JPH05214236A - Polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To obtain a polycarbonate resin composition of excellent transparency by mixing a terminal-modified polycarbonate resin obtained by using a specified terminator with a glass less different from the resin in refractive index. CONSTITUTION:The title composition is obtained by mixing 40-95wt.% terminal- modified polycarbonate resin obtained by using as a terminator a carboxylic acid (halide) of formula I (wherein X is -COOH, -COCl or -COBr; and n is 5-30), an alkylphenol, alkyloxyphenol or alkyl hydroxybenzoate of formula II (wherein Y is a single bond, -O- or -OCO-; n is as defined above; and m is 1-5) or sec. amine of formula III (wherein n is as defined above; and p is 1-30) with 60-5wt.% glass so that the difference (in terms of an absolute value) between the refractive index of the resin and that of the glass may be 0.01 or below. This composition has excellent transparency as well as the mechanical properties inherent in the polycarbonate and can effectively be used as a substitute material for, e.g. conventional glass articles.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polycarbonate resin composition, and more particularly to a polycarbonate resin composition having excellent transparency.

[0002]

2. Description of the Related Art Polycarbonate resins are excellent in mechanical strength, electrical characteristics, transparency and the like, and are widely used as engineering plastics in various fields such as electric / electronic equipment fields and automobile fields. ing. As the polycarbonate resin having such characteristics, a glass fiber reinforced polycarbonate resin to which glass fiber is added in order to improve rigidity and dimensional stability is well known. However, the polycarbonate resin has a drawback that the transparency is significantly lowered by adding glass fiber, and the polycarbonate resin has a semi-transparent or hazy appearance. This is due to the difference in the refractive index (n _D ) between the polycarbonate resin and the glass fiber. The refractive index of polycarbonate resin is about 1.5
85, which is widely used for glass fiber reinforced resins, that of "E" glass is about 1.545, which is a considerable difference. As a method of improving this drawback, for example,
Japanese Laid-Open Patent Publication No. 49-47408 discloses an improved technique using "ECR" glass (n _D : 1.579), but a considerable improvement can be seen, but it is still not sufficient. Further, as disclosed in Japanese Examined Patent Publication No. 62-1338, a special glass fiber obtained by adding ZrO ₂ or TiO ₂ having a refractive index improving effect to SiO ₂ which is a main component of glass is used as a polycarbonate resin. Blending. However, there is a problem that the glass is colored brown by adding TiO ₂ . Furthermore, the addition of ZrO ₂ or TiO ₂ to glass has a drawback that it becomes expensive.

[0003]

Therefore, the present inventor has conducted extensive studies to solve the drawbacks of the conventional method and to develop a polycarbonate resin having excellent transparency. As a result, p, which is commonly used in the production of polycarbonate,
A polycarbonate having an end group structure composed of an aliphatic chain having a specific structure at its end is introduced, rather than a polycarbonate having a terminal terminating agent such as -tert-butylphenol, phenol, p-cumylphenol, p-tert-octylphenol, It has been found that the refractive index can be lowered and the transparency can be greatly improved by mixing with glass. The present invention has been completed based on such findings. That is, the present invention is
As the (A) terminal stopper, a compound represented by the general formula (I)

[0004]

[Chemical 4]

(In the formula, X represents --COOH, --COCl or --COBr, and n is 5 to 30, preferably 7 to 3
It is an integer of 0. ) Or a carboxylic acid halide represented by the general formula (II)

[0006]

[Chemical 5]

(In the formula, Y is a single bond, -O- or -OC.
Represents O-, n is the same as above, and m is an integer of 1 to 5. ) Alkylphenol, alkyloxyphenol or hydroxybenzoic acid alkyl ester represented by the general formula (III)

[0008]

[Chemical 6]

(Wherein n is the same as above, and p is 1
It is an integer of -30, preferably 1-10. 40 to 95% by weight of a terminal-modified polycarbonate resin obtained by using a secondary amine represented by the formula (4) and (B) glass 60 to 5
A polycarbonate resin composition, characterized by comprising a weight percentage and having a difference (absolute value) between the refractive index of (A) and the refractive index of (B) is 0.01 or less.

In the present invention, as the terminal stopper used in the production of the terminal-modified polycarbonate resin as the component (A), the compound represented by the general formula (I) is used.

[0011]

[Chemical 7]

As the carboxylic acid represented by the formula (wherein X and n are the same as above), specifically,
Examples thereof include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, arachidic acid, behenic acid, lignoceric acid and cerotic acid. Examples of carboxylic acid halides include chlorides and bromides of the above carboxylic acids.

Further, as the terminal stopper, a compound represented by the general formula (II)

[0014]

[Chemical 8]

(Wherein Y, n and m are the same as defined above), and the alkylphenol in which Y is a single bond is specifically amylphenol, hexylphenol, heptylphenol or octylphenol. , Nonylphenol, laurylphenol, palmitylphenol, stearylphenol and the like.
Specific examples of the alkyloxyphenol in which Y is -O- include amyloxyphenol, hexyloxyphenol, heptyloxyphenol, octyloxyphenol, and the like. Furthermore, Y is -OC
Specific examples of the hydroxybenzoic acid alkyl ester, which is O-, include amyl hydroxybenzoate, hexyl hydroxybenzoate, heptyl hydroxybenzoate, octyl hydroxybenzoate, nonyl hydroxybenzoate, lauryl hydroxybenzoate, and hydroxybenzoic acid. Stearyl etc. are illustrated.

Further, as the terminal stopper, a compound represented by the general formula (III)

[0017]

[Chemical 9]

The secondary amine represented by the formula (wherein n and p are the same as above) specifically include methylpentylamine, methylhexylamine, methylheptylamine, methyloctylamine and methyl. Decylamine, ethylpentylamine, ethylhexylamine, ethylheptylamine, ethyloctylamine,
Examples thereof include ethyldecylamine, propylhexylamine, propyloctylamine, propyldecylamine, propyldodecylamine, dihexylamine and dioctylamine. These end terminators may be used alone or in combination. Further, in the production of polycarbonate resin, for example, phenol, p-tert-butylphenol (PTBP), p-cumylphenol, p-tert-, which are usually used as a terminal stopper, are used.
You may use it, mixing with octyl phenol etc.

There are various methods for producing the terminal-modified polycarbonate resin as the component (A) using these terminal terminators. For example, it can be produced by producing a polycarbonate oligomer (PC oligomer) in advance and then carrying out an interfacial reaction using a terminal terminating agent. First, the polycarbonate oligomer has, for example, the general formula (IV):

[0020]

[Chemical 10]

[Wherein Z is a hydrogen atom, a halogen atom (for example, chlorine, bromine, fluorine, iodine) or a carbon number 1)
~ 8 alkyl groups, when this Z is plural, they may be the same or different, and a and b are each an integer of 1 to 4. G is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, and 5 to 5 carbon atoms.
15 cycloalkylidene groups or -S-, -SO-,-
A bond such as SO ₂ —, —O—, —CO— is shown. ] The repeating unit having a structure represented by
Is an oligomer of. The polycarbonate oligomer having the repeating unit represented by the general formula (IV) has the general formula (V)

[0022]

[Chemical 11]

[In the formula, Z, G, a and b are the same as defined above, and Hal represents a halogen atom (eg chlorine, bromine, fluorine, iodine), and t = 1 to 20. Represented by the general formula (VI) in the solvent method, that is, in the presence of a known acid acceptor and molecular weight modifier in a solvent such as methylene chloride.

[0024]

[Chemical 12]

(3) wherein Z, G, a and b are the same as defined above, and easily produced by reacting a dihydric phenol with a carbonate precursor such as phosgene or a carbonate compound. You can That is, for example, by reacting a dihydric phenol with a carbonate precursor such as phosgene in a solvent such as methylene chloride in the presence of a known acid acceptor or a molecular weight regulator, or by reacting dihydric phenol with diphenyl carbonate. It is produced by a transesterification reaction with another carbonate precursor. There are various dihydric phenols represented by the above general formula (VI), and particularly 2,2-bis (4
-Hydroxyphenyl) propane [bisphenol A]
Is preferred. Examples of the dihydric phenol other than bisphenol A include bis (4-hydroxyphenyl) alkanes other than bisphenol A, handloquinone; 4,4′-dihydroxydiphenyl; bis (4-hydroxyphenyl)
Cycloalkane; bis (4-hydroxyphenyl) oxide; bis (4-hydroxyphenyl) sulfide; bis (4-hydroxyphenyl) sulfone; bis (4-hydroxyphenyl) sulfoxide; bis (4-hydroxyphenyl) ether; bis ( 4-hydroxyphenyl) ketone and the like and halogen-substituted compounds thereof can be mentioned. These dihydric phenols may be used alone or in combination of two or more. Examples of the carbonic acid ester compound include diaryl carbonate such as diphenyl carbonate and dialkyl carbonate such as dimethyl carbonate and diethyl carbonate. The polycarbonate oligomer may be a homopolymer using one kind of these dihydric phenols or a copolymer using two or more kinds. Further, it may be a thermoplastic random branched polycarbonate obtained by using a polyfunctional aromatic compound in combination with the dihydric phenol.

The terminal-modified polycarbonate resin of the component (A) of the present invention is prepared by dissolving the polycarbonate oligomer thus produced and the above-mentioned terminal terminator in a solvent such as methylene chloride, chlorobenzene, pyridine, etc. to hydroxylate bisphenol. An aqueous sodium solution is added, and triethylamine, trimethylbenzylammonium chloride or the like is used as a catalyst, and the reaction can be carried out by an interface reaction. The terminal-modified polycarbonate resin as the component (A) can also be produced by directly reacting the above-mentioned dihydric phenol, phosgene or carbonic acid ester compound, a terminal stopper, and the like. The refractive index of the terminal-modified polycarbonate resin of the component (A) thus obtained falls from about 1.585 of the polycarbonate resin to about 1.570. These end-modified polycarbonate resins may be used alone or in admixture of two or more.

On the other hand, as the glass (B) constituting the present invention, various kinds or forms can be applied. For example, glass fibers, glass beads, glass flakes, glass powder and the like can be used. These may be used alone or in combination of two or more. Among these, glass fibers widely used for resin reinforcement may be any of alkali-containing glass, low-alkali glass and non-alkali glass. The fiber length is 1 to 8 mm, preferably 3 to 6 mm, and the fiber diameter is 3 to 30 μm, preferably 5 to 25 μm. Further, the form of the glass fiber is not particularly limited, and examples thereof include various types such as roving, milled fiber and chopped strand. Further, these glass materials are surface-treated with silane coupling agents such as aminosilane-based, epoxysilane-based, vinylsilane-based, methacrylsilane-based, chromium complex compounds, boron compounds, etc. in order to enhance the affinity with resins. It may be Among these, the refractive index n _D is 1.560 to 1.5.
A glass of 85 is preferable.

The polycarbonate resin composition of the present invention comprises the above-mentioned components (A) and (B),
The compounding ratio thereof is 40 to 95% by weight of (A) terminal modified polycarbonate resin, preferably 50 to 90% by weight, and (C) 60 to 5% by weight of glass, preferably 50 to 10%.
% By weight. In the polycarbonate-based resin composition of the present invention, the compounding ratio of the component (B) glass is 5% by weight.
When it is less than 1, the dimensional stability is lowered, which is not preferable. Also,
If it exceeds 60% by weight, it is difficult or impossible to knead the resin composition and the appearance is further deteriorated, which is not preferable. In the present invention, the difference (absolute value) in refractive index (n _D ) between the (A) terminal-modified polycarbonate resin and the (B) glass is set to 0.01 or less, preferably 0.0005 or less.
If the difference (absolute value) between the refractive index of this terminal-modified polycarbonate resin and the refractive index of glass exceeds 0.01, the transparency of the blended product will decrease. In addition, in the polycarbonate-based composition of the present invention, in order to adjust the difference in refractive index to 0.01 or less, in addition to the terminal-modified polycarbonate resin, a commercially available polycarbonate resin containing a usual end-stopping agent is used in an amount of 0 to 85 wt. It is also possible to mix in the range of%.

In the polycarbonate resin composition of the present invention, the terminal-modified polycarbonate resin using the above-mentioned terminal stopper is used as (A), and the component (A) glass as the component (B) and various kinds used as necessary. Add additional ingredients,
It is kneaded and used for various moldings. Here, the compounding and kneading of the resin composition are commonly used methods such as ribbon blender, Henschel mixer, Banbury mixer, drum tumbler, single-screw extruder, twin-screw extruder, co-kneader, multi-screw. It can be performed by a method using an extruder or the like. The heating temperature for kneading is usually selected in the range of 250 to 300 ° C. The polycarbonate resin composition thus obtained is applied to various known molding methods such as injection molding, blow molding, extrusion molding, compression molding, calender molding, rotational molding, etc. It is possible to manufacture a molded product of the above and a molded product in the field of home appliances. In addition,
If necessary, various additives, other synthetic resins, elastomers and the like can be added to the resin composition of the present invention within a range that does not impair the object of the present invention. For example, various additives include antioxidants such as hindered phenol-based, phosphite ester-based, phosphoric acid ester-based, and amine-based antioxidants, ultraviolet absorbers such as benzotriazole-based and benzophenone-based antioxidants, and hindered amine-based light absorbers. Examples include stabilizers, external lubricants such as aliphatic carboxylic acid ester-based and paraffin-based lubricants, commonly used flame retardants, release agents, antistatic agents, and colorants.

[0030]

EXAMPLES Next, the present invention will be described in more detail with reference to production examples, examples and comparative examples. The following two types of glass were used. Glass A: Asahi Fiber Glass Co., Ltd., ECR glass (glass fiber, n _D = 1.579) Glass B: Asahi Fiber Glass Co., Ltd., MA-409
C (glass fiber, n _D = 1.545) Production Example 1 (Synthesis of Polycarbonate Oligomer) 60.0 kg of bisphenol A (BPA) was dissolved in 400 liters of a 5% sodium hydroxide aqueous solution. Then, the aqueous sodium hydroxide solution of BPA kept at room temperature was flown at a flow rate of 138 liter / hour, and methylene chloride was added at 69 liter / hour.
At a flow rate of time, it was introduced into a tubular reactor having an inner diameter of 10 mm and a tube length of 10 m through an orifice plate, and phosgene was co-currently flown into the reactor at a flow rate of 10.7 kg / hour to continuously react for 3 hours. The tubular reactor used here was a double tube, and cooling water was passed through the jacket to keep the reaction solution discharge temperature at 25 ° C. The pH of the discharged liquid is 10 to
Prepared to show 11. By leaving the reaction solution thus obtained stationary, the aqueous phase is separated and removed, a methylene chloride phase (220 liters) is collected, 170 liters of methylene chloride is further added thereto, and the mixture is sufficiently stirred, P
A C oligomer was obtained (concentration: 317 g / liter).

Production Example 2-1 (Synthesis of Terminal-Modified Polycarbonate Resin A) Into 9.0 liters of the PC oligomer obtained in Production Example 1 was dissolved 112 g of nonylphenol as a terminal stopper. On the other hand, 23.5 g of sodium hydroxide was dissolved in 600 cc of water and 5.2 cc of triethylamine was added, and this was added to the PC oligomer in which the terminal stopper was dissolved, and stirred at 500 rpm for 1 hour at room temperature. Then, 9.6 liters of methylene chloride and a sodium hydroxide aqueous solution of bisphenol A (containing 611 g of bisphenol A and 357 g of NaOH) were added, and the mixture was stirred at 500 rpm for 2 hours at room temperature. After that, 5 liters of methylene chloride was added, and further washed with 5 liters of water, washed with 5 liters of 0.01N aqueous sodium hydroxide solution, washed with 5 liters of 0.1N hydrochloric acid, and washed with acid.
Finally, the product was washed with 5 liters of water to remove methylene chloride, and a flaky terminal-modified polycarbonate resin was obtained.

Production Example 2-2 (Synthesis of Terminal-Modified Polycarbonate Resin B) Production Example 2-
In Production Example 2, except that 177 g of stearylphenol was used instead of 112 g of nonylphenol in Example 1.
The same procedure as in 1 was performed. Production Example 2-3 (Synthesis of Terminal Modified Polycarbonate Resin C) Production Example 2-
Production Example 2 except that 99 g of hexyloxyphenol was used in place of 112 g of nonylphenol in Example 1.
It carried out like -1. Production Example 2-4 (Synthesis of Terminal-Modified Polycarbonate Resin D) Production Example 2-
Example 1 was repeated except that 113 g of stearylphenol and 19 g of p-tert-butylphenol were used instead of 112 g of nonylphenol.

Production Example 2-5 (Synthesis of Terminal-Modified Polycarbonate Resin E) 91 g of bisphenol A and 4.5 g of stearic acid chloride were dissolved in a mixed solvent of 100 g of pyridine and 650 g of methylene chloride. While maintaining the temperature at 20 ° C and stirring, 40 g of phosgene was about 90
Blow in minutes, add 400 g of methylene chloride,
700 g of 10% hydrochloric acid was added, and the mixture was vigorously stirred for 15 minutes.
The aqueous phase and the organic phase were separated, and washing with water was repeated until the washing liquid for the organic phase became neutral. After that, methylene chloride was removed to obtain a flaky terminal-modified polycarbonate resin.

Production Example 2-6 (Synthesis of Polycarbonate Resin F Modified at Terminal) Production Example 2-
5, instead of 4.5 g of stearyl chloride,
Production Example 2-except that 4.6 g of hydroxybenzoic acid was used
The same procedure as 5 was performed. Production Example 2-7 (Synthesis of Terminal-Modified Polycarbonate Resin G) Production Example 2-
In Example 1, except that 112 g of nonylphenol was used and 95 g of ethyldecylamine was used, the same procedure as in Production Example 2-1 was carried out. Production Example 2-8 (Preparation of end-modified polycarbonate resin H) End-modified polycarbonate resin A: end-modified polycarbonate resin B = 1: 1 (weight ratio) was blended in methylene chloride,
After that, methylene chloride was removed to obtain a flaky terminal-modified polycarbonate resin. Using the terminal-modified polycarbonate resins A to H obtained in Production Examples 2-1 to 8, each was press-molded (thickness 1 mm) at 290 ° C., and its refractive index (n _D ) was measured. The measurement results are shown in Table 1.

[0035]

[Table 1]

The refractive index (n _D ) was measured using an Abbe refractometer. Then, the terminal-modified polycarbonate resin B obtained in Production Example 2-2 and a commercially available polycarbonate resin [trade name FN-2200, Idemitsu Petrochemical Co., Ltd.
Manufactured by using PTBP as a terminal modifier] was mixed at a ratio (weight) of 3: 1 at 300 ° C. using an extruder. The n _{D of} this mixed resin was 1.579. This mixed resin was used in Example 13.

Examples 1 to 13 and Comparative Examples 1 to 6 The terminal-modified polycarbonate resins A to H and FN-2200 (PTBP-terminated polycarbonate) obtained in the above Production Examples 2-1 to 8 were used, and as the glass, Using the glasses A and B, the ratio (weight) shown in Table 2 is 30
Pellets were prepared at 300 ° C. by an extruder with mm vent. The glass was supplied from the downstream side of the hopper supply position of the raw material resin of the extruder. 30 pellets obtained
It was press molded at 0 ° C. The haze of the molded articles obtained in Examples and Comparative Examples was measured as a performance evaluation. The results of performance evaluation are shown in Table 2. The haze was measured by measuring a test piece having a thickness of 3 mm in accordance with JIS K7105.

[0038]

[Table 2]

[0039]

[Table 3]

[0040]

As described above, according to the present invention, it is possible to obtain a polycarbonate resin composition having excellent transparency while having the original mechanical properties of polycarbonate. Therefore, the polycarbonate resin composition of the present invention can be effectively used widely as a substitute material for conventional transparent glass products, various transparent molded products and the like in the fields of electric / electronic devices, automobiles, construction materials and the like.

Claims (2)

[Claims] 1. A compound represented by the general formula (I): (In the formula, X is -COOH, -COCl or -COBr.
Is shown and n is an integer of 5-30. ) A carboxylic acid or carboxylic acid halide represented by the general formula (II) (In the formula, Y represents a single bond, -O- or -OCO-,
n is the same as the above, m is an integer of 1-5. ) Alkylphenol, alkyloxyphenol or hydroxybenzoic acid alkyl ester represented by the general formula (III) (In the formula, n is the same as above, and p is an integer of 1 to 30.) 40 to 95% by weight of a terminal-modified polycarbonate resin obtained by using a secondary amine represented by (B) A polycarbonate resin composition comprising 60 to 5% by weight of glass and having a difference (absolute value) between the refractive index of (A) and the refractive index of (B) is 0.01 or less. 2. The polycarbonate resin composition according to claim 1, wherein the glass is glass fiber.