JPH04337351A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide a thermoplastic resin composition composed of a polyarylate, a polyamide, a modified polyolefin, etc., and having excellent impact resistance, especially high-speed punching impact resistance, surface appearance, weld strength and residence heat-stability in molten state. 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 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 copolymer containing epoxy group and (C) 0.1-10 pts.wt. of a compound containing epoxy group (e.g. phenyl glycidyl ether).

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to a thermoplastic resin for molding that has excellent impact resistance, particularly high-speed punching impact resistance, surface properties, and weld strength, and has excellent retention thermal stability in the molten state. Regarding the composition.

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. 52-9876.
It is disclosed in Publication No. 5.

[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] Furthermore, resin compositions made of polyarylate and polyamide generally have poor thermal stability when molten at high temperatures such as during injection molding. There are problems in that the viscosity decreases and the mechanical properties of the molded product decrease.

[0008]

[Problems to be Solved by the Invention] The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a molded article made of a resin composition in which a modified polyolefin is further added to polyarylate and polyamide. This was done for the purpose of imparting extraction impact resistance, good surface properties, and weld part strength, and secondly, improving thermal stability during melt retention at high temperatures.

[0009]

[Means for Solving the Problem] As a result of extensive research to achieve the above object, the present inventors have discovered that polyarylate having a specific functional group is used by mixing with ordinary polyarylate, and modified polyolefin is used. The present inventors have discovered that all of the objects of the present invention can be achieved to an extremely high level by adding an epoxy group-containing compound, and have completed the present invention.

That is, the present invention comprises a mixture of 20 to 80% (by weight, the same shall apply hereinafter) of polyarylate having acid chloride groups and polyarylate not having acid chloride groups, and 80 to 20% of polyamide. A thermoplastic resin prepared by blending 1 to 40 parts of a modified polyolefin (B) and 0.1 to 10 parts of an epoxy group-containing compound (C) to 100 parts (parts by weight, same hereinafter) of the resin composition (A). The composition of the invention relates to a composition of the invention.

[0011]

[Example] The skeleton of the polyarylate used in the present invention, whether containing an acid chloride group or not, is generally made of bisphenols and/or derivatives thereof and aromatic dicarboxylic acids and/or derivatives thereof. This is an aromatic polyester that can be obtained, and there are no particular restrictions on its main chain structure. Furthermore, the main chain structures of the polyarylate having an acid chloride group and the polyarylate having no acid chloride group may be the same or different.

[0012] The above-mentioned bisphenols have, for example, the general formula:

[0013]

[Chemical formula 1]

(In the formula, -X- is -O-, -S-, -SO
2-, -CO-, alkylene group or alkylidene group, R1, R2, R3, R4, R5, R6,
R7 and R8 are each represented by a group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group having 1 to 20 carbon atoms. It is desirable because it improves the properties, heat resistance, and impact resistance of molded products.

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.

Further, examples of the derivatives of bisphenols include alkali metal salts and diacetates of bisphenols.

[0018] 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 used 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 from the viewpoint of improving the moldability of the resulting composition and improving the heat resistance, impact resistance, etc. of the molded product. The weight ratio of acid and terephthalic acid in the polymer is 10/0
It is more preferable that it is 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.

The polyarylate having no acid chloride group used in the present invention can be produced by known methods such as interfacial polycondensation, solution polymerization, and melt polymerization.

[0022] The method for producing the polyarylate having an acid chloride group used in the present invention is not particularly limited and may be any method. It can be easily produced by carrying out polymerization using a certain amount. According to such a method, acid chloride groups are introduced at the ends of the polymer.

In order to effectively exhibit the impact resistance of the molded article according to the present invention, particularly excellent high-speed punching impact resistance, surface properties, and weld part strength, the polyarylate must be a polyester having an acid chloride group. It is essential to contain an arylate, and it is desirable that the acid chloride group be a terminal acid chloride group because the above effects are particularly pronounced. 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) is in the range of 10 x 10-6 to 250 x 10-6 equivalents/g. It is desirable that it is, more preferably 30×10-6
~100x10-6 equivalent/g. Further, the content of the polyarylate having such an acid chloride group in the polyarylate is preferably 10 to 60 parts based on 100 parts of the total polyarylate.

[0024] If the acid chloride value of the polyarylate having an acid chloride group is outside the above range, or if the content of the polyarylate having an acid chloride group in the polyarylate is outside the above range, the high-speed punching impact resistance This is not preferable because it tends to lower the weld strength and surface properties.

The polyarylate having an acid chloride group and the polyarylate having no acid chloride group may be used simply by mixing them, or they may be used after melt-mixing the two in advance. It is also desirable to dissolve both in a solvent, mix them, and distill off the solvent to mix them uniformly.

[0026] Although it is not clear why a remarkable effect is achieved by incorporating a polyarylate having an acid chloride group in addition to a normal polyarylate in the polyarylate, it is not clear why polyarylates having no acid chloride groups It has been observed that the dispersed particle size of the polyarylate dispersed phase in the polyamide is much smaller and more uniform than when the composition of the present invention is used. It is presumed that the interface between the polyarylate particles and polyamide is stabilized.

As described above, by using a mixture of polyarylate having an acid chloride group and polyarylate not having an acid chloride group as the arylate, and further adding an epoxy group-containing compound, the conventional polyarylate and polyamide can be used. It is completely unexpected and surprising that many of the problems with resin compositions made of modified polyolefins are solved. Furthermore, the effects of polyarylates having such acid chloride groups have not been known at all.

The molecular weight of the polyarylate having an acid chloride group and the polyarylate having no acid chloride group is 0 in terms of intrinsic viscosity (chloroform solution, 30°C).
．． The range is preferably from 2 to 1.5, more preferably 0
．． It is in the range of 4 to 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.

[0029] As the polyamide used in the present invention,
Examples include polyamides containing 90% or more of aliphatic amino acids, lactams or diamines and dicarboxylic acids as main components.

[0030] As a representative example of the main component, for example, 6
-aminocaproic acid, 11-aminoundecanoic acid, 1
Amino acids such as 2-aminododecanoic acid, lactams such as ε-caprolactam and ω-laurolactam, diamines such as tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, and dodecamethylene diamine, adipic acid, azelaic acid, sebacic acid, Examples include dicarboxylic acids such as dodecanedioic acid and diglycolic acid. In addition to these aliphatic components, for example, 20%
It is also possible to use copolyamides into which small amounts of aromatic components or alicyclic components are introduced, such as those described below.

Particularly useful polyamides for use in the present invention include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), and polyamide (nylon 66).
), polytetramethylene adipamide (nylon 46),
Examples include polydodecanamide (nylon 12). Among these, nylon 6 and nylon 66 are particularly preferred since the moldability of the resulting composition and the heat resistance of the molded product are well-balanced.

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 type selected from carboxylic acid groups, carboxylic acid metal bases, carboxylic acid ester groups, acid anhydride groups, epoxy groups, acid amide groups, imide groups, etc. A polyolefin is modified by introducing a monomer component having a functional group, for example, by a method such as a copolymerization method or a graft polymerization method. Among these modified polyolefins, those which exhibit the effects of the present invention more markedly include acid anhydride group-containing olefin copolymers, epoxy group-containing olefin copolymers, or 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.

[0037] The content of the dicarboxylic acid anhydride having an unsaturated bond by copolymerization or graft polymerization is preferably 0.01 to 10% of the olefin copolymer,
More preferably it is 0.1 to 5%. 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 olefin copolymer, more preferably 1 to 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.

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.
A preferable range is about 0.05 to 50 g/10 minutes.

[0043] The modified olefin is preferably used in combination with an acid anhydride group-containing olefin copolymer and an epoxy group-containing olefin copolymer because the weld strength becomes particularly high. In that case, it is preferable to use 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.

The epoxy group-containing compound used in the present invention is different in structure and function from the epoxy group-containing olefin copolymer described above. That is, the molecular weight is 2
A low molecular weight compound having 000 or less epoxy groups,
It is used to prevent the composition from decreasing in viscosity and physical properties when it is retained in a molten state. Examples include glycidyl ethers, novolak-type epoxy resins, glycidyl ethers of alcohols such as long-chain alcohols, alicyclic epoxy resins, and glycidyl esters of aliphatic carboxylic acids. The epoxy equivalent of these epoxy group-containing compounds is 100 to 2000 g/
Equivalent range is desirable, 150-1000g/
A range of equivalents is more desirable.

The composition of the present invention is a mixture of the polyarylate having acid chloride groups and the polyarylate not having acid chloride groups, preferably 20 to 80%, preferably 30 to 6%.
0% and said polyamide 80-20%, preferably 70-20%
40% of the resin composition (A), 1 to 40 parts, preferably 3 to 20 parts of the modified polyolefin (B), and 0.1 part of the epoxy group-containing compound (C).
~10 parts, preferably 0.5 to 5 parts.

If the proportion of the polyarylate in the resin composition (A) is less than 20%, the heat resistance will decrease, and if it exceeds 80%, the fluidity during molding will decrease. 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. Furthermore, if the amount of the epoxy group-containing compound (C) based on 100 parts of the resin composition (A) is less than 0.1 part, the effect of improving retention heat stability in the molten state will not be exhibited, and if it exceeds 10 parts, the resistance will be lowered. Impact resistance decreases.

The resin composition of the present invention may further contain lubricants such as wax, stabilizers such as phosphites and phenols, ultraviolet absorbers, pigments, flame retardants, plasticizers,
Inorganic fillers, fillers, reinforcing fibers, etc. may be added.

[0048] Although there are no particular limitations on the method for producing the resin composition of the present invention, a method using melt mixing is preferred;
For example, an extruder, hot roll, Brabender, Banbury mixer, etc. can be used.

There are no particular restrictions on the order of mixing the components of the present invention, and any order is possible. The method of adding and kneading later is particularly effective in the present invention and is a desirable method.

When the resin composition of the present invention is used, for example, injection molding, extrusion molding, blow molding, compression molding, etc. can be used to achieve excellent high-speed punching impact resistance, surface properties, and weld part strength. These molded products can be suitably used as various automobile exterior parts, automobile outer panels, mechanical parts, electrical/electronic parts, etc.

The composition of the present invention will be explained below based on Examples, but the present invention is not limited to these Examples. .

Production Example 1 Production of Polyarylates Various polyarylates shown in Table 1 were produced using isophthalic acid dichloride, terephthalic acid dichloride and bisphenol A by an interfacial polycondensation method. that time,
The excess mole number of carboxylic acid dichloride relative to bisphenol A was adjusted within the range of 0 to 13 mol%, and polyarylates having various acid chloride values were produced.

Measurement of acid chloride value: about 0.1 g of sample
was accurately weighed, and 10 ml of chloroform was added to dissolve it. After dissolving, add a small amount of 2 ml of methanol and 0.2% thymol blue methanol solution as an indicator, stir for 60 minutes at room temperature to react, and then remove the liberated hydrogen chloride with 0.1N tributylamine/chloroform solution until the indicator turns pink. The titration was carried out with the end point being the point at which the color turned from yellow to yellow. A blank test was conducted without adding any additional sample.

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 (g)

[0056]

[Table 1]

Examples 1 to 17 and Comparative Examples 1 to 5 The polyarylates shown in Table 1 and the following polyamide and acid anhydride group-containing olefin copolymers were blended in the proportions shown in Table 2, and the mixture was heated in a twin-screw extruder. The epoxy group-containing olefin copolymer and the epoxy group-containing compound were fed from a hopper at the base and side-fed, and the mixture was 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.

Table 2 shows the composition of the test piece obtained.

Polyamide: Nylon 6: Manufactured by Toray Industries, Inc.
Amilan CM1026 (polyε-caprolactam) nylon 66: manufactured by Ube Industries Co., Ltd., Ube Nylon 2026
B (polyhexamethylene adipamide) acid anhydride-containing olefin copolymer: maleic anhydride grafted ethylene
-Propylene copolymer (T77 manufactured by Japan Synthetic Rubber Co., Ltd.)
11SP, maleic anhydride content 0.8%, melt index 2.4) Epoxy group-containing olefin copolymer: ethylene-glycidyl methacrylate copolymer (Bond Fast E manufactured by Sumitomo Chemical Co., Ltd., containing glycidyl methacrylate) rate 11.5%) Epoxy group-containing compound: phenyl glycidyl ether

[0060]

[Table 2]

The obtained test piece was evaluated in the following manner. The results are shown in Table 3.

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. The test was conducted at 23°C and -30°C.

Strength of weld part: A flat plate (100 mm x 100 mm x 3 mm) formed by a two-point gate 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 tip of the punch touching the weld portion.

[0064] Surface quality of molded product: 100mm x 100m
A flat plate of m 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.

×: Extremely poor △: Slightly poor ○: Almost no defects Thermal stability during retention: Tensile elongation at break (2
3°C, ASTM D638) and Izod impact strength (23°C, V-notched, ASTM D256) were measured.

[0066] The melt viscosity of the pellets was also measured using a capillary rheometer, immediately after melting at 290°C, and after melting at 290°C.
Measurements were taken after residence at 90° C. for 20 minutes (shear rate 1216S-1).

[0067]

[Table 3]

Table 3 shows that the composition of the present invention has a small decrease in melt viscosity due to retention at high temperatures, and the molded products obtained using the composition have good high-speed punching impact strength, weld part strength, and surface properties. It turns out that it is.

[0069]

EFFECTS OF THE INVENTION When the composition of the present invention is used, molded products with good impact resistance, particularly high-speed punching impact strength, weld part strength, and moldability can be obtained. Furthermore, the decrease in melt viscosity and physical properties after residence at high temperatures is significantly improved.

Claims (11)

[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) and 0.1 to 10 parts by weight of an epoxy group-containing compound (C). 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 composition. 3. The polyarylate having an acid chloride group has an acid chloride value of 10×10 −6 to 250×10
-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 comprising bisphenol A and terephthalic acid and/or isophthalic acid. 5. The polyarylate having an acid chloride group and the polyarylate having no acid chloride group have an intrinsic viscosity (chloroform solution, 30°C) of 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 polyamide is nylon 6. 7. The thermoplastic resin composition according to claim 1, wherein the polyamide is nylon 66. 8. The thermoplastic resin composition according to claim 1, wherein the modified polyolefin is an olefin copolymer containing an acid anhydride group. 9. The thermoplastic resin composition according to claim 1, wherein the modified polyolefin is an epoxy group-containing olefin copolymer. 10. The modified polyolefin according to claim 1, wherein the modified polyolefin comprises a mixture of 0.8 to 30 parts by weight of an acid anhydride group-containing olefin copolymer and 0.2 to 10 parts by weight of an epoxy group-containing olefin copolymer. Thermoplastic composition. 11. The thermoplastic resin composition according to claim 1, wherein the epoxy group-containing compound is phenyl glycidyl ether.