JPH02283760A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To prepare a thermoplastic resin compsn. excellent in the dimensional stability with no decrease in the MW by compounding a resin component mainly comprising an arom. polycarbonate resin with an inrog. filler and a specific phosphorus compd. each in a specified amt. CONSTITUTION:100 pts.wt. arom. polycarbonate resin or said resin contg. up to 70wt.% other thermoplastic resin is compounded with at least 1 pt.wt. at least one inorg. filler selected from the group consisting of an alkaline earth metal carbonate, alkaline earth metal sulfate, alumina, silica, iron oxide, antimony oxide, metal powder, metal fiber, mica, potassium titanate, talc, diatomaceous earth, steel slag, and shirasu balloon and 0.1-10wt.% (based on said inorg. filler) phosphorus compd. of the formula [wherein A and B are each -OH, -OR, -R'; R is a monovalent hydrocarbon group or alkali (alkaline earth) metal; R' is a monovalent hydrocarbon group; and n is 0 or 1].

Description

Detailed Description of the Invention Field of Application The present invention is mainly directed to aromatic polycarbonate resins or aromatic polycarbonate resins and other thermoplastic resins that retain the excellent properties of aromatic polycarbonate resins and have excellent dimensional stability. The present invention relates to a thermoplastic resin composition as a component.

<Prior Art> It has been known to improve dimensional stability by incorporating an inorganic filler into a resin composition comprising an aromatic polycarbonate resin or an aromatic polycarbonate resin and another thermoplastic resin. However, when an inorganic filler is blended into an aromatic polycarbonate resin, carbonate bonds in the molecular chain are exposed and the molecular weight is reduced, which is a serious drawback.

As a method for solving this drawback, a method is known in which the inorganic filler is treated with a silane coupling agent in advance, but this method has not been able to fully satisfy the problem.

<Objective of the Invention> The object of the present invention is to produce an aromatic polycarbonate resin that does not have a lower molecular weight even when an inorganic filler is added to it, maintains the excellent properties inherent to the aromatic polycarbonate resin, and has excellent dimensional stability. It is an object of the present invention to provide an aromatic polycarbonate resin composition or a resin composition containing an aromatic polycarbonate resin and another thermoplastic resin as main components.

As a result of extensive studies aimed at achieving the above object, the inventors of the present invention found that when blending an inorganic filler into an aromatic polycarbonate resin, if a specific amount of an acidic compound, especially a specific phosphorus compound, is used in combination, the molecular weight can be reduced. I learned that it can be significantly reduced. The present invention was completed as a result of further studies based on this knowledge.

<Structure of the Invention> The present invention provides a resin component 100 in which 100% by weight or less of a thermoplastic resin is added to an aromatic polycarbonate resin or an aromatic polycarbonate resin, and (^) an alkaline earth metal salt of carbonic acid, Alkaline earth metal salts of sulfuric acid, alumina, silica, iron oxide, antimony oxide, metal powder, metal am1
Mica, potassium titanate, talc, diatomaceous earth, steel slag,
1 part by weight or more of at least one type of inorganic filler selected from the group consisting of whitebait balloons, and (8) an amount of 0.1 to 10% by weight based on the inorganic filler according to the following binding margin % formula % [Formula Middle A and B are -OH, -OR, -R' (here R
is a monovalent hydrocarbon group, an alkali metal or an alkaline earth metal, and R' is a monovalent hydrocarbon group), and A and B may be the same or different.

phosphorus compound represented by n is 0 or 1] This relates to a thermoplastic resin composition containing the following.

The aromatic polycarbonate resin used in the present invention has a viscosity average molecular weight of to or oo derived from dihydric phenol.
o-so, ooo, preferably 15,000-30,0
00 aromatic polycarbonate resin, and is usually produced by a solution method or a melt method using dihydric phenol and a carbonate precursor. Typical examples of dihydric phenols include 2,2
-bis(4-hydroxyphenyl)propane [bisphenol A], bis(4-hydroxyphenyl)methane,
1.1-bis(4-hydroxyphenyl)ethane, 2.
Examples include 2-bis(4-human 0xy-3-methylphenyl)propane. A preferred dihydric phenol is bis(
4-hydroxyphenyl)alkane compounds, especially bisphenol 8.

Dihydric phenols can be used alone or in combination of two or more. Examples of the carbonate precursor include carbonyl halides, carbonates, heroformates, and typical examples include phosgene, diphenyl carbonate, dihaloformates of dihydric phenols, and mixtures thereof. Furthermore, when producing an aromatic polycarbonate resin, a molecular weight regulator, a branching agent, a catalyst, etc. can be used as necessary.

The thermoplastic resin to be mixed with the aromatic polycarbonate resin may be any resin that can be mixed with the aromatic polycarbonate resin, such as thermoplastic polyester resin, polyarylene ester resin, polystyrene resin, polyethylene resin, polypropylene. Examples include one type or a mixture of two or more types selected from polyamide resins, diene resins, polyamide resins, polyether resins, polysulfone resins, polyphenylene sulfide resins, and the like.

Thermoplastic polyester resins are polymers or copolymers obtained by condensation reaction of aromatic dicarboxylic acids or their ester-forming derivatives and diols or their ester-forming derivatives as main raw materials.

Preferred aromatic dicarboxylic acids used here include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, etc., and preferred diols include linear methylene chain type aliphatic diols having 2 to 10 carbon atoms, It is an alicyclic diol type with 6 to 15 alicyclic diols, and specific examples include ethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, 3-methylbentanediol (2,4), 2
-Methylbentanediol (1,4), 2-ethylhexanediol (1,3), diethylene glycol,
Examples include cyclohexane dimetatool.

Preferred thermoplastic polyester resins are polyethylene terephthalate, polybutylene terephthalate, and copolymerized polyesters in which 30 mol% or less of their acid components and/or diol components are replaced with other components.

Polyarylene ester resin is a polymer or copolymer obtained by condensation reaction using dihydric phenol or its derivative and aromatic dicarboxylic acid or its derivative as main raw materials. 21i used here! As the Ii phenol, those explained in the above-mentioned aromatic polycarbonate resin are preferably used, and the dihydric phenol derivatives are:
It is a diester of the dihydric phenol and an aliphatic or aromatic carboxylic acid. As the aromatic dicarboxylic acid, those explained in connection with the thermoplastic polyester resin are preferably used. 21iffi Interfacial polycondensation method for producing polyarylene ester resin from phenol or its derivative and aromatic dicarboxylic acid or its derivative;
Any method such as a solution polycondensation method or a melt polycondensation method may be employed.

Examples of polystyrene resins include general polystyrene, impact-resistant polystyrene, As resin, ABS resin, AES resin, MBS resin, MASAs resin, ASAs resin, tyrene/butadiene block copolymer, styrene/maleic anhydride copolymer, etc. be able to.

As polyethylene resin, high density polyethylene resin,
Low density polyethylene resin, linear low density polyethylene resin, ethylene/vinyl acetate copolymer, ethylene/propylene copolymer, ethylene/acrylic acid ester copolymer,
Examples include ethylene/glycidyl (meth)acrylate copolymer.

Examples of the polypropylene resin include polypropylene resin, propylene/vinyl acetate copolymer, propylene/vinyl chloride copolymer, and the like.

The diene resin is a bioisomer having a diene structure, such as a 1,2-polybutadiene resin or a trans-1,4-polybutadiene resin, or a copolymer thereof with a monomer copolymerizable therewith, or a mixture thereof.

The polyamide resin is a polymer consisting of an aminocarboxylic acid compound alone or a dicarboxylic acid compound and a diamine compound, or a polymer obtained by ring-opening polymerization of α,ω-caprolactam.

Polyphenylene ether (
Co)polymers are preferred.

The inorganic filler used in the present invention is an alkaline earth metal salt of carbonic acid such as calcium carbonate,! ii! IM calcium,
Alkaline earth gold yss of sulfuric acid such as magnesium sulfate and barium sulfate, mH1 metal powder of metals such as alumina, silica, iron oxide, antimony oxide, stainless steel and brass,
Mica, potassium titanate, talc, diatomaceous earth, steel slag,
It is a white glass balloon, and calcium carbonate, alumina, metal mH, mica, potassium titanate, talc, and steel slag are preferable, and among them, potassium titanate, talc, and steel slag, which have a large decrease in the molecular weight of aromatic polycarbonate resin,
Alumina is particularly preferable because it has remarkable effects according to the present invention. These inorganic fillers may be used alone or in combination of two or more, and the surface of these inorganic fillers may be treated with a treatment agent such as a silane coupling agent before use.

The amount of inorganic filler used does not need to be specified, but it is an amount that affects the reduction of the molecular weight of the aromatic polycarbonate resin, that is, 1 part per 100 parts of the aromatic polycarbonate resin.
The present invention is effective when the amount is 5 parts by weight or more.
Remarkable effects can be obtained when the amount is more than 30%.

The phosphorus compound used in the present invention is represented by the following symbol: (0)n 1 "-P-OH where A and B are -OH, -OR, -R', and R is a monovalent hydrocarbon groups, alkali metals or alkaline earth metals,
R' is a monovalent hydrocarbon group, and preferable -valent hydrocarbon groups are alkyl groups having 1 to 8 carbon atoms, and 6 to 2 carbon atoms.
0 aryl group, and an aralkyl group having 7 to 20 carbon atoms, and particularly preferred examples include phenyl group, naphthyl group, nonylphenyl group, benzyl group, and the like. Particularly preferred examples of alkali metals and alkaline earth metals include sodium and potassium. Further, A and B may be the same or different.

By using such a phosphorus compound, it is possible to significantly suppress a decrease in the molecular weight of the aromatic polycarbonate resin caused by the inorganic filler. If the amount of the phosphorus compound used is too small, a sufficient effect of suppressing molecular weight reduction will not be obtained, and if it is too large, the effect will become saturated. The amount used is usually selected from the range of 0.1 to 10% by weight based on the inorganic filler, and the optimum amount used is 2% by weight based on the inorganic filler.
-10% by weight.

The composition of the present invention can be produced by mixing the above-mentioned components using any method such as a tumbler blender, a Nauta mixer, a Banbury mixer-1 mixed roll, or an extruder.

Other additives, such as antioxidants, flame retardants, antistatic agents, mold release agents, ultraviolet absorbers, etc., may be mixed into the composition of the present invention as necessary within a range that does not deviate from the purpose of the composition. .

<Effects of the Invention> Even when a sufficient amount of inorganic filler is blended into the aromatic polycarbonate resin, the composition of the present invention does not have a lower molecular weight, retains the resin's original excellent properties, and has excellent dimensional stability. Because of its excellent properties, it can be applied to any melt molding method such as injection molding, extrusion molding, compression molding, rotation molding, etc., and is especially suitable for applications that could not be used conventionally, such as large precision machine parts and large automobile parts. It has excellent industrial effects, such as making it possible to

<Examples> The present invention will be explained in detail below using examples. In the examples, parts mean parts by weight, and the viscosity average molecule IM is the specific viscosity η3. It was calculated by inserting into the formula below.

η,, /C-[η] + 0.45 [η]2G[η]
-1,23 1250) To 100 parts by weight, add the inorganic filler and phosphorus compound listed in Table 1 in the amount listed in the table, and extrude at a cylinder temperature of 280°C using a 3011Φ vent extruder (vS-30 manufactured by Nakatani ■) to form pellets. I got it.

The obtained pellets were heated to 120°C using a hot air circulation dryer.
After drying for 5 hours or more, physical property test pieces were prepared using an injection molding machine (J-1203^ manufactured by Japan Steel Works, Ltd.) at a cylinder temperature of 290°C and a mold temperature of 80°C.

Viscosity average molecular m of pellets and molded products (physical property test pieces)
M and the physical properties of the test pieces are shown in Table 1.

(Left below) Examples 6 to 8 and Comparative Examples 6 to 8 Same viscosity average molecule m24.9 as used in the above examples
The inorganic filler and phosphorus compound listed in Table 2 were added to 100 parts by weight of polycarbonate powder obtained from Bisphenol A of No. 00, and pellets were obtained in the same manner as in the above example. Physical property test pieces were prepared in the same manner.

The viscosity average molecular weights M of the pellets and molded articles (physical property test pieces) are shown in Table 2.

(Margin below) Procedural amendment June 1989?

Claims (1)

[Scope of Claims] 100 parts by weight of an aromatic polycarbonate resin or an aromatic polycarbonate resin to which 70% by weight or less of another thermoplastic resin is added, (A) an alkaline earth metal salt of carbonate, an alkaline earth metal salt of sulfuric acid; Similar metal salts, alumina, silica, iron oxide, antimony oxide,
Metal powder, metal fiber, mica, potassium titanate, talc,
1 part by weight or more of at least one inorganic filler selected from the group consisting of diatomaceous earth, steel slag, and shirasu balloon, and (8) the following general formula ▲ in an amount of 0.1 to 10% by weight based on the inorganic filler. There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, A and B are -OH, -OR, -R' (where R is a monovalent hydrocarbon group, an alkali metal or an alkaline earth metal,
R' is a monovalent hydrocarbon group), and A and B may be the same or different. A thermoplastic resin composition containing a phosphorus compound represented by n is 0 or 1.