JPH04337352A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide a thermoplastic resin composition composed of a polyarylate, a polyamide and a modified polyolefin and having excellent impact resistance, especially high-speed punching impact resistance, weld strength and surface appearance. CONSTITUTION:The objective composition is produced by compounding (A) 100 pts.wt. of a resin composition composed of (A1) 20-80wt.% of a mixture of 10-60wt.% of a polyarylate containing acid chloride group and having an acid chloride value of 10X10<-6> to 250X10<-6> equivalent/g and a polyarylate free from acid chloride group and (A2) 80-20wt.% of a polyamide (e.g. nylon 6 and nylon 66) with (B) 1-40 pts.wt. of a modified polyolefin composed of 0.8-30 pts.wt. of an olefinic copolymer containing acid anhydride group and 0.2-10 pts.wt. of an olefinic polymer containing epoxy group.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition for molding which has excellent impact resistance, particularly high-speed punching impact resistance, surface properties and weld strength.

0002

[Prior Art] Polyarylate is an engineering plastic made from aromatic dicarboxylic acid or its derivatives and bisphenol or its derivatives, and is known to have a high heat distortion temperature and a high thermal decomposition temperature. .

[0003] In addition, a resin composition composed of polyarylate and polyamide has an excellent balance of physical properties as a molding material that combines the good moldability and chemical resistance of polyamide with the heat deformation resistance of polyarylate. It is expected that it will have the following characteristics. The usefulness of such resin compositions is disclosed in Japanese Patent Publication No. 56-14699 and Japanese Patent Application Laid-open No. 52-98.
It is disclosed in Japanese Patent No. 765.

[0004] However, resin compositions consisting only of polyarylate and polyamide have a drawback of low impact resistance. Methods using various impact resistance imparting agents have been disclosed for the purpose of improving such drawbacks. For example, Japanese Patent Publication No. 62-944, Japanese Patent Application Publication No. 61-183353
Publication No. 62-277462, Japanese Patent Application Laid-open No. 62-277462
No. 2-283146 discloses a method using a specific modified polyolefin.

[0005] As described above, when a specific modified polyolefin is used as an impact resistance imparting agent, the Izod impact strength is certainly improved, but the high-speed punching impact resistance, which is more important in practical terms, remains low. In particular, the high-speed punching impact resistance at a low temperature of about -30°C remains extremely low. These drawbacks are a major hindrance in applications that require impact resistance at low temperatures, such as automobile exterior panels.

Furthermore, when modified polyolefins are used, the surface properties of the molded products are generally poor, and there are problems in that silver marks and flow marks are observed, and there are problems in that the strength of the weld portion is low.

[0007]

[Problems to be Solved by the Invention] The present invention has been made in view of the above circumstances, and provides a molded article made from a resin composition in which a modified polyolefin is further added to polyarylate and polyamide, and has high high-speed punching impact resistance. This was done for the purpose of imparting good surface properties and weld strength.

[0008]

[Means for Solving the Problems] As a result of intensive research to achieve the above object, the present inventors have achieved the present invention by mixing a polyarylate having a specific functional group with a normal polyarylate. We have discovered that all of the objectives can be achieved at an extremely high level, and have completed the present invention.

That is, the present invention provides a resin composition comprising 20 to 80% (by weight, the same shall apply hereinafter) of a polyarylate having an acid chloride group and a polyarylate having no acid chloride group and 80 to 20% of a polyamide. Things (A
) A thermoplastic resin composition in which 1 to 40 parts of a modified polyolefin (B) is added to 100 parts (parts by weight, the same applies hereinafter).

0010

[Example] The polyarylate used in the present invention, with or without an acid chloride group, is generally an aromatic compound obtained from bisphenols and/or its derivatives and aromatic dicarboxylic acids and/or its derivatives. It refers to something that has a polyester skeleton, and there are no particular restrictions on its main chain structure.

[0011] The above-mentioned bisphenols have, for example, the general formula:

0012

[Chemical formula 1]

(In the formula, -X- is -O-, -S-,
-SO2-, -CO-, alkylene group or alkylidene group, R1, R2, R3, R4, R5
, R6, R7, and R8 are each a group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group having 1 to 20 carbon atoms. , desirable in terms of moldability, impact resistance, etc.

Specific examples of such bisphenols include 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), bis(4-hydroxyphenyl)methane, and bis(4-hydroxy-3,5-dimethyl). phenyl)methane, bis(4-hydroxy-3,
5-dichlorophenyl)methane, 1,1-bis(4-
hydroxyphenyl)cyclohexylmethane, 1,1-
Bis(4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)phenylmethane, 1,1-bis(4
- hydroxyphenyl)-1-phenylethane,
4,4'-dihydroxydiphenyl ether, bis(
4-hydroxy-3,5-dimethylphenyl)ether, bis(4-hydroxyphenyl)sulfone, bis(4
-Hydroxy-3,5-dimethylphenyl)sulfone, 4,4'-dihydroxybenzophenone, 2,2-
Bis(4-hydroxy-3,5-dimethylphenyl)
Examples include propane.

Among these, bisphenol A is particularly preferred.

[0016] Examples of the bisphenol derivatives include alkali metal salts and diacetates of bisphenols.

[0017] The bisphenols and/or their derivatives may optionally be supplemented with a small amount of other divalent compounds such as 4,4'-biphenol, hydroquinone, resorcinol, 2,6-dihydroxynaphthalene, etc., such as alcohol. It may be added in an amount of about 20% or less of the ingredients.

Examples of the aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, diphenyl ether-
4,4'-dicarboxylic acid, benzophenone-4,4'
- Dicarboxylic acids, naphthalene-2,6-dicarboxylic acids, etc. can be used. Among these, isophthalic acid and/or terephthalic acid are preferred in terms of heat resistance, moldability, impact resistance, etc., and the weight ratio of isophthalic acid and terephthalic acid in the polymer is 1.
More preferably, the ratio is 0/0 to 7/3.

Examples of the aromatic dicarboxylic acid derivatives include dihalides such as dichloride of aromatic dicarboxylic acids, and diesters such as dialkyl esters and diaryl esters.

[0020] The polyarylate having no acid chloride group used in the present invention contains the above-mentioned bisphenols and (
Alternatively, it can be produced by polymerizing its derivative with an aromatic dicarboxylic acid and/or its derivative by any method such as an interfacial polycondensation method, a solution polymerization method, or a melt polymerization method.

[0021] The method for producing the polyarylate having an acid chloride group used in the present invention is not particularly limited and may be arbitrary, but for example, aromatic dicarboxylic acid dichloride may be used in an excess molar amount relative to the bisphenols in an interfacial polycondensation method. It can be easily produced by polymerization. According to such a method, acid chloride groups are introduced at the ends of the polymer.

The main chain structure of the polyarylate having an acid chloride group and the main chain structure of the polyarylate having no acid chloride group may be the same or different.

In order to effectively exhibit the impact resistance of the molded article according to the present invention, especially the effects of excellent high-speed punching impact resistance, surface properties, and weld part strength, it is necessary to use a polyarylate having an acid chloride group. It is essential that polyarylate is contained, and it is desirable that the acid chloride group be a terminal acid chloride group because the above effect is particularly noticeable. In addition, the content expressed as the number of moles of acid chloride groups per unit weight of polyarylate having acid chloride groups (hereinafter referred to as acid chloride value)
As 10 x 10-6 to 250 x 10-6 equivalent/g
The range is preferably 30 x 10, more preferably 30 x 10
-6 to 100 x 10-6 equivalents/g.

The content of the polyarylate having acid chloride groups is preferably 10 to 60% of the total polyarylate. A polyarylate having an acid chloride group may be used simply by being mixed with a polyarylate not having an acid chloride group, or the two may be used after melt-mixing the two in advance. It is also desirable to dissolve both in a solvent, mix them, and then distill off the solvent to uniformly mix them.

[0025] If the acid chloride value is outside the above range or the amount of polyarylate having acid chloride groups in the total polyarylate is out of the above range, high-speed punching impact resistance, surface properties, and weld part strength will deteriorate. This is undesirable since it tends to decrease.

It is not clear why a remarkable effect is achieved by containing a polyarylate having an acid chloride group, preferably a polyarylate having an acid chloride group at the end, but it is not clear why the polyarylate does not have an acid chloride group. It has been observed that the dispersed particle size of the polyarylate dispersed phase in polyamide is much smaller and more uniform than when polyarylate is used. It is presumed that the polyarylate having a chloride group acts as a so-called compatibilizer and stabilizes the interface between the polyarylate particles and polyamide.

[0027] As described above, by mixing polyarylate having a specific functional group with ordinary polyarylate, all the problems with conventional resin compositions made of polyarylate, polyamide, and modified polyolefin are solved. The fact that this happened is completely unexpected and surprising. Moreover, the effects exerted by the acid chloride groups of polyarylates have been completely unknown heretofore.

The molecular weight of the polyarylate having an acid chloride group and the polyarylate having no acid chloride group is 0.2 in intrinsic viscosity (chloroform solution, 30°C).
The range is preferably from 1.5 to 1.5, more preferably 0.4
~0.8. If the intrinsic viscosity of the polyarylate is outside the above range, it is not preferable because the high-speed punching impact resistance tends to decrease and the moldability tends to decrease.

The polyamide used in the present invention is a polyamide whose main components are an aliphatic amino acid, a lactam or a diamine, and a dicarboxylic acid.

Representative examples of the main components of the polyamide include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid;
ε- Lactams such as caprolactam, ω- laurolactam, diamines such as tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, diglycolic acid, etc. Examples include dicarboxylic acids. In addition to these aliphatic components, it is also possible to use a copolyamide containing a small amount of an aromatic component or an alicyclic component, for example, 20% or less.

Particularly useful polyamides used in the present invention include polycaproamide (nylon 6),
Examples include polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46), and polydodecanamide (nylon 12). Among these, nylon 6 and nylon 66 are particularly important from the viewpoint of the balance between moldability and heat resistance.

The molecular weight of the polyamide is determined by the relative viscosity (d) measured at 25°C in a 1% concentrated sulfuric acid solution.
l/g) within the range of 2.0 to 5.0 from the viewpoint of balance between impact strength and moldability.

The modified polyolefin used in the present invention refers to α-olefins and dienes having 2 to 30 carbon atoms, such as ethylene, propylene, 1-butene, 4-methylpentene-1, isobutylene, 1,4-hexadiene, and diene. Cyclopentadiene, 2,5-norbornadiene, 5-
The main constituents are ethylidene norbornene, butadiene, isoprene, etc., and at least one group selected from carboxylic acid groups, carboxylic acid metal bases, carboxylic ester groups, acid anhydride groups, epoxy groups, acid amide groups, and imide groups.
A monomer component having various functional groups is prepared by, for example, a copolymerization method,
Polyolefins are modified by introducing methods such as graft polymerization. Among these modified polyolefins, those that exhibit the effects of the present invention more markedly include:
Examples include acid anhydride group-containing olefin copolymers, epoxy group-containing olefin copolymers, and mixtures of both.

Examples of the acid anhydride group-containing olefin copolymer include homopolymers of olefins such as polyethylene, polypropylene, and polybutene-1, ethylene-propylene copolymers, and ethylene-butene-1 copolymers.
1 copolymer, ethylene-propylene-diene copolymer, ethylene-vinyl acetate copolymer, etc., copolymerized or graft-polymerized with a dicarboxylic acid anhydride having an unsaturated bond.

Examples of the dicarboxylic anhydride having an unsaturated bond include maleic anhydride, methylmaleic anhydride, chloromaleic anhydride, citraconic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, Examples include endo-bicyclo-[2,2,1]-5-heptene-2,3-dicarboxylic acid anhydride.

As a copolymerization component of the acid anhydride group-containing olefin copolymer used in the present invention, methacrylic acid esters such as methyl methacrylate and ethyl methacrylate, methyl acrylate, ethyl acrylate, acrylic Acrylic acid esters such as butyl acid may also be used.

The content of the unsaturated bond-containing dicarboxylic acid anhydride by copolymerization or graft polymerization is preferably 0.01 to 10%, more preferably 0.1 to 5%, based on the modified polyolefin. If it is out of the above range, the impact resistance tends to decrease and the surface properties of the molded product tend to decrease, which is not preferable.

Examples of the epoxy group-containing olefin copolymer include homopolymers of olefins such as polyethylene, polypropylene, and polybutene-1, ethylene-propylene copolymers, and ethylene-butene-1 copolymers.
Preferably, an epoxy compound having an unsaturated group is copolymerized or graft-polymerized with a copolymer such as 1 copolymer, ethylene-propylene-diene copolymer, or ethylene-vinyl acetate copolymer.

Specific examples of the epoxy compound having an unsaturated group include glycidyl methacrylate, itaconic acid monoglycidyl ether, p-glycidylstyrene, p-glycidyloxystyrene, and allylglycidyl ether.

As a copolymerization component of the epoxy group-containing olefin copolymer used in the present invention, methacrylic acid esters such as methyl methacrylate and ethyl methacrylate, methyl acrylate, ethyl acrylate, and butyl acrylate may be used as necessary. You may also use acrylic esters such as.

The content of the epoxy compound having an unsaturated group by copolymerization or graft polymerization is preferably 0.01 to 50% of the modified polyolefin, more preferably 1%.
~15%. If it deviates from the above range, it is not preferable because impact resistance tends to decrease and the surface properties of the molded product tend to decrease.

Further, when a mixture of 0.8 to 30 parts of an olefin copolymer containing an acid anhydride group and 0.2 to 10 parts of an olefin copolymer containing an epoxy group is used as the modified olefin, it is particularly preferable that the weld It is preferable because the strength is high.

There are no particular restrictions on the degree of polymerization of these modified polyolefins, but from the viewpoint of impact resistance and moldability, they usually have a molecular weight of 10,000 or more and a melt index of 0.05 to 50 g/10 min, preferably 0. .1～
A range of about 30 g/10 minutes is preferable.

The composition of the present invention is a mixture of the polyarylate having an acid chloride group and the polyarylate not having an acid chloride group in an amount of 20 to 80%, preferably 30 to 60%.
% and said polyamide 80-20%, preferably 70-4
100 parts of the resin composition (A) consisting of 0% and 1 to 40 parts, preferably 3 parts of the modified polyolefin (B).
-20 parts.

[0045] When the proportion of the mixture of the polyarylate having acid chloride groups and the polyarylate having no acid chloride groups in the resin composition (A) is less than 20%, heat resistance decreases, and when it exceeds 80%, heat resistance decreases. Molding fluidity decreases. Furthermore, if the amount of the modified polyolefin (B) is less than 1 part based on 100 parts of the resin composition (A), the impact resistance will decrease, and if it exceeds 40 parts, the heat resistance and strength will decrease.

If necessary, the resin composition of the present invention may further contain a lubricant such as a wax, a stabilizer such as a phosphite type or a phenol type, an ultraviolet absorber, a pigment, a flame retardant, a plasticizer, an inorganic filler, and a filler. , reinforcing fibers, etc. may be added.

The method for producing the resin composition of the present invention is not particularly limited, but a method using melt mixing is particularly preferred, and for example, an extruder, hot roll, Brabender, Banbury mixer, etc. can be used.

[0048] In producing the resin composition, there is no particular restriction on the order of mixing the components, and any order is possible.
The method of adding and kneading after melting and kneading the other three components is particularly preferred because the present invention is highly effective.

The resin composition of the present invention can be used to obtain molded products with excellent high-speed punching impact resistance, surface properties, and weld part strength by injection molding, extrusion, blow molding, compression molding, or other methods. These molded products can be suitably used as various automobile exterior parts, automobile outer panels, mechanical parts, electrical/electronic parts, etc.

[0050] The composition of the present invention will be explained below with reference to Examples, but the present invention is not limited only to these Examples.

Production Example 1 Production of polyarylate Using isophthalic acid dichloride, terephthalic acid dichloride and bisphenol A, the number of excess moles of carboxylic acid dichloride to bisphenol A is adjusted from 0 to 1.
Polyarylates having various acid chloride values adjusted within the range of 3 mol % were produced by an interfacial polycondensation method. Table 1 shows the composition and properties of each polyarylate produced.

The acid chloride value was measured as follows.

Approximately 0.1 g of the sample (polyarylate) was accurately weighed, and 10 ml of chloroform was added to dissolve it. After dissolving, add 2 ml of methanol and a small amount of 0.2% thymol blue methanol solution as an indicator, and incubate at room temperature for 60 minutes.
After stirring for a minute to react, liberated hydrogen chloride was titrated with a 0.1N tributylamine/chloroform solution, with the end point being the point at which the indicator turned from pink to yellow. A blank test was conducted without adding any additional sample.

[0054] The acid chloride value was determined by the following formula.

Acid chloride value (equivalent/g) = {(Ts-
Tb) x 0.1 x F x 10-3}/WTs: Amount of 0.1N tributylamine/chloroform solution required for titration of the sample (ml) Tb: Amount of 0.1N tributylamine/chloroform solution required for titration of the blank test Amount of chloroform solution (ml) F: Factor W of 0.1N tributylamine chloroform solution: Weight of sample (polyarylate) (g)

[0056]

[Table 1]

Examples 1 to 17 and Comparative Examples 1 to 3 The polyarylates shown in Table 1 and the following polyamides and acid anhydride group-containing polyolefins were blended in the proportions shown in Table 2, and the mixture was placed in a hopper at the base of a twin-screw extruder. Further, an amount of the epoxy group-containing olefin copolymer shown in Table 2 was side-fed and kneaded at 270°C to obtain pellets.

The obtained pellets were vacuum dried at 120° C. for 15 hours, and test pieces were obtained by injection molding.

Polyamide: Nylon-6: manufactured by Toray Industries, Inc., Amilan CM1026 (polyε-caprolactam) Nylon-66: manufactured by Ube Industries, Ltd., Ube Nylon 2026B (polyhexamethylene adipamide) Contains acid anhydride Olefin copolymer: Maleic anhydride grafted ethylene-propylene copolymer (manufactured by Japan Synthetic Rubber Co., Ltd., T7711SP, maleic anhydride content
0.8%, melt index 2.4) Epoxy group-containing olefin copolymer: Ethylene glycidyl methacrylate copolymer (manufactured by Sumitomo Chemical Co., Ltd., Bond Fast E, glycidyl methacrylate content 11.5%) The test pieces were evaluated using the following method. The results are shown in Table 2.

High-speed punching impact strength: Rheometric H
Using a RIT8000 high-speed punching impact tester, test pieces (100
mm x 100 mm x 3 mm), and the energy required for punching was measured.

Strength of weld part: A flat plate (100 mm x 100 mm x 3 mm) formed by two-point gates so that a weld line was formed in the center was used as a test piece. As the molding conditions, an injection pressure higher than the limit injection pressure for complete filling by 5 kg/cm2 (gauge pressure) was adopted. The strength was measured under the same conditions as in the case of the high-speed punching impact strength, with the punch tip hitting the center of the weld line.

[0062] Surface quality of molded product: 100 mm x 100
A flat plate of mm x 3 mm was molded, and the presence or absence of defects such as flow marks and silver marks near the gate was visually observed and evaluated.

[0063] ×: Extremely defective △: Slightly defective ○: Almost no defects

[0064]

[Table 2]

From Table 2, it can be seen that the molded articles obtained using the composition of the present invention have excellent properties such as high-speed punching impact strength, weld part strength, and surface properties.

[0066]

[Effect of the invention] When the composition of the present invention is used, impact resistance,
In particular, molded products with good high-speed punching impact resistance, welded part strength, and surface properties can be obtained.

Claims (10)

[Claims] 1. 100 parts by weight of a resin composition (A) comprising 20 to 80% by weight of a mixture of a polyarylate having an acid chloride group and a polyarylate not having an acid chloride group, and 80 to 20% by weight of a polyamide. 1 to 40 parts by weight of a modified polyolefin (B) is added to the thermoplastic resin composition. 2. The polyarylate according to claim 1, wherein the proportion of the polyarylate having an acid chloride group in the mixture of the polyarylate having an acid chloride group and the polyarylate having no acid chloride group is 10 to 60% by weight. Thermoplastic resin composition. 3. The polyarylate having an acid chloride group has an acid chloride value of 10 x 10-6 to 250 x 10
-6 equivalent/g of the thermoplastic resin composition according to claim 1 or 2. 4. A polyarylate having an acid chloride group and a polyarylate having no acid chloride group are
4. The thermoplastic resin composition according to claim 1, wherein the main skeleton is an aromatic polyester composed of bisphenol A and terephthalic acid and/or isophthalic acid. 5. The intrinsic viscosity of the polyarylate having an acid chloride group and the polyarylate having no acid chloride group (chloroform solution, 30°C) is 0.2 to 1.5.
The thermoplastic resin composition according to claim 1, 2, 3 or 4. 6. The thermoplastic resin composition according to claim 1, wherein the modified polyolefin is an olefin copolymer containing an acid anhydride group. 7. The thermoplastic resin composition according to claim 1, wherein the modified polyolefin is an epoxy group-containing olefin copolymer. 8. The modified polyolefin according to claim 1, comprising a mixture of 0.8 to 30 parts by weight of an olefin copolymer containing an acid anhydride group and 0.2 to 10 parts by weight of an olefin copolymer containing an epoxy group. Thermoplastic resin composition. 9. The thermoplastic resin composition according to claim 1, wherein the polyamide is nylon 6. 10. The thermoplastic resin composition according to claim 1, wherein the polyamide is nylon 66.