JPH05140440A - Polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition excellent in transparency by mixing a polycarbonate acryl copolymer with glass and a polycarbonate resin under specified conditions of the refractive indexes of the components. CONSTITUTION:The objective composition comprises 10-95wt.% polycarbonate acryl copolymer (A), 5-60wt.% glass (B) and 0-85wt.% polycarbonate resin (C), wherein the difference (in terms of an absolute value) in the refractive index between the mixture of components A and C and that of component B is 0.01 or below. The viscosity-average molecular weight of component A may be suitably selected according to its use or the like and is usually 10000-200000, desirably 15000-100000. The refractive index of component A can be freely changed by changing the content of its acryl part.

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 and transparency and are widely used as engineering plastics in various fields such as electric and electronic equipment fields and automobile fields. There is. 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 the addition of the glass fiber, and an unpleasant semi-transparent or hazy appearance is exhibited. 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 1.585, and that of "E" glass widely used for glass fiber reinforced resin is about 1.545, which is a considerable difference.
As a method for improving this drawback, Japanese Patent Publication No. 62-133.
As disclosed in Japanese Patent Publication No. 8, ZrO ₂ and TiO ₂ which have a refractive index improving effect on SiO ₂ which is a main component of glass.
It is blended with a polycarbonate resin using a special glass fiber added with. However, the compounding of TiO ₂ causes a problem that the glass is colored brown. Further, adding ZrO ₂ or TiO ₂ to glass has a drawback that it becomes expensive.

Therefore, the inventor of the present invention has conducted intensive studies to solve the drawbacks of the conventional method and develop a polycarbonate resin composition having excellent transparency. As a result, it has been found that a polycarbonate resin composition having desired properties can be obtained with a resin composition comprising a polycarbonate-acrylic copolymer, glass and a polycarbonate resin. The present invention has been completed based on such findings.

[0004]

That is, the present invention is
(A) Polycarbonate-acrylic copolymer 10-95
%, (B) 5 to 60% by weight of glass and (C) 0 to 85% by weight of polycarbonate resin, and the difference between the refractive index of the mixed resin of (A) and (C) and the refractive index of glass (absolute value ) Is 0.01 or less, the polycarbonate resin composition is provided.

First, the polycarbonate-acrylic copolymer as the component (A) of the present invention is a copolymer composed of a polycarbonate part and an acrylic part (correctly, a polyacrylate part), and there are various kinds. A typical one of them is the general formula (I)

[0006]

[Chemical 1]

(In the formula, X is a hydrogen atom, a halogen atom (for example, chlorine, bromine, fluorine, iodine) or a carbon number of 1 to 8)
When the number of X is plural, they may be the same or different, and a and b
Are integers of 1 to 4, respectively. Y is a single bond, an alkyl 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, or 5 to 5 carbon atoms.
15 cycloalkylidene groups, -S-, -SO-, -S
O ₂ -, - shows a O- or -CO- bond. Z represents a single bond, -O-, -COO- or -NH-. R ¹ is
A hydrogen atom or a methyl group, and R ² has 1 to 18 carbon atoms
Represents an alkyl group of or a cycloalkyl group having 3 to 18 carbon atoms. And m = 2-40, n = 3-41, h = 10
.About.500, i = 1 to 10. ) A polycarbonate-based graft copolymer represented by the general formula (II)

[0008]

[Chemical 2]

(Where X, a, b, Y, Z, R ¹ and R
² is the same as above. Also, p = 10 to 500, q
= 10 to 500, r = 3 to 80. ) Is a polycarbonate block copolymer. These polycarbonate-based graft copolymers and block copolymers can be synthesized by various methods. For example, it can be synthesized by reacting a prepolymer obtained by reacting a polycarbonate oligomer and an acrylic resin macromonomer with bisphenol A. Here, the polycarbonate oligomer has the general formula
(III)

[0010]

[Chemical 3]

[Wherein X, a, b and Y are the same as defined above, and Hal is a halogen atom (for example, chlorine, bromine,
(Fluorine, iodine), and t = 2 to 80. ] Is represented. This polycarbonate oligomer has the general formula (I
V)

[0012]

[Chemical 4]

[In the formula, X, a, b and Y are the same as defined above. ] It can be easily produced by reacting a dihydric phenol represented by the above with a phosgene or a carbonate precursor such as a carbonate compound. 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, but 2,2-bis (4-hydroxyphenyl) propane [bisphenol A] is particularly preferable. As the dihydric phenol other than bisphenol A, 1,1- (4-hydroxyphenyl) methane; 1,
1- (4-hydroxyphenyl) ethane; hydroquinone; 4,4'-dihydroxydiphenyl; bis (4-hydroxyphenyl) cycloalkane; bis (4-hydroxyphenyl) sulfide; bis (4-hydroxyphenyl) sulfone; bis ( 4-hydroxyphenyl) sulfoxide; bis (4-hydroxyphenyl) ether;
Compounds such as bis (4-hydroxyphenyl) ketone or bis (3,5-dibromo-4-hydroxyphenyl) propane; halogenated bisphenols such as bis (3,5-dichloro-4-hydroxyphenyl) propane Can be mentioned. These dihydric phenols may be used alone or in combination of two or more. In addition, examples of carbonate precursors other than phosgene include bromophosgene, diphenyl carbonate, di-p-tolyl carbonate, and phenyl-p.
-Tolyl carbonate, di-p-chlorophenyl carbonate, dinaphthyl carbonate, dimethyl carbonate, diethyl carbonate and the like can be mentioned.

On the other hand, various types of acrylic resin macromonomers are available. For example, when producing the above-mentioned polycarbonate-based graft copolymer,
General formula (V)

[0015]

[Chemical 5]

[Wherein R ¹ , R ² , h and Z are the same as defined above. ] An acrylic resin macromonomer represented by the following is used. Further, in producing the above-mentioned polycarbonate block copolymer, the general formula (VI)

[0017]

[Chemical 6]

[Wherein R ¹ , R ² , p and Z are the same as defined above. ] An acrylic resin macromonomer represented by the following formula may be used. The acrylic resin macromonomer represented by the general formula (V) has a polymerization degree of 10 in the case of an acrylic ester and / or a methacrylic ester.
Is 500, preferably a 20 to 300, -OH terminated, -COOH, -NH _2, = is preferably one having any of NH. Examples of the acrylate ester include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate and the like. Further, as the methacrylic acid ester,
Examples thereof include methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate and the like. In addition, such an acrylic resin macromonomer,
For example, it is manufactured as follows. That is, an acrylic acid ester and / or a methacrylic acid ester is dissolved in a solvent, a chain transfer agent and a polymerization initiator are added, and
The reaction is performed within a temperature range of 70 ° C. for 30 minutes to 5 hours. Then, the reaction product can be obtained by pouring into a precipitating agent to cause precipitation, filtration, drying and purification. Here, as the solvent, a polar solvent such as tetrahydrofuran or dimethylformamide, an aromatic hydrocarbon solvent such as benzene, toluene, or xylene, an aliphatic hydrocarbon such as hexane, heptane, or octane can be used. Of these, tetrahydrofuran is particularly preferably used. As the chain transfer agent, thiomalic acid, 2-methicapto-1,4-butanedicarboxylic acid, etc. can be used. As the polymerization initiator, a radical initiator such as azobisisobutyronitrile, benzoyl peroxide, lauroyl peroxide can be used. The acrylic resin macromonomer represented by the general formula (VI) is used as a chain transfer agent in -OH, -COOH, -N.
It can be prepared in the same manner as the acrylic resin macromonomer of the general formula (V) by using a mercaptan having one H ₂ ═NH (for example, thioglycolic acid).

The viscosity average molecular weight of the thus obtained polycarbonate-acrylic copolymer is not particularly limited,
It may be appropriately selected according to the purpose of use. Usually 100,000
0 to 200,000, preferably 15,000 to 100,000
It is 0. The refractive index (n _D ) of this polycarbonate-acrylic copolymer can be freely changed by changing the content of the acrylic portion in the copolymer. That is, it is possible to change from n _D = 1.585 of the homopolymer having only the polycarbonate part (PC part) to n _D = 1.489 of the homopolymer having only the acrylic part.
Therefore, the ratio of the polycarbonate part to the acrylic part in the (A) polycarbonate-acrylic copolymer varies depending on the required refractive index and cannot be uniquely determined.

The polycarbonate resin (PC) which is the component (C) of the present invention may be various ones, but it is usually represented by the general formula (IV)

[0021]

[Chemical 7]

[In the formula, X, a, b and Y are the same as defined above. ] It can be easily produced by reacting a dihydric phenol represented by the above with a carbonate precursor such as phosgene or a carbonate ester compound. That is, for example, in a solvent such as methylene chloride, in the presence of a known acid acceptor and a molecular weight modifier, by the reaction of a dihydric phenol and a carbonate precursor such as phosgene,
Alternatively, it is produced by a transesterification reaction between a dihydric phenol and a carbonate precursor such as diphenyl carbonate. Here, specific examples of the dihydric phenol include those listed as the raw dihydric phenol when the polycarbonate oligomer is synthesized, and the types thereof may be the same or different.

On the other hand, as the (B) glass used together with the (A) polycarbonate-acrylic copolymer or the (C) polycarbonate resin, various kinds or forms can be applied. For example, glass fibers, glass beads, glass flakes, glass powder and the like can be used, and these may be used alone or in combination of two or more kinds. Among these, the 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 20 μm, preferably 5 to 15 μm.
m. Further, the form of the glass fiber is not particularly limited, and various forms such as roving, milled fiber, chopped strand and the like can be mentioned. These glass fibers may be used alone or in combination of two or more. 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

The resin composition of the present invention comprises:
Although it is composed of the component (C), the blending ratio thereof is (A) the polycarbonate-acrylic copolymer 10
-95 wt%, preferably 10-90 wt%, (B) glass 5-60 wt%, preferably 10-50 wt% and (C) polycarbonate resin 0-85 wt%, preferably 0-80 wt% is there. Here, the (A) polycarbonate-acrylic copolymer can reduce the compounding amount of the (C) polycarbonate resin when a copolymer having a high copolymerization ratio of the polycarbonate portion of the dihydric phenol is used. In some cases, it may not be necessary to blend the polycarbonate resin as the component (C). In the resin composition of the present invention, if the compounding ratio of the glass (B) is less than 5% by weight, the dimensional stability is lowered, which is not preferable. On the other hand, if it exceeds 60% by weight, it is difficult or impossible to knead the resin, which is not preferable. When "E" glass is used as the glass, the refractive index n _D of the E glass is about 1.545, so that the proportion of the polycarbonate part in the copolymer (A) is 3%.
Polycarbonate-by adjusting 0-55% by weight
Since the n _D of the acrylic copolymer can be made close to 1.555 to 1.535 and the refractive index can be made close, it is very effective in improving transparency. In the present invention, the difference (absolute value) between the refractive index of the mixed resin containing (A) polycarbonate-acrylic copolymer and (C) polycarbonate and (C) glass is 0.01 or less, preferably Set to 0.005 or less. The difference (absolute value) in refractive index between this resin and glass is 0.0
When it exceeds 1, the transparency of the molded product obtained from the resin composition is lowered, which is not preferable.

The resin composition of the present invention can be obtained by blending the above-mentioned components (A), (B), (C) and various additive components used as necessary and kneading. The compounding and kneading are carried out by a commonly used method, for example, a method using a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single-screw extruder, a twin-screw extruder, a co-kneader or a multi-screw extruder. It can be carried out. The heating temperature during kneading is usually 250 to 300 ° C.
It is selected in the range of. The polycarbonate resin composition thus obtained is subjected to various known molding methods such as injection molding, blow molding, extrusion molding, compression molding, calender molding,
By applying rotational molding and the like, it is possible to manufacture molded articles in the automotive field such as automotive glass and sunroofs, and molded articles in the home appliance field. And various additives, other synthetic resins, elastomers, etc. can be mix | blended with the resin composition of this invention in the range which does not impair the objective of this invention as needed. 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.

[0026]

EXAMPLES Next, the present invention will be described in more detail with reference to production examples, examples and comparative examples. Production Example 1 (Synthesis of PC Oligomer) 60 kg of bisphenol A was dissolved in 400 liter of 5% sodium hydroxide aqueous solution to prepare a sodium hydroxide aqueous solution of bisphenol A. Next, this sodium hydroxide aqueous solution of bisphenol A kept at room temperature was introduced at a flow rate of 138 liters / hr and methylene chloride at a flow rate of 69 liters / hr into a tubular reactor having an inner diameter of 10 mm and a pipe length of 10 m through an Oriches plate. Then, phosgene was co-currently flown thereinto at a flow rate of 10.7 kg / hr to continuously react for 3 hours. The reaction tube used here was a double tube, and cooling water was passed through the jacket portion to keep the discharge temperature of the reaction solution at 25 ° C. Further, the pH of the discharged liquid was adjusted to be 10-11.
By allowing the reaction solution thus obtained to stand,
The aqueous phase was separated and removed, and the methylene chloride phase (220 liters)
Was collected. Methylene chloride was removed by evaporation to obtain a flake-shaped polycarbonate oligomer. The degree of polymerization of the polycarbonate oligomer obtained here was 3 to 4.

Production Example 2-1 (Synthesis of Reactive PMMA-A) 2 kg of tetrahydrofuran, 1 kg of methyl methacrylate, 11.5 g of azobisisobutyronitrile (polymerization initiator) and 31.0 of thiomalic acid (chain transfer agent). 7 g was dissolved, heated to 60 ° C. and reacted for 3 hours. The reaction product was poured into petroleum ether with stirring, and the polymer was precipitated, separated by filtration and dried. Next, the obtained polymer was dissolved in methylene chloride, washed with water, and the methylene chloride was evaporated to dryness to obtain flaky reactive PMMA. The number average molecular weight was 10,000 as determined by titration of the carboxyl group with KOH. Production Example 2-2 (Synthesis of Reactive PMMA-B) In Production Example 2-1,
The procedure of Example 2-1 was repeated, except that 19.5 g of thioglycolic acid was used instead of thiomalic acid. The number average molecular weight is 9,0 by titration of carboxyl group with KOH.
It was 00.

Production Example 3-1 (Synthesis of PC-PMMA Copolymer A: Graft Copolymer) The PC obtained in Production Example 1 was added to 2 liters of methylene chloride.
450 g of the oligomer and the reactive P obtained in Production Example 2-1
Dissolve 410 g of MMA-A, and triethylamine 11.4
After adding cc and reacting for 1 hour with stirring, the mixture was washed with 0.1N hydrochloric acid, and the organic phase was separated to obtain a prepolymer solution. Add methylene chloride to the obtained prepolymer solution and add 4
The mixture was made up to a liter, and 4 g of p-tert-butylphenol was added to make an organic solvent. On the other hand, 81 g of bisphenol A, 50 g of sodium hydroxide and 0.54 cc of triethylamine were dissolved in water to make 1.1 liter, and the organic solvent solution and 500
Interfacial polycondensation was carried out at room temperature for 1 hour at rpm. After that, 4 liters of methylene chloride was added, further washed with 4 liters of water, washed with 5 liters of 0.01N sodium hydroxide aqueous solution with alkali, washed with 5 liters of 0.1N hydrochloric acid and washed with 5 liters of water. To remove methylene chloride,
A chip-shaped PC-PMMA copolymer was obtained. The obtained copolymer was dried at 100 ° C. for 6 hours, press-molded at 290 ° C., and the refractive index was measured. Production Example 3-2 (Synthesis of PC-PMMA Copolymer B: Graft Copolymer) In Production Example 3-1, 66 of reactive PMMA-A was added.
0g, triethylamine 18.4cc, bisphenol A
Was carried out in the same manner as in Production Example 3-1 except that 78 g and 47 g of sodium hydroxide were used. Production Example 3-3 (Synthesis of PC-PMMA Copolymer C: Block Copolymer) In Production Example 3-1, 410 g of reactive PMMA-B was used instead of reactive PMMA-A, and 5.7 cc of triethylamine was used. , Bisphenol A and 52 g of sodium hydroxide were used, and p-tert-butylphenol was not added, and the same procedure as in Production Example 3-1 was carried out. Production Example 3-4 (Synthesis of PC-PMMA Copolymer D: Block Copolymer) In Production Example 3-3, 66 reactive PMMA-B was used.
Example 3-3 was repeated except that 0 g, triethylamine of 9.2 cc, bisphenol A of 83 g and sodium hydroxide of 51 g were used. Production Example 3-5 (Synthesis of PC-PMMA Copolymer E: Graft Copolymer) In Production Example 3-1, reactive PMMA-A 60 g.
Was used, and triethylamine was 1.7 cc, bisphenol A was 87 g and sodium hydroxide was 43 g, and the same procedure as in Production Example 3-1 was carried out. PC-PMM obtained in Production Example 3-1, 2, 3, 4, 5
The PMMA content and the refractive index (n _D ) of the A copolymer are first
Shown in the table. In addition, the PC-PMM obtained in Production Example 3-2
A copolymer B and FN-22 as a polycarbonate resin
00 [made by Idemitsu Petrochemical Co., Ltd.] using an extruder
Mixed at a ratio of 76:24 (weight) at 0 ° C. The n _D of the obtained mixed resin was 1.545. This mixed resin was used in Examples 5, 7, 8 and 9. Furthermore, PC-PMMA copolymer D obtained in Production Example 3-4 and FN-2200 as a polycarbonate resin were mixed at a ratio of 76:24 (weight) at 300 ° C. using an extruder. The n _D of the obtained mixed resin was 1.545. This mixed resin was used in Example 6. The PMMA content of the PC-PMMA copolymer was measured by nuclear magnetic resonance spectrum (NMR). Then, the refractive index was measured using an Abbe refractometer.

[0029]

[Table 1]

Examples 1 to 8 and Comparative Examples 1 to 5 As PC-PMMA copolymers, Production Examples 3-1, 2 and
PC-PMMA copolymers A, B, C
D was used. On the other hand, as the polycarbonate resin (PC), FN-2200 (manufactured by Idemitsu Petrochemical Co., Ltd.) was used. And as a glass fiber, MA-409
Using C [Asahi Fiber Glass Co., Ltd., n _D = 1.545], pellets were prepared at 300 ° C. by a 30 mm vented extruder at a ratio shown in Table 2. The glass fiber was supplied from the downstream side of the hopper supply position of the raw material resin of the extruder. The obtained pellets were press-molded at 300 ° C. Example 9 and Comparative Example 6 Except that glass beads [EGB-731A: manufactured by Toshiba Parodyni Co., Ltd., n _D = 1.545] were used as glass, they were blended in the proportions shown in Table 2, The same procedure as in 1 was performed. Example 10 As glass, glass fiber [ECR (electric c
orrosion resistant) glass: Example 1 except that n _D = 1.579] manufactured by Asahi Fiber Glass Co., Ltd. was used.
It carried out similarly to. Example 11 The PC-PMMA copolymer obtained in Production Example 3-1 and FN-2200 (manufactured by Idemitsu Petrochemical Co., Ltd.) as a polycarbonate resin were used in an extruder at a ratio of 15:85 at 300 ° C ( By weight). N _{D of} this mixed resin = 1.57
It was 8. It carried out like Example 1 except having used ECR glass as the obtained mixed resin and glass fiber. For the molded products obtained in Examples and Comparative Examples, haze and refractive index were measured as performance evaluations. The results of performance evaluation are shown in Table 2. The performance evaluation was performed according to the following test method. 1) Measurement of haze A test piece having a thickness of 3 mm was measured according to JIS K7105. 2) Measurement of n _D An Abbe refractometer was used.

[0031]

[Table 2]

[0032]

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,
It is effectively used as a material for various molded products that are widely used in the fields of electric and electronic devices, automobiles, etc.

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C08L 33/06 LJE 7921-4J 69/00 LPS 8416-4J

Claims (4)

[Claims] 1. A polycarbonate-acrylic copolymer of 10 to 95% by weight, (B) glass of 5 to 60% by weight, and (C) a polycarbonate resin of 0 to 85% by weight,
A polycarbonate resin composition, wherein the difference (absolute value) between the refractive index of the mixed resin of (A) and (C) and the refractive index of glass is 0.01 or less. 2. The polycarbonate resin composition according to claim 1, wherein the acrylic is polymethylmethacrylate. 3. The polycarbonate resin composition according to claim 1, wherein the glass is E glass. 4. The polycarbonate resin composition according to claim 1, wherein the glass is glass fiber.