JPS6099159A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition of high impact resistance at low temperatures, good fluidity in molding operation and high releasability, capable of giving molded articles of good appearance, by incorporating a specific (partial) ester in composite rubbery polymer-blended aromatic polycarbonate resin. CONSTITUTION:The objective composition can be obtained by incorporating 100pts.wt. of a resin composition comprising (A) 70-98 (pref. 80-98) wt% of an aromatic polycarbonate resin and (B) 2-30 (pref. 2-20) wt% of composite rubbery polymer selected from MBS resin (pref. containing 30-70wt% of butadiene polymer), MAS resin (pref. containing 5-40wt% of rubber component) and acrylic ester graft copolymer with (C) 0.01-2 (pref. 0.1-1) pts.wt. of an (partial) ester from 12-30C saturated aliphatic monovalent carboxylic acid and 1-30C saturated aliphatic mono- or polyhydric alcohol.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermoplastic resin composition that exhibits street impact resistance of 6 at low temperatures and good mold release properties during molding, and specifically relates to A, aromatic polycarbonate resin 70~ 98wt% and one or more composite rubbery polymers selected from the group consisting of B, (alMBS resin, Tb)MAS resin, and (C) acrylic acid ester graft copolymer 2 To 100 parts by weight of a resin composition consisting of ~30 wt%, an ester or partial ester of a C9 aliphatic saturated carboxylic acid having 12 to 30 carbon atoms and an aliphatic saturated carboxylic acid or polyhydric alcohol having 30 or less carbon atoms is added. It is a thermoplastic resin composition containing .01 to 2M parts, and has excellent impact resistance especially at low temperatures, has no thickness dependence of impact resistance, and has excellent fluidity and mold release properties during molding. The object of the present invention is to provide a molding material that exhibits excellent weather resistance and heat resistance, and exhibits a good molded product appearance.

□ It is known that a resin composition in which an acrylic rubber is mixed with an aromatic polycarbonate resin has excellent ffi impact resistance. For example, MBS in Special Publication No. 39-71
resin, MAS resin in Japanese Patent Publication No. 4B-29308,
Japanese Unexamined Patent Publication No. 57-341.53 has a.

Acrylic acid ester-based graft copolymers are taught.

Although these materials are useful as engineering plastics, their release from the mold during injection molding is not sufficient, leading to problems such as deformation of the molded product and the time it takes to remove the molded product from the mold. , it was difficult to automate injection molding. As a result of intensive research to improve the mold releasability of the above resin composition, the present inventors found that fatty acids such as stearic acid, which is known as a lubricant for resins, Aliphatic alcohols such as stearyl alcohol and aliphatic amides such as stearylamide tend to decompose polycarbonate resins, whereas aliphatic saturated alcohols with 12 to 30 carbon atoms tend to decompose polycarbonate resins.
By blending an ester or partial ester of a saturated carboxylic acid with an aliphatic saturated or polyhydric alcohol having 30 or less carbon atoms, it is possible to greatly improve the mold release properties, and also to improve the appearance and physical properties of the molded product. The present invention was completed based on the discovery that a product can be obtained.

The present invention will be explained in detail below.

The aromatic polycarbonate resin of component A of the present invention is an optionally branched thermoplastic polycarbonate polymer made by reacting aromatic dihydroxy or a small amount of a polyhydroxy compound with phosgene or a diester of carbonic acid. . Examples of aromatic dihydroxy compounds include 2.2-bis(4-hydroxyphenyl)propane (bisphenol A), tetramethylbisphenol A1 tetrabromobisphenol A, bis(4-hydroxyphenyl)-p-diisopropylbenzene, hydroquinone, These include resorcinol, 4,4'-dihydroxydiphenyl, etc., and bisphenol 8 is particularly preferred. Further, in order to obtain a branched aromatic polycarbonate resin, phloroglucin, 4,6-cymethyl-2,4.
6-tri(4-hydroxyphenyl)hebutene-2,4
゜6-dimethyl-2.4.6-)li(4-hydroxyphenyl)hebutane, 2.6-dimethyl-2.4.6
- ) li (4-hydroxyphenyl)hebutene-3,
4,6-dimethyl-2.4.6-tri(4-hydroxyphenyl)hebutane, 1+3+5~tri(4-hydroxyphenyl)benzene, 1,1.1-tri(4
-hydroxyphenyl)ethane, and 3,3-bis(4-hydroxyaryl)oxindole (-isatinbisphenol), 5-chloroisatin, 5,7-dichloroisatin,
A portion of the dihydroxy compound, such as 5-bromysatin, is substituted with a polyhydroxy compound, for example 0.2 to 2 mol%. Furthermore, monovalent aromatic hydroxy compounds suitable for controlling molecular weight include m- and p-methylphenol, m- and p-propylphenol, p-bromophenol, p-tertbutylphenol and p-long chain alkyl-substituted phenol. is preferred. Typical aromatic polycarbonate resins include polycarbonates whose main raw material is bis(4-hydroxyphenyl)alkane dihydroxy compounds, particularly bisphenol A, which can be obtained by using two or more aromatic dihydroxy compounds in combination. Also included are polycarbonate copolymers and branched polycarbonates prepared by using a small amount of trivalent phenol compounds. Aromatic polycarbonate resins may be used as a mixture of two or more types.

The composite rubbery polymer (a) of the component B of the present invention refers to a butadiene-based rubbery polymer such as polybutadiene or butadiene-styrene copolymer, and a methacrylic acid ester, an aromatic monovinyl compound, and cyanide. It is obtained by graft polymerizing -filtration or more of a vinyl compound by a method such as bulk polymerization, suspension polymerization, bulk suspension polymerization, solution polymerization or emulsion polymerization, particularly by emulsion polymerization.

Here, the amount of the butadiene-based polymer used is 10 to 85% by weight, preferably 30 to 70% by weight, and when the butadiene-based polymer is a copolymer, the butadiene component in the copolymer is It is preferable to use one having a content of 50% by weight or more. If the amount used is less than 10% by weight, the impact resistance of the resulting composition will be low, and if the amount exceeds 85% by weight, the moldability of the composition obtained will decrease, which is not preferable. Moreover, as the methacrylic acid ester, an alkyl ester having 1 to 4 carbon atoms, particularly methyl methacrylate, is preferable. Examples of aromatic monovinyl compounds include styrene, halogenated styrene, vinyltoluene, α-methylstyrene, and vinyl-di-phthalene, with styrene being particularly preferred. As vinyl cyanide compounds, acrylonitrile, methacrylonitrile,
Examples include α-halogenated acrylonitrile, and acrylonitrile is particularly good.

The MAS resin, which is component (b) of B of the present invention, is a rubber mainly composed of an alkyl ester of acrylic acid or methacrylic acid having an alkyl group having 1 to 7.18 carbon atoms, and an aromatic hydrocarbon polymer. Alternatively, it is composed of a copolymer (■) of an aromatic hydrocarbon monomer and one or more vinyl or vinylipin monomers, and a part or all of the monomer (■) is polymerized in the presence of (■). The obtained one is 5~4゜M
It is preferable that the rubber content be %. Rubber (2) contains 70% by weight or more, preferably 80% by weight or more of one or more types of alkyl esters of acrylic acid or methacrylic acid having an alkyl group having 1 to 18 carbon atoms, and is copolymerized with this. Possible vinyl aromatic I! 30% by weight of polymer, vinyl cyanide, and aliphatic vinyl ester components
Contains the following, and has a secondary transition temperature of 0°C or less and a swelling degree of 4 to 12 when measured at 30°C in methyl ethyl ketone.
It is preferable to use one that is cross-linked. Crosslinking is carried out by reacting a polyfunctional monomer such as benzoyl peroxide or other peroxide, divinylbenzene, ethylene dimethacrylate, allyl cyanurate, triallyl phosphate, etc. in an amount of 10% by weight or less. Also, ■ is
It is a homopolymer or a copolymer consisting of 40-100% by weight of vinyl aromatic monomer and 60-0% by weight of vinyl cyanide or aliphatic vinyl ester.

The acrylic ester-based graft copolymer, which is (C) of B of the present invention, is a polyester having a conjugated diene type double bond represented by an alkyl ester of acrylic acid having 2 to 12 carbon atoms in the alkyl group and butadiene. It refers to a graft copolymer obtained by graft polymerizing one or more vinyl compounds as an essential component to a rubbery copolymer obtained by copolymerizing a functional polymerizable monomer as an essential component. In addition to the above-mentioned butadiene, examples of polyfunctional polymerizable monomers having a conjugated diene double bond include 1-methyl-2-, vinyl-4,6-hebutadiene-1=ol, and 7-methyl- 3-methylene-1,6-'octadiene, L3.7-
This can be done by listing octatrienes, etc. In addition, when copolymerizing an alkyl ester of acrylic acid and a polyfunctional polymerizable m-form having a conjugated diene type double bond, aromatic compounds represented by styrene, vinyl compounds, and methyl methacrylate may be added as desired. as appropriate from among methacrylic acid esters represented by , vinyl cyanide compounds represented by acrylonitrile, vinyl ether compounds represented by methyl vinyl ether, halogenated vinyl compounds represented by vinyl chloride, and vinyl ester compounds represented by vinyl acetate. A selected monofunctional polymerizable monomer and a crosslinking agent represented by ethylene dimethacrylate and divinylbenzene are appropriately selected and used. Vinyl compounds used in graft polymerization include methacrylic acid esters represented by methyl methacrylate, aromatic vinyl compounds represented by styrene, vinyl cyanide compounds represented by acrylonitrile, and halogenated vinyl compounds represented by vinyl chloride. Examples include polymerizable monomers selected from the group consisting of: two or more of these monomers may be used in combination. Furthermore, the above-mentioned crosslinking agent may be used in combination during graft polymerization.

In producing the acrylic acid ester-based graft copolymer, the polyfunctional polymerizable monomer having a conjugated diene type double bond is added in an amount of 0.1% in the copolymer with the alkyl ester of acrylic acid. It is used in an amount accounting for ~10% by weight.

A typical example is acrylic ester (e.g. n
-butyl acrylate, 2-ethylhexyl acrylate), butadiene, a small amount of a crosslinking agent (e.g., ethylene dimethacrylate-1, divinylhenzene), and optionally a meccrylic acid ester (e.g., methyl methacrylate) in a conventional manner. A graft copolymer obtained by copolymerizing by emulsion polymerization method, adding a vinyl compound appropriately selected from styrene, methyl methacrylate, acrylonitrile, vinyl chloride, etc. as a graft component monomer to the obtained latex, and performing graft polymerization according to a conventional method. Polymer; acrylic ester (e.g., n-butyl acrylate-1,
2-ethylhexyl acrylate) and a compound that has a non-conjugated double bond in addition to a conjugated diene type double bond in one molecule (
For example, 1-vinyl-2-vinyl-4,6-hebutadien-1-ol) and an ester of methacrylic acid, if desired, are copolymerized by a conventional method, and a graft component monomer is added to the resulting latex. , a graft copolymer obtained by graft polymerization according to a conventional method, and the like.

These graft polymerizations may be performed by lIR, or the graft component monomers may be changed in multiple stages to carry out multistage polymerization. Although a typical production example is shown using the emulsion polymerization method, it is a matter of course that the desired acrylic ester graft copolymer can be produced by other known polymerization methods as well. It is.

As such an acrylic ester graft copolymer,
Product name rHIA-15 from Prefectural Chemical Industry 01), rH
Resins commercially available as IA-284 or rF (IA-30) are preferably used.

In the present invention, the above aromatic polycarbonate resin (A) and the composite rubbery polymer (B) are combined with an aliphatic saturated carboxylic acid having 12 to 30 carbon atoms and 30 or less carbon atoms. an ester or partial ester (C) with an aliphatic saturated or polyhydric alcohol of 0. OI ~ 2 parts by weight.

Most of the C components of the present invention are known as ester waxes contained in natural products such as plants, animals, insects, and minerals, and are liquid or low-melting-point compounds at room temperature, or mixtures thereof.

Component C is easily soluble in a solvent for aromatic polycarbonate resin, such as methylene chloride, ethylene chloride, etc., so a method is used as a highly concentrated master hatch powder by making a mixed solution of both and removing the solvent. Other additives for the thermoplastic resin composition of the present invention, such as stabilizers, dyes/pigments, iMA agents, and inorganic fillers such as glass fibers, may be used as a mixture, and further, raw material pellets, The powder is made into feathers by adding it to a container and mixing it, and then it is usually pelletized.

The blending ratio of components A and B in the thermoplastic resin composition of the present invention is 70 to 98 wt%, preferably 80 to 98 wt% of component A.
%, the composite polymer of component B is in the range of 2 to 30 wt%, preferably 2 to 20 wt%, and the total amount of L of A and B is 2-30 wt%, preferably 2-20 wt%.
Component C is blended at a ratio of 0.01 to 2 parts by weight, preferably 0.05 to 2 parts by weight, particularly 0.1 to 1 part by weight, per 100 parts by weight of E, and the mold release resistance is , 10~
50% decrease. When the B component is less than 2 wt%, the thickness dependence of the impact resistance of the composition is insufficiently improved, and when it exceeds 301%, the heat resistance becomes insufficient and causes defects. Furthermore, even if the amount of C added exceeds 2 parts by weight, the effect of improving early mold release properties hardly increases, so it is meaningless, and rather causes deterioration of strength properties.

The thermoplastic resin composition of the present invention as described above may contain various additives such as stabilizers, pigments, dyes, flame retardants, and lubricants, reinforcing materials such as inorganic or organic fiber substances, glass beads, etc., as desired. Various fillers may be blended, and other resin components may also be blended within a range that does not impair the characteristics of the present invention. For example, polycarbonate-1 oligomers derived from bisphenol or tetrabromobisphenol A can be used to improve moldability, flame retardancy, and surface properties, and polyester carbonates and polyarylates (e.g., trade names: U Polymer, Unitika (41) f, Any heat-resistant polyester may be added to improve heat resistance.

In preparing the thermoplastic resin composition of the present invention,
Any conventionally known method may be used, and methods of kneading using an extruder, Banbury mixer, rolls, etc. may be selected as appropriate.

Hereinafter, it will be explained by examples and comparative examples, but "%"
and "molecular weight" are on a weight basis unless otherwise specified.

Examples-1 to 4, Comparative Examples-1 to 5 Aromatic polycarbonates made from bisphenol A! ] Fat (manufactured by Mitsubishi Gas Chemical (41, product name Newpiron 5)
-aOoo (molecular weight 22,000), acrylic acid ester graft copolymer (manufactured by Ou Kagaku Kogyo@, trade name: TECHE-15 and III^-28), and butyl stearate, millibil palmite. A compound containing 1 as a seed component (beeswax), a □ mixture containing cetyl palmiteni 1~ as a seed component (product name: spam aceti, Japan, genuine oil←
), moncnic acid noethylene glycol ester (trade name: Hoechstwax E, manufactured by Hoechst), and for comparison, mixtures containing stearic acid and stearyl alcohol as main components, stearylamide, urolylamide, ethylene bisstearamide, etc. A mixture obtained by adding and mixing 0.5 parts of a lubricant was supplied to a 40-hole vented extruder with L/I]=25, and melt-kneaded at a cylinder temperature of 260° C. to form pellets. The pellets were dried in a hot air dryer at 120° C. for 5 hours or more and then injection molded. The molding machine used was a set of inline screws (Taffi Seisakusho 5J-451).
In 1), the molding temperature was 270°C. The heat-resistant and stable type of lubricant was investigated based on the quality of molded products and the improvement in fluidity of pellets. The results are shown in Table 1 below.

Examples 5 to 12 and Comparative Example 6 Pellets obtained in the same manner as Examples 1 to 4 were dried in a hot air dryer at 120°C for 5 hours or more and then injection molded to determine mold release resistance and mold internal pressure. was measured.

The molding machine is a set of inline screws (Nikko An□Kelberg V25/200) with a molding temperature of 270℃, and the mold is a two-cavity molded rod-shaped product (5" x z" x χ") with a protruding plate. A strain gauge was attached so that the mold internal pressure and mold release resistance could be measured. Also, test pieces for physical property testing were molded and physical property measurements were performed.
For comparison, Comparative Example 6 was prepared without using the h agent.
It was shown as

These results are shown in Table 2.

From the results in Tables 1 and 2, it is clear that the thermoplastic resin composition of the present invention has a good balance of thermal stability, appearance, strength, impact resistance, etc., and is practical.

Table 2 Note) *1: Elevated solo tester, 280'c, 1
60 kg / Cl1l load, nozzle 1 tuna φ x 10
mml

Claims (1)

[Claims] C. Aromatic cinnabar polycarbonate resin 70-98-t% and B, (a) MBS resin, (b) M'AS resin, and (e) Acrylic Ji/Ashiya stellate graft. To 100 parts by weight of a resin composition consisting of 2 to 3'Owt% of one or more selected composite rubbery polymers, an aliphatic saturated carbon having 12 to 30 carbon atoms is added. A thermoplastic resin composition comprising an acid and a saturated aliphatic or polyhydric alcohol stop ester or partial ester having 30 or more carbon atoms in an amount of 0.01 to 2*.