JPH0980213A - Reflection mirror - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a lightweight reflection mirror capable of easily producing and excellent in durability and reflection image property by proving a reflection layer on a sheet formed from a polycarbonate containing substantially no chlorine atom. SOLUTION: The reflection layer is provided on the sheet formed from the polycarbonate substantially containing no chlorine atom. The polycarbonate is obtained by an ester exchange reaction of an aromatic dihydroxy compound with a carbonic diester. The aromatic dihydroxy compound is a compound expressed by HO-Ar-Oh. The Ar expresses a bivalent aromatic group, for example, an organic group expressed by a formula. In the formula, each of R<1> and R<2> individually expresses hydrogen atom, a halogen atom, a 1-10C alkyl group, a 1-10C alkoxy group, a cycloalkyl group or phenyl group having ring structural carbon number of 5-10. Each of (m) and (n) is integer of 1-4.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lightweight reflecting mirror suitable for an optical path bending mirror for a rear projection type projection television.

[0002]

2. Description of the Related Art Conventionally, there is a glass reflecting mirror in which a metal such as aluminum is deposited on the surface of a glass substrate to form a reflecting surface, and then an inorganic protective film having a thickness of several angstroms is deposited on the reflecting surface by a vapor deposition process. It's being used.

The glass reflecting mirror is excellent in plane accuracy, durability and optical performance, but has a drawback that it is heavy and easily broken.
For this reason, it is necessary to make the mounting frame and cabinet of the reflecting mirror sturdy, in order to prevent workability when mounting the reflecting mirror on a large-screen projection TV and to prevent damage to the reflecting mirror. This hinders the weight reduction of projection TVs.

Further, Japanese Patent Laid-Open No. 273405/1993 proposes a lightweight reflecting mirror composed of a film mirror and a low specific gravity structure. However, there is a sticking of the film mirror and the structure using an adhesive. Therefore, the process is complicated and it is very difficult to obtain an excellent reflection image property.

A reflecting mirror in which a metal film of silver or the like is formed on polycarbonate by vapor deposition, sputtering or the like is applied to an interior mirror of an automobile or the like. However, a reflecting mirror using a polycarbonate produced by an ordinary phosgene method is inferior in durability due to corrosion of a reflecting layer due to chlorine atoms remaining in the polymer, and the polycarbonate has a large surface smoothness because it contains many impurities. It was inferior and the reflection image property was poor, and it could not be used as a reflection mirror for electric products such as projection televisions.

[0006]

DISCLOSURE OF THE INVENTION The present invention provides a light-weight reflecting mirror which improves the above-mentioned heavy and fragile defects of the glass reflecting mirror, can be easily manufactured, and has excellent durability and reflection image quality. The purpose is to do.

[0007]

As a result of intensive studies to solve this problem, the present inventor found a reflecting mirror which can achieve the above object by providing a reflecting layer on a specific polycarbonate. .

That is, the present invention provides a durable and reflective image in which a reflective layer is provided on a sheet molded from a polycarbonate containing substantially no chlorine atom, which is produced from an aromatic dihydroxy compound and a carbonic acid diester by a transesterification method. It is possible to provide a reflecting mirror having excellent properties.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The specific polycarbonate containing substantially no chlorine atom of the present invention is obtained by a transesterification reaction between an aromatic dihydroxy compound and a carbonic acid diester.

In the present invention, the aromatic dihydroxy compound is a compound represented by HO-Ar-OH. In the formula, Ar represents a divalent aromatic group, for example, an organic group represented by the following formula.

[0011]

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(In the formula, R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms in the ring. An alkyl group or a phenyl group, wherein m and n are 1
Is an integer of 4 and each R ¹ may be the same or different when m is 2 to 4, and each R ² may be the same or different when n is 2 to 4. It may be. )

The aromatic group Ar is, for example, --Ar ₁
A divalent aromatic group represented by —Y—Ar ₂ — (wherein Ar ₁ and Ar ₂ each independently have 5 to 5 carbon atoms).
Represents a divalent carbocyclic or heterocyclic aromatic group having 70, and Y represents a divalent alkane group having 1 to 30 carbon atoms. ).

In the divalent aromatic groups Ar ₁ and Ar ₂ , 1
One or more hydrogen atoms do not adversely affect the reaction, other substituents, for example, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a phenyl group, a phenoxy group, a vinyl group, It may be substituted by a cyano group, an ester group, an amide group, a nitro group or the like.

Preferred specific examples of the heterocyclic aromatic group include aromatic groups having one to a plurality of ring-forming nitrogen atoms, oxygen atoms or sulfur atoms.

The divalent aromatic groups Ar ₁ and Ar ₂ are, for example,
It represents a group such as substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, or substituted or unsubstituted pyridylene.
The substituent here is as described above.

The divalent alkane group Y is, for example, an organic group represented by the following formula.

[0018]

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(In the formula, R ³ , R ⁴ , R ⁵ , and R ⁶ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, and 1 to 10 carbon atoms.
A cycloalkyl group having 5 to 10 ring carbon atoms, a carbocyclic aromatic group having 5 to 10 ring carbon atoms, and a carbocyclic aralkyl group having 6 to 10 carbon atoms. k is 3 to 1
Represents an integer of 1, R ⁷ and R ⁸ are individually selected for each X and independently of each other represent hydrogen or an alkyl group having 1 to 6 carbon atoms, and X represents carbon. In addition, R ³ , R ⁴ ,
In R ⁵ , R ⁶ , R ⁷ , and R ⁸ , other substituents such as a halogen atom, an alkyl group having 1 to 10 carbon atoms, and a carbon number of 1 are used as long as one or more hydrogen atoms do not adversely affect the reaction. ~
It may be substituted with 10 alkoxy groups, phenyl groups, phenoxy groups, vinyl groups, cyano groups, ester groups, amide groups, nitro groups and the like. )

As such a divalent aromatic group Ar,
For example, the one represented by the following formula may be mentioned.

[0021]

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[0022]

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[0023]

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[0024]

[Chemical 6]

[0025]

[Chemical 7]

[0026]

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[0027]

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[0028]

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[0029]

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[0030]

[Chemical 12]

(In the formula, R ¹ , R ² , m and n are as described above.)

Further, the divalent aromatic group Ar is --Ar ₁
It may be one represented by —Z—Ar ₂ —.

(In the formula, Ar ₁ and Ar ₂ are as described above, and Z
Is a single bond or -O -, - CO -, - S -, - SO 2 -,
-SO -, - COO -, - CON (R 1) - represents a divalent group, such as. However, R ¹ is as described above. )

As such a divalent aromatic group Ar,
For example, the one represented by the following formula may be mentioned.

[0035]

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[0036]

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[0037]

[Chemical 15]

[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

[Chemical 21]

(In the formula, R ¹ , R ² , m and n are as described above.)

The aromatic dihydroxy compound used in the present invention may be a single type or two or more types. A typical example of the aromatic dihydroxy compound is bisphenol A. Further, it is preferable that the content of chlorine atom and alkali or alkaline earth metal in these aromatic dihydroxy compounds is small, and it is preferable that they are substantially not contained.

The diaryl carbonate used in the present invention is represented by the following formula.

[0047]

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(In the formula, Ar ³ and Ar ⁴ each represent a monovalent aromatic group.)

Ar ³ and Ar ⁴ represent a monovalent carbocyclic or heterocyclic aromatic group. In Ar ³ and Ar ⁴ ,
One or more hydrogen atoms having no adverse effect on the reaction, for example, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a phenyl group,
It may be substituted by a phenoxy group, vinyl group, cyano group, ester group, amide group, nitro group, or the like. Ar ³ and Ar ⁴ may be the same or different.

Typical examples of the monovalent aromatic groups Ar ³ and Ar ⁴ include a phenyl group, a naphthyl group, a biphenyl group and a pyridyl group. These may be substituted with one or more types of the above-mentioned substituents.

Examples of preferable Ar ³ and Ar ⁴ include the following formulas.

[0052]

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[0053]

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[0054]

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[0055]

[Chemical formula 26]

[0056]

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Representative examples of the diaryl carbonate include substituted or unsubstituted diphenyl carbonates represented by the following formula.

[0058]

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(In the formula, R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms.
An alkoxy group having 10; a cycloalkyl group having 5 to 10 ring carbon atoms; or a phenyl group;
When R is an integer of 5 and p is 2 or more, each R ⁹ may be different, and when q is 2 or more, each R ¹⁰ may be different. )

Among these diphenyl carbonates,
Unsubstituted diphenyl carbonate, ditolyl carbonate, symmetric diaryl carbonates such as lower alkyl-substituted diphenyl carbonates such as di-t-butylphenyl carbonate are preferred, and diphenyl carbonate which is a diaryl carbonate having the simplest structure is particularly preferred. It is.

These diaryl carbonates may be used alone or in combination of two or more. Further, it is preferable that the content of chlorine atom and alkali or alkaline earth metal in these diaryl carbonates is small, and it is preferable that they are substantially not contained if possible.

The usage ratio (charge ratio) of the aromatic dihydroxy compound and the diaryl carbonate is the kind of the aromatic dihydroxy compound and the diaryl carbonate used, the polymerization temperature and other polymerization conditions, and the molecular weight and terminal ratio of the polycarbonate to be obtained. Depending on the amount of diaryl carbonate, the amount of diaryl carbonate is usually 0.9 to 2.5 mol, preferably 0.
It is used in a proportion of 95 to 2.0 mol, more preferably 0.98 to 1.5 mol.

Further, in the present invention, an aromatic polyhydric hydroxy compound for introducing a branched structure may be used in combination within a range not impairing the object of the present invention, and an aromatic compound for terminal modification or molecular weight control may be used. A group monohydroxy compound may be used in combination.

The polycarbonate of the present invention has a weight average molecular weight of usually 1,000 to 300,000, preferably 1,000 to 100,000.

In the present invention, the polycarbonate contains substantially no chlorine atom, and specifically,
Chlorine ion is 0.5 ppm or less by a potentiometric titration method using a silver nitrate solution, and at the same time, chlorine atom is a detection limit of 10 ppm or less by a combustion method. Preferably, the chlorine ion content is 0.1 ppm or less, which is lower than the detection limit of the above-described measurement method, and the chlorine atom content is 10 ppm or less at the same time. When the chlorine atom exceeds the above range, the metal forming the reflective layer is corroded and the durability of the reflecting mirror is deteriorated, which is not preferable.

Further, as the polycarbonate, (a)
The content of alkali metal and / or alkaline earth metal is 1 to
800 ppb, (b) aromatic monohydroxy compound content of 1 to 200 ppm, (c) oligomer component having a molecular weight of 1000 or less and residual monomer content of T _{1 to} T ₂ wt%
(However, T ₁ = 1,130,000 × (weight average molecular weight of the polycarbonate) ^−1.60 , T ₂ = 1,520,00
0 × (weight average molecular weight of the polycarbonate) ^-1.44 ), and (d) the proportion of terminal hydroxy groups in all terminals is in the range of 1 to 30%, which is excellent in thermal stability and fluidity, and has good moldability. Preferably, the reflection image of the obtained reflecting mirror is excellent.

The alkali metal and / or alkaline earth metal contained in the polycarbonate of the present invention is more preferably 1 to 400 ppb, further preferably 1 to 200.
It is the range of ppb.

Examples of alkali metals and alkaline earth metals include lithium, sodium, potassium, cesium, magnesium, calcium, strontium and barium. These metals are mixed in the polycarbonate as catalyst residues, impurities in raw materials, and foreign substances mixed in during the manufacturing process, and the state thereof is also ions, inorganic compounds, salts with organic compounds, complexes, etc., which are present in the polycarbonate. The form to be performed is not particularly limited. The measurement of the metals is not particularly limited, but a method of measuring by an atomic absorption method after ashing the polycarbonate is preferable.

The aromatic monohydroxy compound contained in the polycarbonate of the present invention is more preferably 1 to 1
The range is 50 ppm, more preferably 5 to 90 ppm.

The aromatic monohydroxy compounds include aromatic monohydroxy compounds generated in the polycondensation process,
Aromatic monohydroxy compounds used for molecular weight control or specific end groups are mentioned. In the former case, the type of aromatic monohydroxy compound generated varies depending on the type of carbonic acid diester used as a raw material. For example, when diphenyl carbonate is used as carbonic acid diester, phenol is generated. In the latter case, for example,
Generally used are t-butylphenol, t-octylphenol, cumylphenol, chromanylphenol, and nuclear substitution products thereof.

The content of the oligomer component having a molecular weight of 1000 or less and the content of the residual monomer contained in the polycarbonate of the present invention is preferably within the above range.

The content of the oligomer component having a molecular weight of 1000 or less and the content of the residual monomer vary greatly depending on the molecular weight of the polycarbonate, the amount of the aromatic monohydroxy compound used for controlling the molecular weight or the specific end group, the production method, the production conditions and the like. . In the present invention, the residual monomer means the above-mentioned aromatic dihydroxy compound and carbonic acid ester.

The terminal ratio is such that the ratio of terminal hydroxy groups to all the terminals of the polycarbonate is more preferably in the range of 1 to 20 mol%, and further preferably 1 to 20 mol%.
It is in the range of 15 mol%.

The polycarbonate of the present invention is produced from the above-mentioned aromatic dihydroxy compound and carbonic acid diester by the transesterification method.
A method of polycondensation in a transesterification reaction in a molten state while heating the above compound in the presence or absence of a catalyst under reduced pressure and / or under an inert gas flow, and its polymerization method, equipment, etc. are limited. There is no. For example, a stirred tank reactor, a thin-film reactor, a centrifugal thin-film evaporation reactor, a surface-renewal twin-screw kneading reactor, a twin-screw horizontal stirring reactor, a wet-wall reactor,
A perforated plate type reactor that polymerizes while freely falling, a perforated plate type reactor with wire that polymerizes while falling along a wire, and the like can be easily manufactured by using these alone or in combination. Alternatively, a solid-state polymerization method in which a prepolymer is produced by performing a transesterification reaction in a molten state and then the degree of polymerization is increased under reduced pressure and / or an inert gas flow in a solid state is also possible. The temperature of the transesterification reaction is
It is usually selected in the temperature range of 50 to 350 ° C., preferably 100 to 300 ° C., and there is no particular limitation. Generally, at a temperature higher than the above range, the obtained polycarbonate tends to be highly colored and inferior in thermal stability. If the temperature is lower than the above range, the polymerization reaction is slow and not practical. The reaction pressure varies depending on the molecular weight of the polycarbonate during melt polymerization, and when the number average molecular weight is 1000 or less, a range of 50 mmHg to normal pressure is generally used, and when the number average molecular weight is 1000 to 2000, 3 to 80 mm.
When the Hg range is a number average molecular weight of 2000 or more, 10 mmHg or less, particularly 5 mmHg or less is used.

In particular, in order to obtain the polycarbonate of the present invention having a minor component content within a specific range, it is preferable to polymerize at a temperature not exceeding 280 ° C. At temperatures above this range, the contents of the aromatic monohydroxy compound and the oligomer component having a molecular weight of 1000 or less tend to increase.
Among the above-mentioned polymerization apparatus and polymerization method, a surface renewal type biaxial kneading reactor, a biaxial horizontal stirring reactor, a perforated plate type reactor that polymerizes while free fall, and a wire that polymerizes while dropping along a wire A porous plate reactor and a solid-state polymerization method are preferable because they can efficiently polymerize even at a temperature not exceeding 280 ° C. In particular, a method using a perforated plate reactor that polymerizes while freely falling, a method using a perforated plate reactor with wire that polymerizes while falling along a wire, and a solid-state polymerization method are preferable.

It is also possible to produce the polycarbonate of the present invention by removing trace components from the polycarbonate after polymerization. For example, a method of dissolving the polycarbonate in a good solvent, filtering and then re-precipitating with a poor solvent, a method of dissolving a trace component and a solvent not dissolving the polycarbonate, for example, a method of extracting a trace component with a solvent such as acetone, accompanying Examples thereof include a method of adding a solvent (or no addition) to forcibly remove a trace component under high vacuum, a method of drying at a temperature at which a polycarbonate does not dissolve, or under vacuum or atmospheric pressure.

The polymerization by the transesterification method can be carried out without adding a catalyst, but it is carried out in the presence of a catalyst, if necessary, in order to increase the polymerization rate. The polymerization catalyst is not particularly limited as long as it is used in this field, but it is a hydroxide of an alkali metal or an alkaline earth metal such as lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide. Kinds; Alkali metal salts, alkaline earth metal salts, quaternary ammonium salts of hydroxides of boron or aluminum such as lithium aluminum hydroxide, sodium borohydride, tetramethylammonium borohydride; lithium hydride, hydrogenation Hydrogen compounds of alkali metals and alkaline earth metals such as sodium and calcium hydride; alkali metal and alkaline earth metal alkoxides such as lithium methoxide, sodium ethoxide and calcium methoxide; lithium phenoxide, sodium phenoxide, magnesium Phenoxy , LiO-Ar-OLi, NaO-Ar-
ONa (Ar is an aryl group) and other alkali metal and alkaline earth metal aryloxides; lithium acetate, calcium acetate, sodium benzoate and other alkali metal and alkaline earth metal organic acid salts; zinc oxide, zinc acetate, zinc Zinc compounds such as phenoxide; boron oxide, boron, sodium boron, boron trimethyl, boron tributyl, boron triphenyl, (R ³ R ⁴ R
⁵ R ⁶ ) NB (R ³ R ⁴ R ⁵ R ⁶ ) or (R ³ R ⁴ R ⁵ R ⁶ ) PB
Compounds of boron such as ammonium borate or phosphonium borate represented by (R ³ R ⁴ R ⁵ R ⁶ ) (R ³ , R ⁴ , R ⁵ , and R ⁶ are as described above); silicon oxide, silicic acid Compounds of silicon such as sodium, tetraalkyl silicon, tetraaryl silicon, diphenyl-ethyl-ethoxy silicon; compounds of germanium such as germanium oxide, germanium tetrachloride, germanium ethoxide, germanium phenoxide; tin oxide, dialkyl tin oxide, Compounds of tin such as dialkyltin carboxylate, tin acetate, ethyltin tributoxide and other alkoxy groups or aryloxy groups, tin compounds such as organotin compounds; lead oxide, lead acetate, lead carbonate,
Lead compounds such as basic carbonates, lead and organic lead alkoxides or aryloxides; onium compounds such as quaternary ammonium salts, quaternary phosphonium salts, quaternary arsonium salts; antimony oxides, antimony acetate and other antimony compounds Compounds of manganese acetate, manganese carbonate,
Compounds of manganese such as manganese borate; titanium compounds such as titanium oxide, alkoxide of tin oxide or aryloxide; zirconium acetate, zirconium oxide, alkoxide or aryloxide of zirconium,
Mention may be made of catalysts such as zirconium compounds such as zirconium acetylacetone.

When a catalyst is used, these catalysts may be used alone or in combination of two or more. The amount of these catalysts used is usually 10 ^-8 to 1% by weight based on the aromatic dihydroxy compound as a raw material,
It is preferably selected in the range of 10 ^-7 to 10 ^-1 % by weight. Further, when the removal work after polymerization is not performed using an alkali or alkaline earth metal-based catalyst, the total content of alkali and / or alkaline earth metal in the polycarbonate after polymerization is in the range of 1 to 800 ppb. It is preferably used.

In the polycarbonate of the present invention, conventional additives such as a heat stabilizer, an antioxidant, a flame retardant, a release agent, a colorant, a lubricant, and an improvement in weather resistance can be added to the polycarbonate so long as the object of the present invention is not impaired. Agents, rust preventives and the like can be added.

As the heat resistance stabilizer, for example, phosphorus stabilizers, phenol stabilizers, sulfur stabilizers, epoxy stabilizers, hindered amine stabilizers and the like can be used. A phosphorus stabilizer is particularly preferable.

Examples of the phosphorus-based stabilizers include phosphoric acid, phosphorous acid ester, phosphinic acid ester, phosphoric acid ester and phosphonic acid ester. Specifically, as phosphoric acids, phosphoric acid, phosphorous acid, hypophosphorous acid,
Examples include pyrophosphoric acid, polyphosphoric acid, and phenylphosphonic acid.

Examples of the phosphite ester include phosphite triester, phosphite diester and phosphite monoester, and specifically, tris (2,4-di-t-butylphenyl) phosphite. , Tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, triphenylphosphite, tetraphenyldipropylene glycol phosphite, tetra (tridecyl) 4,4'-isopropylidene diphenyldiphosphite, bis (nonyl) Phenyl) pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,
6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, hydrogenated bisphenol A, pentaerythritol phosphite polymer, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite, Diphenyl hydrogen phosphite, bis (nonylphenyl) hydrogen phosphite, bis (2,4-di-t-butylphenyl) hydrogen phosphite, dicresyl hydrogen phosphite, (bis (pt-butylphenyl) hydrogen phosphite , Bis (p-hexylphenyl) hydrogen phosphite, phenyl dihydrogen phosphite, nonylphenyl dihydrogen phosphite, 2,4-di-t
-Butylphenyl dihydrogen phosphite and the like.

Examples of the phosphinic acid esters include phosphinic acid diesters and phosphinic acid monoesters, and specifically, 4,4'-diphenylenediphosphinic acid tetrakis (2,4-di-t-butylphenyl). To be

Examples of the phosphoric acid esters include phosphoric acid diesters and phosphoric acid monoesters. Specific examples thereof include diphenyl hydrogen phosphate, bis (nonylphenyl) hydrogen phosphate, and bis (2,4-di-t.
-Butylphenyl) hydrogenphosphate, dicresylhydrogenphosphate, bis (pt-butylphenyl) hydrogenphosphate, bis (p-hexylphenyl) hydrogenphosphate, phenyldihydrogenphosphate, nonylphenyldihydrogenphosphate, 2,4-di Examples thereof include -t-butylphenyl dihydrogen phosphate.

Examples of the phosphonates include phosphonate monoesters.

Specific examples of the phenolic stabilizer include 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-p-anisole and 2,6-di-t-. Butyl-4-ethylphenol, 2,2'-methylenebis (6-t-butyl-p-cresol), 2,2'-methylenebis (4-ethyl-6-t-butyl-p-phenol), 4,4 '-Methylenebis (6-t-butyl-p-
Cresol), 4,4'-butylidene bis (6-t-butyl-m-cresol), tetrakis [methylene-3-
(3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, 4,4′-thiobis (6-t-butyl-m-cresol), stearyl-β
-(3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,
4,6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, triethylene Bricol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate and the like can be mentioned. ]

Furthermore, a phenolic stabilizer containing a phosphorus atom, for example, 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, bis (3,
5-di-t-butyl-4-hydroxybenzylphosphonate ethyl) calcium and the like can also be mentioned.

As the sulfur stabilizer, sulfinic acid,
Examples thereof include sulfonic acid and its ester, and thioether compound. Specific examples thereof include benzenesulfinic acid, p-toluenesulfinic acid, benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, and methyl, ethyl, and butyl of these acids. Examples include octyl and phenyl ester. Further, dilauryl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate ,
Pentaerythritol (β-lauryl thiopropionate) and the like can be mentioned.

Examples of the epoxy stabilizer include fats and oils such as epoxidized soybean oil and epoxidized linseed oil, phenyl glycidyl ether, allyl glycidyl ether, t-butylphenyl glycidyl ether, bisphenol A diglycidyl ether, and tetrabromobisphenol A diester. Glycidyl ether, phthalic acid diglycidyl ester,
Hexahydrophthalic acid diglycidyl ester and other glycidyl compounds, 3,4-epoxycyclohexylmethyl-
3,4-epoxycyclohexanecarboxylate,
3,4-epoxy-6-methylcyclohexylmethyl-
3,4-epoxycyclohexanecarboxylate,
2,3-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 4- (3,4-
Epoxy-5-methylcyclohexyl) butyl-3,4
-Epoxycyclohexanecarboxylate, 3,4-
Epoxy cyclohexyl ethylene oxide, cyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, bisepoxycyclohexyl adipate, octadecyl-2,2'-dimethyl-3 , 4-epoxycyclohexanecarboxylate, N-butyl-2, 2'-dimethyl-3, 4-epoxycyclohexanecarboxylate, cyclohexyl-2-methyl-3, 4-epoxycyclohexanecarboxylate, N-butyl-2-isopropyl -3,4, -epoxy-5-methylcyclohexanecarboxylate, octadecyl-3,4-epoxycyclohexanecarboxylate, 2-ethylhexyl-3,4-epoxy Chlorohexanecarboxylate, 4,6-dimethyl-2,3-epoxycyclohexyl-3,4-epoxycyclohexanecarboxylate, diethyl-4,5-epoxy-cis-1,2-cyclohexanecarboxylate, di-n-butyl. -3-t
-Butyl-4,5-epoxy-cis-1,2-cyclohexanecarboxylate, 3,4-dimethyl-1,2-
Epoxy cyclohexane, 3,5-dimethyl-1,2-
Epoxycyclohexane, 3-methyl-5-t-butyl-1, 2-epoxycyclohexane and other epoxycyclohexane compounds, bisepoxydicyclopentadienyl ether, butadiene diepoxide, tetraphenylerenepoxide, epoxidized polybutadiene, 4 , 5-
Epoxy tetrahydrophthalic anhydride, 3-t-butyl-
Examples include 4,5-epoxy tetrahydrophthalic anhydride and the like.

Examples of the hindered amine-based stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1,2,2,6,6-pentamethyl-
4-piperidyl) sebacate, 2- (3,5-di-t-
Butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-
Piperidyl) tetraxy (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 1- [2- {3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionyloxy} ethyl] -4- {3- (3,5-di-t-butyl-
4-hydroxyphenyl) propionyloxy} -2,
2,6,6-tetramethylpiperidine, 8-benzyl-
7,7,9,9-tetramethyl-3-octyl-1,
2,3-triazaspiro {4,5} undecane-2,4
-Dione, 4-benzoyloxy-2,2,6,6-tetramethylpiperazine and the like can be mentioned.

These heat resistance stabilizers may be used alone or in combination. The addition amount is not particularly limited, but it is generally used in the range of 0.0005 to 0.22 parts by weight with respect to 100 parts by weight of the polycarbonate.

The method of mixing the additives such as the heat resistance stabilizer with the polycarbonate may be a conventionally known method and is not particularly limited. For example, after uniformly mixing each component with a Henschel mixer, super mixer, tumbler mixer, ribbon blender, etc., kneading with a single-screw extruder, a twin-screw extruder, a Banbury mixer, or a molten polycarbonate mixing tank. There is also a method of mixing the additives using a static mixer single screw extruder or a twin screw or multi screw extruder.

Other resins may be mixed with the above polycarbonate as long as the characteristics of the polycarbonate are not significantly impaired. For example, polyethylene, polypropylene, polystyrene, ABS resin, polyvinyl chloride, polyamide, polyacetal, modified polyphenylene ether, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, polyimide, polyamide imide, polyether imide, polyarylate, polysulfone, polyether sulfone , Polyetherketone, liquid crystal polymer, polytetrafluoroethylene, thermoplastic elastomer and the like.

When a mixed composition of the aromatic polycarbonate of the present invention and another resin is used, the content of the polycarbonate of the present invention must be 50% by weight or more, preferably 70% by weight or more. If the content of the polycarbonate resin is too low, excellent properties of the polycarbonate resin as an engineering resin cannot be obtained.

Fillers such as glass fiber, carbon fiber, metal fiber, aramid fiber, potassium titanate, silicon carbide, ceramic, silicon nitride, barium sulfate, calcium sulfate, kaolin, clay, pyrophyllite, bentonite, sericite. , Zeolite, mica, mica,
Nepheline sinite, talc, atarupulgite, wollastonite, PMF, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, dolomite,
Zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, graphite, gypsum, glass beads, glass balloons, quartz, quartz glass and the like can be mixed. These fillers may be hollow, or two or more kinds may be used in combination.

The method for molding the sheet produced from the polycarbonate of the present invention is not particularly limited, and the sheet can be produced by extrusion molding, injection molding or compression molding. As molding conditions, it is preferable to gradually cool the molten resin when it is solidified, from the viewpoint of image reflectivity. In the case of extrusion molding, the surface temperature of the mirror surface roll is 180 degrees based on the melting temperature of the resin.
It is within ℃, preferably within 150 ℃. In the case of injection molding or compression molding, the surface temperature of the mold or cooling press is within 240 ° C, preferably within 200 ° C, based on the melting temperature of the resin.

A sheet having a thickness of 2 to 10 mm is used. If it is less than 2 mm, distortion occurs when it is attached to a projection TV mirror holder, which is not preferable. 10
If it exceeds mm, there is little weight reduction effect.

There is a case where a reflective layer is provided on a transparent substrate, a case where it is provided on the front surface of the substrate (front mirror) and a case where it is provided on the back surface (rear surface mirror). The image deteriorates. The front surface mirror is preferable when a highly accurate reflection image is required as in a projection television.

As the metal constituting the reflecting surface, aluminum, silver or the like is used, and silver having an excellent reflectance is particularly preferable. These metals are applied to the surface of the base material by vapor deposition, sputtering or the like. Further, a silicone coating agent or an acrylic coating agent is used to protect the reflecting surface.

The reflection mirror of the present invention preferably has a reflection image property of 3% or less. Here, the reflection image property is JIS
It is a value determined according to the strain inspection method of D 5705 (mirror device for automobiles).

When the reflecting mirror is attached to the projection television cabinet, a support may be provided on the back surface of the reflecting mirror as long as the object of the present invention is not impaired.

[0102]

EXAMPLES Hereinafter, the present invention and comparative examples will be described in more detail. Note that the present invention is not limited to this.

The measuring methods in the examples are as follows.

1. Weight average molecular weight, weight average molecular weight 10
The content of oligomers and residual monomers of 00 or less was measured by gel permeation chromatography. The column used TSK-GEL (made by Toyo Soda Co., Ltd.), and the solvent used THF.

2. Content of alkali and alkaline earth metal After polycarbonate was ashed at low temperature by oxygen plasma asher, it was measured by flameless atomic absorption spectrometry.

3. Aromatic monohydroxy group content was measured by high performance liquid chromatography.

4. Terminal hydroxy group terminal ratio Measured by NMR.

5. Durability The reflecting mirror was stored for 1000 hours under the conditions of 90 ° C. and 85% relative humidity, and then visually judged.

6. Reflective image property It was based on the strain inspection method of JIS D 5705 (mirror device for automobiles).

7. Impact resistance Ten test plates of 120 mm x 120 mm were prepared, steel balls having a diameter of 15 mm were dropped from a height of 2 m, and the state of the test plates was observed.

(Example 1) Bisphenol A containing substantially no chlorine atom as an aromatic dihydroxy compound
As a carbonic acid diester, diphenyl carbonate substantially free of chlorine atom (molar ratio of bisphenol A to 1.10), and a catalyst of disodium salt of bisphenol A (molar ratio of bisphenol A to 2.8 × 10 ⁻⁸ ). It was used to produce a polycarbonate by the melt transesterification method. The production was carried out using a continuous polymerization apparatus consisting of three stirring tank reactors and two perforated plate reactors with wires, while gradually increasing the temperature and the degree of vacuum. Maximum polymerization temperature is 2
It was 50 ° C.

The obtained polycarbonate contained substantially no chlorine atom, the hydroxy group terminal ratio was 7 mol%, and the weight average molecular weight was 22,100. Also,
The trace components of the polycarbonate include an alkali and alkaline earth metal content of 5 ppb, a phenol content of an aromatic monohydroxy compound of 30 ppm, and a molecular weight of 10
The content of oligomer components of not more than 00 and residual monomer content was 0.5% by weight.

100 parts by weight of the polycarbonate, 0.002 parts by weight of bis (nonylphenyl) hydrogen phosphite as a heat-resistant stabilizer and 0.02 parts by weight of tris (2,4-t-butylphenyl) phosphite as a heat-resistant stabilizer were added to a Henschel mixer. After being uniformly mixed with, the mixture was granulated using an extruder to obtain a polycarbonate composition.

Using the polycarbonate composition obtained, a resin temperature of 280 ° C. and a cooling roll surface temperature of 140 ° C.
Then, a sheet having a width of 300 mm and a thickness of 3 mm was slowly cooled by extrusion molding. The obtained sheet was cut into a 120 mm square to prepare a test sheet.

Silver was vapor-deposited on the obtained test sheet by sputtering, and then a photocurable acrylic resin was coated and cured with ultraviolet rays to prepare a reflecting mirror.

Table 1 shows the evaluation results of durability, reflection image property and impact resistance of the reflecting mirror.

Comparative Examples 1 and 2 Polycarbonates were produced from bisphenol A, sodium hydroxide, phosgene, triethylamine as a catalyst, and pt-butylphenol as a molecular weight modifier by a phosgene method using a methylene chloride solvent.

The obtained polycarbonate contained chlorine atoms, the chlorine ion content was 1.2 ppm, and the chlorine atom content was 30 ppm. The hydroxy group terminal ratio was 1 mol% and the weight average molecular weight was 22,800. In addition, the trace components of the polycarbonate have an alkali and alkaline earth metal content of 82 ppb, an aromatic monohydroxy compound pt-butylphenol content of 43 ppm, and an oligomer component having a molecular weight of 1000 or less and a residual monomer content of 1 ppm. It was 0.4% by weight. A heat stabilizer was added in the same manner as in Example 1 to obtain a polycarbonate composition. 3 m thick made using the composition
A reflecting mirror was produced in the same manner as in Example 1 except that the m sheet (Comparative Example 1) and the glass having a thickness of 3 mm (Comparative Example 2) were used, and the same evaluation was performed. The results are shown in Table 1.

(Example 2) The chlorine ion-free polycarbonate of Example 1 was used in an injection molding machine at a cylinder temperature of 300 ° C, a mold temperature of 110 ° C and a thickness of 3 mm.
A 0 mm square flat plate was injection molded. A reflecting mirror was produced from the obtained flat plate in the same manner as in Example 1, and the same evaluation was performed.
The results are shown in Table 1. In the injection molding using the polycarbonate of the present invention, when the injection molding work was once interrupted for 30 minutes and the molding was reunited, the same good molded product as that before the interruption was obtained from the first shot.

Comparative Example 3 A reflecting mirror was prepared in the same manner as in Example 2 except that the polycarbonate of Comparative Example 1 was used, and the same evaluation was carried out. The results are shown in Table 1. In the injection molding using the polycarbonate, when the molding is once interrupted for 30 minutes during the injection molding and the molding is reunited, color unevenness, burns, and black dust are generated until a good molded product is obtained.
It was necessary to throw away more than the shot.

(Examples 3 to 5) Catalyst Bisphenol A
The disodium salt is used in a molar ratio of 2.8 × 10 ⁻⁷ (Example 3) and a molar ratio of 5 × 1 with respect to the bisphenol A used.
Weight average molecular weight 2 in the same manner as in Example 1 except that 0 ⁻⁷ (Example 4) and a molar ratio of 1 × 10 ⁻⁶ (Example 5) were used.
2,500 polycarbonates were obtained. A heat stabilizer was added in the same manner as in Example 1 to obtain a polycarbonate composition. The hydroxy terminal ratio and minor components of each polycarbonate were as follows.

Polycarbonate of Example 3: Hydroxy terminal ratio 6 mol%, alkali and alkaline earth metal content 49 ppb, aromatic monohydroxy compound phenol content 79 ppm, molecular weight 1000 or less oligomer component and residual monomer content 0.51% by weight

Polycarbonate of Example 4: Hydroxyl terminal ratio 3 mol%, alkali and alkaline earth metal content 92 ppb, phenol content of aromatic monohydroxy compound 100 ppm, oligomer component having a molecular weight of 1000 or less and residual monomer content 0.72% by weight

Polycarbonate of Example 5: 4 mol% of hydroxy terminal ratio, content of alkali and alkaline earth metal is 182 ppb, content of phenol which is aromatic monohydroxy compound is 113 ppm, content of oligomer component having molecular weight of 1000 or less and residual monomer 0.78% by weight

A reflecting mirror was prepared in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1.

[0126]

[Table 1]

[0127]

INDUSTRIAL APPLICABILITY The polycarbonate containing substantially no chlorine atom of the present invention is excellent in moldability, and the reflecting mirror made of the polycarbonate is excellent in durability, impact resistance and reflection image property, and is a flat mirror for projection television. Is suitable as

Claims (4)

[Claims] 1. A sheet formed from a substantially chlorine atom-free polycarbonate produced by an ester exchange method from an aromatic dihydroxy compound and a carbonic acid diester and provided with a reflection layer, has durability and reflection imageability. Excellent reflector. 2. The polycarbonate has (a) an alkali metal and / or alkaline earth metal content of 1 to 800 pp.
b, (b) The content of aromatic monohydroxy compound is 1 to 2
00 ppm, (c) The content of oligomer components having a molecular weight of 1000 or less and residual monomer content is T _{1 to} T ₂ % by weight (however, T
₁ = 1,130,000 × (weight average molecular weight of the polycarbonate) ^-1.60 , T ₂ = 1,520,000 × (weight average molecular weight of the polycarbonate) ^-1.44 ), (d) at all terminals of the terminal hydroxy group 1 to 30 mol%
The reflecting mirror according to claim 1, wherein 3. The reflecting mirror according to claim 1, which has a reflection image property of 3% or less. 4. A rear projection type projection television, comprising the reflecting mirror according to any one of claims 1 to 3.