JP3475972B2 - Polycarbonate resin for wet molding - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wet-molding polycarbonate resin, and more particularly to a wet-molding polycarbonate resin having a specific fluorene structure and excellent in solution properties, stress crack resistance and mechanical properties.

[0002]

2. Description of the Related Art Polycarbonate films are used in various fields that make use of their excellent transparency and mechanical properties. The production of polycarbonate film is roughly divided into extrusion molding and wet molding. Among them, wet molding has an advantage that a thin film can be easily obtained and a non-oriented film can be obtained, and is particularly used for manufacturing a film having functionality.

The properties of the polycarbonate required in the wet molding are required to have good solubility in a solvent and solution stability, and to satisfy properties such as mechanical properties of the film after the solvent is removed. Conventionally, bisphenol A type polycarbonates have been mainly used for polycarbonate films, but bisphenol A type polycarbonates have insufficient solvent solubility and solution stability, and are particularly difficult to dissolve in non-halogen type solvents, so long-term solutions cannot be used. When stored, white turbidity or gelation may occur,
There was room for improvement. Moreover, when external contaminants such as oil or alcohol or a cleaning liquid adheres to the bisphenol A type polycarbonate film, a kind of stress crack, which is stress corrosion cracking, is likely to occur from the adhered portion.

In consideration of these problems, various modified polycarbonates having improved solution stability have been developed (for example, JP-A-5-100449 and JP-A-5-80548).
issue). However, although these modified polycarbonates have improved solution stability, stress crack resistance is not taken into consideration.

Further, there has been known a fluorene group-containing polycarbonate which has significantly improved heat resistance as compared with the conventional bisphenol A type polycarbonate. (JP-A-48-64
199, JP-A-63-182336), however, in these fluorene group-containing polycarbonates,
Although heat resistance is improved, solvent crack resistance and abrasion resistance are not sufficiently satisfied.

[0006]

In view of the above circumstances, the present invention provides a polycarbonate resin for wet molding which is excellent in solution properties, stress crack resistance and mechanical properties.

[0007]

The present invention has solved these problems by using a specific polycarbonate resin. That is, the present invention has constitutional units represented by the following general formulas (A) and (B), and the constitutional unit represented by the general formula (A) is 5 mol% or less in all constitutional units.
The upper limit is less than 41 mol% and the intrinsic viscosity is 0.3 to 2.0.
It relates to a polycarbonate resin for wet molding which is dl / g.

[0008]

[Chemical 4]

(In the formula, R _{1 to} R ₄ are hydrogen atoms or halogen atoms selected from fluorine, chlorine and bromine, an alkyl group having 1 to 5 carbon atoms and optionally having a substituent, and 6 to 6 carbon atoms. A 12-aryl group, a C2-C5 alkenyl group, a C1-C5 alkoxy group, and a C7-C17 aralkyl group, each of which may have a substituent having a carbon number of It is an alkyl group or alkenyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, or a dimethylsiloxy group.
At least one of R _{1 and} R ₂ is a group other than a hydrogen atom. m, n, l and p are integers of 1 to 2. )

[0010]

[Chemical 5]

(In the formula, R _{5 to} R ₈ are each a hydrogen atom or a halogen atom selected from fluorine, chlorine and bromine, an alkyl group having 1 to 5 carbon atoms which may have a substituent, and a carbon number of 6 respectively. To C12 aryl group, C2 to C5 alkenyl group, C1 to C5 alkoxy group, C7 to C1
7 is an aralkyl group, and the substituent which may be present on any of these is an alkyl or alkenyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom. , A dimethylsiloxy group. X is one of the groups shown below.

[0012]

[Chemical 6]

Here, R ₉ and R ₁₀ are each a hydrogen atom or a halogen atom selected from fluorine, chlorine, and bromine, an alkyl group having 1 to 5 carbon atoms which may have a substituent, and 6 to 12 carbon atoms. Represents an aryl group, an alkenyl group having 2 to 5 carbon atoms, or a group in which R ₉ and R ₁₀ are directly bonded to each other to form a carbocycle or a heterocycle. Is an alkyl group or alkenyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, or a dimethylsiloxy group. a and b represent the integer of 0-20, c represents the integer of 1-500. )

In the polycarbonate resin of the present invention, a dihydric phenol represented by the following general formulas (C) and (D) is reacted with phosgene, a carbonic acid ester, or a chloroformate to obtain the general formula (A) and It is a polycarbonate having the structural unit (B) and has an intrinsic viscosity of 0.3 to 2.0 dl / g. The reaction mole fraction of the dihydric phenol represented by the general formulas (C) and (D) is generally such that the reaction mole fraction of the dihydric phenol represented by the general formula (C) is 5 or more and less than 41 , preferably It is 30 or more and less than 41 . When the intrinsic viscosity is less than 0.3 dl / g, the strength of the film obtained by wet molding is not sufficient, and when it is 2.0 dl / g or more, the production efficiency by wet molding often decreases, and the treatment after polymerization is also difficult. Often difficult.

The reaction molar ratio of the dihydric phenol represented by the general formula (C) is less than 5 mol% or 41 mol% or more.
When it is above , solubility in a non-halogen organic solvent, stress cracking resistance, and abrasion resistance become insufficient. To maintain a good balance between the solubility in non-halogen organic solvents and the stress cracking resistance against external contaminants such as oils and alcohols and cleaning solutions, the dihydric phenol represented by the general formula (C) is 30 mol%. 41 mol% or more
It is preferably in the full range.

Further, in the dihydric phenol of the general formula (C), since at least one of R ₁ and R ₂ has a substituent, the solvent solubility during polymerization is higher and the reactivity is higher than that of the dihydric phenol having no substituent. In addition, the copolycarbonate after polymerization is excellent in solubility especially in a non-halogen organic solvent, and solution stability is improved.

[0017]

[Chemical 7]

(In the formula, R _{1 to} R ₄ are each represented by the above formula (A).
It has the same meaning as the one inside. )

[0019]

[Chemical 8]

(In the formula, R _{5 to} R ₈ and X are the above formula (B)
It has the same meaning as the one inside. )

Representative compounds of the compound represented by the general formula (C) used as a raw material for the polycarbonate resin of the present invention are shown below.

[0022]

[Chemical 9]

Among these, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene,
9,9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3-)
Trifluoromethylphenyl) fluorene is preferred.
It is also possible to use two or more of these compounds.

Specific examples of the dihydric phenol compound represented by the general formula (D) used as a raw material of the polycarbonate resin of the present invention include bis (4-hydroxyphenyl) methane and bis (4-hydroxyphenyl) ether. , Bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A; BPA), 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl)
Cyclohexane (bisphenol Z; BPZ), 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,4-bis (1-methyl-1-4'-hydroxyphenylethyl) Benzene (bisphenol P; BPP), 2,2-
Bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, 2,2-bis (4-hydroxy-3-)
Methylphenyl) propane (dimethylbisphenol A; DMBPA), 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane , Bis (4-hydroxyphenyl) diphenylmethane, α, ω-bis [3- (O-hydroxyphenyl) propyl] polydimethylsiloxane, etc. are exemplified, and it is also possible to use two or more of them in combination.

Among these, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1 1,1-bis (4-hydroxyphenyl) -1-phenylethane and bis (4-hydroxyphenyl) sulfone are preferable, and 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxy) are particularly preferable. Phenyl) cyclohexane and 2,2-bis (4-hydroxy-3-methylphenyl) propane are preferable from the viewpoint of thermal stability and reactivity.

Further, the polycarbonate in the present invention usually contains a terminal stopper or a molecular weight modifier,
Typical of these are compounds having a monovalent phenolic hydroxyl group. In addition to ordinary phenol, p-tert-butylphenol, tribromophenol, etc., long-chain alkylphenol, fatty acid carboxylic acid chloride,
Examples thereof include fatty acid carboxylic acid, hydroxybenzoic acid alkyl ester, hydroxyphenylalkyl acid ester, alkyl ether phenol and the like. The amount used is in the range of 100 to 0.2 mol, preferably 50 to 2 mol, based on 100 mol of all dihydric phenol compounds used, and it is naturally possible to use two or more compounds in combination. is there.

Further, a branching agent is used in an amount of 0.01 to 3 mol%, particularly 0.1 to 3% based on the above dihydric phenol compound.
A branched polycarbonate can also be obtained by using together in the range of 1.0 mol%. As a branching agent, phloroglucin, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3,4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene -2,1,3,5-tri (2-hydroxyphenyl) benzol, 1,1,1-tri (4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4 -Methylphenol, polyhydroxy compounds exemplified by α, α ', α "-tri (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, and 3,3-bis (4-
Hydroxyaryl) oxindole (= isatin bisphenol), 5-chloroisatin, 5,7-dichloroisatin, 5-bromoisatin and the like are exemplified.

The solvent used when the polycarbonate resin of the present invention is used for wet molding such as a solution casting method or a casting method may be any solvent as long as it dissolves the polycarbonate resin of the present invention and has an appropriate volatility. In consideration of safety and hygiene during wet molding, non-halogen solvents, particularly hydrocarbon solvents exemplified by toluene, xylene, ethylbenzene and the like, and cyclic ether solvents such as tetrahydrofuran and 1,4-dioxane are preferable. . Of course, halogen-based solvents such as chlorobenzene and methylene chloride can be used, but considering the working environment and environmental hygiene,
The above solvents are preferred.

The concentration of the solution is usually 1 to 30% by weight, preferably 5 to 20% by weight. Unlike general polycarbonate resins, the polycarbonate resin of the present invention shows high solubility in non-halogen solvents such as toluene,
It has the advantage that the stability of the solution is high.

If desired, the polycarbonate resin used in the present invention may include various known additives conventionally used in polycarbonate resins, such as stabilizers, ultraviolet absorbers, antistatic agents, lubricants, and release agents. , Dyes, pigments, flame retardants can be added. For example, phosphorous acid or phosphite is particularly suitable as the stabilizer. Examples of the releasing agent include mono- or polyhydric alcohol esters of saturated fatty acids, and stearyl stearate, behenyl behenate, pentaerythritol tetrastearate, dipentaerythritol hexaoctoate, etc. are preferable examples. To be done. Further, in addition to usual polycarbonate, resins such as polyester carbonate and polyarylate can be added appropriately according to the purpose.

[0031]

EXAMPLES The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

Example 1 3.7 kg of sodium hydroxide was dissolved in 42 liters of water, and
Keep it at 0 ℃ and add bisphenol A (BPA) 2.
6 kg, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (DMFL) 2.16 kg and hydrosulfite (HD) 8 g were dissolved. To this, 28 liters of methylene chloride (MC) was added and stirred, 78 g of pt-butylphenol (PTBP) was added, and then phosgene (PG) 2.
34 kg was blown in over 60 minutes. After blowing in phosgene, the reaction solution was emulsified by vigorous stirring. After emulsification, 8 g of triethylamine (TEA) was added and the mixture was stirred for about 1 hour to polymerize. The polymerization liquid is separated into an aqueous phase and an organic phase, the organic phase is neutralized with phosphoric acid, and then repeatedly washed with water until the pH of the washing liquid becomes neutral, and then 35 liters of isopropanol is added to precipitate the polymer. Let The precipitate was filtered and dried to obtain a white powdery polycarbonate resin. Table 1 shows the results obtained by measuring the physical properties of the polycarbonate resin and the cast film.

Example 2 Example 2 was repeated except that 10.5 g of PTBP was used.

Example 3 Example 3 was repeated except that DMFL was changed to 2.39 kg of 9,9-bis (3-chloro-4-hydroxyphenyl) fluorene (DCFL).

Example 4 Example 4 was repeated except that the BPA was changed to 3.7 kg and the DMFL was changed to 0.32 kg.

Example 5 Example 5 was repeated except that BPA was changed to 3.06 kg of bisphenol Z (BPZ).

Example 6 BPA was changed to dimethylbisphenol A (DMBPA) 2.92k.
The same procedure as in Example 1 was repeated except that the amount was changed to g.

Comparative Example 1 The procedure of Example 1 was repeated, except that BPA of 3.9 kg was used instead of BPA of 2.6 kg and DMFL of 2.16 kg.

Comparative Example 2 The procedure of Example 1 was repeated except that BPA was changed to 3.8 kg and DMFL was changed to 0.13 kg.

Comparative Example 3 The procedure of Example 1 was repeated except that BPA was changed to 0.39 kg and DMFL was changed to 5.82 kg. As a result, considerable precipitation of unreacted monomer was observed.

Comparative Example 4 The procedure of Example 1 was repeated except that PTBP was changed to 6 g. As a result, a gel-like substance insoluble in the solvent was formed, and the cast film could not be molded. These results are shown in Table 2.
Shown in.

[0042]

[Table 1]

BPA: Bisphenol A BPZ: Bisphenol Z DMBPA: Dimethylbisphenol A BCFL: 9,9-Bis (3-chloro-4-hydroxyphenyl) fluorene DMFL: 9,9-Bis (3-methyl-4-hydroxyphenyl) ) Fluorene TO: Toluene, DO: 1,4-dioxane, IPA: Isopropanol, MO: Machine oil

Solution stability: A 10 wt / vol% solution was sealed at room temperature, and the presence or absence of gel formation after 1 month was confirmed. (A: No gel generation B: Gel generation C: No initial dissolution)

Stress cracking resistance: A 150 μm thick cast film was prepared with a 10 wt / vol% dichloromethane solution, isopropanol (manufactured by Wako Pure Chemical Industries, Ltd.) and machine oil turbine oil 32 (manufactured by Mitsubishi Yuka Co., Ltd.) About 1 ml was applied, and the presence or absence of cracking after standing for 24 hours was examined. (A: No crack B: Some crack C: Crack crack)

Abrasion resistance: Taber abrasion test (load 1Kg, CS-17 wheel, toluene atmosphere) 24
Measure the amount of wear after hours.

Intrinsic Viscosity: Reduced viscosity of a 0.5 g / 100 cc dichloromethane solution at 20 ° C. was calculated, and the intrinsic viscosity [η] was obtained with a Huggins constant of 0.45.
(Dl / g) was determined.

[0048]

EFFECT OF THE INVENTION The polycarbonate resin according to the present invention has a high solubility in a non-halogen organic solvent and can be used for wet molding as a non-halogen organic solvent solution, and can reduce environmental hygiene problems during molding. it can. Moreover, since the solution stability of the polycarbonate resin solution is excellent, the productivity of the film by wet molding is improved. Further, the polycarbonate film obtained by using the polycarbonate resin of the present invention has an advantage that it is particularly excellent in strength such as stress crack resistance and has high abrasion resistance.

Claims (4)

(57) [Claims] 1. A constitutional unit represented by the following general formula (A) and general formula (B), wherein the constitutional unit represented by the general formula (A) is 5 mol% or more and less than 41 mol% in all constitutional units. And a polycarbonate resin for wet molding having an intrinsic viscosity of 0.3 to 2.0 dl / g. [Chemical 1] (In the formula, R _{1 to} R ₄ are a hydrogen atom or a halogen atom selected from fluorine, chlorine and bromine, an alkyl group having 1 to 5 carbon atoms and an aryl group having 6 to 12 carbon atoms, each of which may have a substituent. Group, C2-C5 alkenyl group, C1-C1
5 is an alkoxy group having 5 to 17 carbon atoms and an aralkyl group having 7 to 17 carbon atoms, and a substituent which may be present on any of these is an alkyl group or alkenyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms
Is an alkoxy group, a fluorine atom, a chlorine atom, a bromine atom, or a dimethylsiloxy group. However, at least one of R _{1 and} R ₂ is a group other than a hydrogen atom. m, n, l,
p is an integer of 1-2. ) [Chemical 2] (In the formula, each of R _{5 to} R ₈ is a hydrogen atom or a halogen atom selected from fluorine, chlorine, and bromine, an alkyl group having 1 to 5 carbon atoms which may have a substituent, and a carbon atom having 6 to 12 carbon atoms. Is an aryl group, a alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and an aralkyl group having 7 to 17 carbon atoms. Are an alkyl group or an alkenyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, and a dimethylsiloxy group, and X is one of the groups shown below. (In the formula, each of R ₉ and R ₁₀ is a hydrogen atom or a halogen atom selected from fluorine, chlorine, and bromine, an alkyl group having 1 to 5 carbon atoms which may have a substituent, and a carbon atom having 6 to 12 carbon atoms. An aryl group, an alkenyl group having 2 to 5 carbon atoms,
Alternatively, R ₉ and R ₁₀ represent a group which is directly bonded to form a carbocycle or a heterocycle, and the substituent which may be present on any of these is an alkyl group or an alkenyl group having 1 to 5 carbon atoms, An alkoxy group having 1 to 5 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom and a dimethylsiloxy group. a and b
Represents an integer of 0 to 20, and c represents an integer of 1 to 500. ) 2. The polycarbonate resin for wet molding according to claim 1, wherein the constitutional unit represented by the general formula (A) is 30 to 40 mol% in all constitutional units. 3. The structural unit represented by general formula (B) is
2,2-bis (4-hydroxyphenyl) propane,
Derived from 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane 2. The polycarbonate resin for wet molding according to claim 1. 4. The structural unit represented by general formula (A) is
9,9-bis (4-hydroxy-3-methylphenyl)
Fluorene, 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3-trifluoromethyl) Phenyl)
The polycarbonate resin for wet molding according to claim 1, which is derived from fluorene.