JP2557931B2 - Aromatic polycarbonate film - Google Patents

Description

TECHNICAL FIELD The present invention relates to an aromatic polycarbonate film used as a component of various electronic / electrical devices. More specifically, the present invention relates to an aromatic polycarbonate film which is essentially amorphous, has excellent transparency, heat resistance and mechanical strength, and has improved low moisture permeability and surface hardness.

[Conventional technology]

Aromatic polycarbonate films are known to have a well-balanced transparency, heat resistance, mechanical strength, electrical properties, etc., and are used as various engineering plastics such as parts for electronic and electric devices. Aromatic polycarbonate films that have been commonly used in the past have a formula obtained from the reaction of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) with a carbonate precursor such as phosgene. Was prepared from a commercially available aromatic polycarbonate having a repeating unit represented by

However, recently, as the properties required for films as parts of electronic / electrical devices have become more sophisticated, the moisture permeability of films formed from commercially available polycarbonate is large,
Defects such as low surface hardness have become apparent. further,
Commercially available polycarbonates have a problem that they tend to gel and crystallize due to a solvent or the like, leading to a reduction in the mechanical strength and transparency of the film.

[Problems to be Solved by the Invention]

The present invention solves the above-mentioned drawbacks and is improved in low moisture permeability and surface hardness, and provides an aromatic polycarbonate film which does not tend to gel or crystallize due to a solvent of the polymer material. The purpose is.

[Means for solving the problem]

That is, the invention of claim 1 has the general formula (I) [In the formula, R ¹ is (Here, R ² and R ³ are a hydrogen atom and a carbon number of 1 to 6 respectively.
Represents an alkyl group or a phenyl group, and may be the same or different from each other. ), CH _{2 n} (where n
Represents an integer of 2 to 10. ), (Here, p represents an integer of 4 to 10), a single bond or -O-. ] It provides an aromatic polycarbonate film molded from a polycarbonate having a repeating unit represented by:

The invention of claim 2 has the general formula (I) and the general formula (II). [In the formula, R ¹ is (Here, R ² and R ³ are a hydrogen atom and a carbon number of 1 to 6 respectively.
Represents an alkyl group or a phenyl group, and may be the same or different from each other. ), CH _{2 n} (where n
Represents an integer of 2 to 10. ), (Here, p represents an integer of 4 to 10), a single bond or -O-, and R ⁴ is A single bond, —O—, —S—, or —SO ₂ —, 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; And m each represent an integer of 0 to 4 and may be the same or different from each other. When the molar fraction of the repeating unit represented by the general formula (I) is q and the molar fraction of the repeating unit represented by the general formula (II) is r, , The present invention provides an aromatic polycarbonate film molded from a polycarbonate having a value of 0.05 or more.

In the polycarbonate used for forming the film of the invention of claim 2, the polymer main chain comprises a repeating unit represented by the general formula (I) and a repeating unit represented by the general formula (II). And has the structure The value of is 0.05 or more. If this value is less than 0.05, the effects of lowering the moisture permeability of the film and improving the surface hardness cannot be obtained. Further, the effect of preventing gelation and crystallization of the polymer material due to the solvent or the like cannot be obtained.

The film of the invention of claims 1 and 2 includes not only a generally called thin film but also a film for thinly coating the surface of an article.

The molecular weight of the aromatic polycarbonate used in the inventions of claims 1 and 2 may be appropriately selected according to the kind of the film, but the molecular weight of the methylene chloride solution having a concentration of 0.5 g / dl is 2
It is desirable that the reduced viscosity [ηsp / c] at 0 ° C. is 0.3 to 4.0 dl / g, preferably 0.4 to 3.5 dl / g. When a film having a reduced viscosity of less than 0.3 dl / g is used, the strength of the obtained film may be insufficient. If it exceeds 4.0 dl / g, it may be difficult to form the film.

In R ¹ and R ⁴ Specific examples of R ² and R ³ therein include, for example, hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, phenyl group and the like.

Particularly preferable examples of R ¹ include, for example, Is mentioned.

Particularly preferable examples of R ² include, for example, Is mentioned.

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

The polycarbonate used in the inventions of claims 1 and 2 can be produced by various conventionally known methods, for example, the general formula (III) [Wherein R ¹ has the same meaning as defined above] and phosgene, or the divalent phenol compound represented by the general formula (III) and the general formula (I
V) [In the formula, X, R ⁴ , l and m have the same meaning as defined above. ] A method such as a direct reaction between the dihydric phenol compound represented by and phosgene, or a transesterification reaction between the dihydric phenol compound and the bisaryl carbonate can be employed.

In the former direct reaction method of 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, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or the like is used, and as the solvent, for example, methylene chloride, chlorobenzene, xylene or the like is used. Furthermore, in order to accelerate the polycondensation reaction, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt is used, and in order to adjust the degree of polymerization, such as pt-butylphenol or phenylphenol. It is desirable to add a molecular weight regulator to carry out the reaction. If desired, a small amount of an antioxidant such as sodium sulfite and hydrosulfide may be added. Reaction is usually 0-150
C., preferably at a temperature in the range 5-40.degree. The reaction time depends on the reaction temperature, but is usually 0.5 minutes to 10 minutes.
The time is preferably 1 minute to 2 hours. During the reaction, it is desirable to maintain the pH of the reaction system at 10 or more.

On the other hand, in the latter transesterification method, the dihydric phenol compound and the bisaryl carbonate are mixed and reacted at a high temperature under reduced pressure. Reaction is usually 150
~ 350 ° C, preferably at a temperature in the range of 200 to 300 ° C, and the degree of vacuum is finally set to preferably 1 mmHg or less, and phenols derived from the bisaryl carbonate produced by the transesterification reaction are removed from the system. Make them evaporate. Although the reaction time depends on the reaction temperature and the degree of reduced pressure, it is usually about 1 to 4 hours. The reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon, and the reaction may be carried out by adding the above-mentioned molecular weight modifier, antioxidant or the like, if desired.

Specific examples of the compound represented by the general formula (III) include:
For example, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 1-phenyl-1,4-bis (3-phenyl-4-hydroxyphenyl) ethane, 1,1-bis (3-phenyl-4) -Hydroxyphenyl) cyclohexane, 3,3-bis (3-phenyl-4-hydroxyphenyl) pentane, 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, 1,3-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) butane, 1 , 4-bis (3-phenyl-
4-hydroxyphenyl) 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) cyclopentane and the like can be mentioned.

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

Specific examples of the dihydric phenol compound represented by the general formula (IV) include, for example, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,2-bis (4 -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) heptane, 1,1-bis (4-hydroxyphenyl) -1,1-diphenylmethane, 1,1-bis (4-hydroxy) Phenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl)-
1-phenylmethane, bis (4-hydroxyphenyl)
Ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, 1,1-
Bis (4-hydroxyphenyl) cyclopentane, 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-t-
Butyl-4-hydroxy-5-methylphenyl) isobutane, 1,1-bis (2-t-butyl-4-hydroxy-
5-methylphenyl) heptane, 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-bromo-4-hydroxyphenyl) propane, 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-bromo-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) ether, 3,3'-difluoro-4,4'-dihydroxybiphenyl and the like can be mentioned.

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

The aromatic polycarbonate used in the inventions of claims 1 and 2 also includes a modified polycarbonate produced by adding another dihydric phenol compound to the extent that the characteristics of the film are not impaired. Examples of the other dihydric phenol compounds include resorcin, hydroquinone and the like. Further, a branched aromatic polycarbonate produced by adding a small amount of, for example, about 0.05 to 2.0 mol% of the dihydric phenol compound used is a polyhydroxy compound.

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

In addition, known additives such as flame retardants, antioxidants, antistatic agents, fillers, impact resistance improvers, ultraviolet absorbers, plasticizers, and hydrolytic stability can be added to these aromatic polycarbonates, if necessary. Agents, pigments, dyes, coloring stabilizers and the like can be added.

As a film forming method of the inventions of claims 1 and 2, a conventionally known film forming method can be used. For example,
Press molding such as hot press molding; extrusion method such as cast roll method, inflation method, tuber method; method of casting polymer solution on belt and evaporating and removing solvent to form thin film; polymer solution applied to article A coating method for removing the solvent afterwards may be mentioned.

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

Further, the film formed in this manner, if necessary, a conventionally used stretching method, for example, a tenter method,
It may be stretched by a tubular method, a multistage stretching method, or the like. Further, heat treatment can be performed if necessary.

Regarding the thickness of the film of the invention of claims 1 and 2,
Although not particularly limited, it is usually 0.1 to 1000 μm, preferably 1
It is selected in the range of up to 500 μm.

The film molded in this way is not only excellent in heat resistance, mechanical strength, electrical insulation, etc. as the conventional aromatic polycarbonate film, but is significantly improved in low moisture permeability and surface hardness. It is a thing. Therefore, it can be suitably used as a heat-resistant film, a low moisture-permeable film, an electrically insulating film, a component of various electronic / electrical devices, a coating film, and the like. Furthermore, because gelation and crystallization of the polymer material due to the solvent etc. have been eliminated,
It became 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 described in more detail based on examples, but these inventions are not limited to the following examples.

Example 1 Synthesis example 60 g of 2,2-bis (3-phenyl-4-hydroxyphenyl) propane and 0.5 g of pt-butylphenol as a molecular weight regulator were dissolved in 500 ml of methylene chloride, 300 ml of water and 1 ml of triethylamine as a catalyst were dissolved. In addition, phosgene gas was bubbled at a rate of 300 to 400 ml / min with stirring. Keep the pH of the reaction system below 10 while blowing phosgene gas.
A 12N concentration aqueous sodium hydroxide solution was added dropwise. After blowing phosgene gas for 25 minutes, the reaction was carried out for 1 hour, the product was diluted with 700 ml of methylene chloride, washed with water, 0.01N hydrochloric acid and water in this order, and poured into methanol to collect a polymer. The yield of the polymer was 96%, and the polymer had a repeating unit having the following structure.

A 10% by weight solution of this polymer in tetrahydrofuran was prepared and allowed to stand at room temperature for one month, and the solution viscosity was measured. After left for 1 month, no cloudiness or gel formation occurred and no change in viscosity was observed.

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

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

 The results of these measurements are shown in Table 1.

Example 2 Example 1 was repeated except that 1-phenyl-1,1-bis (3-phenyl-4-hydroxyphenyl) ethane was used instead of 2,2-bis (3-phenyl-4-hydroxyphenyl) propane. A polymer having a repeating unit of the following structure was obtained by performing the same operation as described in.

Using this polymer, the same operation as in the case of forming the film of Example 1 was performed to obtain a film.

 The results of each test are shown in Table 1.

Example 3 Instead of 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 1,1-bis (3-phenyl-
The same operation as in Example 1 was carried out except that 4-hydroxyphenyl) cyclohexane was used to obtain a polymer having a repeating unit of the following structure.

Using this polymer, the same operation as in the case of forming the film of Example 1 was performed to obtain a film.

 The results of each test are shown in Table 1.

Example 4 Instead of 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4)
-Hydroxyphenyl) propane 38.0 g, 2,2-bis (4
By the same procedure as in Example 1 except that 20 g of -hydroxyphenyl) propane was used, a polymer having a repeating unit of the following structure was obtained.

Using this polymer, the same operation as in the case of forming the film of Example 1 was performed to obtain a film.

 The results of each test are shown in Table 1.

Comparative Example 1 When a 10 wt% tetrahydrofuran solution of a commercially available polycarbonate [Idemitsu Petrochemical Co., Ltd .: Idemitsu Polycarbonate A2500] was prepared and allowed to stand at room temperature for 1 month, white turbidity and gel formation occurred.

Using this commercially available polycarbonate, the same operation as in the case of forming the film of Example 1 was performed to obtain a film.

 The results of each test are shown in Table 1.

[Advantages of the Invention] According to the inventions of claims 1 and 2, aromatics having low moisture permeability, high surface hardness, heat resistance, mechanical properties, etc. are comparable to or higher than those of conventional aromatic polycarbonate films. A polycarbonate film could be obtained. Such an aromatic polycarbonate film is extremely useful as a component and a coating film for various electronic and electric devices. Also, since the polymer is essentially amorphous,
There is no gelation or crystallization due to a solvent and the like, and the mechanical strength and transparency of the film are not deteriorated.

Claims (2)

(57) [Claims] 1. A general formula (I) [Wherein R ¹ is (Here, R ² and R ³ are a hydrogen atom and a carbon number of 1 to 6 respectively.
Represents an alkyl group or a phenyl group, and may be the same or different from each other. ), CH _{2 n} (where n represents an integer of 2 to 10), (Here, p represents an integer of 4 to 10), a single bond or-
Represents O-. ] The aromatic polycarbonate film shape | molded from the polycarbonate which consists of a repeating unit represented by these. 2. General formula (I) and general formula (II) [Wherein R ¹ is (Here, R ² and R ³ are a hydrogen atom and a carbon number of 1 to 6 respectively.
Represents an alkyl group or a phenyl group, and may be the same or different from each other. ), CH _{2 n} (where n represents an integer of 2 to 10), (Here, p represents an integer of 4 to 10), a single bond or-
Represents O-, and R ⁴ is A single bond, —O—, —S—, or —SO ₂ —, 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; And m each represent an integer of 0 to 4 and may be the same or different from each other. ] When the molar fraction of the repeating unit represented by the general formula (I) is q and the molar fraction of the repeating unit represented by the general formula (II) is r, An aromatic polycarbonate film formed from a polycarbonate having a value of 0.05 or more.