JP3151841B2 - 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, since the polycarbonate resin solution generally starts to become cloudy when left for 3 to 4 days, there has been a drawback that a method of preparing a low-concentration solution or an operation such as re-dissolution are required, and the production efficiency of the casting film is poor. Further, the resulting films and films have disadvantages such as low hardness and low abrasion resistance.

The present invention has solved these problems by using a specific polycarbonate resin. That is, the present invention has structural units represented by the following general formulas (1) and (2), the ratio of the structural unit of (2) to the whole is 0.1 to 50% by weight, and the viscosity average molecular weight is 2
A polycarbonate resin solution for casting film formed by dissolving a co-polycarbonate resin having a molecular weight of 0000 to 40,000 in an organic solvent.

[0004]

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[0005] (In the general formula ^(1), R 1 ~R ⁴ is hydrogen, Z is
In the general formula (2), R ⁵ represents an alkylene group or an alkylidene group having 2 to ⁶ atoms, and R ^{6 to} R ⁷ represent an alkyl group or an aryl group having 1 to 3 carbon atoms. the indicated, n represents an <br/> shall relates to a show) an integer of 1 to 200.

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 (3) and (4).

[0007]

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[0008] (R ¹ to R ⁷ in the formula, Z, n the general formula (1), (2)) to phosgene, carbonic esters, or chloroformates co polymerization was the general formula obtained ( It has structural units of 1) and (2) and has a viscosity average molecular weight in the range of 20,000 to 40,000 . The amount of the dihydric phenol represented by the general formula (4) is from 0.1 to 50% by weight, preferably from 0.1 to 50% by weight, based on the entire dihydric phenol.
３０30% by weight. If the amount of the dihydric phenol is less than 0.1% by weight, effects such as lubricity and abrasion resistance do not appear, and
If the amount is more than 0% by weight, film-forming properties such as solubility and solution stability will be reduced.

The dihydric phenolic compound represented by the general formula (3) used as a raw material of the co-polycarbonate resin of the present invention is 1,1-bis (4-hydroxyphenyl).
A; (BPZ piston phenol Z) cyclohexane.

The dihydric phenol used as a raw material of the co-polycarbonate resin of the present invention is represented by the general formula (4), wherein the number of repetitions n is in the range of 1 to 200,
Preferably it is in the range of 5-100. Further, the general formula (4)
Examples of R ⁵ include ethylene, propylene, isopropylene, butylene, pentylene, hexylene, and the like.In particular, -CH ₂ CH ₂ CH _2- , -CHR ⁸ -CH _2- (R ⁸ in the formula is Which is bonded to a carbon atom on the benzene ring side and represents hydrogen or a methyl group). The structural unit of the general formula (2) in the polycarbonate resin is introduced by using a dihydric phenol having a phenolic hydroxyl group at both ends represented by the general formula (4) in the same manner as a normal dihydric phenol or the like. Things. The dihydric phenol represented by the general formula (4) is obtained by converting an olefinic phenol having an unsaturated carbon-carbon bond, preferably vinyl phenol, allyl phenol, or isopropenyl phenol to a predetermined degree of polymerization.
It can be easily produced by subjecting a terminal of a polysiloxane chain having n to a hydrosilation reaction.

[0011] Further, 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.

[0012] The polycarbonate resin used in the present invention may contain, if desired, various additives conventionally known to the polycarbonate resin, 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 an appropriate volatility. For example, halogen solvents such as chlorobenzene and methylene chloride can be used. Can be used for 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.

[0014]

EXAMPLE 1 3.7 kg of sodium hydroxide was dissolved in 42 liters of water, and while maintaining at 20 ° C., 8.57 kg of bisphenol Z (BPZ) and an average repeating unit of a silicone chain as a compound of the general formula (2) were added thereto. Is [Si (CH ₃ ) ₂ O] n [n = 40], R ⁵ is -CH ₂ CH ₂ CH _2- and 94.5 g of ortho bond, and hydrosulfite (HD) 8
g was dissolved. 28 liters of methylene chloride (MC)
Pt-butylphenol (PTBP) 148
g was added, and 3.5 kg of phosgene (PG) 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 polymerization liquid 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 wash became neutral.After that, 35 liters of isopropanol was added to precipitate the polymer. I let it. The precipitate was filtered and then 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 Instead of 8.57 kg of BPZ and 94.5 g of the compound of the general formula (2), BP
A Same as Example 1 except that 7.3 kg was used. Table 1 shows the results.

Examples 2 to 4 and Comparative Examples 2 to 4 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 (4) used in Examples 2 to 5 and Comparative Examples 3 to 4 were in the following order: Real 2: The repeating unit is [Si (CH ₃ ) ₂ O] _n [n = 40], R ⁵ Is -CH ₂ CH ₂ -and para bond Real 3: 〃 [Si (CH ₃ ) ₂ O] _n [n = 75], R ⁵ is -CH ₂ CH ₂ CH ₂ -and ortho bond Real 4: 〃 [Si (Ph) (CH ₃ ) O] _n [n = 30], 〃 〃 ratio 3: 〃 [Si (CH ₃ ) ₂ O] _n [n = 40], where R ⁵ is -CH ₂ CH ₂ CH _2- Ortho bond ratio 4: 〃 [Si (CH ₃ ) ₂ O] _n [n = 40], 〃 結果 The results of measuring the physical properties of these polycarbonate resins are shown in Table 1.

[0017]

[Table 1]

[0018]

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 the advantages of high surface strength and high abrasion resistance.

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

Claims (3)

(57) [Claims] The composition has a structural unit represented by the following general formulas (1) and (2), wherein the ratio of the structural unit of (2) to the whole is 0.1 to 50% by weight, and the viscosity average molecular weight is Is 2
A polycarbonate resin solution for casting film formed by dissolving a co-polycarbonate resin having a molecular weight of 0000 to 40,000 in an organic solvent. Embedded image (In the general formula ^(1), R 1 ~R ⁴ is hydrogen, Z is cyclohex
A group of atoms necessary to form a ring , represented by the general formula (2)
Wherein R ⁵ is an alkylene group or an alkylidene group of 2 to 6,
R ^{6 to} R ⁷ represent an alkyl group or an aryl group having 1 to 3 carbon atoms, 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.