JP3128003B2 - Polycarbonate resin solution for cast film formation - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate resin solution for casting, and more particularly to a solution of a polycarbonate resin for casting having a specific structure and excellent castability and a method for producing the same.

[0002]

2. Description of the Related Art A resin solution is cast on a drum or belt surface in a film form by a casting method, and a solvent is dried with hot air to produce a film, or rolls, plates, and other various members are immersed in the resin solution. Coating or lining its surface is well known. However, in general, a polycarbonate resin solution starts to become cloudy when left for 3 to 4 days, so that a method of preparing a low-concentration solution or an operation such as re-dissolution is required, and there is a disadvantage that the production efficiency of casting film formation is poor. In addition, the resulting films and films have the disadvantage of low mechanical strength, for example, stress cracks are likely to occur.

[0003]

The present invention has solved these problems by using a specific polycarbonate resin. That is, the present invention provides the following general formula (1):
It has a structural unit represented by (2) and (3), and (1) and (2)
The molar ratio of the structural unit represented by is 35/65 to 65/35, the ratio of the structural unit of (3) to the whole is 0.1 to 50% by weight, and the viscosity-average molecular weight is 15,000 to 100,000. -Polycarbonate resin solution for casting film formed by dissolving polycarbonate resin in organic solvent

[0004]

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(In the general formulas (1) and (2), R ^{1 to} R ⁸ represent hydrogen,
A represents a halogen or an alkyl group having 1 to 4 carbon atoms, and A represents a linear, branched or cyclic alkylidene group having 1 to 10 carbon atoms, an aryl-substituted alkylene group, an aryl group, or a sulfonyl group. In the general formula (3), R ⁹ is an alkylene group or alkylidene group of 2 to 6, R ¹⁰ and R ¹¹ are an alkyl group having 1 to 3 carbon atoms, a phenyl group, a substituted phenyl group, and n represents an integer of 1 to 200. . ) And its manufacturing method.

Hereinafter, the configuration of the present invention will be described. The polycarbonate resin used in the present invention is a dihydric phenol represented by the following general formulas (4), (5) and (6)

[0007]

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Is copolymerized with phosgene, carbonate or chloroformate to randomly have the structural units of the above general formulas (1), (2) and (3), and has a viscosity average molecular weight of
15,000 to 100,000, preferably 20,000 to 40,000. The reaction molar ratio of the dihydric phenols of the general formulas (4) and (5) is 35/65 to 65/35. If the molar ratio is out of the range, the solution becomes cloudy at the stage when the polycarbonate resin is made into a solution, or the solution stability is lowered. By random copolymerization, the micro-dispersion becomes uniform compared to the block copolymer, and both in optical properties and in properties such as solution stability,
It is also improved in terms of stress cracks. If the viscosity average molecular weight is less than 15,000, the strength of the film obtained by casting is not sufficient, and 100,000
Above, the production efficiency by casting decreases. Further, by copolymerizing the dihydric phenol represented by the general formula (6), the surface hardness is further increased and the lubricating property is increased, so that the abrasion resistance is further improved. The amount of the dihydric phenol represented by the general formula (6) is 0.1
5050% by weight, preferably 0.1-30% by weight.

The dihydric phenolic compound represented by the general formula (4) used as a raw material of the co-polycarbonate resin of the present invention includes bis (4-hydroxyphenyl) methane, 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), 2,2-bis (4-hydroxy-3,5-
Dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4
-Hydroxy-3-methylphenyl) propane (dimethylbisphenol A; DMBPA), 2,2-bis (4-hydroxy-
3-bromophenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, bis (4-Hydroxyphenyl) sulfone is exemplified, and among them, 2,2-bis (4-
(Hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxy-3-methylphenyl) Propane and bis (4-hydroxyphenyl) sulfone are preferred, and 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane are particularly preferred from the viewpoint of thermal stability.

The dihydric phenolic compound represented by the general formula (5) used as a raw material of the co-polycarbonate resin of the present invention includes bis (4-hydroxyphenyl) sulfide (T
DP), bis (3-methyl-4-hydroxyphenyl) sulfide (DMTDP), bis (3-bromo-4-hydroxyphenyl) sulfide, bis (3-chloro-4-hydroxyphenyl) sulfide, bis (3,5 -Dimethyl-4-hydroxyphenyl) sulfide, bis (3,5-dibromo-4-hydroxyphenyl) sulfide, bis (3,5-dichloro-4-hydroxyphenyl) sulfide and the like. Among them, bis (4 -Hydroxyphenyl) sulfide is preferred.

The dihydric phenol optionally used as a raw material of the co-polycarbonate resin of the present invention has the general formula
(6) where the number of repetitions n in the formula is 1 to
It is in the range of 200, preferably 5-100. Also,
As R ⁹ in the general formula (6), ethylene, propylene,
Examples include isopropylene, butylene, pentylene, hexylene, etc., particularly -CH ₂ CH ₂ CH _2- , -CHR ¹² -CH _2- (where R ¹² is a carbon atom on the benzene ring side. And represents hydrogen or a methyl group). The structural unit of the general formula (3) in the polycarbonate resin is introduced by using a dihydric phenol having a phenolic hydroxyl group represented by the general formula (6) at both terminals in the same manner as a normal dihydric phenol or the like. Things. The dihydric phenol represented by the general formula (6) is a phenol having an olefinically unsaturated carbon-carbon bond, preferably vinyl phenol, allyl phenol, or isopropenyl phenol, having a predetermined polymerization degree n. At the end of the siloxane chain,
It is easily produced by a hydrosilation reaction.

In addition, a terminal terminator or a molecular weight regulator is usually used, and examples thereof include compounds having a monovalent phenolic hydroxyl group, such as ordinary phenol, p-tert-butylphenol, tribromophenol and the like. Other examples include long-chain alkylphenols, aliphatic carboxylic acid chlorides, aliphatic carboxylic acids, hydroxybenzoic acid alkyl esters, hydroxyphenylalkyl acid esters, and alkyl ether phenols. The amount used is in the range of 100 to 0.5 mol, preferably 50 to 2 mol, based on 100 mol of all the dihydric phenol compounds used, and it is naturally possible to use two or more compounds in combination. Further, a branching agent is used in an amount of 0.01 to 3 mol%, particularly 0.1 to 1.0 mol%, based on the above dihydric phenol compound.
Can be used in combination with a branched polycarbonate in the range of, and as a branching agent, phloroglysin, 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,
α, α ', α "-tri (4-hydroxyphenyl) -1,3,5-
Examples include polyhydroxy compounds exemplified by triisopropylbenzene and the like, and 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chlorisatin, 5,7-dichlorisatin, 5-bromoisatin and the like. You.

[0013] The polycarbonate resin used in the present invention may contain various additives conventionally known to the polycarbonate resin, if desired, such as reinforcing materials, fillers, stabilizers, ultraviolet absorbers, and the like. Examples include antistatic agents, lubricants, release agents, dyes, pigments, other flame retardants, and elastomers for improving impact resistance. For example, phosphorous acid or phosphite is particularly suitable as a stabilizer. Examples of the release agent include esters of mono- or polyhydric alcohols of saturated fatty acids, and preferred examples thereof include stearyl stearate, behenyl behenate, pentaerythritol tetrastearate, and dipentaerythritol hexaoctoate. Is done. Glass powder,
Organic or inorganic fillers and reinforcing agents such as glass beads, synthetic mica or fluorinated mica, zinc oxide, carbon fiber, especially glass fiber including those with a fiber diameter of 2 μm or less, zinc oxide whisker, stainless steel fiber, Kevlar fiber, etc. ,
In addition, MBS, MABS, MAS,
Others are exemplified. More regular polycarbonate,
Resins such as polyester carbonate and polyarylate can of course be suitably used according to the purpose.

The solvent used in the polycarbonate resin solution of the present invention can be used as long as it dissolves the polycarbonate resin of the present invention and has a proper volatility. For example, halogen solvents such as chlorobenzene and methylene chloride can be used. Can be used. In consideration of safety and health at the time of casting, non-halogen solvents, especially hydrocarbon solvents exemplified by toluene, xylene, ethylbenzene and the like are preferable. The concentration of the solution is usually 1 to 30% by weight, preferably 5%.
~ 20% by weight. Unlike the general polycarbonate resin, the polycarbonate resin of the present invention has high solubility in non-halogen solvents such as toluene and has the advantage of high solution stability.

[0015]

EXAMPLES Example 1 3.7 kg of sodium hydroxide was dissolved in 42 liters of water, and 3.65 kg of bisphenol A (BPA)
(4-Hydroxyphenyl) sulfide (4,4'-dihydroxydiphenyl sulfide; TDP) 3.49 kg, the repeating unit is [Si (CH ₃ ) ₂ O] _n [n = 60], and R ⁹ is -CH ₂ CH ₂ CH 40.1 g of a dihydric phenol of the general formula (6) having an ortho bond at _2- and 8 g of hydrosulfite (HD) were dissolved. To this, 28 liters of methylene chloride (MC) was added, and with stirring, 148 g of pt-butylphenol (PTBP) was added, followed by 3.5 g of phosgene (PG).
kg was blown in over 60 minutes. After blowing phosgene, the mixture was vigorously stirred to emulsify the reaction solution. After emulsification, 8 g of triethylamine (TEA) was added, and the mixture was stirred for about 1 hour to polymerize. The polymer solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and the water was washed repeatedly until the pH of the washings became neutral.Then, 35 liters of isopropanol was added to precipitate the polymer. I let it. The precipitate was filtered and dried to obtain a white powdery polycarbonate resin. Table 1 shows the measurement results of the physical properties of the polycarbonate resin.

Comparative Example 1 Example 1 was repeated except that 3.65 kg of BPA, 3.49 kg of TDP and 7.3 kg of BPA were used instead of 40.1 g of the dihydric phenol of the general formula (6).
Same as. Table 1 shows the results.

Examples 2 to 5 and Comparative Examples 2 to 3 PCs having the compositions shown in Table 1 were obtained in the same manner as in Example 1. The dihydric phenols of the general formula (6) used in Examples 2 to 5 and Comparative Example 3 are as follows in order. Real 2: repeating unit is [Si (CH ₃ ) ₂ O] _n [n = 20], and R ⁹ is -CH ₂ CH ₂ CH _2- and is ortho-bonded. Real 3: 〃 [Si (Ph) (CH ₃ ) O ] _n [n = 50], 〃 real 4: 〃 [Si (CH ₃ ) ₂ O] _n [n = 90], 〃 real 5: 〃 [Si (CH ₃ ) ₂ O] _n [n = 60], R ⁹ is -CH ₂ CH ₂ -and para bond ratio 3: 〃 [Si (CH ₃ ) ₂ O] _n [n = 60], R ⁹ is -CH ₂ CH ₂ CH ₂ -and ortho bond These polycarbonate resins Table 1 shows the results of measuring the physical properties of the sample.

[0018]

[Table 1]

[0019]

The polycarbonate resin according to the present invention has a high solubility in non-halogen solvents and can be used as a non-halogen solvent solution in cast molding, so that safety and health problems during cast molding can be reduced. Further, since the solution stability of the polycarbonate resin solution is excellent, the productivity of the film by cast molding is improved. Further, the film obtained by using the solution of the present invention has excellent strength such as stress cracks, and has excellent surface hardness and lubricity, and thus has excellent wear resistance.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Toshio Okikawa 2-12 Kamizu-cho, Toyonaka-shi, Osaka Mitsubishi Gas Chemical Co., Ltd. Osaka factory (56) References JP-B-45-20510 (JP, B1) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 64/00-64/42 C08L 69/00 CA (STN) REGISTRY (STN)

Claims (6)

(57) [Claims] 1. It has structural units represented by the following general formulas (1), (2) and (3), and the molar ratio of the structural units represented by (1) and (2) is 35/65. Approximately 65/35, a random-co polycarbonate resin having a ratio of the structural unit of (3) to the whole of 0.1 to 50% by weight and a viscosity average molecular weight of 15,000 to 100,000 is dissolved in an organic solvent. Polycarbonate resin solution for cast film formation (In the general formulas (1) and (2), R ^{1 to} R ⁸ represent hydrogen, halogen, or an alkyl group having 1 to 4 carbon atoms, and A represents 1 to 10 carbon atoms.
Represents a linear, branched or cyclic alkylidene group, aryl-substituted alkylene group, aryl group or sulfonyl group. In the general formula (3), R ⁹ represents an alkylene group or alkylidene group having 2 to 6, R ¹⁰ and R ¹¹ represent an alkyl group having 1 to 3 carbon atoms, a phenyl group, a substituted phenyl group, and n represents an integer of 1 to 200. . ) 2. The solution according to claim 1, wherein the organic solvent is a non-halogen solvent. 3. The solution according to claim 1, wherein the concentration of the resin solution is 1 to 30% by weight. 4. The structural unit represented by the general formula (1) is bisphenol A, 1,1-bis (4-hydroxyphenyl) -cyclohexane, α, α-bis (4-hydroxyphenyl) -ethylbenzene, 2. A compound derived from a dihydric phenol selected from the group consisting of 2,2-bis (3-methyl-4-hydroxyphenyl) -propane and bis (4-hydroxyphenyl) sulfone.
The described solution 5. The solution according to claim 1, wherein the structural unit represented by the general formula (2) is derived from bis (4-hydroxyphenyl) -sulfide. 6. The solution according to claim 1, wherein the viscosity average molecular weight of the polycarbonate resin is 20,000 to 40,000.