JPH06256633A - Polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition improved in reactivity by mixing a polycarbonate resin with a polycarbonate oligomer having terminal chalcone derivative group(s) and obtained from a monohydric phenol derivative of calcone represented by a specified formula. CONSTITUTION:A dihydric phenol compound, such as 2,2-bis(4-hydroxyphenyl) propane, is dissolved in an aqueous alkaline solution. The obtained solution is mixed with an inert organic solvent and then, by stirring, with a monohydric phenol derivative of chalcone represented by the formula (wherein R<1> is H, alkyl, alkoxy, etc.), such as hydroxychalcone. Phosgene is introduced into the mixture to emulsify it by stirring, and a catalyst comprising, e.g. triethylamine is added thereto to effect polymerization. After completion of the reaction, the organic solvent phase is neutralized, and the formed polymer is precipitated, separated by filtration and dried to give a polycarbonate oligomer having a viscosity-average molecular weight of 2,000 to 8,000 and terminal chalcone derivative group(s). This oligomer is incorporated into a polycarbonate resin having a viscosity-average molecular weight of 1.3 to 50,000 to give the objective resin composition having an oligomer content of 0.5-20wt.%.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate resin composition which can be continuously molded by injection molding, extrusion molding and the like and which can be easily subjected to secondary processing. The polycarbonate resin composition of the present invention is a resin composition in which a polycarbonate oligomer having a chalcone derivative at the end is blended,
It has weather resistance outdoors, and by utilizing the reaction activity of the terminal, it is suitably used for various applications such as a raw material for producing a block copolymer with another resin, a reactive resin modifier and a film material.

[0002]

2. Description of the Related Art Polycarbonates having vinyl terminals or conjugated double bonds (Japanese Patent Laid-Open Nos. 55-9696 and 61-141726) are known as terminal reactive polycarbonate resins. Since these have ultraviolet absorption, but have high reaction activity, they will react and polymerize with ultraviolet light even outdoors, and will also lose their activity as long-term storage and lose their function as ultraviolet absorbers. There was a flaw. Polycarbonates having ultraviolet absorption ability of triazole or benzophenone type at the terminal are known (Japanese Patent Laid-Open No. 49-99596).
issue). However, although these UV absorbers have excellent weather resistance, they have the drawbacks that they have low activity as a reactive group and that the UV absorbers are expensive. Further, when the reaction activity of only the surface such as a hard coat of a sheet is required, a polymer having a high molecular weight has a small content of reaction active groups, and thus the reaction activity points on the surface are small and not satisfactory.

[0003]

INDUSTRIAL APPLICABILITY The present invention is used as a raw material for producing a block copolymer with another resin, which is excellent in weather resistance and long-term storability, has a terminal with a high reaction activity, or a reactive resin modifier. Another object of the present invention is to provide a polycarbonate resin composition which can be formed into a molded product having a reaction-active group on its surface.

[0004]

As a result of intensive studies to solve the conventional problems, the present inventors have found that a known polycarbonate resin is blended with a polycarbonate oligomer having a chalcone derivative at its end to improve the weather resistance. It has been found that, when a molded article is excellent in long-term storage stability and is formed into a molded article, a large number of reaction active groups are unevenly distributed on the surface, and the present invention has been completed based on this finding.

That is, the present invention uses a dihydric phenol compound and uses a chalcone derivative monohydric phenol represented by the following general formula (1) as an end terminating agent to obtain a chalcone having a viscosity average molecular weight of less than 10,000. Polycarbonate oligomer with derivative and viscosity average molecular weight 1
The present invention relates to a polycarbonate resin composition having a composition of 0,000 or more known polycarbonate resins, wherein the content of the polycarbonate oligomer having a chalcone derivative at the terminal is 50% by weight or less.

[0006]

[Chemical 2] (In the formula, R ₁ represents hydrogen, an alkyl group, an alkoxy group, a dialkylamino group or a nitro group.)

The polycarbonate oligomer in the present invention is the same as the conventional method for producing a polycarbonate oligomer except that a chalcone derivative monohydric phenol, which is a compound represented by the general formula (1), is used as a molecular weight modifier or an end terminating agent. It can be obtained by the method of.

That is, in the interfacial polymerization method, after reacting the dihydric phenol compound with phosgene in the presence of a reaction-inert organic solvent and an aqueous alkali solution, a terminal terminating agent and a tertiary amine or quaternary ammonium are used. A method of polymerizing by adding a polymerization catalyst such as a salt, the pyridine method is a method in which a dihydric phenol compound and an endcapping agent are dissolved in pyridine or a mixed solution of pyridine and an inert solvent, and phosgene is blown to directly obtain a polycarbonate resin. is there. In the interfacial polymerization method, a method of adding a terminal terminator during the reaction between the dihydric phenol compound and phosgene may be used.

The chalcone derivative monohydric phenol represented by the general formula (1), which is used as a molecular weight regulator or an end terminating agent used in the production of the polycarbonate oligomer of the present invention, is specifically 4'-hydroxy. Chalcone,
3'- hydroxychalcone, 2'- hydroxychalcone, 4-
Ethoxy-2'-hydroxychalcone, 4-ethoxy-3'-hydroxychalcone, 4-ethoxy-4'-hydroxychalcone,
4-diethylamino-4'-hydroxychalcone, 4-methoxy
-4'-hydroxychalcone, 4-nitro-4'-hydroxychalcone, 4-dimethylamino-4'-hydroxychalcone, 4-methyl-4'-hydroxychalcone and the like are exemplified. You may use these chalcone derivative monohydric phenols in combination of 2 or more types.

The preferred dihydric phenol compound used for producing the polycarbonate oligomer of the present invention is specifically bis (4-hydroxyphenyl).
Methane, 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), 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, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-
Hydroxyphenyl) -1-phenylethane, bis (4-
Examples thereof include hydroxyphenyl) diphenylmethane and α, ω-bis [3- (O-hydroxyphenyl) propyl] polydimethylsiloxane. These can be used in combination of two or more kinds, and the known polycarbonate resin is also preferably one derived from these dihydric phenol groups.

The amount of the monohydric phenol represented by the general formula (1) used as the molecular weight regulator or the terminal terminator is 200 to 11 mol, preferably 100 to 20 mol, based on 100 mol of the dihydric phenol compound. Is the range.

As a solvent inert to the reaction, dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chloroform, 1,1,1-trichloroethane, carbon tetrachloride, monochlorobenzene, dichlorobenzene Chlorinated hydrocarbons such as benzene, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; ether compounds such as diethyl ether. These organic solvents should be used as a mixture of two or more kinds. You can also If desired, ethers, ketones, esters other than the above,
Solvents having an affinity for water, such as nitriles, may be used, provided that the mixed solvent system is not completely compatible with water.

As the polymerization catalyst, trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine, tridecylamine, N,
Tertiary amines such as N-dimethylcyclohexylamine, pyridine, quinoline, dimethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride, triethylbenzylammonium chloride and the like.

In the polycarbonate oligomer of the present invention, a branching agent is further used in an amount of 0.01 to 3 mol%, particularly 0.1 to 1.0 mol% with respect to the above dihydric phenol compound to give a branched polycarbonate oligomer. be able to.

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, α, α ′, α ″ -A polyhydroxy compound exemplified by tri (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, and
Examples thereof include 3,3-bis (4-hydroxyphenyl) oxindole (= isatin bisphenol).

The polycarbonate oligomer in the present invention has a viscosity average molecular weight of less than 10,000, but it is preferably in the range of 1,000 to 8,000 when used in injection molding or extrusion molding. Also, the known polycarbonate resin to be blended preferably has a viscosity average molecular weight of 13,000 to 50,000. The viscosity average molecular weight after compounding is preferably 13,000 to 40,000 when used in injection molding, extrusion molding and the like.

In the resin composition of the present invention, the content of the polycarbonate oligomer is 50% by weight or less based on the total composition, but 0.1 to 20% by weight is preferable from the viewpoint of melt viscosity and economy. As for the mixing method, the material flakes may be mixed together,
The polycarbonate resin pellets and the oligomer flakes may be blended, and the oligomer flakes or the oligomer solution may be sequentially added to the molten polycarbonate resin during extrusion or injection molding. Further, in wet molding such as casting, the solution can be mixed as it is.

When producing the composition of the present invention, if desired, antioxidants, light stabilizers, colorants, inorganic and organic fillers, reinforcing agents such as carbon fibers and glass fibers, lubricants, An antistatic agent or the like may be appropriately used in combination.

[0019]

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

Reference Example 1 (Production of Polycarbonate Oligomer Using Chalcone Derivative Monohydric Phenol) 5.8 w / v% sodium hydroxide aqueous solution was added to 5.8 liters.
2,2-bis (4-hydroxyphenyl) propane (BPA)
912 g and hydrosulfite 1 g were added and dissolved. To this, 3.6 liters of methylene chloride was added, 256 g of 4'-hydroxychalcone was added while stirring at 15 ° C, and then 520 g of phosgene was introduced over 60 minutes. After completion of the introduction, vigorously stir to emulsify the reaction solution, and after emulsification
2 ml of triethylamine was added, and the mixture was stirred for about 1 hour for polymerization.

The polymerization solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and the washing solution was repeatedly washed with water until the pH became neutral. Then, 4.7 liters of isopropanol was added, and the polymerization product was added. Allowed to settle. The precipitate is filtered and then vacuum dried to approximately 1.1k.
A polycarbonate oligomer having a chalcone derivative monohydric phenol residue at the terminal of g was obtained. The viscosity average molecular weight of this oligomer was 0.5 × 10 ⁴ .

Reference Example 2 (Production of Polycarbonate Resin Using Known Monohydric Phenol as End Terminator) 2 in 58 liters of 8.8 w / v% sodium hydroxide aqueous solution,
2-bis (4-hydroxyphenyl) propane (BPA) 9.
12 kg and 10 g of hydrosulfite were added and dissolved. To this, 36 liters of methylene chloride was added, and 178 g of P-isopropenylphenol was added while stirring at 15 ° C., and then 5.1 kg of phosgene was introduced over 60 minutes.
After completion of the introduction, the reaction solution was emulsified by vigorous stirring, 20 ml of triethylamine was added after emulsification, and the mixture was stirred for about 1 hour to polymerize.

The polymerization solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and the washing solution was repeatedly washed with water until the pH became neutral. Allowed to settle. The precipitate was filtered and vacuum dried to obtain about 10 kg of polycarbonate resin. The viscosity average molecular weight of this resin was 2.2 × 10 ⁴ .

Example 1 The oligomer of Reference Example 1 was added to Iupiron S-2000 (viscosity average molecular weight 2.4 × 10 ⁴ ) manufactured by Mitsubishi Gas Chemical Co., Inc., which is a commercially available polycarbonate resin, to prepare a blend material having an oligomer ratio of 2.5% by weight. Extruded pellets were obtained at 260 ° C. with a vented 20 mm extruder. The viscosity average molecular weight of this pellet is
It was 2.3 × 10 ⁴ .

[0025] The pellets were heated at a resin temperature of 340 ° C and a mold temperature.
90 ° C, injection pressure 1000Kg / cm ² , holding pressure 300kg / cm ² ,
A disk with an outer diameter of 120 mm and a thickness of 1.2 mm was created with an injection molding machine. A urethane acrylic UV-curable coating (BS575 made by Arakawa Chemical Industry Co., Ltd.) was applied to the molded disc to a thickness of about 30 μm, and the disc surface was hard-coated by irradiating with an 80 W / cm mercury lamp at a dose of 340 mJ for 30 seconds. . The adhesion of the hard coat by the cross-cut test by peeling the cellophane tape and the yellowing test were performed. The degree of yellowing was evaluated by the YI value before coating the coating. The peel test was 100/100 and the YI value was 2.0.

Example 2 The procedure of Example 1 was repeated, except that the molded disc was allowed to stand in the direct sunlight for 8 hours in the summer and then an ultraviolet curable coating material was applied. The peel test result was 100/100 and the YI value was 2.0.

Example 3 A disk was prepared in the same manner as in Example 1 except that the blended materials were used after being left for 2 months in the dark, and the same UV curable coating material was applied and cured to carry out the same test. went. The peel test was 100/100 and the YI value was 2.0.

Comparative Example 1 The polycarbonate resin material synthesized in Reference Example 2 was extruded into pellets as they were, and the pellets molded in the same manner as in Example 1 were coated with the same ultraviolet curable coating material as used in Example 1. Then, the same test was performed. Peel test is 10
The YI value was 2.0 at 0/100.

Then, the molded article of Comparative Example 1 was left in direct sunlight in the same manner as in Example 2, and then the test piece coated with the ultraviolet curable coating material was subjected to the same test as in Example 2 as a result.
The peel test was 52/100 and the YI value was 2.3.

Further, the same test as in Example 3 was carried out except that the polycarbonate obtained in Reference Example 2 was used without mixing the polycarbonate oligomer. As a result, the peel test was 91/100 and the YI value was 2.0. there were.

In the above Examples and Comparative Examples, the viscosity average molecular weight was 20 ° C., and the intrinsic viscosity was determined with a methylene chloride solution, and was determined by the following conversion formula. [Η] = 1.23 × 10 ⁻⁴ M ^0.83 Each test was conducted as follows. Peeling test: Cross-cut, cellophane peeling, residual grid / 100 YI value: Yellow index, Nippon Denshoku Industries Co., Ltd.
Uses SZ-Σ90

[0032]

INDUSTRIAL APPLICABILITY The resin composition of the present invention can be imparted with reactivity by blending a polycarbonate oligomer having a chalcone derivative at its terminal, is highly reactive with other reactive resins, and can be used as a paint composition. Adhesion can be increased. Particularly, in the case of a molded product, the reactive groups are unevenly distributed on the surface of the molded product, which is suitable for surface modification. In addition, it has excellent stability against light and long-term storage stability compared to conventionally known styrene type end-modified polycarbonate.
It can be used for almost the same purpose as a conventional reactive terminal polycarbonate, and an economically excellent resin composition can be provided.

Claims (4)

[Claims] 1. A viscosity average molecular weight 1 obtained by using a dihydric phenol compound and a chalcone derivative monohydric phenol represented by the following general formula (1) as an end terminating agent.
A composition of a polycarbonate oligomer having a chalcone derivative at a terminal of less than 0000 and a known polycarbonate resin having a viscosity average molecular weight of 10,000 or more, wherein the content of the polycarbonate oligomer having a chalcone derivative at a terminal in the composition is 50% by weight. % Or less of the polycarbonate resin composition. [Chemical 1] (In the formula, R ₁ represents hydrogen, an alkyl group, an alkoxy group, a dialkylamino group or a nitro group.) 2. A polycarbonate oligomer having a chalcone derivative at a terminal has a viscosity average molecular weight of 2,000 to 8,000.
And, the viscosity average molecular weight of the known polycarbonate is 1
The polycarbonate resin composition according to claim 1, which is 3,000 to 50,000. 3. The polycarbonate resin composition according to claim 1, wherein the content of the polycarbonate oligomer having a chalcone derivative at the terminal is 0.5 to 20% by weight. 4. The dihydric phenol compound is 2,2-bis (4-hydroxyphenyl) propane.
The polycarbonate resin composition described.