JP3097931B2 - Glass reinforced polycarbonate resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass-reinforced polycarbonate resin composition, and more particularly, to a glass-reinforced resin composition containing copolyestercarbonate as a basic resin.

[0002]

2. Description of the Related Art Glass-reinforced polycarbonate resins having excellent mechanical strength, rigidity, dimensional accuracy, and the like are widely used as materials for housings of cameras and power tools, for example. In these applications, an excellent surface appearance is required in order to increase commercial value.

However, the glass reinforced polycarbonate resin has a so-called floating of glass, in which glass fibers are exposed on the surface, and has an excellent appearance as compared with other resins such as glass reinforced nylon and glass reinforced polyester. Was said to be difficult.

In order to solve such a problem, a method in which molding is performed by increasing the temperature of a mold has conventionally been adopted. However, this method is not preferable because the molding cycle becomes long.

[0005] In addition, a method of obtaining an excellent appearance by performing a finish coating is also performed. However, not only is the cost of the coating expensive but economically disadvantageous, but also the coating is applied to the surface where the glass floats heavily. However, it was difficult to expect a desirable appearance.

Therefore, the present invention provides an improved surface appearance.
An object of the present invention is to provide a glass-reinforced polycarbonate resin composition.

[0007]

The present inventors use a specific copolyestercarbonate as a polycarbonate resin, and mix fine glass fibers having a diameter of 10 μm or less with the polycarbonate resin to significantly improve the surface appearance. The inventors have found that the present invention has been achieved.

That is, the present invention provides: (A) the following formula (Formula 3):

[0009]

Embedded image And the following formula (Formula 4):

[0010]

Embedded image In the above formula, R and R 'are each independently a halogen atom, a monovalent hydrocarbon group or a hydrocarbonoxy group, and W is a divalent hydrocarbon group, -S-, -SS-, -O
-, -S (= O)-,-(O =) S (= O)-, or -C (= O)-, and n and n 'are each independently an integer of 0 to 4, X is a divalent aliphatic group having 6 to 18 carbon atoms, b is 0 or 1, and has a structural unit represented by the formula: ) And 2 to 30 of the total amount of the structural units of
Copolyestercarbonate which accounts for mol%
A glass-reinforced polycarbonate resin composition comprising: 99 to 50 parts by weight; and (B) 1 to 50 parts by weight of a glass fiber having an average fiber diameter of 3 μm to 10 μm .

The copolyester carbonate used in the present invention needs to have the structural units represented by the above formulas (3) and (4). First, the structural unit represented by Chemical Formula 3 is composed of a diphenol component and a carbonate component. The following formula (Formula 5) shows a diphenol that can be used to introduce a diphenol component.

[0012]

Embedded image In the above formula, R, R ', W, n, n' and b have the same meanings as described above. Regarding R and R ', examples of the halogen atom include a chlorine atom and a bromine atom. As a monovalent hydrocarbon group, a carbon number of 1 to 1
Alkyl group having 2 such as methyl group, ethyl group, propyl group, decyl group; cycloalkyl group having 4 to 8 carbon atoms such as cyclopentyl group and cyclohexyl group; aryl group having 6 to 12 carbon atoms such as Phenyl group, naphthyl group, biphenyl group and the like; aralkyl group having 7 to 14 carbon atoms such as benzyl group and cinnamyl group; or alkaryl group having 7 to 14 carbon atoms such as tolyl group and cumenyl group. And preferably an alkyl group. Examples of the hydrocarbon group of the hydrocarbon oxy group include the aforementioned hydrocarbon groups. Such a hydrocarbon oxy group is an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group or an alkaryloxy group, and an alkoxy group and an aryloxy group are preferred.

When W is a divalent hydrocarbon group,
Alkylene groups having 2 to 30 carbon atoms, such as alkylene groups having 1 to 30 carbon atoms, for example, methylene group, ethylene group, trimethylene group, octamethylene group, etc., or ethylidene group, propylidene group, etc .;
And a cycloalkylene group having 6 such as a cyclohexylene group, a cyclododecylene group or the like, or a cycloalkylidene group such as a cyclohexylidene group.

The diphenols useful in the present invention include, for example, 2,2-bis (4-hydroxyphenyl) propane (so-called bisphenol A); 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane ; 2,2-bis (3,5-
Dimethyl-4-hydroxyphenyl) propane; 1,1-bis (4-hydroxyphenyl) cyclohexane; 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane; 1,1-bis (4-hydroxy 1,4-bis (4-hydroxyphenyl) propane; 1,1-bis (4-hydroxyphenyl) cyclododecane; 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclododecane 4,4-
Dihydroxydiphenyl ether; 4,4-thiodiphenol; 4,4-dihydroxy-3,3-dichlorodiphenyl ether; and 4,4-dihydroxy-2,5-dihydroxydiphenyl ether, and the like.
The diphenols described in 2,999,835, 3,028,365, 3,334,154 and 4,131,575 can be used.

[0015] Examples of the precursor for introducing the carbonate component include phosgene and diphenyl carbonate.

Next, the structural unit represented by the chemical formula (4) comprises a diphenol component and a diacid component. For the introduction of the diphenol component, the same diphenol as described above can be used. The monomer used to introduce the diacid component is a diacid or an equivalent thereof. The divalent acid is, for example, an aliphatic diacid having 8 to 20 carbon atoms, preferably 10 to 12 carbon atoms. The divalent acid or its equivalent may be linear, branched, or cyclic. The aliphatic diacid is preferably α, ω-dicarboxylic acid. As such a divalent acid, for example, straight-chain saturated aliphatic dicarboxylic acids such as sebacic acid (decandioic acid), dodecandioic acid, tetradecandioic acid, icodecandioic acid, and the like are preferable, and sebacic acid and dodecane acid are preferable. Diacids are particularly preferred. Examples of the equivalent substance include the above-mentioned divalent acids, for example, acid halides such as acid chloride, and diaromatic esters such as diphenyl ester. However, the carbon number of the ester portion of the ester is not included in the carbon number of the acid described above. The above divalent acid or its equivalent may be used alone or in combination of two or more.

The copolyester carbonate of the component (A) has the above-mentioned two types of structural units represented by the following chemical formulas (3) and (4) in the following proportions. That is, the amount of the structural unit represented by (Chem. 4) is 2 to 30 mol%, preferably 5 to 25 mol%, more preferably 7 to 20 mol% of the total amount of (Chem. 3) and (Chem. 4). It is. If the amount of the compound (Chem. 4) is less than 2 mol%, the transition temperature (Tg) is insufficiently reduced, so that the effect of improving the fluidity is not seen. On the other hand, if it is more than 30 mol%, excellent physical properties equivalent to those of conventional polycarbonate, for example, mechanical strength, heat resistance and the like cannot be obtained.

The weight average molecular weight of the copolyester carbonate of component (A) is usually from 10,000 to 100,000, preferably from 18,000 to 40,000. Here, the weight average molecular weight is a value measured by GPC (gel permeation chromatography) using polystyrene corrected for polycarbonate. (Also, in methylene chloride, 25 ℃
It is preferable that the intrinsic viscosity measured in the step is 0.35 to 0.65 dl / g. The copolyester carbonate of the component (A) can be produced by a known polycarbonate production method, for example, an interfacial polymerization method using phosgene, a melt polymerization method, or the like. For example,
U.S. Pat. No. 4,238,596 to Quinn and U.S. Pat.
It can be produced by the method described in 4,238,597. Specifically, first, an acid halide is formed prior to the reaction between the ester-forming group and the diphenol, and then reacted with phosgene. Incidentally, in the basic solution method of Goldberg (U.S. Pat. No. 3,169,121),
A pyridine solvent can be used, and a dicarboxylic acid is used. Melt polymerization methods using diesters of α, ω-dicarboxylic acids (eg, sebacic acid) (eg, diphenyl esters) can also be used. A preferred method of manufacture is described in Kochanowsk in U.S. Pat. No. 4,286,083.
This is an improved method of i). In this method, a lower diacid such as adipic acid is converted into a salt form (preferably an alkali metal salt such as a sodium salt) in advance, and is added to a reaction vessel in which diphenol is present. During the reaction with phosgene, the aqueous phase is brought to an alkaline pH, preferably about pH 8-9.
And then the remaining minimum of about 5% of the reaction with phosgene
At this point, the pH is raised to 10 to 11.

In the case of the interfacial polymerization method, for example, the bischloroformate method, it is preferable to use a general catalyst system well known in the synthesis of polycarbonate and copolyestercarbonate. Primary catalyst systems include amines such as tertiary amines, amidines or guanidines. Tertiary amines are commonly used, of which trialkylamines such as triethylamine are particularly preferred.

The copolyester carbonate of the component (A) has a sufficient impact strength even if the terminal is phenol, but pt-butylphenol, isononylphenol, isooctylphenol, m- or p-cumylphenol. By introducing a bulkier terminal group such as (preferably p-cumylphenol), a chromanyl compound, for example, chroman, a copolyester carbonate having better low-temperature impact properties can be obtained.

Next, the component (B) has an average fiber diameter of 10 μm.
m, preferably 8 μm or less, particularly preferably 6 μm
The following is a glass fiber. Average fiber diameter is 10μm
If it exceeds 30, the effect of the present invention is not exhibited. As long as the average fiber diameter is 10 μm or less, any of commercially available glass fibers available as chopped glass, roving glass, milled glass and the like can be used. The composition of the glass is not particularly limited, but is preferably E glass.

Component (B) is used in an amount of 1 to 50 parts by weight, preferably (A) 95 to 7 based on 99 to 50 parts by weight of component (A).
5 to 30 parts by weight is blended with respect to 0 parts by weight. If the component (B) is less than 1 part by weight, sufficient rigidity cannot be obtained, and if it exceeds 50 parts by weight, moldability is impaired.

The resin composition of the present invention may further contain other resins in addition to the above components. Examples of such other resins include polyester such as PBT, ABS resin,
AES resin, SAN resin, polystyrene and the like can be mentioned. Such resins can be used in amounts up to 200 parts by weight per 100 parts by weight of component (A).

The resin composition of the present invention may also contain other conventional additives, such as pigments, dyes, etc., at the time of mixing and molding the resin according to the purpose, as long as the physical properties are not impaired.
Heat-resistant agents, antioxidant deterioration inhibitors, weathering agents, lubricants, release agents, plasticizers, flame retardants, flow improvers, antistatic agents and the like can be added.

The method for producing the resin composition of the present invention is not particularly limited, and ordinary methods can be used satisfactorily. However, the melt mixing method is generally preferred. The use of small amounts of solvents is possible but generally not necessary. Examples of the apparatus include an extruder, a Banbury mixer, a roller, a kneader, etc., which are operated batchwise or continuously. The order of mixing the components is not particularly limited.

[0026]

The present invention will be described in more detail with reference to the following examples.
I will tell. In the examples, the following components were used as the components.
Was used.Component (A)  CPEC: Copolyester moss produced as follows
-Carbonate: 7.2 g of dodecane diacid (DDDA) (31
Mmol) and 2.7 g of NaOH tablets (68 mmol)
Is dissolved in 180 ml of water, and disodium
A salt was produced. Next, a sample outlet is provided at the bottom, and
Into a 2000ml Molton flask with 5 ports
Stirrer blade, pH measuring end, injection tube and dry ice condenser
A claisen adapter with a denser was attached. this
In a polymerization flask, add 71 g (311 mm) of bisphenol A.
Mol), 0.9 ml of triethylamine, p-cumylfe
2.0 g (9 mmol) of phenol, methylene chloride 22
0 ml and the previously prepared disodium salt of DDDA
I charged. Subsequently, the flask was charged with 2 phosgene.
Injected at a rate of g / min. At this time, 50% NaOH aqueous solution
The solution was brought to pH 8 for 10 minutes while adding the solution through the injection tube.
Maintained. After that, continue to inject more phosgene
Add a 50% NaOH aqueous solution from the injection tube to
H was adjusted to 10.5 and maintained at this pH for 10 minutes. use
The total amount of phosgene that was added was 40 g (400 mmol)
there were. After the reaction, adjust the pH of the solution to 11 to 11.5.
And the organic solvent phase was separated from the aqueous phase. Organic solvent phase
Three times with 300 ml of 2% hydrochloric acid, and then with 30 parts of ion-exchanged water.
After washing 5 times with 0 ml, dry with anhydrous magnesium sulfate
And filtered. Put this in 1500 ml of methanol
To precipitate the polymer. Filter the resulting polymer by filtration
Separate, once with 500 ml of methanol and then ion exchange.
After washing four times with 500 ml of water replacement, at 110 ° C for 15 hours
Dried. Thus, the structures of the following formulas (Formula 6) and (Formula 7)
Copolyester having units in a 90:10 molar ratio
-Carbonate was obtained. This intrinsic viscosity (25 in methylene chloride)
° C) was 0.46 dl / g. In the following this
Abbreviated as CPEC.

[0027]

Embedded image

[0028]

Embedded imagePC: Poly of bisphenol A used for comparison
Carbonate, trademark LEXAN (Nippon GE Plastics
Co., Ltd.), measured in methylene chloride at 25 ° C.
Viscosity 0.46 dl / gComponent (B)  Glass fiber: average fiber diameter is 13 μm and 10 μm respectively
m, 6 μm chopped glass (this chopped dog
Lath's sizing agent is urethane-based and can be used as a coupling agent.
Containing aminosilane)Examples 1-2 and Comparative Examples 1-4  Each component was mixed at the ratio (weight ratio) shown in Table 1,
Single screw extrusion set at 100 rpm, 60 kg / hour (extrusion speed)
It was extruded with a machine (65 mm) to produce pellets. This peret
Using a 80-ton molding machine at a set temperature of 280 ° C.
Injection molding was performed at a mold temperature of 100 ° C. About the obtained molded product
To evaluate the surface appearance, and to evaluate the Izod impact strength,
The flexural strength and flexural modulus were measured. The results are shown in Table 1.
You.

The surface appearance was evaluated based on the surface roughness. The surface roughness is measured using a surface roughness meter (universal surface shape measuring instrument model SE-3H with a surface information processing function, manufactured by Kosaka Laboratory Co., Ltd.), and the maximum height (R-max) is measured according to JIS B0601. ) 10 point average roughness (Rz) and center line average roughness (Ra) were determined. The measurement distance was 2.5 mm, and the average of three measurements was taken. The smaller the value, the smoother the surface. In addition, Izod impact strength is ASTM
The Izod impact strength with a 1 / 8-inch notch was measured according to D256. Flexural strength and flexural modulus are as per ASTM D79
Measured according to 0.

[0030]

Table 1 Table 1 Example Comparative Example 1 2 1 2 34 4 Component CPEC 90 90---90 PC--90 90 90-Glass fiber Average fiber diameter 13μm--10--10 Average fiber diameter 10μm 10--10--Average fiber diameter 6μm-10--10-─────────────── ───────────────────── Evaluation test Surface appearance Surface roughness R-max (μm) 3.0 1.6 6.2 6.4 6.1 3.6 Rz (μm) 2.1 1.1 4.8 4.6 4.7 2.5 Ra (μm) 0.25 0.13 0.49 0.47 0.48 0.31 Izod impact strength (kg-cm / cm) 10 11 10 10 10 10 Flexural strength (kg / cm ² ) 1190 1200 1170 1180 1200 1190 Flexural modulus (kg / cm ² ) 41000 41500 41000 41000 42000 41000 ─────────────────────────── ────────

[0031]

The surface appearance of the glass-reinforced polycarbonate resin composition of the present invention has been improved very well. Therefore, in addition to excellent mechanical strength, rigidity, dimensional stability, etc., it can be widely used in applications where the surface appearance affects commercial value.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Hiroshi Miyake 2-2 Kinugaoka, Moka-shi, Tochigi Japan G-E plastics Co., Ltd. (56) References JP-A-62-115060 (JP, A) International Publication 91 / 9896 (WO, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 63/64 C08L 67/00 C08L 69/00

Claims (1)

(57) [Claims] (A) The following formula (Formula 1): And the following formula (Formula 2): In the above formula, R and R 'are each independently a halogen atom, a monovalent hydrocarbon group or a hydrocarbonoxy group, and W is a divalent hydrocarbon group, -S-, -SS-, -O
-, -S (= O)-,-(O =) S (= O)-, or -C (= O)-, and n and n 'are each independently an integer of 0 to 4, X is a divalent aliphatic group having 6 to 18 carbon atoms, b is 0 or 1, and has a structural unit represented by the formula: ) And 2 to 30 of the total amount of the structural units of
Copolyestercarbonate which accounts for mol%
A glass-reinforced polycarbonate resin composition comprising: 99 to 50 parts by weight; and (B) 1 to 50 parts by weight of a glass fiber having an average fiber diameter of 3 μm to 10 μm .