JPH01201328A - Aromatic polycarbonate film - Google Patents

Abstract

PURPOSE:To obtain the title film having a low moisture permeability and a high surface hardness, excelling in heat resistance, mechanical properties, etc., and being useful for components of electronic and electrical devices and machines and paint films, by molding a polycarbonate having repeating units of a specified formula. CONSTITUTION:This film is produced by molding a polycarbonate having repeating units of formula I, wherein R1 is formula II (wherein R2 and R3 are each H, a 1-6C alkyl or a phenyl), formula III (wherein n is 2-10), formula IV (wherein p is 4-10), a direct bond, -O-, -S- or -SO2-. This film is one having a low moisture permeability and a high surface hardness and being equivalent superior to a conventional aromatic polycarbonate film in heat resistance, mechanical properties, etc., and is markedly useful for components of various electronic and electrical devices and machines and paint films. It undergoes neither gelation nor crystallization with a solvent or the like and therefore does not suffer any decrease in mechanical strengths and transparency.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to aromatic polycarbonate films used as parts of various electronic and electrical devices. More particularly, the present invention is inherently indecent;
The present invention relates to an aromatic polycarbonate film that has excellent transparency, heat resistance, and mechanical strength, as well as improved low moisture permeability and surface hardness.

[Conventional technology] Aromatic polycarbonate film has transparency, heat resistance,
It is known for its well-balanced mechanical strength and electrical properties, and is used as a variety of engineering plastics, including parts for electronic and electrical equipment. The aromatic polycarbonate film that has been commonly used is 2,2-bis(4-hydroxyphenyl)
It was made from a commercially available aromatic polycarbonate consisting of repeating units represented by the formula obtained from the reaction of propane (bisphenol A) and a carbonate precursor such as phosgene.

However, in recent years, as the properties required of films used as parts of electronic and electrical equipment have become more sophisticated, the drawbacks of films molded from commercially available polycarbonate, such as high moisture permeability and low surface hardness, have become apparent. It's arrived. Furthermore, commercially available polycarbonates have a tendency to gel and crystallize due to solvents and the like, resulting in a problem of lowering the mechanical strength and transparency of the film.

[Problem to be solved by the invention]

An object of the present invention is to provide an aromatic polycarbonate film which eliminates the above-mentioned drawbacks, has improved low moisture permeability and surface hardness, and has no tendency to gel or crystallize due to solvents of the polymer material. The purpose is to

[Means to solve the problem]

In other words, the invention of claim 1 provides -i formula (1) [wherein R
1 is -C- (here, R2 and R3 each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and may be the same or different from each other), -+CLh
(Here, n represents an integer from 2 to 10.

), ), represents a single bond, -O-, -S-, or -5O2-. ] An aromatic polycarbonate film molded from polycarbonate having a repeating unit represented by the following is provided.

The invention of claim 2 provides -format (1) and -format (n) [wherein R1 and R4 represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, and may be the same or different from each other. moyoi), 4CHzh
(Here, n represents an integer from 2 to 10.

), ), represents a single bond, -O-, -S-, or -SO,-, and each X represents an alkyl group having 1 to 6 carbon atoms or a halogen atom, and may be the same or different from each other. Well done! and m each represent an integer of 0 to 4 and may be the same or different from each other, and have a repeating unit represented by ], and the molar fraction of the repeating unit represented by -format CI). The present invention provides an aromatic polycarbonate film formed from a polycarbonate in which q is the molar fraction of repeating units represented by the -format (n).

The polycarbonate used for forming the film of the invention of claim 2 is such that the main chain of the polymer is composed of repeating units represented by the above-mentioned form (1) and repeating units represented by the above-mentioned form (I). If this value is less than 0.05, the effect of lowering the moisture permeability of the film and improving the surface hardness cannot be obtained.In addition, the gelation and crystallization of the polymer material due to solvents etc. cannot be obtained. The prevention effect will no longer be obtained.

The films of the inventions according to claims 1 and 2 include films that thinly cover the surface of articles in addition to the generally referred to thin films.

The molecular weight of the aromatic polycarbonate used in the inventions of claims 1 and 2 may be appropriately selected depending on the type of film, but the reduced viscosity at 20°C of a methylene chloride solution with a concentration of 0.5 g/d1 (7731) /C) is 0
．． 3-4.0 d1/g, preferably 0.4-3,5
It is desirable that the ratio is d/g.

If this reduced viscosity is less than 0.3a7g,
The strength of the resulting film may be insufficient. Moreover, if it exceeds 4.0411 g, it may become substantially difficult to form a film.

Specific examples of (2) include hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group,
Examples include phenyl group.

Particularly preferable examples of R1 include ■ H3 can be mentioned.

Specific examples of the X include halogen atoms such as fluorine atom, bromine atom, and chlorine atom, methyl group, ethyl group,
Examples include propyl group, isopropyl group, butyl group, isobutyl group, heptyl group, hexyl group, isohexyl group, and the like.

The polycarbonate used in the inventions of claims 1 and 2 can be produced by various conventionally known methods, for example -form (II[) [wherein R1 has the same meaning as defined above] A dihydric phenol compound and phosgene represented by the formula (I[[) and a dihydric phenol compound represented by the formula (IV) [wherein, X, R', ! , and m have the same meaning as defined above. ] Methods such as a direct reaction between the dihydric phenol compound represented by the following and phosgene, or a transesterification reaction between the dihydric phenol compound and bisaryl carbonate can be employed.

In the former method of direct reaction between a dihydric phenol compound and phosgene, the dihydric phenol compound and phosgene are usually reacted in the presence of an acid binder and a solvent. As the acid binder, for example, pyridine or an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is used, and as the solvent, for example, methylene chloride, chlorobenzene, xylene, etc. are used. Furthermore, in order to accelerate the polycondensation reaction, catalysts such as tertiary amines such as triethylamine or quaternary ammonium salts are added, and in order to adjust the degree of polymerization, p-t-7" methylphenol and phenyl It is desirable to carry out the reaction by adding a molecular regulator such as phenol.Additionally, if desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added.
°C1 Preferably carried out at a temperature in the range of 5 to 40 °C. The reaction time depends on the reaction temperature, but 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 higher.

On the other hand, in the latter transesterification method, the dihydric phenol compound and bisaryl carbonate are mixed,
The reaction is carried out at elevated temperature under reduced pressure.

The reaction is usually carried out at 150-350°C, preferably 200-350°C.
The reaction is carried out at a temperature in the range of 00°C, and the degree of vacuum is preferably set to 1 mmHg or less at the end, so that the phenols derived from the bisaryl carbonate produced by the transesterification reaction are distilled out of the system. The reaction time depends on the reaction temperature, degree of pressure reduction, etc., but it is usually about 1 to 4 hours.The reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon, and if desired, the above-mentioned The reaction may be carried out by adding a molecular weight regulator, an antioxidant, or the like.

Specific examples of the compound represented by general formula (III) include:
For example, 2,2-bis(3-phenyl-4-hydroxyphenyl)propane, 1-phenyl-1゜1-bis(3-
Phenyl-4-hydroxyphenyl)ethane, 1.1-
Bis(3-phenyl-4-hydroxyphenyl)cyclohexane, 3.3-bis(3-phenyl-4-hydroxyphenyl)pentane, bis(3-phenyl-4-hydroxyphenyl)sulfone, 3.3'-diphenyl- 4
゜4'-dihydroxybiphenyl, bis(3-phenyl-4-hydroxyphenyl)methane, 1-phenyl-1
,1-bis(3-phenyl-4-hydroxyphenyl)
Methane, 1.1-bis(3-phenyl-4-hydroxyphenyl)ethane, 1゜2-bis(3-phenyl-4-
hydroxyphenyl)ethane, l,3-bis(3-phenyl-4-hydroxyphenyl)propane, 2,2-bis(3-phenyl-4-hydroxyphenyl)butane,
1.4-bis(3-phenyl-4-hydroxydiphenyl)butane, 1.1-bis(3-phenyl-4-hydroxyphenyl)-1-phenylbutane, 2.2-bis(3
-phenyl-4-hydroxyphenyl)octane, 1.
8-bis(3-phenyl-4-hydroxyphenyl)octane, bis(3-phenyl-4-hydroxyphenyl)ether, bis-(3-phenyl-4-hydroxyphenyl)sulfide, 1.1-bis(3- phenyl-4
-hydroxyphenyl)cyclopenkune, and the like.

Among these, 2,2-bis(3-phenyl-4-
hydroxyphenyl)propane, 1-phenyl-1,1
-bis(3-phenyl-4-hydroxyphenyl)ethane, 1,1-bis(3-phenyl-4-hydroxyphenyl)cyclohexane, and bis(3-phenyl-4-
Hydroxyphenyl) sulfone is preferably used.

Specific examples of the dihydric phenol compound represented by the above-mentioned format (IV) include bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, and 1,2-bis(4-hydroxyphenyl)ethane. -hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane,
2,2-bis(3-methyl-4-hydroxyphenyl)
Propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, 4,4-bis(4-hydroxyphenyl)hebutane, 1,1-bis(4- hydroxyphenyl)-1,1-
Diphenylmethane, 1.1-bis(4-hydroxyphenyl)-1-phenylethane, 1.1-bis(4-hydroxyphenyl)-1-phenylmethane, bis(4-hydroxyphenyl) ether, bis(4-hydroxy phenyl) sulfide, bis(4-hydroxyphenyl)
Sulfone, 1.1-bis(4-hydroxyphenyl)cyclopenkune, 1.1-bis(4-hydroxyphenyl)cyclohexane, 2.2-bis(3-methyl-4-hydroxyphenyl)propane, 2.2-bis (3,5-
dimethyl-4-hydroxyphenyl)propane, 2-
(3-methyl-4-hydroxyphenyl)-2-(4-
hydroxyphenyl)propane, 1,1-bis(3-methyl-4-hydroxyphenyl)-1-phenylethane, bis(3-methyl-4-hydroxyphenyl) sulfide, bis(3-methyl-4-hydroxyphenyl) Sulfone, bis(3-methyl-4-hydroxyphenyl)
Methane, 1,1-bis(3-methyl-4-hydroxyphenyl)cyclohexane, 4,4'-dihydroxybiphenyl, 2,2-bis(2-methyl-4-hydroxyphenyl)propane, 1,1-bis( 2-butyl-4-
Hydroxy-5-methyl-hydroxyphenyl)butane, 1,1-bis(2-t-butyl-4-hydroxy-5
-methylphenyl)ethane, 1゜1-bis(2-t-butyl-4-hydroxy-5-methylphenyl)propane, 1,1-bis(2-t-butyl-4-hydroxy-5
-methylphenyl)butane, 1.1-bis(2-tert-butyl-4-hydroxy-5-methylphenyl)isobutane, 1.1-bis(2-mo-butyl-4-hydroxy-
5-methylphenyl)hebutane, 1,1-bis(2-t
-butyl-4-hydroxy-5-methylphenyl)-1
-phenylmethane, 1,1-bis(2-t-amyl-4
-hydroxy-5-methylphenyl)butane, bis(3
-chloro-4-hydroxyphenyl)methane, bis(3
,5-dibromo-4-hydroxyphenyl)methane, 2
゜2-bis(3-chloro-4-hydroxyphenyl)propane, 2.2-bis(3-fluoro-4-hydroxyphenyl)propane, 2.2-bis(3-7'romo4
-hydroxyphenyl)furopane, 2,2-bis(3,
5-dichloro-4-hydroxyphenyl)propane, 2
．． 2-bis(3゜5-difluoro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4
-hydroxyphenyl)propane, 2,2-bis(3-
Fromo 4-hydroxy-5-chlorophenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)butane, 2,2-bis(3,5-dibromo-
4-hydroxyphenyl)butane, 1,1-bis(3-
Fluoro-4=hydroxyphenyl)-1-phenylethane, bis(3-fluoro-4-hydroxyphenyl)
Examples include ether, 3,3'-difluoro-4,4'-dihydroxybiphenyl, and the like.

Among them, 2,2-bis(4-hydroxyphenyl)propane is particularly preferred.

The aromatic polycarbonate used in the inventions of claims 1 and 2 also includes modified polycarbonate produced by adding other dihydric phenol compounds to the extent that the properties of the film are not impaired. Other dihydric phenol compounds mentioned above include resorcinol, hydroquinone, and the like.

Furthermore, aromatic polycarbonates having branches produced by adding a small amount, for example, about 0.05 to 2.0 mol % of a polyhydroxy compound based on the dihydric phenol compound used, are also included.

In producing the film of the invention of claims 1 and 2, polyalkylene terephthalate, polyolefin, other polycarbonate, polyether sulfone, polyarylate may be added to the above-mentioned one or more aromatic polycarbonates as necessary. Thermoplastic resins such as polysulfone, polyphenylene sulfide, etc. can be blended.

These aromatic polycarbonates may also contain known additives, such as flame retardants, antioxidants, antistatic agents, fillers, impact modifiers, ultraviolet absorbers, plasticizers, and hydrolytic stabilizers, as necessary. Agents, pigments, dyes, coloring stabilizers, etc. can be added.

The film forming method of the invention of claims 1 and 2 includes:
A conventionally known film forming method can be used.

For example, press molding such as hot press molding; extrusion methods such as cast roll method, inflation method, and tubular method; methods of casting a polymer solution on a belt and evaporating the solvent to form a thin film; Examples include a coating method in which the solvent is removed after application.

Examples of the solvent used for preparing the polymer solution include halogen solvents such as chloroform and methylene chloride, aromatic solvents such as toluene, and ether solvents such as tetrahydrofuran.

In addition, the film thus produced may be stretched, if necessary, by a conventionally used stretching method, such as a tenter method, a Cheapler method, a multi-stage stretching method, etc.
Further, heat treatment can also be performed if necessary.

The thickness of the film according to the first and second aspects of the invention is not particularly limited, but is usually selected in the range of 0.1 to 1000 μm, preferably 1 to 500 μm.

The film formed in this way not only has excellent heat resistance, mechanical strength, electrical insulation, etc., as well as conventional aromatic polycarbonate films, but also has significantly improved low moisture permeability and surface hardness. It is something that Therefore, it can be suitably used as a heat-resistant film, a low moisture permeable film, an electrically insulating film, parts of various electronic and electrical devices, coating films, etc. Furthermore, since gelation and crystallization of the polymer material due to solvents and the like have been eliminated, it has become possible to form a film by a film forming method using a polymer solution.

〔Example〕

Hereinafter, the inventions of claims 1 and 2 will be explained in more detail based on examples, but these inventions are not limited to the following examples in any way.

Example 1 Gold bottom ■ 2. Dissolve 60 g of 2-bis(3-phenyl-4-hydroxyphenyl)propane and 0.5 g of pt-butylphenol, a molecular weight regulator, in 500 d of methylene chloride, and dissolve 3 d of water.
00d, triethylamine ld was added as a catalyst, and phosgene gas was blown in at a rate of 300 to 400 d/min while stirring. While blowing phosgene gas, the pH of the reaction system is 10.
An aqueous solution of sodium hydroxide having a concentration of 12N was added dropwise so that the concentration did not exceed 12N. After blowing in phosgene gas for 25 minutes, the reaction was allowed to proceed for 1 hour, and the product was dissolved in 700 d of methylene chloride.
diluted with water, washed with water, 0.01N hydrochloric acid, and water in that order.
The polymer was recovered by injecting it into 51 methanol. The yield of the polymer was 96%, and it had a repeating unit with the following structure.

A 10% by weight solution of this polymer in tetrahydrofuran was prepared, allowed to stand at room temperature for one month, and the solution viscosity was measured. - Even after being left for a month, no clouding or gel formation occurred, and no change in viscosity was observed.

1 part by weight of the polymer obtained here was dissolved in 50 parts by weight of chloroform to prepare a polymer solution. This polymer solution was cast onto a glass plate using a doctor knife and dried under reduced pressure at 120°C for 24 hours to obtain a film with a thickness of 20 μm.

Next, the obtained film was subjected to a tensile test using an autograph. In addition, moisture permeability was measured according to JI 5-Z-0208, cup method B (40°C, humidity 90%), and a pencil hardness test was conducted according to JIS-5400 to measure surface hardness.

The results of these measurements are shown in Table 1.

Example 2 1-phenyl-1,1-bis(
The same operation as in Example 1 was carried out except for using 3-phenyl-4-hydroxyphenyl)ethane to obtain a polymer having a repeating unit having the following structure.

Using this polymer, operations similar to those for forming the film in Example 1 were performed to obtain a film.

The results of each test are shown in Table 1.

Example 3 1,1-bis(3-phenyl-
A polymer having repeating units having the following structure was obtained by carrying out the same operation as in Example 1 except for using 4-hydroxyphenyl)cyclohexane.

Using this polymer, operations similar to those for forming the film in Example 1 were performed to obtain a film.

The results of each test are shown in Table 1.

Example 4 The same operation as in Example 1 was carried out except that bis(3-phenyl-4-hydroxyphenyl) sulfone was used instead of 2.2-bis(3-phenyl-4-hydroxyphenyl)propane, and the following was carried out. A polymer having structural repeating units was obtained.

Using this polymer, operations similar to those for forming the film in Example 1 were performed to obtain a film.

The results of each test are shown in Table 1.

Example 5 2.2-bis(3-phenyl-4-hydroxyphenyl) instead of 2.2-bis(3-phenyl-4-hydroxyphenyl)propane
-Hydroxyphenyl)propane 38,0 g, 2.2
The same operation as in Example 1 was carried out except that 20 g of -bis(4-hydroxyphenyl)propane was used to obtain a polymer having a repeating unit of the following structure.

Using this polymer, operations similar to those for forming the film in Example 1 were performed to obtain a film.

The results of each test are shown in Table 1.

Comparative Example 1 A 10% by weight solution of a commercially available polycarbonate (Idemitsu Polycarbonate A2500 manufactured by Idemitsu Petrochemical Co., Ltd.) in tetrahydrofuran was prepared and left to stand at room temperature for one month, but clouding and gel formation occurred.

Using this commercially available polycarbonate, operations similar to those for forming the film in Example 1 were performed to obtain a film.

The results of each test are shown in Table 1.

[Effects of the Invention] According to the inventions of claims 1 and 2, the aromatic polycarbonate film has low moisture permeability and high surface hardness, and is comparable to or superior to conventional aromatic polycarbonate films in terms of heat resistance, mechanical properties, etc. A polycarbonate film could be obtained. Such aromatic polycarbonate films are useful as parts and coatings for various electronic and electrical devices. Furthermore, since the polymer is essentially non-grade, it does not undergo gelation or crystallization due to solvents, etc., and does not cause a decrease in the mechanical strength or transparency of the film.

Claims (1)

[Claims] 1. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R^1 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Here, R ^2 and R^3 each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and may be the same or different.), ▲There are mathematical formulas, chemical formulas, tables, etc.▼( Here, n is 2~
Represents an integer of 10. ), ▲Mathematical formulas, chemical formulas, tables, etc.▼(Here, p is 4~
Represents an integer of 10. ), represents a single bond, -O-, -S-, or -SO_2-. ]
An aromatic polycarbonate film molded from polycarbonate having repeating units represented by: 2. General formula (I) and general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) [In the formula, R^1 and R^4 ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Here, R^2 and R^3 each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and they may be the same or different. ), ▲Mathematical formulas, chemical formulas, tables, etc.▼(Here, n is 2 to
Represents an integer of 10. ), ▲Mathematical formulas, chemical formulas, tables, etc.▼(Here, p is 4~
Represents an integer of 10. ), represents a single bond, -O-, -S-, or -SO_2-, and X
each represents an alkyl group having 1 to 6 carbon atoms or a halogen atom, and may be the same or different from each other, l and m each represent an integer from 0 to 4, and may be the same or different from each other. You can. ], when the mole fraction of the repeating unit represented by general formula (I) is q, and the mole fraction of the repeating unit represented by general formula (II) is r , the value of q/(q+r) is 0.
An aromatic polycarbonate film formed from polycarbonate having a polycarbonate of 05 or higher.