodiment contains phosphate esters. By containing phosphate esters, the glass transition temperature of the resulting polycarbonate resin film or sheet can be lowered, and its influence on other properties can be suppressed.

[0085] There are no particular restrictions on the types of phosphate esters; widely known compounds can be used.

[0086] The phosphate ester preferably contains aromatic rings, more preferably two or more aromatic rings, and even more preferably two to ten aromatic rings. The presence of aromatic rings improves compatibility with aromatic resin compounds and enhances the transparency of the molded article. Furthermore, the phosphate ester is preferably a condensed phosphate ester and its derivative compounds, or their condensates. Using condensed phosphate esters and their derivative compounds, or their condensates, results in lower volatility compared to conventional phosphate esters, reducing the likelihood of gas generation during molding. Additionally, compared to conventional phosphate esters, the larger molecular weight helps prevent a decrease in the overall mechanical properties of the resin. Further, in this embodiment, the phosphate ester is preferably an aromatic condensed phosphate ester and its derivative compounds, or their condensates, and even more preferably an aromatic condensed phosphate ester.

[0087] Phosphate esters may also contain halogen atoms, but are preferably free of halogen atoms.

[0088] From the viewpoint of compatibility and dispersibility with resin components, the molecular weight of phosphate ester is preferably 500 to 1500.

[0089] Examples of phosphate esters that can be used in this embodiment include the following compounds.

[0090] Aromatic phosphates and their derivatives, as well as their condensates, including monoethyl phosphate, monobutyl phosphate, methyl phosphate, ethyl phosphate, butyl phosphate, dibutyl phosphate, trimethyl phosphate (TMP), triethyl phosphate (TEP), triphenyl phosphate (TPP), tricresyl phosphate (TCP), tri(xyl) phosphate (TXP), toluene diphenyl phosphate (CDP), 2-ethylhexyl diphenyl phosphate (EHDP), etc.

[0091] • Reaction products of phosphorus oxychloride with divalent phenolic compounds and phenol (or alkylphenol). Examples include aromatic condensed phosphates such as resorcinol bis-diphenyl phosphate, resorcinol poly(di-2,6-dimethyl) phosphate, and bisphenol A polytoluene phosphate, as well as their derivative compounds and their condensates.

[0092] • Tri(chloroethyl) phosphate, tri(chloropropyl) phosphate, tri(dichloropropyl) phosphate, tri(dibromopropyl) phosphate, bis(2,3-dibromopropyl)-2,3-dichloropropyl phosphate, bis(chloropropyl)octyl phosphate, and their derivative compounds and their condensates.

[0093] As commercially available products, examples include "JAMP-2", "JAMP-4P", "JP-501", "JP-502", "JP-504", and "DBP" manufactured by Johoku Chemical Co., Ltd., and "TMP", "TEP", "TPP", "TCP", "TXP", "CDP", "PX-110", "#41", "CR-733S", "CR-741", "PX-200", "DAIGUARD-400 / 540 / 580 / 610", "TMCPP", "CRP", "CR-900", "CR-504L", "CR-570", and "DAIGUARD-540" manufactured by Daihachi Chemical Co., Ltd.

[0094] The phosphate ester content in the resin composition of this embodiment is preferably 1 to 12% by mass. Setting it to 1% by mass or more effectively suppresses springback, while setting it to 12% by mass or less effectively suppresses warping of the thermoformed multilayer. The upper limit of the phosphate ester content is preferably 8% by mass or less, more preferably 6% by mass or less. Furthermore, the lower limit is preferably 1.5% or more, more preferably 2% or more.

[0095] <Blending of Components>

[0096] In this embodiment, the blending ratio of the aromatic polycarbonate resin having the end structure shown in formula (1), the phosphate ester, and the other thermoplastic resins described above in the resin composition is 70–99 parts by mass: 1–12 parts by mass: 0–29 parts by mass, more preferably 74–99 parts by mass: 1–8 parts by mass: 0–25 parts by mass. By setting such a ratio, a resin composition with a good balance and excellent properties such as thermal bending characteristics can be obtained.

[0097] When the resin composition of this embodiment does not contain other thermoplastic resins, the blending ratio of the aromatic polycarbonate resin having the end structure shown in formula (1) to the phosphate ester is preferably 90 to 99 parts by mass: 10 to 1 part by mass, more preferably 93 to 98 parts by mass: 7 to 2 parts by mass, and even more preferably 94 to 98 parts by mass: 6 to 2 parts by mass.

[0098] When the resin composition of this embodiment contains other thermoplastic resins, the blending ratio of the aromatic polycarbonate resin having the end structure shown in formula (1), the phosphate ester, and other thermoplastic resins is preferably 70-94 parts by mass: 1-12 parts by mass: 5-35 parts by mass, more preferably 70-80 parts by mass: 2-7 parts by mass: 10-30 parts by mass. As described above, the other thermoplastic resins are preferably aromatic polycarbonate resins, more preferably aromatic polycarbonate resins having the end structure shown in formula (2).

[0099] Regarding the resin composition of this embodiment, the total amount of the aromatic polycarbonate resin having the terminal structure shown in formula (1), the phosphate ester, and the other thermoplastic resins described above is preferably 95% by mass or more, preferably 98% by mass or more, and can be 99% by mass or more. In addition, the upper limit of the above total amount is 100% by mass or less.

[0100] The resin composition of this embodiment may contain only one aromatic polycarbonate resin having the terminal structure shown in formula (1), a phosphate ester, and other thermoplastic resins as needed, or it may contain two or more. When it contains two or more, the total amount is preferably within the range described above.

[0101] <Other ingredients>

[0102] In addition to the above, the resin composition of this embodiment may also contain mold release agents, heat stabilizers, flame retardants, flame retardant additives, ultraviolet absorbers, colorants, antistatic agents, fluorescent whitening agents, antifogging agents, flow improvers, plasticizers, dispersants, antibacterial agents, anti-blocking agents, impact improvers, slip improvers, hue improvers, acid traps, etc. One of these components may be used, or two or more may be used in combination.

[0103] The total amount of the other components mentioned above is preferably 0.001 to 5% by mass of the resin composition, more preferably 0.001 to 2% by mass, and even more preferably 0.01 to 1% by mass. Anti-blocking refers to the effect of inhibiting the adhesion between the films, which can be achieved by adding anti-blocking agents, etc.

[0104] <<Mold Release Agent>>

[0105] The resin composition of this embodiment preferably contains a mold release agent. By containing a mold release agent, a polycarbonate resin film or sheet with better mold release properties can be obtained.

[0106] As a release agent, at least one compound selected from aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds with a number average molecular weight of 200 to 15,000, and polysiloxane-based silicone oils may be used, with esters of aliphatic carboxylic acids and alcohols being preferred.

[0107] Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture with beeswax palmitate as the main component), stearate, benzyl benzyl acid, benzyl stearate, glyceryl monopalmitate, glyceryl monostearate, glyceryl distearate, glyceryl tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, and pentaerythritol tetrastearate.

[0108] In addition, as a release agent, the release agents described in paragraph 0032 of Japanese Patent Application Publication No. 2017-226848 and paragraph 0056 of Japanese Patent Application Publication No. 2018-199745 may also be used, and this content is incorporated into this specification.

[0109] The content of the release agent in the resin composition is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, and preferably 2 parts by mass or less, more preferably 1 part by mass or less, and even more preferably 0.5 parts by mass or less, relative to 100 parts by mass of the resin component.

[0110] One type of release agent may be used, or two or more types may be used. When using two or more types, the preferred total amount is within the range described above.

[0111] <Physical Properties of Resin Compositions>

[0112] The glass transition temperature of the resin composition of this embodiment, as determined by differential scanning calorimetry, is preferably 120°C or lower, more preferably 119°C or lower, even more preferably 118°C or lower, even more preferably 117°C or lower, and even more preferably 116°C or lower. By setting this to the upper limit or below, the effect of suppressing springback during hot bending tends to be further improved. Furthermore, the glass transition temperature of the resin composition of this embodiment, as determined by differential scanning calorimetry, is preferably 100°C or higher, more preferably 102°C or higher, even more preferably 105°C or higher, even more preferably 107°C or higher, and even more preferably 110°C or higher. By setting this to the lower limit or above, the durability in environmental tests such as damp heat tests and high temperature tests tends to be further improved.

[0113] The glass transition temperature can be determined according to the method described in the examples below.

[0114] The resin composition of this embodiment preferably exhibits excellent transparency after a damp heat resistance test.

[0115] Specifically, the haze of the resin composition of this embodiment after being molded into a flat plate with a thickness of 100 μm and treated at 85°C and 85% relative humidity for 200 hours is preferably 20% or less, more preferably 10% or less, further preferably 5% or less, even more preferably 2% or less, and even more preferably 1% or less. The ideal lower limit of the above haze is 0%, but in practice it is 0.01% or more.

[0116] Furthermore, when the resin composition of this embodiment is treated at 85°C and 85% relative humidity for 200 hours, the difference in weight-average molecular weight (Mw) before and after treatment is preferably 10,000 or less, more preferably 8,000 or less, and even more preferably 6,000 or less. The ideal lower limit of the above difference is 0, but in practice it is 100 or more.

[0117] <Plate-shaped molded body>

[0118] The resin composition of this embodiment is preferably processed into a flat molded body for use. That is, the flat molded body of this embodiment is formed from the resin composition of this embodiment. The flat molded body of this embodiment has excellent resistance to damp heat.

[0119] Examples of flat-shaped molded bodies include plates, films, and sheets. Furthermore, as detailed later, the flat-shaped molded body can also be incorporated into a multilayer body formed by laminating other substrates. Additionally, the flat-shaped molded body of this embodiment can be bent or subjected to other processing after being incorporated into a part of a multilayer body.

[0120] The lower limit of the thickness of the flat molded body is preferably 10 μm or more, more preferably 20 μm or more, even more preferably 50 μm or more, and can be 100 μm or more. By setting it to the above lower limit or above, it tends to be easier to mold and have higher hardness. In addition, there is no particular limitation on the upper limit of the thickness of the flat molded body, and it is practical to be 5,000 μm or less.

[0121] The flat molded body of this embodiment is formed by injection molding, extrusion molding using a T-die, etc.

[0122] <Multi-layered structure>

[0123] The flat molded body of this embodiment can be used in the form of a multilayer body. The multilayer body of this embodiment has the flat molded body of this embodiment and a layer containing acrylic resin (acrylic resin layer).

[0124] The thickness (total thickness) of the multilayer is not particularly limited, but is preferably 10 μm or more, and more preferably 20 μm or more. Furthermore, the thickness of the multilayer is preferably 10,000 μm or less, more preferably 5,000 μm or less, and can be 2,000 μm or less.

[0125] Preferably, the multilayer body of this embodiment further includes a hard coating layer. By providing the hard coating layer, the surface hardness of the multilayer body tends to be further improved. The hard coating layer is preferably stacked in the following order: flat molded body, acrylic resin-containing layer, and hard coating layer.

[0126] Figure 1 This is a schematic diagram illustrating an example of a multilayer body according to this embodiment. As described above, 1 represents a multilayer body, 2 represents a flat molded body (polycarbonate resin film or sheet), 3 represents an acrylic resin layer, and 4 represents a hard coating layer. The flat molded body 2, the acrylic resin layer 3, and the hard coating layer 4 may have other layers as long as they are stacked in the order described above, without departing from the spirit of this embodiment, but it is preferable that they do not have other layers, i.e., they are adjacent to each other.

[0127] Next, the acrylic resin layer will be described. The acrylic resin layer in the multilayer of this embodiment is a layer containing acrylic resin (preferably 80% or more by mass, more preferably 90% or more by mass of acrylic resin). By including such an acrylic resin layer, the multilayer of this embodiment tends to have further improved hardness (especially pencil hardness).

[0128] The thickness of the acrylic resin layer is preferably 10 μm or more, more preferably 20 μm or more, further preferably 40 μm or more, even more preferably 60 μm or more, and even more preferably 80 μm or more. Furthermore, the upper limit of the acrylic resin layer thickness is preferably 300 μm or less, more preferably 200 μm or less, even more preferably 180 μm or less, even more preferably 150 μm or less, and even more preferably 120 μm or less. By setting such a layer thickness, sufficient scratch resistance and impact resistance can be obtained.

[0129] The acrylic resin used in this embodiment is a polymer of (meth)acrylate or a polymer of (meth)acrylate and monomers other than (meth)acrylate, and there is no particular limitation on its type. Regarding the polymer of (meth)acrylate and monomers other than (meth)acrylate, the proportion of (meth)acrylate is preferably 50 mol% or more, more preferably 60 mol% or more.

[0130] (Meth)acrylates can be aliphatic (meth)acrylates or aromatic (meth)acrylates, but aliphatic (meth)acrylates are preferred. By using a polymer with aliphatic (meth)acrylates as the main component (e.g., more than 90% by mass), the generation of foreign matter in the resulting multilayer can be effectively suppressed.

[0131] In addition to (meth)acrylates, other monomers that can be used include styrene monomers such as styrene, maleic anhydride, maleimide monomers such as N-phenylmaleimide, glutaric acid, and glutarimide. Furthermore, monomers that form lactone ring units are also preferred.

[0132] In this embodiment, regarding the acrylic resin, at least one polymer selected from aliphatic (meth)acrylates, such as methyl methacrylate, methyl acrylate, and ethyl acrylate, can be mentioned. Preferably, the main component (e.g., 85% by mass or more) is a methyl methacrylate resin (PMMA: also known as poly(meth)acrylate) obtained by polymerizing methyl methacrylate.

[0133] The weight-average molecular weight of the acrylic resin is not particularly limited, but is preferably 10,000 or more, more preferably 30,000 or more, even more preferably 50,000 or more, even more preferably 60,000 or more, and even more preferably 70,000 or more. Setting it to the lower limit or above, it tends to effectively suppress cracking during hot bending. Furthermore, the weight-average molecular weight of the acrylic resin is preferably 250,000 or less, more preferably 200,000 or less, even more preferably 150,000 or less, even more preferably 100,000 or less, and even more preferably 90,000 or less. Setting it to the upper limit or below, it tends to further improve the effect of suppressing flow marks during multilayer molding.

[0134] The glass transition temperature of the acrylic resin layer used in this embodiment is preferably 113°C or higher, more preferably 114°C or higher, even more preferably 115°C or higher, even more preferably 117°C or higher, and even more preferably 120°C or higher. By setting the temperature to the lower limit or higher mentioned above, the effect of preventing cracking of the molded article during hot bending molding of the multilayer body tends to be further improved. The upper limit is not particularly limited; for example, 200°C or lower is practical.

[0135] The acrylic resin layer is preferably formed from a composition containing acrylic resin (a composition for forming an acrylic resin layer). Besides acrylic resin, the composition containing acrylic resin may also contain other components without departing from the spirit of this embodiment. Specific examples of other components include other thermoplastic resins, heat stabilizers, flame retardants, flame retardant additives, ultraviolet absorbers, colorants, antistatic agents, fluorescent whitening agents, antifogging agents, flow improvers, plasticizers, dispersants, antibacterial agents, anti-blocking agents, impact improvers, slip improvers, hue improvers, acid traps, etc. One or more of these components may be used.

[0136] The total amount of the other components mentioned above in the acrylic resin layer forming composition is preferably 0.001 to 5% by mass of the composition, more preferably 0.001 to 2% by mass, and even more preferably 0.01 to 1% by mass.

[0137] Next, the details of the hard coating will be explained. The hard coating included in the multilayer of this embodiment is a layer with a surface hardness higher than that of a polycarbonate resin film or sheet. By including such a hard coating, the surface hardness of the multilayer or molded article can be improved.

[0138] The thickness of the hard coating is preferably 0.5 μm or more, more preferably 1 μm or more, further preferably 2 μm or more, even more preferably 4 μm or more, and even more preferably 5 μm or more. By setting the thickness to the above lower limit or above, there is a tendency to further improve the pencil hardness of the multilayer body obtained by the hard coating. The upper limit of the thickness of the hard coating is preferably 20 μm or less, more preferably 15 μm or less, further preferably 12 μm or less, even more preferably 10 μm or less, and even more preferably 8 μm or less. By setting the thickness to the above upper limit or below, there is a tendency to further improve the processability during hot bending.

[0139] The hard coating is preferably obtained by applying a hard coating material that can be thermosetting or cured by active energy rays and then curing it.

[0140] As an example of a coating cured using active energy rays, a resin composition consisting of one or more monofunctional or polyfunctional (preferably 2 to 10 functional) (meth)acrylate monomers or oligomers can be cited. Preferably, a resin composition containing monofunctional or polyfunctional (preferably 2 to 10 functional) polyurethane (meth)acrylate oligomers can be cited. A photopolymerization initiator as a curing catalyst is preferably added to these resin compositions.

[0141] In addition, examples of thermosetting resin coatings include polysiloxane-based and cross-linked acrylic coatings. Such resin compositions are also commercially available as hard coatings for acrylic or polycarbonate resin films or sheets; the appropriate product should be selected based on its compatibility with the coating line.

[0142] As a hard coating, reference can be made to paragraphs 0045 to 0055 of Japanese Patent Application Publication No. 2013-020130, paragraphs 0073 to 0076 of Japanese Patent Application Publication No. 2018-103518, and paragraphs 0062 to 0082 of Japanese Patent Application Publication No. 2017-213771, and these contents are incorporated into this specification.

[0143] In addition to the above, the multilayer body of this embodiment may also have other layers. Specific examples include adhesive layers, bonding layers, and antifouling layers.

[0144] Furthermore, regarding multilayer bodies, at least one of the following treatments can be applied to at least one surface: fingerprint resistance treatment, anti-glare treatment, weather resistance treatment, antistatic treatment, anti-fouling treatment, and anti-blocking treatment. As an example of the outermost surface of such a multilayer body, a hard coating can be cited. Additionally, anti-blocking treatment refers to a treatment that allows for easy peeling even when the films are tightly adhered to each other; examples include adding an anti-blocking agent and creating irregularities on the surface of the multilayer body.

[0145] Regarding the multilayer body of this embodiment, a main extruder for extruding the resin composition of this embodiment and a secondary extruder for extruding the acrylic resin layer forming composition are used. The resin is melted and extruded according to the conditions of the resin used and introduced into the mold. The layers are stacked inside the mold to form a sheet, or the layers are stacked after the sheet is formed, thereby forming a multilayer body.

[0146] <Molded articles and methods for manufacturing molded articles>

[0147] Next, the molded article of the multilayer body using this embodiment and the manufacturing method of the molded article will be described.

[0148] The molded article of this embodiment is a molded article formed from a multilayer body of this embodiment.

[0149] Furthermore, the multilayer body of this embodiment is also suitable for applications with curved portions due to its excellent heat bending resistance. For example, it is also preferably used for molded articles with a radius of curvature of 50 mmR or less (preferably a radius of curvature of 40 to 50 mmR).

[0150] The molded article of this embodiment can be obtained, for example, by hot bending the multilayer body of this embodiment at 105 to 117°C. The multilayer body of this embodiment has excellent hot bending resistance, which is particularly advantageous when manufacturing molded articles with portions having a radius of curvature of 50 mmR or less. From the viewpoint of springback and crack formation, hot bending at 110°C or higher and 115°C or lower is further preferred.

[0151] <Uses>

[0152] The flat molded body, multilayer body, and molded article of this embodiment can be applied to optical components, design products, anti-reflective molded bodies, etc.

[0153] The flat molded body, multilayer body, and molded article of this embodiment can be applied to components of display devices, electrical and electronic equipment, OA equipment, portable information terminals, mechanical parts, home appliances, vehicle parts, various containers, lighting equipment, etc. Among these, they are particularly suitable for housings of various displays, electrical and electronic equipment, OA equipment, portable information terminals, and home appliances; surface films, optical materials, and optical discs of lighting equipment and vehicle parts (especially vehicle interior trim parts), smartphones, and touch panels. In particular, the molded body of this embodiment is preferably used as a sensor film for touch panels and an anti-reflective molded body for various displays.

[0154] Furthermore, the multilayer body of this embodiment is also suitable for applications with bending portions due to its excellent thermal bending resistance. For example, it is also preferred for multilayer bodies and molded articles having portions with a radius of curvature of 50 mmR or less (preferably a radius of curvature of 40 to 50 mmR).

[0155]

Example

[0156] The present invention will be described in more detail below with examples. The materials, amounts, proportions, processing contents, processing order, etc., shown in the following examples can be appropriately changed without departing from the spirit of the invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[0157] When the measuring equipment used in the embodiments is not readily available due to obsolescence or other reasons, other equipment with equivalent performance can be used for measurement.

[0158] 1. Raw material: Polycarbonate resin

[0159] T-1380: Bisphenol A type polycarbonate resin using hexadecyl p-hydroxybenzoate as a capping agent, manufactured by Mitsubishi Gas Chemical Co., Ltd., weight average molecular weight: 55,000, Tg: 124℃.

[0160] E-2000: Bisphenol A type polycarbonate resin with p-tert-butylphenyl terminal structure, manufactured by Mitsubishi Engineering Plastics Co., Ltd., E-2000F, weight average molecular weight: 53,000, Tg: 149℃.

[0161] <Phosphate>

[0162] PX-200: Resorcinol poly(di-2,6-dimethyl) phosphate, manufactured by Daihachi Chemical Industry Co., Ltd.

[0163] CR-741: Bisphenol A bis(diphenyl) phosphate, manufactured by Daihachi Chemical Industry Co., Ltd.

[0164] <Phosphites (for comparison)>

[0165] HP-10: manufactured by ADEKA Co., Ltd.

[0166] S-9228PC: Manufactured by DOVER Chemical Corporation.

[0167] <Mold Release Agent>

[0168] S-100A: Glyceryl monostearate, manufactured by Riken Vitamin Co., Ltd., RIKEMAL S-100A.

[0169] <Acrylic resin layer>

[0170] HT121: Manufactured by Arkema Corporation, acrylic resin (PMMA), ALTUGLAS (registered trademark) HT121, Tg: 115℃, weight average molecular weight: 75,800.

[0171] TN001: Manufactured by Mitsubishi Chemical Corporation, acrylic resin (PMMA), TN001 Tg: 118℃, weight average molecular weight: 82,600.

[0172] hw55: Manufactured by Daicel-Evonik Ltd., acrylic resin (styrene: maleic anhydride: MMA mass ratio = 15%: 9%: 76%), PLEXIIGLAS hw55, Tg: 120℃, weight average molecular weight: 109,000.

[0173] PM120N: Manufactured by Asahi Kasei Chemicals Co., Ltd., acrylic resin (styrene: N-phenylmaleimide: MMA mass ratio = 4%: 15%: 81%), DELPET PM120N, Tg: 124℃, weight average molecular weight: 121,000.

[0174] 2. Examples 1-7, Comparative Examples 1-7

[0175] <Preparation of polycarbonate resin granules (resin composition)>

[0176] The components listed in Tables 1-4 were measured according to the amounts added (the amounts added in Tables 1-4 are expressed in parts by mass). After mixing for 15 minutes using a drum, the mixture was melt-blended at a barrel temperature of 280°C using a vented twin-screw extruder with a screw diameter of 32 mm. Polycarbonate resin granules (resin composition) were then obtained using a sprue cutter.

[0177] <Manufacturing of Polycarbonate Resin Films (Flat-Shaped Molded Body)>

[0178] Using the obtained polycarbonate resin granules (Examples 1-7, Comparative Examples 1-7), polycarbonate resin films were manufactured according to the following method.

[0179] Using a T-die melt extruder with a vented twin-screw extruder (manufactured by Nippon Steel Corporation, "TEX30α") ​​containing a 32mm barrel diameter and a screw L / D = 31.5, the aforementioned polycarbonate resin granules were molten and extruded through the first and second rolls. The granules were not pressed together using the first and second rolls; instead, only the second roll was used for cooling and solidification to produce a polycarbonate resin film. The barrel and die temperatures were maintained at 280°C.

[0180] The speed of the second roller is changed to adjust the final film thickness to 100 μm.

[0181] The details of the second roller used are as follows.

[0182] • Second roller: Manufactured by JSW, rigid metal roller (surface: hard chrome treated).

[0183] Mandrel diameter: 250mm outer diameter × 600mm width

[0184] Roller temperature: 130℃

[0185] <Determination of Glass Transition Temperature (Tig)>

[0186] Regarding the glass transition temperature (Tig) of various resins and resin compositions, the glass transition temperature during the second heating cycle was determined by performing two cycles of heating and cooling under the differential scanning calorimetry (DSC) conditions described below.

[0187] The intersection of the line obtained by extending the baseline from the low temperature side to the high temperature side and the tangent at the inflection point is taken as the glass transition temperature at the start. The intersection of the line obtained by extending the baseline from the high temperature side to the low temperature side and the tangent at the inflection point is taken as the glass transition temperature at the end. The midpoint between the glass transition temperature at the start and the end is taken as the intermediate glass transition temperature. In this invention, the glass transition temperature at the start is used as the glass transition temperature (Tig). The starting temperature was measured to be 30°C, the heating rate was 10°C / min, the reaching temperature was 250°C, and the cooling rate was 20°C / min.

[0188] The measuring apparatus used was a differential scanning calorimeter (DSC, manufactured by Hitachi Advanced Technology Co., Ltd., “DSC7020”).

[0189] <Membrane damp heat test>

[0190] Cut a 50mm long and 50mm wide sheet from near the center of the polycarbonate resin film obtained above. Next, immerse the polycarbonate resin sheet in an environmental testing chamber set at 85°C and 85% relative humidity (RH) for 200 hours. Then, move it, along with its support, to an environmental testing chamber set at 23°C and 50% relative humidity for 4 hours.

[0191] <Measurement of Haze>

[0192] The haze (%) of the polycarbonate resin film (before the damp heat test) obtained above was measured using a haze meter under D65 light source and 10° field of view conditions.

[0193] In addition, the haze of the polycarbonate resin film after the above-mentioned damp heat test was also measured.

[0194] The haze meter used is the "HM-150" manufactured by Murakami Color Technology Research Institute Co., Ltd.

[0195] <Methods for determining weight-average molecular weight>

[0196] The weight-average molecular weight (Mw) of the polycarbonate resin membrane obtained above (before the damp heat test) and the polycarbonate resin membrane after the damp heat test were determined by gel permeation chromatography.

[0197] Specifically, the gel permeation chromatography apparatus used was an LC-20AD system (manufactured by Shimadzu Corporation) as the column, connected to an LF-804 (manufactured by Shodex Corporation). The column temperature was 40°C. An RID-10A (manufactured by Shimadzu Corporation) RI detector was used. Chloroform was used as the eluent, and a calibration curve was prepared using standard polystyrene manufactured by Tosoh Corporation.

[0198] When the aforementioned gel permeation chromatography apparatus, column, and detector are not readily available, other apparatuses with equivalent performance can be used for the determination.

[0199] <Manufacturing of Multilayers (Multilayer Sheets) of Polycarbonate Resin Sheets and Acrylic Resin Layers>

[0200] Multilayer bodies are formed using a multilayer extrusion apparatus having a manifold die connected to each extruder on a multilayer extruder. This multilayer extruder includes a single-screw extruder with a screw diameter of 32 mm, a single-screw extruder with a screw diameter of 65 mm, a feed block connected to all extruders, and a 650 mm wide T-die connected to the feed block. Acrylic resin granules for layer formation, as shown in Tables 1-4, are introduced into the single-screw extruder with a screw diameter of 32 mm, and extrusion is performed at a barrel temperature of 250°C and an ejection rate of 3.6 kg / h. Alternatively, resin compositions (polycarbonate resin granules) as shown in Tables 1-4 are continuously introduced into the single-screw extruder with a screw diameter of 65 mm, and extrusion is performed at a barrel temperature of 280°C and an ejection rate of 32.4 kg / h. The feed block, connected to the entire extruder, has two types of two-layer distribution pins. At a temperature of 270°C, it feeds in acrylic resin granules (as shown in Tables 1-4) and polycarbonate resin granules (as shown in Tables 1-4) and laminates them. The material is extruded into a sheet using a T-die connected to its front end at a temperature of 270°C. While cooling, a mirror finish is transferred using three mirror-finishing rollers with temperatures of 130°C, 140°C, and 180°C from the upstream side, resulting in a multilayer of acrylic resin layers and polycarbonate resin sheets. The total thickness of the central portion of the resulting multilayer is 1000 μm, and the thickness of the acrylic resin layer is 100 μm.

[0201] <Appearance of flow marks>

[0202] During the formation of the polycarbonate resin sheet-acrylic resin layer multilayer, the presence of flow marks is visually inspected. The evaluation is conducted by five experts, and a majority vote is used to determine the outcome.

[0203] <Foreign Object>

[0204] Under the extrusion conditions described above for the manufacture of a multilayer (multilayer sheet) of polycarbonate resin sheet and acrylic resin layer, after 2 hours of continuous operation, the resulting multilayer was visually inspected, and the number of gel-like foreign matter defects was counted and evaluated. Gel-like foreign matter defects are high molecular weight components of a transparent resin composition; they are defects that disrupt the interface layer of the multilayer and are counted. Evaluation was conducted by 5 experts, and the decision was made by majority vote.

[0205] A: In 2m 2 Within the area, the average number of defects is less than 3;

[0206] B: In 2m 2 Within the area, the average number of defects is more than 3.

[0207] <Coating of Hard Coatings>

[0208] A total of 100 parts by weight of a mixture consisting of 60 parts by weight of a 6-functional polyurethane acrylate oligomer (product name: U6HA, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 35 parts by weight of PEG200# diacrylate (product name: 4EG-A, manufactured by Kyoei Chemical Co., Ltd.), and 5 parts by weight of an oligomer containing fluorinated, hydrophilic, lipophilic, and UV-reactive groups (product name: RS-90, manufactured by DIC Co., Ltd.), with the addition of 1% by weight of a photopolymerization initiator (product name: I-184 [compound name: 1-hydroxy-cyclohexylphenyl ketone] manufactured by BASF Co., Ltd.), was applied to the surface of the acrylic resin layer of the multilayer material using a bar coater and irradiated with a metal halide lamp (20mW / cm²). 2 The hard coating is cured in 5 seconds. The resulting hard coating is 6 μm thick.

[0209] <Hot pressing processability>

[0210] For the multilayer body with hard coating obtained above, convex (male) and concave (female) molds with a radius of curvature of 50 mmR are made. Before molding, the body is preheated at 90°C for 1 minute, positioned in the mold with the hard coating side convex, and pressed at the mold temperature of 115°C for 3 minutes, followed by natural cooling, thereby producing a hot-pressed body.

[0211] <<Cracks in the Bending Section>>

[0212] The cracks in the bent portions of the hot-pressed body were visually evaluated. The evaluation of the cracks in the bent portions was conducted according to the following criteria and as described below. The evaluation was performed by five experts, and the judgment was made by majority vote.

[0213] A: No cracks were observed in the bent portion of the hot-pressed molded body;

[0214] B: Cracks can be seen in the bent parts of the hot-pressed molded body.

[0215] <<Rebound>>

[0216] The hot-pressed body was subjected to springback evaluation along a 50mmR cylinder according to the following criteria. The evaluation was conducted by five experts, with a majority vote determining the outcome.

[0217] A: Along the cylinder. (No springback)

[0218] B: Not along the cylinder. (There is springback.)

[0219] <Damp heat test after hot pressing>

[0220] The hot-pressed multilayer body was placed in an environmental testing machine set at 85°C and 85% relative humidity and maintained at this condition for 200 hours. Afterwards, the appearance of the sheet was evaluated as follows. The evaluation was conducted by five experts, with a majority vote determining the final result.

[0221] A: The appearance remains unchanged;

[0222] B: We have observed some changes, such as whitening of the film and inability to maintain the shape of the thermoformed product.

[0223] Table 1

[0224]

[0225] Table 2

[0226]

[0227] Table 3

[0228]

[0229] Table 4

[0230]

Claims

1. A resin composition, characterized by, contains: an aromatic polycarbonate resin having a terminal structure represented by formula (1) 70 to 99 parts by mass; a phosphoric acid ester 1 to 12 parts by mass; and another thermoplastic resin other than the aromatic polycarbonate resin having the terminal structure represented by formula (1) 0 to 29 parts by mass, the content of the phosphoric acid ester in the resin composition is 1.5 to 12 mass%, the phosphoric acid ester is selected from the group consisting of resorcinol poly(di-2,6-dimethylphenyl) phosphate and bisphenol A bisdiphenyl phosphate, In formula (1), R 1 represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 30 carbon atoms, R 2 each independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms, n represents an integer of 0 to 4, and * is a bonding site with another site.

2. The resin composition according to claim 1, wherein: the other thermoplastic resin comprises an aromatic polycarbonate resin having a terminal structure represented by formula (2), In formula (2), R 2 each independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms, t-Bu represents a tert-butyl group, n represents an integer of 0 to 4, and * represents a bonding site with another site.

3. The resin composition according to claim 1 or 2, wherein: the glass transition temperature of the resin composition, as measured by differential scanning calorimetry, is 120°C or lower.

4. The resin composition according to claim 1 or 2, wherein: the glass transition temperature of the resin composition, as measured by differential scanning calorimetry, is 100°C or higher.

5. The resin composition according to claim 1 or 2, wherein: the haze of a flat plate-shaped molded body of the resin composition, having a thickness of 100 μm, after being treated at 85°C and 85% relative humidity for 200 hours, is 20% or lower.

6. The resin composition according to claim 1 or 2, wherein: the difference in weight average molecular weight Mw before and after treatment of the resin composition at 85°C and 85% relative humidity for 200 hours is 10,000 or lower.

7. A flat plate-shaped molded body, wherein: it is formed from the resin composition according to any one of claims 1 to 6.

8. The flat plate-shaped molded body according to claim 7, wherein: the thickness is 10 to 5,000 μm.

9. A multi-layer body, wherein: it has a flat plate-shaped molded body according to claim 7 or 8 and a layer containing an acrylic resin.

10. The multi-layer body according to claim 9, wherein: the total thickness of the multi-layer body is 10 to 10,000 μm.

11. The multi-layer body according to claim 9 or 10, wherein: it further has a hard coat layer, which is laminated in the order of flat plate-shaped molded body, layer containing an acrylic resin, and hard coat layer.

12. A molded article, wherein: it is formed from the multi-layer body according to any one of claims 9 to 11 and has a portion having a radius of curvature of 50 mmR or lower.

13. A method for producing a molded article, comprising the step of heat-bending the multi-layer body according to any one of claims 9 to 11 at 105 to 117°C.

14. The method for producing a molded article according to claim 13, wherein: the molded article has a portion having a radius of curvature of 50 mmR or lower. ​

Images