JP3077711B2 - Polycarbonate resin solution for casting film - 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.

[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) and
A co-polycarbonate resin having a structural unit represented by (2), wherein the ratio of the structural unit of (2) to the whole is 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 casting

[0004]

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(In the general formula (1), R ¹ and R ² represent hydrogen, halogen or an alkyl group having 1 to 4 carbon atoms, R ³ and R ⁴ represent an alkyl group having 1 to ⁴ carbon atoms, A represents a linear, branched, aryl, or sulfonyl group having 1 to 10 carbon atoms, and in the general formula (2), R ⁵ represents an alkylene group or an alkylidene group having 2 to ⁶ ; R ^{6 to} R ⁷ represent a carbon atom; And n represents an integer of 1 to 200.) and a method for producing the same.

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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(Wherein R ^{1 to} R ⁷ , A and n are the general formulas (1) and (2)
The same as above), by copolymerizing phosgene, carbonate, or chloroformate to have the structural units of the general formulas (1) and (2), and having a viscosity average molecular weight of 15,000 to 100,000, preferably 20,000 to 50,000. Of the range. General formula
The amount of the dihydric phenol used in (4) is 0.1 to 50% by weight, preferably 0.1 to 30% by weight, based on the total amount of the dihydric phenol. If the amount of the dihydric phenol is less than 0.1% by weight, no effect such as lubricity and abrasion resistance will be exhibited, and if it is more than 50% by weight, the film-forming properties such as solubility and solution stability will decrease.

The dihydric phenolic compound represented by the general formula (3) used as a raw material of the co-polycarbonate resin of the present invention includes bis (4-hydroxy-3-methylphenyl) methane, 1,1- Bis (4-hydroxy-3-methylphenyl) ethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane (dimethylbisphenol A: DMBPA), 2,
2-bis (4-hydroxy-3-methylphenyl) butane, 2,
2-bis (4-hydroxy-3,5-dimethylphenyl) propane (tetramethylbisphenol A: TMBPA), 2,2-bis
(4-hydroxy-3-chloro-5-methylphenyl) propane, 2,2-bis (4-hydroxy-3-bromo-5-methylphenyl) propane, 2,2-bis [4-hydroxy-3- ( 2-propyl) phenyl] propane (diisopropylbisphenol A: DPBPA), 1,1-bis (4-hydroxy-3-methylphenyl) ethane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) ethane , Bis (4-hydroxy-3-methylphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, and the like, and among them,
2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl)
Propane, 2,2-bis [4-hydroxy-3- (2-propyl) phenyl] propane is preferred.

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 represented by the general formula (4) at both terminals 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.

In addition, a terminal terminator or a molecular weight regulator is generally 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 1 mol, per 100 mol of all the dihydric phenolic 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 releasing agent include esters of mono- or polyhydric alcohols of saturated fatty acids, and preferred examples thereof include stearyl stearate, behenyl behenate, pentaerythritol tetrastearate, dipentaerythritol hexaoctoate and the like. 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】

Example 1 3.7 kg of sodium hydroxide was dissolved in 42 liters of water, and dimethyl bisphenol A (DMBPA) was added thereto while maintaining the temperature at 20 ° C.
8.18 kg of the compound represented by the general formula (2) wherein the average repeating unit of the silicone chain is [Si (CH ₃ ) ₂ O] n [n = 50], and R ⁵ is -CH ₂ CH ₂
0.18 kg of CH _2- ortho-bound and 8 g of hydrosulfite (HD) were dissolved. Methylene chloride
(MC) 28 liters were added and stirred, 96 g of pt-butylphenol (PTBP) was added, and then 3.5 kg of phosgene (PG) was blown in over 60 minutes. After blowing phosgene, the reaction solution was vigorously stirred to emulsify the reaction solution.After emulsification, 8 g of triethylamine (T
EA) 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, and the organic phase is neutralized with phosphoric acid.
After repeated washing with water until the pH became neutral, 35 l of isopropanol was added to precipitate a polymer. 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 The procedure of Example 1 was repeated except that 7.3 kg of BPA was used instead of 8.18 kg of DMBPA and 0.18 kg of the compound of the formula (2). Table 1 shows the results.

Examples 2 to 5 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 (6) used in Examples 2 to 5 and Comparative Examples 3 to 4 were in the following order: Actual 2: The repeating unit was [Si (CH ₃ ) ₂ O] _n [n = 10], R ⁵ Is an ortho bond with -CH ₂ CH ₂ CH _2- Real 3: 〃 [Si (CH ₃ ) ₂ O] _n [n = 90], and R ⁵ is a para bond with -CH ₂ CH _2- Real 4: 〃 [Si (Ph) (CH ₃ ) O] _n [n = 40], and R ⁵ is —CH ₂ CH ₂ CH ₂ — and is ortho-bonded. Real 5: 〃 [Si (CH ₃ ) ₂ O] _n [n = 50], 〃 〃 Real 6: 〃 [Si (CH ₃ ) ₂ O] _n [n = 50], R ⁵ is -CH ₂ CH ₂ CH ₂ -and ortho bond ratio 3: 〃 [Si (CH ₃ ) ₂ O] _n [n = 50], 〃 ratio 4: 〃 [Si (CH ₃ ) ₂ O] _n [n = 50], 〃 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 front page (56) References JP-A-4-268369 (JP, A) JP-A-4-268368 (JP, A) JP-A-4-268367 (JP, A) JP-A-4-268366 (JP) JP-A-4-268363 (JP, A) JP-A-4-268362 (JP, A) JP-A-4-268364 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB Name) C08J 5/18 C08G 64/08 C08G 64/18 C08L 69/00

Claims (6)

(57) [Claims] [Claim 1] It has structural units represented by the following general formulas (1) and (2), and the ratio of the structural unit of (2) to the whole
0.1 to 50% by weight and a viscosity average molecular weight of 15,000 to 100,0
Polycarbonate resin solution for cast film formation prepared by dissolving the co-polycarbonate resin in an organic solvent. (In the general formula (1), R ¹ and R ² represent hydrogen, halogen or carbon number.
R 1 represents an alkyl group having 1 to ⁴ carbon atoms, R ³ and R ⁴ represent an alkyl group having 1 to ⁴ carbon atoms, and A represents a straight chain, branched chain, aryl group, or sulfonyl group having 1 to 10 carbon atoms; (2) Inside, R ⁵ is
2 to 6 alkylene or alkylidene groups, R ^{6 to} R ⁷ are
Represents an alkyl group or an aryl group having 1 to 3 carbon atoms, and n is
Indicates an integer from 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 2,2-
The solution according to claim 1, which is derived from bis (4-hydroxy-3-methylphenyl) propane. 5. The solution according to claim 1, wherein the viscosity average molecular weight of the polycarbonate resin is 20,000 to 50,000. 6. A dihydric phenol represented by the following general formulas (3) and (4) is interfacially copolymerized so that the ratio of (4) is 0.1 to 50% by weight with respect to the whole, and the viscosity average is obtained. Molecular weight 15,0
A method for producing a polycarbonate resin suitable for cast film formation, characterized by producing a co-polycarbonate resin having a mass of 100 to 100,000. (In the general formula (1), R ¹ and R ² represent hydrogen, halogen or carbon number.
R 1 represents an alkyl group having 1 to ⁴ carbon atoms, R ³ and R ⁴ represent an alkyl group having 1 to ⁴ carbon atoms, and A represents a straight chain, branched chain, aryl group, or sulfonyl group having 1 to 10 carbon atoms; (2) Inside, R ⁵ is
2 to 6 alkylene or alkylidene groups, R ^{6 to} R ⁷ are
Represents an alkyl group or an aryl group having 1 to 3 carbon atoms, and n is
Indicates an integer from 1 to 200. )