JP5437939B2 - Polycarbonate resin and laminated molded member using the same - Google Patents

Description

  The present invention relates to a polycarbonate having a predetermined structure and a laminated molded member using the same. More specifically, the present invention relates to a polycarbonate having a predetermined structure, and a laminated molded member using the same, which has excellent wear resistance and surface hardness and has a good appearance.

  Polycarbonate resin exhibits excellent electrical properties, flame retardancy, transparency, dimensional stability, mechanical properties, and is lightweight, so it is widely used in the fields of electrical and electronics, automobiles, and building materials. Yes. In particular, polycarbonate resin derived from bisphenol A is inexpensive and has excellent transparency and impact strength. Therefore, it is molded into sheets and films as an alternative to inorganic glass, and is widely used in electrical and electronic parts and building materials. Yes. However, the polycarbonate resin derived from bisphenol A has a drawback of being inferior in surface hardness.

As means for solving this problem, various methods for modifying the surface of a molded article of a polycarbonate resin derived from bisphenol A have been proposed. For example, a method of applying a hard coat to a surface using a silicone or acrylic material, and acrylic A method of laminating layers of a polymer material has been proposed. Patent Document 1 proposes to improve the surface strength by forming a thin layer made of a resin composition in which a predetermined filler is dispersed in a transparent resin matrix on the surface of a polycarbonate resin substrate. Yes.
In these methods, it is necessary to laminate a layer made of a material different from the polycarbonate resin on the surface of a substrate mainly made of a polycarbonate resin such as a polycarbonate resin derived from bisphenol A. There has been a problem that warpage is likely to occur due to the difference in linear expansion coefficient and the difference in linear expansion coefficient. In addition, from the viewpoint of recycling after use, there is also a drawback that it is difficult to separate and collect.

  Patent Document 2 discloses a scratch resistance property (surface) by using a polycarbonate resin having 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane (hereinafter abbreviated as CBPZ) as one of the starting materials. It has been proposed to improve (hardness). However, the polycarbonate resin made of CBPZ has a drawback that it tends to be thermally deteriorated (easily burnt) when a molded body is obtained by a heat-melt molding method, and has an appearance when used as a display panel mounted on an electric / electronic device. A good laminated molded body could not be obtained.

Japanese Patent Laid-Open No. 2007-14450 Special table 2009-500195 gazette

The problem to be solved by the present invention is to improve the appearance of a laminated molded member made of a polycarbonate resin having excellent wear resistance and surface hardness.
More specifically, an object of the present invention is to provide a polycarbonate that is useful as a raw material for a molded product that requires wear resistance, high surface hardness, and good appearance.
The present invention also provides a polycarbonate capable of producing a laminated molded member having wear resistance, high surface hardness and good appearance by co-extrusion with heat and polycarbonate together with a polycarbonate resin derived from bisphenol A. Is an issue.
Another object of the present invention is to provide a polycarbonate resin which is not easily deteriorated by heat and is suitable as a raw material for a molded body by a heat-melt molding method.
Moreover, this invention makes it a subject to provide the lamination molded member which consists of a polycarbonate resin composition which is excellent in abrasion resistance and surface hardness, and has a favorable external appearance.

  As a result of intensive studies to solve the conventional problems, the present inventors have found that a polycarbonate using a compound having a predetermined structure that does not have an aliphatic ring in a bisphenol skeleton and has a methyl group in an aromatic ring as a raw material. In addition to being a material that is difficult to be thermally deteriorated (easily burned), it has been found that it can be a formed body having excellent flex resistance and high surface hardness. Furthermore, as a result of various investigations based on this finding, in particular, the polycarbonate having the above-described structure having a glass transition temperature (Tg) in a predetermined range can be heated and melt-coextruded together with a polycarbonate resin derived from bisphenol A. It has been found that a laminated molded member having wear resistance, high surface hardness and good appearance can be obtained by a suitable heat-melting co-extrusion molding method, and the present invention has been completed.

（式中、Ｘは、 That is, the means for solving the above problems are as follows.
[1] A polycarbonate obtained by reacting one or more compounds represented by the general formula (A) and one or more compounds represented by the general formula (B) with a carbonate-forming compound, Polycarbonate having a glass transition temperature (Tg) of 130 to 160 ° C.

(Where X is

であり；Ｒ¹及びＲ²はそれぞれ、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、又は各々置換基を有してもよい、炭素原子数１〜２０のアルキル基、炭素原子数１〜５のアルコキシ基、もしくは炭素原子数６〜１２アリール基を表し；Ｒ³及びＲ⁴はそれぞれ、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、又は各々置換基を有してもよい、炭素原子数１〜９のアルキル基、炭素原子数１〜５のアルコキシ基、炭素原子数２〜１２のアルケニル基、もしくは炭素原子数６〜１２アリール基を表し；Ｒ⁵は置換基を有してもよい１〜９のアルキレン基であり；ａは１〜２０の整数を表し、ｂは１〜５００の整数を表す。）

R ¹ and R ² are each a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an alkyl group having 1 to 20 carbon atoms, each having a substituent, and the number of carbon atoms Represents an alkoxy group having 1 to 5 or an aryl group having 6 to 12 carbon atoms; R ³ and R ⁴ each have a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or each having a substituent; Or an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms; R ⁵ is a substituent. And a represents an integer of 1 to 20, and b represents an integer of 1 to 500. )

（式中、Ｒ⁶及びＲ⁷はそれぞれ、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、又は各々置換基を有してもよい、炭素原子数２〜２０のアルキル基、炭素原子数１〜５のアルコキシ基、もしくは炭素原子数６〜１２アリール基を表し；Ｒ⁸は水素原子又はメチル基を表し、Ｒ⁹はメチル基又はエチル基を表すが、Ｒ⁸及びＲ⁹は同時にメチル基にはならない）。

(Wherein R ⁶ and R ⁷ are each a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an alkyl group having 2 to 20 carbon atoms and a carbon atom, each of which may have a substituent) represents the number 1-5 alkoxy or -C 6-12 aryl,; R ⁸ represents a hydrogen atom or a methyl group, but R ⁹ represents a methyl group or an ethyl group, R ⁸ and R ⁹ are simultaneously Not a methyl group).

[2] Polycarbonate of [1] whose intrinsic viscosity [η] is 0.2 to 1.0 [dl / g].
[3] The one or more compounds represented by the general formula (A) are 2,2-bis (4-hydroxy-3-methylphenyl) propane and 1,1-bis (4-hydroxy-3-methyl). The polycarbonate of [1] or [2], which is a compound selected from the group consisting of (phenyl) -1-phenylethane.
[4] The one or more compounds represented by the general formula (B) are selected from the group consisting of 1,1-bis (4-hydroxyphenyl) ethane and 2,2-bis (4-hydroxyphenyl) butane. The polycarbonate according to any one of [1] to [3].
[5] The polycarbonate according to any one of [1] to [4], wherein the carbonate-forming compound is phosgene.
[6] A layer composed of the first composition mainly comprising the polycarbonate of any one of [1] to [5], and 2,2-bis (4-hydroxyphenyl) adjacent to the first layer. And a layer formed of a second composition mainly composed of polycarbonate derived from propane.
[7] The laminated molded member according to [6], wherein the first and second compositions are molded by a melt coextrusion method.
[8] The laminated molded member according to [6] or [7], which is in the form of a sheet or film.

  Since the polycarbonate of the present invention contains bisphenols having a predetermined structure as a structural unit, it is difficult to be thermally deteriorated, and is useful as a raw material for a molded article having flexibility and high surface hardness. Further, since the polycarbonate of the present invention has a glass transition temperature within a predetermined range, it can be laminated together with a polycarbonate widely derived from bisphenol A, which is usually used, by a heat-melt coextrusion molding method. As a result, there is an effect that it is possible to easily provide a laminated molded member having excellent wear resistance, surface hardness and good appearance.

Hereinafter, the present invention will be described in detail.
1. Polycarbonate The present invention is a polycarbonate obtained by reacting one or more compounds represented by the general formula (A) with a carbonate ester-forming compound, and has a glass transition temperature (Tg) of 130 to 160 ° C. Relates to polycarbonate. In the present invention, each of the compound represented by the following general formula (A) and the compound represented by the following general formula (B) may be used alone or in combination of two or more. However, the polycarbonate of the present invention does not substantially contain a unit derived from a bisphenol other than the compound represented by the following general formula (A) and the compound represented by the following general formula (B).

式中、Ｘは、

であり；Ｒ¹及びＲ²はそれぞれ、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、又は各々置換基を有してもよい、炭素原子数１〜２０のアルキル基、炭素原子数１〜５のアルコキシ基、もしくは炭素原子数６〜１２アリール基を表し；Ｒ³及びＲ⁴はそれぞれ、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、又は各々置換基を有してもよい、炭素原子数１〜９のアルキル基、炭素原子数１〜５のアルコキシ基、炭素原子数２〜１２のアルケニル基、もしくは炭素原子数６〜１２アリール基を表し；Ｒ⁵は置換基を有してもよい１〜９のアルキレン基であり；ａは１〜２０の整数を表し、ｂは１〜５００の整数を表す。 ・ Compound of general formula (A)

Where X is

R ¹ and R ² are each a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an alkyl group having 1 to 20 carbon atoms, each having a substituent, and the number of carbon atoms Represents an alkoxy group having 1 to 5 or an aryl group having 6 to 12 carbon atoms; R ³ and R ⁴ each have a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or each having a substituent; Or an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms; R ⁵ is a substituent. And a represents an integer of 1 to 20, and b represents an integer of 1 to 500.

Among them, X is

  Is preferred.

  In general formula (A), the substitution position of the methyl group and the hydroxy group is not particularly limited, but with respect to X, either the methyl group or the hydroxy group is in the meta position and the other is in the para position. It is preferable that the methyl group is in the meta position and the hydroxy group is in the para position.

  Specific examples of the compound represented by the general formula (A) include bis (4-hydroxy-3-methylphenyl) sulfoxide, bis (4-hydroxy-2-methylphenyl) sulfoxide, and bis (4-hydroxy-3). -Methylphenyl) sulfide, bis (4-hydroxy-2-methylphenyl) sulfide, bis (4-hydroxy-3-methylphenyl) ketone, bis (4-hydroxy-2-methylphenyl) ketone, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-2-methylphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) hexafluoropropane, 2, 2-bis (4-hydroxy-2-methylphenyl) hexafluoropropane, 1,1-bis (4-hydroxy-3) Methylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-2-methylphenyl) -1-phenylethane, bis (4-hydroxy-3-methylphenyl) diphenylmethane, bis (4-hydroxy-2) -Methylphenyl) diphenylmethane, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-2-methylphenyl) fluorene, 3,3'-dimethyl-4,4 '-[1,4-phenylenebis (1-methylethylidene)] bisphenol, 2,2'-dimethyl-4,4'-[1,4-phenylenebis (1-methylethylidene)] bisphenol, 3,3 ' -Dimethyl-4,4 '-[1,3-phenylenebis (1-methylethylidene)] bisphenol and 2,2'-dimethyl-4,4' [1,3-phenylene bis (1-methylethylidene)] include bisphenols such.

  Of these, 2,2-bis (4-hydroxy-3-methylphenyl) propane and 1,1-bis (4-hydroxy-3-methylphenyl) -1-phenylethane are particularly preferable.

・ Compound of general formula (B)

In the formula, R ⁶ and R ⁷ are each a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an alkyl group having 2 to 20 carbon atoms, each having a substituent, and the number of carbon atoms 1-5 alkoxy groups, or represents a carbon atoms 6 to 12 aryl group; R ⁸ represents a hydrogen atom or a methyl group, but R ⁹ represents a methyl group or an ethyl group, R ⁸ and R ⁹ are simultaneously methyl It is not based.
R ⁶ and R ⁷ are preferably a hydrogen atom, an alkyl group having 2 to 20 carbon atoms (for example, an ethyl group), or an aryl group having 6 to 12 carbon atoms (for example, a phenyl group), and is a hydrogen atom. Is more preferable.

In formula (B), the hydroxy group is preferably substituted at the para-position or ortho-position, respectively, and more preferably substituted at the para-position with respect to each phenyl group. In the example where R ⁶ and R ⁷ are not a hydrogen atom but a predetermined substituent, there are no particular restrictions on the substitution positions of R ⁶ and R ⁷ . A plurality of R ⁶ and R ⁷ may be present up to 4 and may be the same or different.

  Specific examples of the compound represented by the general formula (B) include 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxy-3-methylphenyl) ethane, 1,1 -Bis (4-hydroxy-2-methylphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxy-3-methylphenyl) butane, and 2,2-bis (4-hydroxy-2-methylphenyl) butane and the like are included.

  Of these, 1,1-bis (4-hydroxyphenyl) ethane and 2,2-bis (4-hydroxyphenyl) butane are particularly preferable.

The ratio of the compound represented by the general formula (A) in all bisphenols constituting the polycarbonate of the present invention is preferably 40 mol% or more, more preferably 45 mol% or more, and 50 mol% or more. More preferably. If it is less than 40 mol%, the glass transition temperature (Tg) tends to decrease and may be less than 130 ° C. On the other hand, when the proportion of the compound represented by the general formula (A) exceeds 99 mol% and the proportion of the compound represented by the general formula (B) is less than 1 mol%, the glass transition temperature (Tg) increases, May exceed 160 ° C. Moreover, when MVR also falls and it is set as a sheet-like molded object, the problem that many spots generate | occur | produce on the surface may arise. Therefore, from these viewpoints, the ratio of the compound represented by the general formula (A) is preferably 99 mol% or less, and more preferably 95% mol% or less.
Further, the preferred ratio varies depending on the type of the compound of the general formula (A). For example, when the compound of the general formula (A) is 1,1-bis (4-hydroxy-3-methylphenyl) -1-phenylethane, the ratio is in the range of 40 to 99 mol%. The above inconvenience does not occur, preferably 45 to 99 mol%, more preferably 50 to 95 mol%. Further, when the compound of the general formula (A) is 2,2-bis (4-hydroxy-3-methylphenyl) propane, it is preferable that the amount is in the range of 40 to 60 mol% because the above disadvantage does not occur. More preferably, it is 45-55 mol%.

  In the present invention, as the bisphenols represented by the general formula (A) and the general formula (B), it is preferable to use a compound having a purity of 98% or more, and further purified to 99% or more. More preferably, a compound is used. In particular, the use of materials containing various isomers such as isomers including 2,4'-dihydroxy compounds is not preferred because the reactivity is lowered and the control of polymerization becomes difficult.

Carbonate ester forming compound On the other hand, examples of the carbonate ester forming compound usable in the present invention include phosgene, diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, And bisaryl carbonates such as dinaphthyl carbonate.
In the production of the polycarbonate of the present invention, only one type of carbonate ester-forming compound may be used, or two or more types may be used in combination.

-Polycarbonate production method of the present invention The polycarbonate of the present invention can be produced by various methods used for producing a polycarbonate from bisphenol A and a carbonate-forming compound, for example, direct reaction of bisphenols with phosgene (phosgene method). And any method such as a transesterification reaction (transesterification method) between a bisphenol and a bisaryl carbonate can be used.

  In the phosgene method and the transesterification method, the phosgene method is preferable in consideration of the reactivity of the compound represented by the general formula (A).

  In the phosgene method, the bisphenols of the formulas (A) and (B) are usually reacted with phosgene in the presence of an acid binder and a solvent. Examples of the acid binder include pyridine and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and examples of the solvent include methylene chloride and chloroform. Furthermore, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt is used to accelerate the condensation polymerization reaction, and phenol, pt-butylphenol, p-cumylphenol are used for adjusting the degree of polymerization. It is preferable to add a monofunctional compound such as a long-chain alkyl-substituted phenol as a molecular weight regulator. If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfite, or a branching agent such as phloroglucin or isatin bisphenol may be added. The reaction is usually performed in the range of 0 to 150 ° C, preferably 5 to 40 ° C. Although a preferable range of the reaction time depends on the reaction temperature, it is usually 0.5 minutes to 10 hours, preferably 1 minute to 2 hours. Further, during the reaction, it is desirable to maintain the pH of the reaction system at 10 or more.

On the other hand, in the transesterification method, the bisphenols of the formulas (A) and (B) and bisaryl carbonate are mixed and reacted at high temperature under reduced pressure. The reaction is usually carried out at a temperature in the range of 150 to 350 ° C., preferably 200 to 300 ° C., and the degree of vacuum is preferably 1 mmHg or less at the end, and phenols derived from the bisaryl carbonate produced by the transesterification reaction Is distilled out of the system. The reaction time depends on the reaction temperature and the degree of reduced pressure, but is usually about 1 to 24 hours. The reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon. Moreover, you may react by adding a molecular weight regulator, antioxidant, and a branching agent as needed.
The polycarbonate of the present invention can be produced by various methods used in producing a polycarbonate from bisphenol A and a carbonate ester-forming compound, for example, a direct reaction between bisphenols and phosgene (phosgene method), and bisphenols and bisaryl carbonates. It can be produced by adopting any method such as transesterification reaction (transesterification method).

-Properties of the polycarbonate of the present invention The polycarbonate of the present invention can be molded by a known molding method such as melt extrusion molding, injection molding, compression molding or wet molding in order to form a sheet film. In particular, since it does not easily deteriorate due to heat, it is suitable as a raw material for heat melt molding methods such as melt extrusion molding. In particular, as described later, together with other polycarbonates, it can be molded as a laminated molded member by a heat-melt coextrusion method.

  In order to use as a raw material for melt extrusion molding, the intrinsic viscosity of the polycarbonate of the present invention is preferably in the range of 0.2 to 1.0 dl / g, more preferably in the range of 0.3 to 0.6 dl / g. A range of 0.45 to 0.55 dl / g is particularly preferable. When the intrinsic viscosity of the polycarbonate is lower than 0.2 dl / g, the mechanical strength is low when formed into a sheet film, and when it is higher than 1.0 dl / g, the moldability is inferior.

  In order to use as a raw material for melt extrusion molding, the melt volume rate (MVR) of the polycarbonate of the present invention is preferably in the range of 2.5 to 7.0, and in the range of 3.0 to 6.0. More preferably.

  The polycarbonate of the present invention has a glass transition temperature (Tg) of 130 to 160 ° C, preferably 140 to 160 ° C. Since the polycarbonate of the present invention has a glass transition temperature in the above range, it can be molded as a laminated molded member by a simple method such as a heat-melt coextrusion method together with a polycarbonate resin derived from bisphenol A, which will be described later.

2. Laminated molded member The present invention relates to a layer composed of the first composition mainly composed of the polycarbonate of the present invention, and 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) adjacent to the first layer. And a layer formed of a second composition composed mainly of a polycarbonate derived from (1)).

  There is no restriction | limiting in particular about the manufacturing method of the laminated molded member of this invention, It can shape | mold by well-known shaping | molding methods, such as melt extrusion molding, injection molding, compression molding, and wet molding. A heat melt molding method such as a melt extrusion method is preferable because it is a simple and widely used method. In particular, it is advantageous to use this method because the polycarbonate of the present invention used as a raw material is hardly thermally deteriorated.

  The first composition used for the production of the laminated molded member of the present invention contains the polycarbonate of the present invention as a main component, and the second composition has a polycarbonate derived from bisphenol A as a main component. To do. Here, “containing as a main component” refers to a state of containing 50% by weight or more based on the total weight of all components of the composition (all components excluding the solvent when a solvent is included), more preferably 70% by weight or more, more preferably 90% by weight or more.

  The polycarbonate which the second composition contains as a main component may be any as long as it is a polycarbonate having a repeating unit derived from bisphenol A. However, when the laminated molded member of the present invention is formed by the melt coextrusion method, the difference in glass transition temperature between the first composition and the second composition is 10 ° C. or less (more preferably 5 ° C. or less). The glass transition temperature of the polycarbonate contained in the second composition as a main component is preferably about 140 to 155 ° C. Some polycarbonates having units derived from bisphenol A having a glass transition temperature in the above range are commercially available, for example, “Iupilon E-2000R”, “Iupilon S-1000R”, “ Examples include "Iupilon S-2000R", "Iupilon S-3000R", "Iupilon H-3000R" and "Iupilon H-4000" (all manufactured by Mitsubishi Engineering Plastics). It is also preferable to do this.

Each of the first and second compositions may contain one or more additives in addition to the polycarbonate as the main component. Examples of additives include additives added for the purpose of ensuring the stability and releasability required during molding, specifically, hindered phenolic and phosphite antioxidants; Silicone, fatty acid ester, fatty acid, fatty acid glyceride, beeswax and other natural oils and mold release agents; benzotriazole, benzophenone, dibenzoylmethane, salicylate, and other light stabilizers; polyalkylene glycol And antistatic agents such as fatty acid glycerides; These will be added in an amount of about 1% by weight or less based on the polycarbonate which is the main component.
In the present invention, it is preferable that each of the first and second compositions does not contain a polycarbonate resin other than the polycarbonate resins contained as a main component.

An example of the manufacturing method of the laminated molded member of the present invention is as follows.
First, the first and second compositions are prepared. For example, the first composition is prepared by mixing the polycarbonate resin powder of the present invention and optionally an additive. The second composition is prepared similarly. Next, the second composition is introduced into the main extruder and the first composition is introduced into the sub-extruder, respectively, the cylinder temperature is set to about 220 to 320 ° C., and each is melted. Extrude. The melt extruded into a sheet is then passed between two horizontal rolls set at a surface temperature of about 110 to 160 ° C. to obtain a sheet-shaped or film-shaped laminated molded member.
The above method is an example and is not limited to this condition. Manufacturing conditions such as temperature conditions can be set as appropriate. Moreover, although the example of the manufacturing method of the laminated molded member which consists of two layers was shown above, it is of course possible to manufacture the laminated molded member which consists of three layers or more in the coextrusion method.

  There is no restriction | limiting in particular about the shape of the laminated molding member of this invention. The thing shape | molded by the sheet form and the film form is mentioned. Moreover, there is no restriction | limiting in particular also about the thickness of the layer which consists of a 1st composition, and the layer which consists of a 2nd composition, and there is no restriction | limiting in particular also about the relative relationship. Since the layer made of the first composition containing the polycarbonate of the present invention as a main component exhibits particularly high hardness, for example, the substrate made of the second composition (for example, the thickness is about 20 to 30,000 μm). An example is a mode in which a layer having a high surface hardness (for example, a thickness of about 30 to 300 μm) made of the first composition is formed on the surface.

The laminated molded member of the present invention can be widely used as a member in the electric / electronic field, automobile field, and building material field. In particular, it has a high surface hardness and a good appearance, so that it is useful as a member for a display panel mounted on an electric / electronic device.
Since the two layers constituting the laminated molded member of the present invention both contain polycarbonates as the main component, the adhesion is good, and warping due to differences in water absorption and linear expansion coefficients occurs. It is hard to occur. Moreover, compared with the member mixed with other polymers, and the member which formed the coating layer which consists of other polymers, it is preferable also from a viewpoint of recycling.
In addition, a known heat-curing or ultraviolet-curing hard coat is applied to the surface layer (opposite the substrate composed of the second composition) of the first composition layer mainly composed of the siloxane copolymer polycarbonate of the present invention. Further, the surface hardness can be improved by laminating.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention does not receive a restriction | limiting at all by the following examples.
1. Synthesis of polycarbonate of the present invention [Synthesis Example 1]
To 700 ml of a 9.0 w / w% aqueous sodium hydroxide solution, 21.4 g (0.100 mol) of 1,1-bis (4-hydroxyphenyl) ethane (Honshu Chemical Co., Ltd., hereinafter abbreviated as “BPE”) 1,1-bis (4-hydroxy-3-methylphenyl) -1-phenylethane (manufactured by Honshu Chemical Industry Co., Ltd., hereinafter abbreviated as “CBPAP”) 95.4 g (0.300 mol), triethylbenzylammonium chloride 5 g and 0.2 g of hydrosulfite were dissolved.
To this, 500 ml of methylene chloride was added and stirred, and 55 g of phosgene was continuously blown in for 30 minutes while maintaining the temperature at 15 ° C.
After completion of the phosgene blowing, 2.66 g of pt-butylphenol (hereinafter abbreviated as “PTBP”) is added, and the mixture is vigorously stirred to emulsify the reaction solution. After emulsification, 1 ml of triethylamine is added, and the temperature is 20 to 25 ° C. For about 1 hour to polymerize.

After completion of the polymerization, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washing with water was repeated until the conductivity of the previous solution (aqueous phase) became 10 μS / cm or less. The obtained polymer solution was dropped into warm water maintained at 60 ° C., and the solvent was removed by evaporation to obtain a white powdery precipitate. The obtained precipitate was filtered and dried at a temperature of 120 ° C. for 24 hours to obtain a polymer powder.
The intrinsic viscosity at 20 ° C. of a solution having a concentration of 0.5 g / dl using methylene chloride as a solvent of this polymer was 0.47 dl / g. The results obtained polymer was analyzed by infrared absorption spectrum, absorption by carbonyl group at the position in the vicinity of 1770 cm ^-1, observed absorption by ether bond position near 1240 cm ^-1, the polycarbonate resin (hereinafter PC having a carbonate bond -1).

[Synthesis Example 2]
Example 1 except that 21.4 g (0.100 mol) of BPE and 95.4 g (0.300 mol) of CBPAP were changed to 42.8 g (0.200 mol) of BPE and 63.6 g (0.200 mol) of CBPAP. Synthesis was performed in the same manner. The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-2) was 0.52 dl / g. Confirmation of the polycarbonate resin was carried out in the same manner as in Synthesis Example 1.

[Synthesis Example 3]
Example 1 except that 21.4 g (0.100 mol) of BPE and 95.4 g (0.300 mol) of CBPAP were changed to 4.3 g (0.020 mol) of BPE and 120.8 g (0.380 mol) of CBPAP. Synthesis was performed in the same manner. The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-3) was 0.49 dl / g. Confirmation of the polycarbonate resin was carried out in the same manner as in Synthesis Example 1.

[Synthesis Example 4]
2. 21.4 g (0.100 mol) of BPE and 95.4 g (0.300 mol) of CBPAP and 2,2-bis (4-hydroxyphenyl) butane (manufactured by Honshu Chemical Industry Co., Ltd., hereinafter abbreviated as “BPB”) The synthesis was performed in the same manner as in Example 1 except that the amount was changed to 7 g (0.100 mol) and 95.4 g (0.300 mol) of CBPAP. The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-4) was 0.48 dl / g. Confirmation of the polycarbonate resin was carried out in the same manner as in Synthesis Example 1.

[Synthesis Example 5]
21.4 g (0.100 mol) of BPE and 95.4 g (0.300 mol) of CBPAP, 51.4 g (0.200 mol) of BPB and 2,2-bis (4-hydroxy-3-methylphenyl) propane (Honshu Chemical) The synthesis was performed in the same manner as in Example 1 except that it was changed to 51.2 g (0.200 mol). The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-5) was 0.52 dl / g. Confirmation of the polycarbonate resin was carried out in the same manner as in Synthesis Example 1.

[Synthesis Example 6]
Example 1 except that 21.4 g (0.100 mol) of BPE and 95.4 g (0.300 mol) of CBPAP were changed to 5.1 g (0.020 mol) of BPB and 120.8 g (0.380 mol) of CBPAP. Synthesis was performed in the same manner. The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-6) was 0.51 dl / g. Confirmation of the polycarbonate resin was carried out in the same manner as in Synthesis Example 1.

2. Synthesis of Comparative Example Polycarbonate [Synthesis Example 7]
Example 1 except that 21.4 g (0.100 mol) of BPE and 95.4 g (0.300 mol) of CBPAP were changed to 4.3 g (0.020 mol) of BPE and 97.3 g (0.380 mol) of BPC. Synthesis was performed in the same manner. The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-7) was 0.47 dl / g. Confirmation of the polycarbonate resin was carried out in the same manner as in Synthesis Example 1.

[Synthesis Example 8]
21.4 g (0.100 mol) of BPE and 95.4 g (0.300 mol) of CBPAP, 42.8 g (0.200 mol) of BPE and 9,9-bis (4hydroxy-3-methylphenyl) fluorene (Honshu Chemical Industry) The synthesis was carried out in the same manner as in Example 1 except that the product was changed to 75.6 g (0.200 mol). The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-8) was 0.52 dl / g. Confirmation of the polycarbonate resin was carried out in the same manner as in Synthesis Example 1.

[Synthesis Example 9]
BPE 21.4 g (0.100 mol) and CBPAP 95.4 g (0.300 mol), BPE 21.4 g (0.100 mol) and 2,2-bis (4-hydroxyphenyl) propane (Mitsui Chemicals, Synthesis was carried out in the same manner as in Example 1 except that it was changed to 68.4 g (0.300 mol). The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-9) was 0.50 dl / g. Confirmation of the polycarbonate resin was carried out in the same manner as in Synthesis Example 1.

[Synthesis Example 10]
Example 1 except that 21.4 g (0.100 mol) of BPE and 95.4 g (0.300 mol) of CBPAP were changed to 25.7 g (0.100 mol) of BPB and 76.8 g (0.300 mol) of BPC. Synthesis was performed in the same manner. The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-10) was 0.49 dl / g. Confirmation of the polycarbonate resin was carried out in the same manner as in Synthesis Example 1.

[Synthesis Example 11]
Example 1 except that 21.4 g (0.100 mol) of BPE and 95.4 g (0.300 mol) of CBPAP were changed to 51.4 g (0.200 mol) of BPB and 75.6 g (0.200 mol) of BCFL. Synthesis was performed in the same manner. The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-11) was 0.53 dl / g. Confirmation of the polycarbonate resin was carried out in the same manner as in Synthesis Example 1.

[Synthesis Example 12]
21.4 g (0.100 mol) of BPE and 95.4 g (0.300 mol) of CBPAP were abbreviated as “CBPZ” from 1,1-bis (4hydroxy-3-methylphenyl) cyclohexane (Honshu Chemical Co., Ltd.). ) Synthesis was performed in the same manner as in Example 1 except that the amount was changed to 118.4 g (0.400 mol). The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-10) was 0.35 dl / g. Confirmation of the polycarbonate resin was carried out in the same manner as in Synthesis Example 1. CBPZ is a polycarbonate used in Patent Document 2.

[Synthesis Example 13]
The synthesis was performed in the same manner as in Example 1 except that 21.4 g (0.100 mol) of BPE and 95.4 g (0.300 mol) of CBPAP were changed to 85.6 g (0.400 mol) of BPE. The intrinsic viscosity of the obtained polycarbonate resin (hereinafter abbreviated as PC-13) was 0.53 dl / g. Confirmation of the polycarbonate resin was carried out in the same manner as in Synthesis Example 1.

3. Properties of the synthesized polycarbonate The properties of the polycarbonates produced in Synthesis Examples 1 to 13 are summarized in Table 1 below.
The intrinsic viscosity is a value measured by preparing a 0.5% dichloromethane solution of each polymer at a temperature of 20 ° C. and using a Huggins constant of 0.45.
The glass transition temperature (Tg) is a value (Tg calculated by the tangent method) measured under a nitrogen stream with Shimadzu Corporation DCS-50.
The melt volume rate (MVR) is a value measured at 300 ° C. and a 1.2 kg load by Toyo Seiki Co., Ltd .: DA.

4). Production of Laminated Molded Member A scale-up trial was carried out at the same raw material charge ratio as in each of Synthesis Examples 1 to 6, and 30 kg or more of each polymer powder capable of sheet forming was produced. Tris (2,4-ditertiary butylphenyl) phosphite (0.01% by weight) was mixed with each of the obtained PC-1 to 6 powders, and the mixed powder was then sub-extruded (25 mm single screw extrusion with a vent). Machine, MK-25 manufactured by Musashino Kikai Co., Ltd., cylinder temperature 290 ° C), and commercially available polycarbonate resin ("Iupilon E-2000R" manufactured by Mitsubishi Engineering Plastics Co., Ltd.); polycarbonate containing repeating units of bisphenol A; 150 ° C.) was introduced into the main extruder (30 mm single-screw extruder with vent, MK-30 manufactured by Musashinoki Kai Co., Ltd., cylinder temperature 290 ° C.). The melt is coextruded through a feed block type T die, cooled by two horizontal rolls (roll temperature: 150 ° C.), and laminated extruded sheets (layers composed of PC-1 to 6 having a thickness of 100 μm on the surface, back surface) To 200 μm thick polycarbonate resin layer). Thus, the laminated extrusion sheet samples 1-6 of the Example were produced.

  A scale-up trial was carried out at the same raw material charge ratio as in each of Synthesis Examples 7 to 13, and 30 kg or more of each powder of the polymer (PC-7 to 13) capable of sheet forming was produced. The obtained powders of PC-7 to 13 and “Iupilon S-3000R” (Mitsubishi Engineering Plastics Co., Ltd .; polycarbonate having units derived from bisphenol A; hereinafter abbreviated as “PC-14”) are used. Except having used, it carried out similarly to the above, and produced the lamination | stacking extrusion sheet | seat samples 7-14 for comparative examples.

5. Evaluation of Laminated Molding Member A pencil scratch test (based on JIS-K5600-5-4) was performed on the surface of each of the obtained laminated sheet samples to evaluate the surface hardness.
Specifically, using the UNI made by Mitsubishi Pencil, the surface of the laminated molded member (the surface of the layer consisting of PC-1 to 14) is measured five times in accordance with JIS-K5600-5-4, and scratches are generated. If it was less than 2 times, it was considered acceptable.
In addition, the appearance of the sheet was evaluated visually.
About each obtained lamination sheet sample, abrasion resistance evaluation was performed regarding the surface.
Specifically, using TYPE: HHS2000 manufactured by Shinto Kagaku Co., Ltd., a polycarbonate ball (diameter) while varying the load (10 g to 100 g) on the surface of the laminated sheet (the surface of the layer composed of PC-1 to 14). 4 mm) was linearly reciprocated (moving distance 20 mm), and the wear depth (μm) at the 25th load of 50 g was measured.
The results are shown in Table 2 below.

  From the results shown in the above table, the polycarbonate of the present invention can be molded by melt coextrusion with a polycarbonate having a unit derived from bisphenol A, and each of the produced laminates of the examples has surface hardness and wear resistance. It can be understood that the appearance is good as well as excellent properties.

Claims (8)

A polycarbonate obtained by reacting a compound represented by one or more general formulas (A) and a compound represented by one or more general formulas (B) with a carbonate-forming compound, and having a glass transition Polycarbonate having a temperature (Tg) of 130 to 160 ° C.

(Where X is

R ¹ and R ² are each a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an alkyl group having 1 to 20 carbon atoms, each having a substituent, and the number of carbon atoms Represents an alkoxy group having 1 to 5 or an aryl group having 6 to 12 carbon atoms; R ³ and R ⁴ each have a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or each having a substituent; Or an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms; R ⁵ is a substituent. And a represents an integer of 1 to 20, and b represents an integer of 1 to 500. )

(Wherein R ⁶ and R ⁷ are each a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an alkyl group having 2 to 20 carbon atoms and a carbon atom, each of which may have a substituent) represents the number 1-5 alkoxy or -C 6-12 aryl,; R ⁸ represents a hydrogen atom or a methyl group, but R ⁹ represents a methyl group or an ethyl group, R ⁸ and R ⁹ are simultaneously Not a methyl group). The polycarbonate according to claim 1, which has an intrinsic viscosity [η] of 0.2 to 1.0 [dl / g]. The one or more compounds represented by the general formula (A) are 2,2-bis (4-hydroxy-3-methylphenyl) propane and 1,1-bis (4-hydroxy-3-methylphenyl)- The polycarbonate according to claim 1 or 2, which is a compound selected from the group consisting of 1-phenylethane. The compound represented by the one or more general formulas (B) is a compound selected from the group consisting of 1,1-bis (4-hydroxyphenyl) ethane and 2,2-bis (4-hydroxyphenyl) butane. The polycarbonate according to any one of claims 1 to 3. The polycarbonate according to any one of claims 1 to 4, wherein the carbonate-forming compound is phosgene. A layer made of the first composition mainly comprising the polycarbonate according to any one of claims 1 to 5, and 2,2-bis (4-hydroxyphenyl) propane adjacent to the first layer. And a layer formed of a second composition mainly composed of polycarbonate derived from the above. The laminated molded member according to claim 6, wherein the first and second compositions are molded by a melt coextrusion method. The laminated molded member according to claim 6 or 7, which is in the form of a sheet or a film.