CN114507434A

CN114507434A - Resin composition, flat plate-like molded article, multilayer body, and method for producing molded article

Info

Publication number: CN114507434A
Application number: CN202111356769.3A
Authority: CN
Inventors: 山口圆; 樱井香里; 冨田惠介
Original assignee: Mitsubishi Gas Chemical Co Inc
Current assignee: Mitsubishi Gas Chemical Co Inc
Priority date: 2020-11-17
Filing date: 2021-11-16
Publication date: 2022-05-17
Also published as: JP2022080269A

Abstract

The present invention addresses the problem of providing a resin composition for producing a polycarbonate resin film or sheet that does not cause springback even when subjected to thermal bending molding together with an acrylic resin layer and that can provide a multilayer body having excellent moist heat resistance, and a method for producing a flat plate-shaped molded article, a multilayer body, and a molded article using the resin composition. The solution is a resin composition comprising: 70 to 99 parts by mass of an aromatic polycarbonate resin having a terminal structure represented by the formula (1); 1-12 parts by mass of a phosphate ester; and 0 to 29 parts by mass of a thermoplastic resin other than the aromatic polycarbonate resin having a terminal structure represented by the formula (1). In the formula (1), R¹Represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 30 carbon atoms.

Description

Resin composition, flat plate-like molded article, multilayer body, and method for producing molded article

Technical Field

The present invention relates to a resin composition, a flat plate-like molded article, a multilayer body, and a method for producing a molded article.

Background

Polycarbonate resins are widely used in various fields because they are excellent not only in transparency but also in processability and impact resistance as compared with glass and also in the production of toxic gases as compared with other plastic materials, and are also used as materials for thermoforming such as vacuum forming and air pressure forming.

On the other hand, since polycarbonate resins generally have low surface hardness, the surface of molded articles made of polycarbonate resins tends to be easily damaged. In view of the above, when a polycarbonate resin is formed into a film, it has been considered to form a layer containing an acrylic resin or a hard coat layer (protective layer) on the surface thereof so as to prevent damage to the surface of the product.

For example, patent document 1 discloses a resin sheet for molding, which is a laminated sheet having a coating layer mainly composed of an acrylic resin (B) on one surface of a base material layer mainly composed of a polycarbonate resin composition (a) composed of a polymer alloy of an aromatic polycarbonate (a1) and another resin (a2), wherein the absolute value of the difference between the glass transition temperatures of the polycarbonate resin composition (a) and the acrylic resin (B) is within 30 ℃.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 2009-196153

Disclosure of Invention

Technical problem to be solved by the invention

As described above, when a multilayer body in which an acrylic resin layer and a hard coat layer are formed on a film or sheet made of a polycarbonate resin, the acrylic resin generally has a lower glass transition temperature than the polycarbonate resin, and therefore, when thermoforming is performed, particularly when molding is performed using a mold having a small radius of curvature, the acrylic resin layer is excessively elongated, the hard coat layer cannot follow deformation, and cracks may occur in the hard coat layer. In order to eliminate this phenomenon, it is conceivable to suppress the amount of deformation of acrylic by thermoforming at a low temperature, but when the multilayer body is subjected to hot bending at a low temperature, a phenomenon (springback) occurs in which the multilayer body after hot bending returns to its original shape. Further, it is known that the multilayer body may have a changed appearance when subjected to a test for moisture-heat resistance.

An object of the present invention is to solve the above-described problems and to provide a resin composition for producing a polycarbonate resin film or sheet which does not cause springback even when subjected to thermal bending molding together with an acrylic resin layer and can provide a multilayer body excellent in moist heat resistance, and a method for producing a flat plate-shaped molded article, a multilayer body, and a molded article using the resin composition.

Technical solution for solving technical problem

The present inventors have studied based on the above-mentioned problems, and as a result, have found that the above-mentioned problems can be solved by using a resin composition containing an aromatic polycarbonate resin having a predetermined terminal structure and a phosphoric acid ester.

Specifically, the technical problem is solved by the following technical solutions.

< 1 > a resin composition comprising: 70 to 99 parts by mass of an aromatic polycarbonate resin having a terminal structure represented by the formula (1); 1-12 parts by mass of a phosphate ester; and 0 to 29 parts by mass of a thermoplastic resin other than the aromatic polycarbonate resin having a terminal structure represented by the formula (1).

(in the formula (1), R¹Represents an alkyl group having 8 to 36 carbon atoms or a carbon atom8-30 alkenyl. R²Each 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. The bonding site to other sites. )

< 2 > the resin composition of < 1 >, wherein the other thermoplastic resin comprises an aromatic polycarbonate resin having a terminal structure represented by the formula (2).

(in the formula (2), R²Each 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. The bonding site to other sites. )

< 3 > such as < 1 > or < 2 >, wherein the glass transition temperature of the resin composition measured by differential scanning calorimetry is 120 ℃ or lower.

The resin composition according to any one of < 4 > to < 1 > -to < 3 >, wherein the glass transition temperature of the resin composition is 100 ℃ or higher as measured by differential scanning calorimetry.

The resin composition as described in any of < 5 > to < 4 >, wherein the phosphate contains an aromatic ring.

The resin composition of any one of < 6 > to < 1 > -to < 5 >, wherein the resin composition is molded into a flat plate-like molded article having a thickness of 100 μm, and the haze is 20% or less after treatment at 85 ℃ and a relative humidity of 85% for 200 hours.

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

< 8 > a flat plate-like molded body comprising the resin composition as defined in any one of < 1 > to < 7 >.

A plate-like shaped body of < 9 > such as < 8 > and having a thickness of 10 to 5,000 μm.

< 10 > a multilayer body having the flat plate-shaped molded body < 8 > or < 9 > and a layer containing an acrylic resin.

A multilayer body of < 11 > or < 10 > wherein the total thickness of the multilayer body is 10 to 10,000 μm.

A multilayer body of < 12 > such as < 10 > or < 11 > further having a hard coat layer laminated in the order of the flat plate-like molded body, the acrylic resin-containing layer, and the hard coat layer.

< 13 > a molded article comprising the multilayer body as defined in any one of < 10 > -to < 12 > and having a portion with a radius of curvature of 50mmR or less.

< 14 > a method for producing a molded article, comprising the step of hot-bending the multilayer body of any one of < 10 > -12 > at 105-117 ℃.

< 15 > and < 14 > are the molded articles, wherein the molded articles have a curvature radius of 50mmR or less.

Effects of the invention

The present invention can provide a resin composition for producing a polycarbonate resin film or sheet which does not cause springback even when subjected to hot bending molding together with an acrylic resin layer and which can provide a multilayer body having excellent moist heat resistance, and a flat plate-shaped molded article, a multilayer body, and a method for producing a molded article using the resin composition.

Drawings

Fig. 1 is a schematic view showing a layer structure of a multilayer body of the present invention.

Description of the symbols

1: a multilayer body; 2: a flat plate-like molded body (polycarbonate resin film or sheet); 3: an acrylic resin layer; 4: and (3) hard coating.

Detailed Description

Hereinafter, specific embodiments of the present invention (hereinafter, simply referred to as "the present embodiment") will be described in detail. The following embodiments are examples for illustrating the present invention, and the present invention is not limited to the embodiments.

In the present specification, "to" is used to include numerical values before and after the "to" as a lower limit value and an upper limit value.

In the present specification, unless otherwise specified, various physical property values and characteristic values are values at 23 ℃.

The flat plate-like molded body and the multilayer body in the present specification each include a case of forming a shape of a film or a sheet. "film" and "sheet" each refer to a thin, generally flat shaped body with respect to length and width. There is no clear distinction between "film" and "sheet", and in general, a film having a thickness of 250 μm or less is referred to as "film"; a sheet having a thickness of 250 μm or more is referred to as a "sheet". In the present specification, "film" and "sheet" may be a single layer or a plurality of layers.

In addition, "parts by mass" in the present specification means relative amounts of the components; "mass%" means the absolute amount of the component.

In the present specification, "(meth) acrylic acid" means both or either one of acrylic acid and methacrylic acid.

In the present specification, a flat plate-shaped molded article formed from the resin composition of the present embodiment may be referred to as a "polycarbonate resin film" or a "polycarbonate resin sheet"; the layer containing an acrylic resin is referred to as an "acrylic resin layer".

When the measurement method of the standard shown in the present specification and the like are different depending on the year, the standard is set to the standard at the time of application unless otherwise specified.

The resin composition of the present embodiment is characterized by containing: 70 to 99 parts by mass of an aromatic polycarbonate resin having a terminal structure represented by the formula (1); 1-12 parts by mass of a phosphate ester; and 0 to 29 parts by mass of a thermoplastic resin other than the aromatic polycarbonate resin having a terminal structure represented by the formula (1). With such a configuration, a polycarbonate resin film or sheet which does not cause springback and can provide a multilayer body excellent in moist heat resistance can be provided. Further, a polycarbonate resin film or sheet having low initial haze and low haze after a wet heat test and having little change in molecular weight after the wet heat test can be obtained. Further, when the acrylic resin layer and the polycarbonate resin film or sheet are formed into a multilayer body, the occurrence of flow marks and foreign matter can be suppressed, and the occurrence of cracks after thermal bending can be suppressed.

(in the formula (1), R¹Represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 30 carbon atoms. R²Each 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. The bonding site to other sites. )

The reason for this is presumed to be that the glass transition temperature of the resin composition can be lowered and other performances are less likely to be affected by using an aromatic polycarbonate resin having a predetermined terminal structure and blending a phosphoric acid ester. As a result, thermal deterioration of the resin composition after the wet heat test can be suppressed. Further, it is presumed that when a multilayer body of a polycarbonate resin film or sheet and an acrylic resin layer is formed, the difference in glass transition temperature between the polycarbonate resin film or sheet and the acrylic resin layer is small, and thus the multilayer body has excellent thermal bending properties.

When an additive is added to a resin, the glass transition temperature is lowered, but other properties are often adversely affected. For example, phosphites readily react with peroxides in the resin. In the present embodiment, various studies have been conducted as additives, and it has been found that phosphate esters are suitable.

< aromatic polycarbonate resin >

The resin composition of the present embodiment contains an aromatic polycarbonate resin having a terminal structure represented by formula (1). By using the aromatic polycarbonate resin having a terminal structure represented by formula (1), the glass transition temperature of the polycarbonate resin can be lowered.

R¹Represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 30 carbon atoms, preferably an alkyl group or alkenyl group having 10 or more carbon atoms, more preferably an alkyl group or alkenyl group having 12 or more carbon atoms, and still more preferably an alkyl group 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 body. In addition, R¹Preferably an alkyl group or alkenyl group having 22 or less carbon atoms, and more preferably an alkyl group or alkenyl group having 18 or less carbon atoms. This improves the compatibility with other resins. R¹Preferably an alkyl group. The alkyl group and the alkenyl group are preferably linear or branched, and more preferably linear.

In the present embodiment, R¹Cetyl is particularly preferred.

In addition, R¹It may be in any of the meta, para, or ortho positions, preferably in the meta or para position, and more preferably in the para position.

R²Each independently represents 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.

n represents an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.

The terminal structure represented by the formula (1) can be added to the polycarbonate resin by using an end-capping agent such as cetyl paraben. The details of these can be referred to the descriptions in paragraphs 0022 to 0030 of Japanese patent application laid-open Nos. 2019 and 002023, and these contents are incorporated into the present specification.

In the aromatic polycarbonate resin having a terminal structure represented by formula (1) in the present embodiment, the terminal structure represented by formula (1) may be 1 kind or 2 or more kinds.

In the present embodiment, the aromatic polycarbonate resin having a terminal structure represented by 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 1 terminal structure represented by formula (1).

The bisphenol a polycarbonate resin may have a structural unit derived from a material other than a carbonate structural unit of bisphenol a and a derivative thereof. Examples of the dihydroxy compound constituting such another structural unit include aromatic dihydroxy compounds described in paragraph 0014 of Japanese patent application laid-open No. 2018-154819, which are incorporated herein by reference.

In the bisphenol polycarbonate resin of the present embodiment, the carbonate structural unit derived from bisphenol a and a derivative thereof is preferably 90% by mass or more, more preferably 95% by mass or more, and still more preferably 97% by mass or more of the total structural units excluding the terminal structure.

The method for producing the bisphenol a polycarbonate resin is not particularly limited, and any method may be employed. Examples thereof include interfacial polymerization, melt transesterification, pyridine method, ring-opening polymerization of cyclic carbonate compounds, and solid-phase transesterification of prepolymers.

The weight average molecular weight of the aromatic polycarbonate resin having a terminal structure represented by formula (1) is not particularly limited, but is preferably 10,000 or more, more preferably 20,000 or more, further preferably 30,000 or more, further preferably 40,000 or more, and further preferably 50,000 or more. When the lower limit value is not less than the above-mentioned lower limit value, the impact resistance and the flow mark suppression during molding of the multilayer body tend to be further improved. The weight average molecular weight of the aromatic polycarbonate resin having a terminal structure represented by formula (1) is preferably 200,000 or less, more preferably 150,000 or less, still more preferably 100,000 or less, yet more preferably 80,000 or less, and yet more preferably 60,000 or less. When the upper limit value is not more than the above-mentioned upper limit value, the moldability of the multilayer body tends to be improved.

The glass transition temperature of the aromatic polycarbonate resin having a terminal structure represented by formula (1) used in the present embodiment is preferably 145 ℃ or lower, more preferably 140 ℃ or lower, still more preferably 135 ℃ or lower, yet more preferably 130 ℃ or lower, and yet more preferably 125 ℃ or lower. When the upper limit value is not more than the above-mentioned upper limit value, the multilayer body tends to have further improved hot bending formability. The glass transition temperature of the aromatic polycarbonate resin having a terminal structure represented by formula (1) used in the present embodiment is preferably 121 ℃ or higher, more preferably 122 ℃ or higher, and still more preferably 123 ℃ or higher. When the lower limit value is not less than the above lower limit value, the durability in an environmental test such as a damp heat test or a high temperature test tends to be further improved.

< other thermoplastic resin >

The resin composition of the present embodiment may contain a thermoplastic resin other than the aromatic polycarbonate resin having a terminal structure represented by formula (1). The inclusion of another thermoplastic resin tends to adjust the glass transition temperature of the resin and improve the durability in environmental tests such as a moist heat test and a high temperature test.

The other thermoplastic resin is not particularly limited as long as it is a thermoplastic resin that can be melt-blended with the aromatic polycarbonate resin having a terminal structure represented by formula (1), and a known thermoplastic resin can be used.

Examples of the other thermoplastic resin include other polycarbonate resins other than the aromatic polycarbonate resin having a terminal structure represented by formula (1), polyester resins (preferably aromatic polyester resins), and acrylic resins (preferably aromatic acrylic resins), and preferably other polycarbonate resins other than the aromatic polycarbonate resin having a terminal structure represented by formula (1).

The other polycarbonate resin is preferably an aromatic polycarbonate resin, and more preferably a bisphenol a polycarbonate resin.

The other polycarbonate resin is preferably an aromatic polycarbonate resin having a terminal structure represented by formula (2). By using such an aromatic polycarbonate resin, in addition to the above-described effects, the transparency of the flat plate-like molded article tends to be further improved.

In the formula (2), R²And n is as defined for R in formula (1)²The same as n, and the same preferable ranges.

In the aromatic polycarbonate resin having a terminal structure represented by formula (2) in the present embodiment, the terminal structure represented by formula (2) may be 1 kind or 2 or more kinds.

In the present embodiment, the aromatic polycarbonate resin having a terminal structure represented by formula (2) is preferably a bisphenol a polycarbonate resin. Further, it is preferable that 50 mol% or more of the bisphenol A polycarbonate resin has at least 1 terminal structure represented by the formula (2).

The bisphenol a polycarbonate resin may contain other structural units than carbonate structural units derived from bisphenol a and derivatives thereof. Examples of the dihydroxy compound constituting such another structural unit include aromatic dihydroxy compounds described in paragraph 0014 of Japanese patent application laid-open No. 2018-154819, which are incorporated herein by reference.

The carbonate structural unit derived from bisphenol a and its derivatives in the bisphenol type polycarbonate resin in the present embodiment is preferably 90 mass% or more, more preferably 95 mass% or more, and still more preferably 97 mass% or more of the total structural units excluding the terminal structure.

The weight average molecular weight of the other thermoplastic resin (preferably, the aromatic polycarbonate resin having a terminal structure represented by 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, further preferably 40,000 or more, and further preferably 50,000 or more. When the lower limit value is not less than the above-mentioned lower limit value, the impact resistance and the flow mark suppression during molding of the multilayer body tend to be further improved. The weight average molecular weight of the other thermoplastic resin (preferably, the aromatic polycarbonate resin having a terminal structure represented by formula (2)) is preferably 200,000 or less, more preferably 150,000 or less, still more preferably 100,000 or less, yet more preferably 80,000 or less, and yet more preferably 60,000 or less. When the content is not more than the above upper limit, the compatibility with the aromatic polycarbonate resin having a terminal structure represented by the formula (1) tends to be improved, and the transparency of the molded article tends to be further improved.

The glass transition temperature of the other thermoplastic resin (preferably, the aromatic polycarbonate resin having a terminal structure represented by formula (2)) used in the present embodiment is preferably 155 ℃ or lower, more preferably 154 ℃ or lower, even more preferably 153 ℃ or lower, even more preferably 152 ℃ or lower, and even more preferably 151 ℃ or lower. When the upper limit value is not more than the above-mentioned upper limit value, the multilayer body tends to have further improved hot bending formability. The glass transition temperature of the other thermoplastic resin used in the present embodiment (preferably, the aromatic polycarbonate resin having a terminal structure represented by formula (2)) is preferably 145 ℃ or higher. When the lower limit value is not less than the above lower limit value, the durability in an environmental test such as a damp heat test or a high temperature test tends to be further improved.

< phosphate ester >

The resin composition of the present embodiment contains a phosphate ester. By containing the phosphoric acid ester, the glass transition temperature of the obtained polycarbonate resin film or sheet can be lowered, and the influence on other properties can be suppressed.

The kind of the phosphate is not particularly limited, and a known compound can be widely used.

The phosphate preferably contains an aromatic ring, more preferably 2 or more aromatic rings, and further preferably 2 to 10 aromatic rings. By containing an aromatic ring, the compatibility with the aromatic resin compound is improved, and the transparency of the molded article is improved. The phosphate ester is preferably a condensed phosphate ester, a derivative compound thereof, or a condensate thereof. When a condensed phosphoric ester, a derivative compound thereof, or a condensate thereof is used, the volatility is low as compared with that of a general phosphoric ester, and gas is less likely to be generated during molding. In addition, the molecular weight is large as compared with that of a general phosphate ester, and the mechanical properties of the whole resin can be prevented from being reduced. In the present embodiment, the phosphate ester is preferably an aromatic condensed phosphate ester, a derivative compound thereof, or a condensate thereof, and is more preferably an aromatic condensed phosphate ester.

The phosphoric acid ester may also contain halogen atoms, but preferably contains no halogen atoms.

The molecular weight of the phosphate is preferably 500 to 1500 from the viewpoint of compatibility with the resin component and dispersibility.

Examples of the phosphate ester that can be used in the present embodiment include the following compounds.

Aromatic phosphates such as monoethyl phosphate, monobutyl phosphate, methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, dibutyl phosphate, trimethyl phosphate (TMP), triethyl phosphate (TEP), triphenyl phosphate (TPP), tricresyl phosphate (TCP), trixylenyl phosphate (TXP), cresyldiphenyl phosphate (CDP), and 2-ethylhexyl diphenyl phosphate (EHDP), and derivatives and condensates thereof.

The reaction product of phosphorus oxychloride with a divalent phenolic compound and phenol (or alkylphenol). Aromatic condensed phosphates such as resorcinol bis-diphenyl phosphate, resorcinol poly (di-2, 6-xylyl) phosphate, and bisphenol A methylpolyphosphoric acid ester, and their derivative compounds and their condensates.

Tris (chloroethyl) phosphate, tris (chloropropyl) phosphate, tris (dichloropropyl) phosphate, tris (dibromopropyl) phosphate, bis (2, 3-dibromopropyl) -2, 3-dichloropropyl phosphate, bis (chloropropyl) octyl phosphate, and the like, and derivative compounds thereof, and condensates thereof.

Examples of commercially available products include "JAMP-2", "JAMP-4P", "JP-501", "JP-502", "JP-504", "DBP", manufactured by Tokyo chemical Co., Ltd., "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 Daxibo chemical Co., Ltd.

The content of the phosphate ester in the resin composition of the present embodiment is preferably 1 to 12% by mass of the resin composition. By setting the amount to 1% by mass or more, springback can be effectively suppressed, and by setting the amount to 12% by mass or less, warpage of the multilayer body after thermoforming can be effectively suppressed. The upper limit of the content of the phosphate ester is preferably 8% by mass or less, and more preferably 6% by mass or less. The lower limit is preferably 1.5% or more, and more preferably 2% or more.

< blending of the respective ingredients >

The blending ratio of the aromatic polycarbonate resin having a terminal structure represented by formula (1), the phosphate ester and the other thermoplastic resin in the resin composition of the present embodiment is 70 to 99 parts by mass: 1 to 12 parts by mass: 0 to 29 parts by mass, and more preferably 74 to 99 parts by mass: 1 to 8 parts by mass: 0 to 25 parts by mass. By setting such a ratio, a resin composition having a good balance of thermal bending properties and the like can be obtained.

When the resin composition of the present embodiment does not contain any other thermoplastic resin, the blending ratio of the aromatic polycarbonate resin having a terminal structure represented by formula (1) to the phosphoric acid 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 still more preferably 94 to 98 parts by mass/6 to 2 parts by mass.

When the resin composition of the present embodiment contains another thermoplastic resin, the blending ratio of the aromatic polycarbonate resin having a terminal structure represented by formula (1), the phosphate ester and the other thermoplastic resin is preferably 70 to 94 parts by mass: 1 to 12 parts by mass: 5 to 35 parts by mass, and more preferably 70 to 80 parts by mass: 2 to 7 parts by mass: 10 to 30 parts by mass. Among them, as described above, the other thermoplastic resin is preferably an aromatic polycarbonate resin, and more preferably an aromatic polycarbonate resin having a terminal structure represented by formula (2).

In the resin composition of the present embodiment, the total amount of the aromatic polycarbonate resin having a terminal structure represented by formula (1), the phosphate ester, and the other thermoplastic resin is preferably 95% by mass or more, preferably 98% by mass or more, and may be 99% by mass or more of the resin composition. The upper limit of the total amount is 100 mass% or less.

The resin composition of the present embodiment may contain only 1 kind of the aromatic polycarbonate resin having a terminal structure represented by the formula (1), the phosphate ester, and the other thermoplastic resin if necessary, or 2 or more kinds. When 2 or more species are contained, the total amount is preferably in the above range.

< other ingredients >

In addition to the above, the resin composition of the present embodiment may further contain a release agent, a heat stabilizer, a flame retardant aid, an ultraviolet absorber, a colorant, an antistatic agent, a fluorescent brightener, an antifogging agent, a flowability improver, a plasticizer, a dispersant, an antibacterial agent, an antiblocking agent, an impact improver, a slip improver, a hue improver, an acid trapping agent, and the like. These components may be used in 1 kind, or 2 or more kinds may be used in combination.

The total amount of the other components is preferably 0.001 to 5% by mass, more preferably 0.001 to 2% by mass, and still more preferably 0.01 to 1% by mass of the resin composition. The anti-blocking means an effect of inhibiting adhesion between films, and can be achieved by adding an anti-blocking agent or the like.

Mold release agent

The resin composition of the present embodiment preferably contains a release agent. By containing the release agent, a polycarbonate resin film or sheet having more excellent releasability can be obtained.

The release agent includes at least 1 compound selected from the group consisting of an aliphatic carboxylic acid, an ester of an aliphatic carboxylic acid and an alcohol, an aliphatic hydrocarbon compound having a number average molecular weight of 200 to 15,000, and a silicone oil, and preferably an ester of an aliphatic carboxylic acid and an alcohol.

Specific examples of the ester of an aliphatic carboxylic acid and an alcohol include beeswax (a mixture containing melissa palmitate as a main component), stearyl stearate, behenyl behenate, stearyl behenate, glyceryl monopalmitate, glyceryl monostearate, glyceryl distearate, glyceryl tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate, and the like.

Further, as the release agent, the release agents described in paragraphs 0032 of jp 2017 a-226848 and 0056 of jp 2018 a-199745 may be used, and the contents thereof are incorporated in the present specification.

The content of the release agent in the resin composition, when contained, is preferably 0.001 part by mass or more, more preferably 0.005 part by mass or more, and preferably 2 parts by mass or less, more preferably 1 part by mass or less, and further preferably 0.5 part by mass or less with respect to 100 parts by mass of the resin component.

The release agent may be used in 1 kind or 2 or more kinds. When 2 or more species are used, the total amount is preferably in the above range.

< Properties of resin composition >

The glass transition temperature of the resin composition of the present embodiment measured by differential scanning calorimetry is preferably 120 ℃ or lower, more preferably 119 ℃ or lower, still more preferably 118 ℃ or lower, yet more preferably 117 ℃ or lower, and still more preferably 116 ℃ or lower. When the upper limit value is equal to or less than the above-described upper limit value, the effect of suppressing springback during thermal bending tends to be further improved. The glass transition temperature of the resin composition of the present embodiment measured by differential scanning calorimetry is preferably 100 ℃ or higher, more preferably 102 ℃ or higher, still more preferably 105 ℃ or higher, yet more preferably 107 ℃ or higher, and still more preferably 110 ℃ or higher. When the lower limit value is not less than the above lower limit value, the durability in an environmental test such as a damp heat test or a high temperature test tends to be further improved.

The glass transition temperature can be measured by the method described in the examples described later.

The resin composition of the present embodiment preferably has excellent transparency after a wet heat resistance test.

Specifically, the resin composition of the present embodiment has a haze of preferably 20% or less, more preferably 10% or less, further preferably 5% or less, further preferably 2% or less, and further preferably 1% or less after being molded into a flat plate-like molded body having a thickness of 100 μm and treated at 85 ℃ and a relative humidity of 85% for 200 hours. The lower limit of the haze is preferably 0%, but is actually 0.01% or more.

In addition, in the resin composition of the present embodiment, when treated at 85 ℃ and 85% relative humidity for 200 hours, the difference in weight average molecular weight (Mw) between before and after treatment is preferably 10,000 or less, more preferably 8,000 or less, and still more preferably 6,000 or less. The ideal lower limit of the difference is 0, but actually 100 or more.

< Flat shaped body >

The resin composition of the present embodiment is preferably processed into a flat plate-like molded article. That is, the flat plate-like molded body of the present embodiment is formed of the resin composition of the present embodiment. The flat plate-shaped molded article of the present embodiment is excellent in moist heat resistance.

Examples of the flat plate-like molded article include a plate, a film, and a sheet. The flat plate-like molded article may be included in a multilayer body formed by laminating other base materials or the like, as described in detail later. The flat plate-like molded body of the present embodiment may be subjected to bending or the like after being incorporated into a part of the multilayer body.

The lower limit of the thickness of the flat plate-like shaped article is preferably 10 μm or more, more preferably 20 μm or more, further preferably 50 μm or more, and may be 100 μm or more. When the lower limit value is not less than the above-mentioned lower limit value, the molding is easier and the hardness tends to be improved. The upper limit of the thickness of the flat plate-like shaped article is not particularly limited, and is practically 5,000 μm or less.

The flat plate-like molded article of the present embodiment is molded by injection molding, extrusion molding using a T-die, or the like.

< multilayer body >

The flat plate-like molded article of the present embodiment can be used in the form of a multilayer body. The multilayer body of the present embodiment includes the flat plate-like molded body of the present embodiment and a layer containing an acrylic resin (acrylic resin layer).

The thickness (total thickness) of the multilayer body is not particularly limited, but is preferably 10 μm or more, and more preferably 20 μm or more. The thickness of the multilayer body is preferably 10,000 μm or less, more preferably 5,000 μm or less, and may be 2,000 μm or less.

Preferably, the multilayer body of the present embodiment further comprises a hard coat layer. By providing the hard coat layer, the surface hardness of the multilayer body tends to be further improved. The hard coat layer is preferably formed by laminating a flat plate-like molded body, an acrylic resin-containing layer, and a hard coat layer in this order.

Fig. 1 is a schematic view showing an example of the multilayer body of the present embodiment, and as described above, 1 denotes the multilayer body, 2 denotes a flat plate-shaped molded body (polycarbonate resin film or sheet), 3 denotes an acrylic resin layer, and 4 denotes a hard coat layer. The flat plate-like molded body 2, the acrylic resin layer 3, and the hard coat layer 4 may have other layers as long as they are laminated in the above-described order, but preferably do not have other layers, that is, are adjacent to each other, without departing from the spirit of the present embodiment.

Next, the acrylic resin layer will be described. The acrylic resin layer contained in the multilayer body of the present embodiment is a layer containing an acrylic resin (preferably, 80% by mass or more of the layer, more preferably, 90% by mass or more of the layer is an acrylic resin layer). The multilayer body of the present embodiment tends to further increase the hardness (particularly pencil hardness) of the multilayer body by including such an acrylic resin layer.

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, further preferably 60 μm or more, and further preferably 80 μm or more. The upper limit of the thickness of the acrylic resin layer 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 the thickness to such a layer, sufficient scratch resistance and impact resistance can be obtained.

The acrylic resin used in the present embodiment is a polymer of (meth) acrylic acid ester or a polymer of (meth) acrylic acid ester and a monomer other than (meth) acrylic acid ester, and the kind thereof is not particularly limited. The ratio of the (meth) acrylate to the (meth) acrylate is preferably 50 mol% or more, and more preferably 60 mol% or more, with respect to the polymer of the (meth) acrylate and the monomer other than the (meth) acrylate.

The (meth) acrylate may be an aliphatic (meth) acrylate or an aromatic (meth) acrylate, and preferably includes an aliphatic (meth) acrylate. By using a polymer containing an aliphatic (meth) acrylate as a main component (for example, 90 mass% or more), the occurrence of foreign matter in the obtained multilayer body can be effectively suppressed.

Examples of the monomer other than the (meth) acrylate ester include a styrene monomer such as styrene, a maleimide monomer such as maleic anhydride or N-phenylmaleimide, glutaric acid, and glutarimide. In addition, monomers forming a lactone ring unit are also preferably used.

In the present embodiment, as the acrylic resin, at least 1 polymer of methyl methacrylate, methyl acrylate, and ethyl acrylate can be cited as the aliphatic (meth) acrylate. Among them, a methyl methacrylate resin (PMMA: also referred to as poly (methyl (meth) acrylate)) in which a main component (for example, 85 mass% or more) is polymerized from methyl methacrylate is preferable.

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, further preferably 50,000 or more, further preferably 60,000 or more, and further preferably 70,000 or more. By setting the lower limit value or more, the occurrence of cracks during thermal bending can be effectively suppressed. The weight average molecular weight of the acrylic resin is preferably 250,000 or less, more preferably 200,000 or less, still more preferably 150,000 or less, yet more preferably 100,000 or less, and yet more preferably 90,000 or less. When the amount is equal to or less than the upper limit, the effect of suppressing the occurrence of flow marks during the molding of the multilayer body tends to be further improved.

The glass transition temperature of the acrylic resin layer used in the present embodiment is preferably 113 ℃ or higher, more preferably 114 ℃ or higher, still more preferably 115 ℃ or higher, still more preferably 117 ℃ or higher, and still more preferably 120 ℃ or higher. When the lower limit value is not less than the above-described lower limit value, the effect of preventing the occurrence of cracks in the molded article during hot bending of the multilayer body tends to be further improved. The upper limit is not particularly limited, and is practical, for example, at 200 ℃ or lower.

The acrylic resin layer is preferably formed from a composition containing an acrylic resin (composition for forming an acrylic resin layer). The composition containing an acrylic resin may contain other components in addition to the acrylic resin within a range not departing from the gist of the present embodiment. Specific examples of the other components include other thermoplastic resins, heat stabilizers, flame retardants, flame retardant aids, ultraviolet absorbers, colorants, antistatic agents, fluorescent brighteners, antifogging agents, flow improvers, plasticizers, dispersants, antibacterial agents, antiblocking agents, impact improvers, slip improvers, hue improvers, acid scavengers, and the like. These components may be used in 1 kind, or 2 or more kinds may be used in combination.

The total amount of the other components in the composition for forming an acrylic resin layer is preferably 0.001 to 5% by mass, more preferably 0.001 to 2% by mass, and still more preferably 0.01 to 1% by mass of the composition.

Next, the details of the hard coat layer will be described. The hard coat layer contained in the multilayer body of the present embodiment is a layer having a surface hardness higher than that of the polycarbonate resin film or sheet. The inclusion of such a hard coat layer can improve the surface hardness of the multilayer body or the molded article.

The thickness of the hard coat layer is preferably 0.5 μm or more, more preferably 1 μm or more, further preferably 2 μm or more, further preferably 4 μm or more, and further preferably 5 μm or more. When the lower limit value is not less than the above lower limit value, the pencil hardness of the entire multilayer body obtained by the hard coat layer tends to be further improved. The upper limit of the thickness of the hard coat layer is preferably 20 μm or less, more preferably 15 μm or less, further preferably 12 μm or less, further preferably 10 μm or less, and further preferably 8 μm or less. When the upper limit value is not more than the above-described upper limit value, the workability at the time of hot bending tends to be further improved.

The hard coat layer is preferably obtained by coating a hard coat material capable of being cured thermally or capable of being cured by active energy rays and then curing it.

Examples of the active energy ray-curable coating material include resin compositions composed of a single or plural kinds of 1-functional or polyfunctional (preferably 2 to 10-functional) urethane (meth) acrylate monomers or oligomers, and preferably resin compositions containing 1-functional or polyfunctional (preferably 2 to 10-functional) urethane (meth) acrylate oligomers. It is preferable to add a photopolymerization initiator as a curing catalyst to these resin compositions.

Examples of the thermosetting resin coating material include polyorganosiloxane-based coating materials and crosslinking-type acrylic coating materials. Such a resin composition may be commercially available in the form of an acrylic resin, a polycarbonate resin film, or a hard coat agent for sheets, and may be appropriately selected in consideration of compatibility with a coating line.

The hard coat layer can be described in paragraphs 0045 to 0055 in japanese patent application laid-open No. 2013-020130, paragraphs 0073 to 0076 in japanese patent application laid-open No. 2018-103518, and paragraphs 0062 to 0082 in japanese patent application laid-open No. 2017-213771, which are incorporated herein by reference.

The multilayer body of the present embodiment may have other layers in addition to the above. Specific examples thereof include an adhesive layer, and an antifouling layer.

In addition, as for the multilayer body, any one or more of fingerprint resistance treatment, antiglare treatment, weather resistance treatment, antistatic treatment, anti-staining treatment, and anti-blocking treatment may be performed on at least one surface. As an example of the outermost surface of the multilayer body in this case, a hard coat layer can be cited. The anti-blocking treatment is a treatment that can be easily peeled off even if the films adhere to each other, and examples thereof include addition of an anti-blocking agent and provision of irregularities on the surface of the multilayer body.

The multilayer body of the present embodiment can be formed by using a main extruder for extruding the resin composition of the present embodiment and a sub-extruder for extruding the composition for forming an acrylic resin layer, melt-extruding the resins under the conditions of the resins used, introducing the resins into a die, laminating the resins inside the die to form a sheet, or laminating the resins after forming the resin into a sheet.

< molded article and method for producing molded article >

Next, a molded article using the multilayer body of the present embodiment and a method for producing the molded article will be described.

The molded article of the present embodiment is a molded article formed of the multilayer body of the present embodiment.

The multilayer body of the present embodiment is excellent in heat bending resistance, and therefore is suitable for use in applications having a bent portion. For example, the resin composition is also preferably used for a molded article having a portion with a radius of curvature of 50mmR or less (preferably, 40 to 50 mmR).

The molded article of the present embodiment can be obtained by, for example, hot-bending the multilayer body of the present embodiment at 105 to 117 ℃. The multilayer body of the present embodiment is excellent in heat bending resistance, and is particularly advantageous in the case of producing a molded article having a portion with a radius of curvature of 50mmR or less. Among them, from the viewpoint of springback and generation of cracks, it is more preferable to perform hot bending at 110 ℃ or higher and 115 ℃ or lower.

< use >)

The flat plate-like molded body, the multilayer body, and the molded article of the present embodiment can be applied to an optical member, a design product, an antireflection molded body, and the like.

The flat plate-like molded article, multilayer body, and molded article according to the present embodiment can be suitably used for components of display devices, electric and electronic devices, OA devices, portable information terminals, machine parts, home electric appliances, vehicle parts, various containers, lighting devices, and the like. Among these, the resin composition is particularly suitable for various displays, housings of electric and electronic devices, OA devices, portable information terminals, home electric appliances, surface films for lighting devices, vehicle parts (particularly, interior parts for vehicles), smart phones, touch panels, and the like, optical materials, and optical disks. In particular, the molded article of the present embodiment is preferably used as a sensor film for a touch panel and an antireflection molded article for various display panels.

The multilayer body of the present embodiment is excellent in heat bending resistance, and therefore is suitable for use in applications having a bent portion. For example, the resin composition is also preferably used for a multilayer body and a molded article having a portion with a radius of curvature of 50mmR or less (preferably, 40 to 50 mmR).

[ examples ] A method for producing a compound

The present invention will be described more specifically with reference to examples. The materials, the amounts used, the ratios, the contents of the processes, the order of the processes, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

When the measurement device used in the examples is not easily available due to, for example, abolishment of model, the measurement can be performed using other devices having equivalent performance.

1. Raw material polycarbonate resin

T-1380: bisphenol a polycarbonate resin using hexadecyl p-hydroxybenzoate as an end-capping agent, produced by mitsubishi gas chemical co., ltd., weight average molecular weight: 55,000, Tg: at 124 ℃.

E-2000: bisphenol a polycarbonate resin having a terminal structure of p-tert-butylphenyl group, manufactured by mitsubishi engineering plastics corporation, E-2000F, weight average molecular weight: 53,000, Tg: 149 ℃ in a vacuum vessel.

< phosphate ester >

PX-200: resorcinol poly (di-2, 6-xylyl) phosphate, manufactured by Daihachi chemical industries, Ltd.

CR-741: bisphenol A bis diphenyl phosphate, Daba chemical industries, Ltd.

< phosphite (for comparison) >

HP-10: manufactured by ADEKA corporation.

S-9228 PC: manufactured by DOVER Chemical Corporation.

< Release agent >

S-100A: glyceryl monostearate, RikeMAL S-100A available from RikeMAL corporation.

< acrylic resin layer >

HT 121: manufactured by akoma corporation, acrylic resin (PMMA), ALTUGLAS (registered trademark) HT121, Tg: 115 ℃ and weight average molecular weight: 75,800.

TN 001: mitsubishi chemical corporation, acrylic resin (PMMA), TN001 Tg: 118 ℃ and weight average molecular weight: 82,600.

hw 55: manufactured by Daicel-Evonik ltd., acrylic resin (styrene: maleic anhydride: MMA: 15 wt.: 9 wt.: 76 wt%), PLEXIGLAS hw55, Tg: 120 ℃ and weight average molecular weight: 109,000.

PM 120N: manufactured by Asahi Kasei corporation, acrylic resin (styrene: N-phenylmaleimide: MMA: 4 mass%: 15 mass%: 81 mass%), DELPET PM120N, Tg: 124 ℃ and weight average molecular weight: 121,000.

2. Examples 1 to 7 and comparative examples 1 to 7

< production of polycarbonate resin pellets (resin composition) >

The amounts of the respective components described in tables 1 to 4 were measured in the amounts described in tables 1 to 4 (the amounts of the respective components added in tables 1 to 4 are expressed in parts by mass). Thereafter, the mixture was mixed for 15 minutes by a tumbler, and then melt-kneaded at a cylinder temperature of 280 ℃ by a twin-screw extruder (TEX 30. alpha.) with a vent having a screw diameter of 32mm by a strand cutter to obtain polycarbonate resin pellets (resin composition).

< production of polycarbonate resin film (Flat plate-shaped molded article) >

Using the obtained polycarbonate resin pellets (examples 1 to 7 and comparative examples 1 to 7), a polycarbonate resin film was produced by the following method.

The polycarbonate resin pellets obtained above were extruded in a molten state using a T-die melt extruder (manufactured by japan steel-making corporation, "TEX 30 α") comprising a double-screw extruder with a vent having a cylinder diameter of 32mm and a screw L/D of 31.5, at a discharge rate of 10Kg/h and a screw rotation speed of 63rpm, and passed between a first roll and a second roll, and cooled and solidified only by the second roll without being pressed by the first roll and the second roll, thereby producing a polycarbonate resin film. In such a way that the barrel and die temperature was 280 ℃.

The film thickness finally obtained was adjusted to 100 μm by changing the roll speed of the second roll.

Details of the second roller used are as follows.

A second roller: metal rigid body roll manufactured by JSW corporation (surface: hard chrome treatment)

Diameter of the mandrel: outer diameter 250mm x width 600mm

Roll temperature: 130 deg.C

< determination of glass transition temperature (Tig) >

The glass transition temperature (Tig) of each resin and resin composition was measured by performing two-cycle temperature rise and temperature fall under the following differential scanning calorimetry (DSC measurement) conditions, and measuring the glass transition temperature at the time of temperature rise in the second cycle.

When the intersection of a straight line extending from the base line on the low temperature side to the high temperature side and a tangent to the inflection point is defined as a starting glass transition temperature, the intersection of a straight line extending from the base line on the high temperature side to the low temperature side and a tangent to the inflection point is defined as an ending glass transition temperature, and the intermediate point between the starting glass transition temperature and the ending glass transition temperature is defined as an intermediate glass transition temperature, the starting glass transition temperature is defined as a glass transition temperature (Tig) in the present invention. The measurement start temperature was 30 ℃, the rate of temperature rise was 10 ℃/min, the arrival temperature was 250 ℃, and the rate of temperature decrease was 20 ℃/min.

The measurement apparatus used was a differential scanning calorimeter (DSC, manufactured by Hitachi Kagaku K.K. 'DSC 7020').

< damp Heat test of Membrane >

A film piece 50mm in length and 50mm in width was cut out from the vicinity of the center of the polycarbonate resin film obtained above. Subsequently, the polycarbonate resin film was put into an environmental tester set at a temperature of 85 ℃ and a Relative Humidity (RH) of 85%, and kept in this state for 200 hours. Then, the sample was transferred together with the holder to an environmental tester set at 23 ℃ and 50% relative humidity, and the sample was held in this state for 4 hours.

< determination of haze >

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

In addition, the haze of the polycarbonate resin film after the above-mentioned wet heat test was also measured.

The haze meter used "HM-150" manufactured by color technology research institute in village.

< method for measuring weight average molecular weight >

The weight average molecular weights (Mw) of the polycarbonate resin film obtained above (before the moist heat test) and the polycarbonate resin film after the moist heat test were measured by gel permeation chromatography.

Specifically, an LC-20 AD system (manufactured by Shimadzu corporation) was used as a gel permeation chromatography apparatus, and LF-804 (manufactured by Shodex) was connected to the apparatus as a column. The column temperature was 40 ℃. As the detector, an RI detector of RID-10A (manufactured by Shimadzu corporation) was used. As the eluent, chloroform was used, and a calibration curve was prepared using standard polystyrene manufactured by Tosoh corporation.

When the gel permeation chromatography, the column, and the detector are not easily available, the measurement can be performed using other devices having equivalent performance.

< production of multilayer body (multilayer sheet) of polycarbonate resin sheet-acrylic resin layer >

Multilayer bodies were molded using a multilayer extrusion apparatus having a manifold die attached to each extruder on a multilayer extruder having a single screw extruder with a screw diameter of 32mm, a single screw extruder with a screw diameter of 65mm, a feed block attached to all extruders, and a 650mm width T die attached to the feed block. The pellets for forming an acrylic resin layer shown in tables 1 to 4 were introduced into a single-screw extruder having a screw diameter of 32mm, and extruded under conditions of a cylinder temperature of 250 ℃ and a discharge rate of 3.6 kg/h. Further, the resin compositions (polycarbonate resin pellets) shown in tables 1 to 4 were continuously introduced into a single-screw extruder having a screw diameter of 65mm, and extruded at a cylinder temperature of 280 ℃ and an ejection rate of 32.4 kg/h. The feeder block connected to all the extruders had two kinds of distribution pins, and the acrylic resin layer-forming pellets shown in tables 1 to 4 and the polycarbonate resin pellets shown in tables 1 to 4 were introduced at a temperature of 270 ℃ and laminated. The sheet was extruded into a sheet form by a T die connected at the tip thereof and having a temperature of 270 ℃ and cooled while transferring the mirror surface by 3 mirror-finished rolls having a temperature of 130 ℃, 140 ℃ and 180 ℃ from the upstream side, to obtain a multilayer body of an acrylic resin layer and a polycarbonate resin sheet. The thickness of the entire central portion of the obtained multilayer body was 1000 μm, and the thickness of the acrylic resin layer was 100 μm.

< appearance of flow marks >

When a multilayer body of a polycarbonate resin sheet-acrylic resin layer was formed, the presence or absence of flow marks was visually confirmed. Evaluation was performed by 5 experts and judged in a majority voting manner.

< foreign body >

After 2 hours of continuous operation under the extrusion conditions in the above production of the multilayer body (multilayer sheet) of the polycarbonate resin sheet-acrylic resin layer, the obtained multilayer body was visually observed, and the number of defects in the gel-like foreign matter was counted and evaluated. The gel-like foreign matter is a high molecular weight material of the resin composition exhibiting transparency, and is a defect due to disturbance of the interface layer of the multilayer body and counted. Evaluation was performed by 5 experts and judged in a majority voting manner.

A: at 2m²The number of defect points in the area of (2) is less than 3 on average;

b: at 2m²The number of defect points in the area (2) is averagely more than 3.

< hard coating application >

To 100 parts by mass of a total of 60 parts by mass of a 6-functional urethane acrylate oligomer (product name: U6HA, manufactured by Mitsumura chemical Co., Ltd.), 35 parts by mass of PEG200# diacrylate (product name: 4 EG-A, manufactured by Kyowa chemical Co., Ltd.), and 5 parts by mass of an oligomer containing a fluorine group, a hydrophilic group, a lipophilic group and a UV reactive group (product name: RS-90, manufactured by DIC Co., Ltd.), 1 part by mass of a photopolymerization initiator (product name: I-184 (product name: 1-hydroxy-cyclohexylphenyl ketone) was added, and the resulting coating material was applied to the surface of the acrylic resin layer of the multilayer body prepared above by a bar coater, and a metal halide lamp (20 mW/cm) was irradiated²) And 5 seconds, curing the hard coating. The thickness of the formed hard coat layer was 6 μm.

< processability by Hot Press Molding >

For the multilayer body having a hard coat layer obtained above, a male (male) mold and a female (female) mold having a curvature radius of 50mmR were prepared. The hot-pressed molded article was prepared by preheating at 90 ℃ for 1 minute before molding, placing the article in a mold so that the hard coat layer side is convex, pressing the article at a mold temperature of 115 ℃ for 3 minutes, and then naturally cooling the article.

< cracks in curved parts >

The crack in the bent portion of the hot-pressed molded article was evaluated visually. The cracks in the bent portions were evaluated as follows according to the following criteria. Evaluation was performed by 5 experts and judged in a majority voting manner.

A: no cracks were observed in the bent portions of the hot-pressed molded bodies;

b: cracks were observed in the bent portions of the hot-pressed molded bodies.

(rebound) >

The hot-pressed molded article was pressed along a cylinder of 50mmR, and the springback was evaluated as follows according to the following criteria. Evaluation was performed by 5 experts and judged in a majority voting manner.

A: along the cylinder. (without rebound)

B: not along the cylinder. (with rebound)

< test on Wet Heat after Hot Press Molding >

The multilayer body after hot press molding was put into an environmental tester set at a temperature of 85 ℃ and a relative humidity of 85%, and kept in this state for 200 hours. After that, the sheet appearance was evaluated as follows. Evaluation was performed by 5 experts and judged in a majority voting manner.

A: the appearance is not changed;

b: some variations were seen such as sheet whitening, failure to maintain the shape of the hot press molding, etc.

[ TABLE 1 ]

[ TABLE 2 ]

[ TABLE 3 ]

[ TABLE 4 ]

Claims

1. A resin composition characterized by comprising:

70 to 99 parts by mass of an aromatic polycarbonate resin having a terminal structure represented by the formula (1);

1-12 parts by mass of a phosphate ester; and

0 to 29 parts by mass of a thermoplastic resin other than the aromatic polycarbonate resin having a terminal structure represented by the formula (1),

in the formula (1), R¹Represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 30 carbon atoms, R²Each 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 represents a bonding site with another site.

2. The resin composition of claim 1, wherein:

the other thermoplastic resin comprises an aromatic polycarbonate resin having a terminal structure represented by the formula (2),

in the formula (2), R²Each 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 the other moiety is a bonding site.

3. The resin composition according to claim 1 or 2, wherein:

the resin composition has a glass transition temperature of 120 ℃ or lower as measured by differential scanning calorimetry.

4. The resin composition according to any one of claims 1 to 3, wherein:

the glass transition temperature of the resin composition is 100 ℃ or higher as measured by differential scanning calorimetry.

5. The resin composition according to any one of claims 1 to 4, wherein:

the phosphate ester contains an aromatic ring.

6. The resin composition according to any one of claims 1 to 5, wherein:

the resin composition is molded into a flat plate-shaped molded body having a thickness of 100 [ mu ] m, and the haze of the molded body after treatment at 85 ℃ and a relative humidity of 85% for 200 hours is 20% or less.

7. The resin composition according to any one of claims 1 to 6, wherein:

when the resin composition is treated at 85 ℃ and a relative humidity of 85% for 200 hours, the difference in weight average molecular weight Mw between before and after the treatment is 10,000 or less.

8. A flat plate-like molded article characterized by:

formed from the resin composition according to any one of claims 1 to 7.

9. The flat shaped article according to claim 8, wherein:

the thickness is 10 to 5,000 μm.

10. A multilayer body characterized by:

comprising the flat plate-like molded article according to claim 8 or 9 and a layer containing an acrylic resin.

11. The multilayer body of claim 10, wherein:

the total thickness of the multilayer body is 10-10,000 mu m.

12. A multi-layer body as claimed in claim 10 or 11, characterized in that:

the sheet is further provided with a hard coat layer, wherein the hard coat layer is formed by laminating a flat plate-shaped molded body, an acrylic resin-containing layer and the hard coat layer in this order.

13. A molded article characterized by:

the multilayer body according to any one of claims 10 to 12, which has a portion with a radius of curvature of 50mmR or less.

14. A method for manufacturing a molded article, comprising:

comprising the step of hot bending the multilayer body according to any one of claims 10 to 12 at 105 to 117 ℃.

15. The method for producing a molded article according to claim 14, wherein:

the molded article has a portion with a curvature radius of 50mmR or less.