JPS5812303B2 - Polycarbonate resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polycarbonate resin compositions.

especially. The present invention relates to a polycarbonate resin composition containing a glass filler.

Polycarbonate resins, especially polycarbonate resins reinforced with gas-based fillers. It is used for various purposes due to its excellent mechanical properties and heat resistance. It is known to be particularly useful as an engineering plastic.

However, polycarbonate resin containing glass filler... Because it requires high temperatures during molding, it has the disadvantage of being susceptible to discoloration due to thermal deterioration and oxidation.

Conventionally, several methods have been proposed to improve the thermal stability of polycarbonate resin, and the most suitable method is to add phosphite esters such as triphenyl phosphite and tricresyl phosphite. If the polycarbonate resin does not contain any additives, it is possible to prevent the polycarbonate resin from deteriorating and discoloring by adding such a phosphite ester.

However, in the case of polycarbonate resin containing glass-based fissures. The current situation is that the addition of phosphite ester actually makes the coloring more pronounced.

The present inventors have arrived at the present invention as a result of intensive research aimed at obtaining a polycarbonate resin that does not have the above-mentioned drawbacks.

In other words, the gist of the present invention is that (1) polycarbonate resin, (2) glass filler, (3) a small amount of phosphite, and (4) a small amount of phenolic antioxidant (excluding bisphenol). ) A polycarbonate resin composition characterized by containing the following.

The present invention will be explained in detail below.

As the polycarbonate resin and C which are the components of the composition of the present invention, any known ones can be used.

Various polycarbonate resins are well known. The typical ones are: Divalent residues selected from the following general formula group are shown.

R represents a monovalent residue selected from the group consisting of a hydrogen atom, a hydrocarbon group, and a halogen atom, and may be the same or different; R' represents a divalent hydrocarbon residue.

] It is a polycarbonate resin shown by.

These polycarbonate resins have the general formula [In the formula, X and R have the same meanings as above.

] is a polymeric carbonate ester of bisphenol, but such bisphenols include, for example, 4,
4'-dihydroxy-diphenylmethane, 1.1'-bis(4-hydroxyphenyl)ethane, 1,1'-bis(4-hydroxyphenyl)propane, 1.1'-bis(4-hydroxyphenyl)tane ,1,l'-bis(
4-Hydroxyphenyl)-2-methylbutylene. 1,
1'-bis(4-hydroxyphenyl)hebutane, I,
1'-bis(4-hydroxyphenyl)-1-phenylmethane, 1,1'-bis(4-hydroxyphenyl)-1(4-methylphenyl)-methane, l,1'-bis(4
-hydroxyphenyl)-(4--ruphenyl)methane, 1.1'-bis(4-hydroxyphenyl)-(4
-7propylphenyl)methane, 1.1'-bis(4
-Hydroxyphenyl)-(4--f-ruphenyl)methane, 1,1'-bis(4-hydroxyphenyl)benzyl-methane, 2,2'-bis(4-hydroxyphenyl)bu0/n. 2,2'-bis(4-hydroxyphenyl)butane. 2.2'-bis(4-hydroxyphenyl)
Pentane, 2,2'-bis(4-hydroxyphenyl)
-4-Methylpentane, 2.2'-bis(4-hydroxyphenyl)hebane, 2.2'-bis(4-hydroxyphenyl)octane, 2.2'-bis(4-hydroxyphenyl) enyl)nonane, 1,1'-bis(4-hydroxyphenyl)-1-phenylethane, 3,3'-bis(4
-hydroxyphenyl)pentane, 4,4'-bis(4
-hydroxyphenyl)hebutane, 1,1'-bis(4
-hydroxyphenyl)cyclopenkune, 1,1'-bis(4-hydroxyphenyl)cyclohexane, 2,2
'-bis(4-hydroquinphenyl)decahydronaphthalene, 2,2'-bis(4-hydroxy-3-cyclohexylphenyl)propane, 2,2'-(4,4'-dihydroxy-3-methylphenyl) phenyl)b0/n,2,
2'-(4,4'-dihydroxy-3-isobropyrudiphenyl)butane, 1,1'-bis(4-hydroxy-3-methylphenyl)cyclohexane, 2,2'-bis(4-hydroxy-3 −bu+ruphenyl)propane,
2.2'-bis(4-hydroxy-3-phenyl)propane, 2,2'-bis(4-hydroxy-2-methylphenyl)propane, 1,1'-bis(4-hydroxy-
3-Methyl-6-butylphenyl)butane, l,1'-
Bis(4-hydroxy-3-methyl-6-tert-butylphenyl)ethane, 1,1'-bis(4-hydroxy-3-methyl-6-tert-butylphenyl)propane,
1,1'-bis(4-hydroxy-3-methyl-6-tert-butylphenyl)butane, 1,1'-bis(4-hydroxy-3-methyl-6-tert-butylphenyl)isobutane, I, 1'-bis(4-hydroxy-3-methyl-6-tert-butylphenyl)hebutane, 1.1'-bis(4-hydroxy-3-methyl-6-tert-butylphenyl)-1-phenylmethane ,1,1'-bis(4-
hydroxy-3-methyl-9-tert-amyl phenyl)
butane, 4,4'-dihydroxydiphenyl ether,
4.4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4.4'-dihydroxy-3,3'-jetinodiphenyl ether, 4.4'-dihydroxy-3
, 3'-dibropyldiphenyl ether, 4.4'-dihydroxy-3,3'-diisopropyl diphenyl ether, 4.4'-dihydroxy-2,2/-dimethyldiphenyl ether, 4.4'- Dihydroxy-5-droxydiphenyl sulfide, 4.4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 4.4'-dihydroxy-3,3'-diethyldiphenyl sulfide*4.4 '
-dihydroxy-2,2'-dimethyldiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfokide, 4,4'-dihydroxy-2,2'-dimethyldiphenyl sulfoxide. 4,4'-dihydroxy-3,3'
-dimethyldiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-
2.2'-dimethyldiphenylsulfone, 4.4'-dihydroxy-3.3'-dimethyldiphenylsulfone,
4,4'-dihydroxy-3,3',5,5'-tetramethyldiphenylsulfone, 2,2'-bis(4-hydroxy-3,5-di7-phenyl)propane, 2,2
'-Bis(4-hydroxy-3,5-dipromophenyl)propane, 2,2'-bis(4-hydroxy-3-chlorophenyl)butane, 2,2'-bis(4-hydroxy-3-promophenyl) ) Propane 2,2/-bis(
4-Hydroxy-3-bromo-5-chlorophenyl)propane, 2.2'-bis(4-hydroxy-3,5-dichlorophenyl)butane, 2.2'-bis(4-hydroxy-3,5-dibromo) phenyl) t-thane, bis(4-hydroxyphenyl)-bis(difluoro-monochrome-methyl)methane. 1t3-diyrollo1',1',3',
3'-tetrafluoro-2,2'-bis(4-hydroxy-3,5-dichlorodiphenyl)propane, 1,3-
dichloro17,11,3/,3'-tetrafluoro-
Examples include 2,2'-bis(4-hydroxy-3,5-dibromodiphenyl)propane.

In addition, hydroquinone and resorcinol. Polycarbonate resins made from 4,4'-dihydroxydiphenyl and the like can also be used.

Among these polycarbonate resins, l,2,2'-bis(4-hydroxyphenyl) alkanes, especially 2
, 2'-bis(4-hydroxyphenyl)buO/n (hereinafter abbreviated as bisphenol A) is preferred.

Various methods for producing it are known, and it goes without saying that they include, for example, the phosgene method in which bisphenol A and phosgene are reacted, and the transesterification method in which bisphenol A is reacted with a carbonic acid diester such as diphenyl carbonate. Resins can be used regardless of their manufacturing method.

Among these, the effect is particularly remarkable when using polycarbonate resin obtained by the phosgene method.

Of course, in the present invention, one or more polycarbonate resins may be used, and a copolymer may be used.

Polycarbonate resins may be blended with other polymers as long as their compatibility allows. Those used in ordinary injection molding or extrusion molding are suitable, and specifically those with an average molecular weight of usually 10,000 to 100,000, preferably 20,000 to 40,000 are used.

As the glass filler which is a component of the composition of the present invention, any known filler can be used.

in particular. Examples include glass fiber, glass beads, glass powder, and the like.

It is desirable that the glass filler be surface-treated with a silane treatment agent such as an epoxy-based filler.

Among these glass-based fillers, glass fibers are preferably used in consideration of mechanical properties.

Commercially available glass fibers for polycarbonate from Asahi Fiberglass Co., Ltd., Nittobo Co., Ltd., etc. are sufficient.

Specifically, both chopped strands and roving types can be used. Considering ease of handling, chopped strand type glass fibers with a length of 3 to 6 mm are desirable.

The glass filler is contained in the composition of the present invention in an amount of 10 to 60% by weight.
Preferably, it is present.

Outside this range, the reinforcing effect of the polycarbonate resin due to the glass-based filler is undesirable.

The phosphite ester that is a component of the composition of the present invention includes:
General 2P-(OR')3 (wherein candy represents an alkyl group having 1 to 30 carbon atoms, an allyl group, an aralkyl group, a cycloalkyl group or an alkylaryl group, which may be the same or different.

Further, R' may have a substituent.

) can be used.

Specifically, for example, trioctadecylphosphite,
Trioctylphosphite. Triphenylphosphite. Tri-(2-methylphenyl)phosphite.
Tri(4-tertiary butylphenyl) phosphite, tri(2-tertiary butylphenyl) phosphite, tri-(2,6-dimethylphenyl) phosphite. Tri(2,6-diethylphenyl) phosphite, tri(2-methoxy-4-tert-butylphenyl) phosphite, tri(2-methyl-4-tert-butylphenyl) phosphite, tri(2-nonylphenyl) phosphite phyto, tri-(2-nonyl-6-methylphenyl)phosphite, tri-(2-dodecylphenyl)phosphite, tri-(2-17sil-4-tertiarybutylphenyl)phosphite, didecyl-monophenylphosphite. Dioctyl-monophenyl phosphite, monobutyl-di-phenyl phosphite, diisobutyl-monophenyl phosphite, mono-octyl-(4-tertiary butylphenyl) phosphite. Mono-2-methylphenyl (2-cyclohexyl phenyl) phosphite, di(4-tertiary butylphenyl)
Mention may be made of mono-2-nonylphenyl phosphite, trilauryl phosphite and trirabifuryl thiophosphite.

Among these phosphite esters, triphenyl phosphite, tri(methylphenyl) phosphite, and monooctyl diphenyl phosphite are particularly preferred.

These phosphite esters are. Of course, two or more types may be used in combination.

The amount of phosphite used is based on the amount of polycarbonate resin. Usually 0.02 to 0.5 weight factor, preferably 0.0
It has a weight ratio of 5 to 0.2.

If the amount of phosphite used is less than the above range, the desired discoloration prevention effect cannot be obtained, and if it is more than the above range, foaming tends to occur during molding of the composition of the present invention. As the phenolic antioxidant, which is a component of the composition of the present invention, any known phenolic antioxidant can be used, excluding bisphenol, which is undesirable because it causes a decrease in the molecular weight of the polycarbonate resin.

Generally, the general formula [wherein R'} represents a hydrogen atom, a hydroxyl group, an alkoxyl group, or a hydrocarbon residue which may have a substituent, and R"' may be the same or different.

However, at least one of R"' represents a hydrocarbon residue which may have a substituent.

Use the phenolic antioxidant shown in ].

in particular. 2,6-di-tert-butyl-4-methylphenol, 2,4-dimethyl-6-tert-butylphenol, 3-tert-butyl-4-hydroxyanisole,
2,6-Dioctadecyl-p-cresol, 2,4-dimethyl-6-isobonylphenol. Styrenated phenol, 2,4-dimethyl-6-α-methylcyclohexylphenol. 2,6-bis-(2'-hydroxy-
3'-31-Butyl-5'-1methylbenzyl)-4-methylphenol. Tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane. Hydroquinone monobenzyl ether. 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4
-hydroxybenzyl)benzene. 2,4-bis(
4-Hydroxy-3,5-di-tertiary-butylphenoxy)-6-(n-octylthio)1,3.5-triazine,6-(4-hydroxy-3,5-di-tertiary-
(butylanilino)2,4-bis(n-octylthio)-
Examples include 1,3,5-triazine, etc., and considering that the molding temperature of polycarbonate resin is high, one with a high boiling point is preferable.

Desirable phenolic antioxidants have the general formula [wherein tB
u represents a tertiary-butyl group, Y represents a b-valent hydrocarbon or heterocyclic residue having 1 to 30 carbon atoms, a is an integer of 1 to 4, and b
indicates an integer greater than or equal to 1.

] is a phenolic antioxidant.

in particular. Methyl-β-(4'-hydroxy-3
',5'-di-tert-butylphenyl)propionate, ethyl-β-(4'-hydroxy-3',5'-
Di-tertiary-butylphenyl) pionate, octyl-β-(4'-hydroxy-3',5'-di-tertiary)
-butylphenyl) propionate, lauryl β-(
4'-Hydroxy-3',5'-di-3-butylphenyl) pht-pionate, n-octadecyl-β-(
4'-hydroxy-3',5'-di-tert-butylphenyl)propionate, tetrakis[methylene-(3,5-di-tert-butyl-4-hydroxy-hydrocinnamate)]butane. Tetrakis[ethylene-(3,5-di-3-1-f-4-hydroxy-1-drocinnamate)]ttan,tris(r4
Monohydroxy-3,5-di-tert-prophenyl)buopionyloxyethyl isocyanurate, oc^e
Silu α-(4'-hydroxy-3',5/-di-tert-butylphenyl)acetate. octadecyl γ
Examples include 1-(4'-hydroxy-3',5'-1-di-3-butylphenyl)butyrate.

Of course, two or more types of phenolic antioxidants may be used in combination.

These phenolic antioxidants are suitable for polycarbonate resin. Usually 0. OO5 to 0.1 weight factor, preferably o. oos to 0.08% by weight.

If the amount of the phenolic antioxidant is below the above range, the intended coloring prevention effect of the composition of the present invention cannot be obtained, and if the amount of the phenolic antioxidant is above the above range, the polycarbonate resin This is undesirable as it causes a decrease in physical properties.

The composition of the present invention is. It can be prepared by mixing the components described above using any mixing method.

As the mixing method, well-known methods can be used without particular limitations.

Normally, glass fillers are added to polycarbonate resin,
It is preferable to add a phenolic antioxidant before hot molding.

Specifically, for example, (1) a phosphite and a phenolic antioxidant, either as they are or dissolved in an organic solvent, are mixed with a powder or flake polycarbonate resin. Blend with chopped strand glass fiber. Method of mixing in a vent extruder and cutting into pellets containing a predetermined amount of each component; (2) phosphite ester as it is or dissolved in an organic solvent and blended with powder or flake polycarbonate resin. , mixed in a vented extruder. Scrape the pellet.

The pellets are dry blended with a predetermined amount of chopped strand glass fiber and a phenolic antioxidant.
A method of pelletizing through the vent extruder again; (3)
Dry blend the phosphite ester, phenolic antioxidant, and powdered or flaked polycarbonate resin, and mix in a vent extruder. On the other hand, the roving-shaped glass fiber is pulled out from the center of the nozzle. At this time, it is industrially advantageous to coat the surface of the glass fiber with polycarbonate resin in the same manner as coating electric wires, form strands, and cut the strands into pellets.

Of course, the composition of the present invention can be prepared before the polycarbonate resin is polymerized. Flame retardant at any stage up to the final product molding.
Mold release agent, weather resistance improver, stabilizer, heat resistant agent, antistatic agent,
Coloring agents such as dyes and pigments, plasticizers, and reinforcing agents. Additives such as surfactants, inorganic fillers, lubricants, nucleating agents, and crosslinking agents may be used in combination, and polymers such as polytetrafluoroethylene, polyester, and ABS resins may also be added.

As a method for heat molding the final product using the composition of the present invention, any of injection molding, extrusion molding, compression molding, foam molding, etc. can be adopted, and the desired block can be formed. One sheet can be molded into molded products of various shapes.

The composition of the present invention is usually thermoformed at a temperature of 260 to 320°C. In particular, we were able to solve the problem of coloring.

Since coloring does not occur, the desired colored product can be easily obtained by blending dyes and pigments, and it is advantageous because a constant color tone can be obtained.

In addition, if a phenolic antioxidant, which is known to impair thermal stability when added to polycarbonate resin, is used in combination with phosphite, the results will be significantly different when used alone, and the coloring will be improved. Another major effect of the present invention is that the present invention improves the temperature. A glass filler and phosphite ester are added directly to the resulting powder or flake polycarbonate resin. It can be molded with the addition of phenolic antioxidants, compared to when polycarbonate resin pellets are used. The process is also simplified and has many industrial advantages.

The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof.

In the examples, % means % by weight.

Measurement of yellowness (hereinafter abbreviated as Y1). Tensile test and bending test are respectively JIS K-7103 and ASTM-D-
638. It was conducted according to ASTM-D-790.

Example Polycarbonate resin powder with an average molecular weight of 22,000 made from bisphenol A and phosgene by a solvent method,
A phosphite ester mainly composed of monooctyl diphenyl phosphite (Sumilizer EDP manufactured by Sumitomo Chemical Co., Ltd.) was added in an amount of 0.08% to the polycarbonate resin, and mixed in a blender.

This mixture was heated to 270 mm using a 65 mmφ vent extruder.
Pelletized at °C.

To this pellet, 30% of chopped strand type glass fiber (GF) (polycarbonate grade manufactured by Asahi Fiberglass Co., Ltd.) and the following phenolic antioxidant as shown in Table 1 were added and mixed in a blender.
It was made into pellets at 270C using a 1φ vent extruder.

This pellet was molded using a 3 oz injection molding machine at 270C.
1/8-inch plates and tensile and bending test specimens were molded.

Irganox 1010 manufactured by Ciba Geigy: Tetrakis[methylene-(3,5-di-tert-butyl-4-hydroxy-hydro-namate)] butane Irganox 1076 manufactured by Ciba Geigy: n-octadecyl β-(
Table 1 shows the results of yellowness and mechanical strength of 4'-hydroxy-3/,5'-di-3-butylphenyl)propionate.

In addition, as a comparative example, a case in which no phenolic antioxidant was added is also shown.

Claims (1)

[Claims] 1 (1) polycarbonate resin, (2) glass filler, (3) a small amount of phosphite, and (4) a small amount of phenolic antioxidant (excluding bisphenol)
A polycarbonate resin composition containing: