JPH0459867A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide a thermoplastic resin composition having excellent impact resistance, surface property and weld strength and useful for moldings by adding a core-shell type graft copolymer to a resin composition, comprising an epoxy group-containing polyarylate and a polyamide. CONSTITUTION:(C) 1-40 pts.wt. of a core-shell type graft copolymer prepared by graft-polymerizing a vinylic monomer and a functional group-containing monomer to a rubbery elastomer is added to 100 pts.wt. of a resin composition comprising (A) 80-20 pts.wt. of an epoxy group-containing polyarylate, preferably an aromatic polyester prepared from bisphenol A and terephthalic acid and/or isophthalic acid having an epoxy value (10<-6> equivalent of the epoxy groups contained in 1g of the resin) of 2-100 and an intrinsic viscosity (in a chloroform at 30 deg.C) of 0.2-1.5dl/g and (B) 80-20wt.% of a polyamide (preferably nylon 6 or nylon 66) to provide the resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a molding resin composition characterized by excellent impact resistance, particularly high-speed punching impact resistance, surface properties, and weld part strength.

[Conventional technology]

Polyarylate is an engineering plastic obtained from aromatic dicarboxylic acid or its derivative and bisphenol or its derivative, and is known to have a high heat distortion temperature and a high thermal decomposition temperature.

Furthermore, a resin composition composed of polyarylate and polyamide is expected to have an excellent balance of physical properties as a molding material, combining the good moldability and chemical resistance of polyamide with the heat deformation resistance of polyarylate.

The usefulness of such resin compositions is disclosed in Japanese Patent Publication No. 56-14699,
It is disclosed in Japanese Patent Application Laid-Open No. 52-98765. However, resin compositions consisting only of polyarylate and polyamide have a drawback of low impact resistance. In order to improve these drawbacks, methods using various impact resistance imparting agents have been disclosed. For example, Japanese Patent Publications No. 62-944, No. 61183353, No. 62-277462, and No. 62-283146 disclose methods using specific modified polyolefins. As described above, when a specific modified polyolefin is used as an impact resistance imparting agent, the phizoso impact strength is certainly improved, but the high-speed punching impact resistance, which is more important in practical terms, remains low. Especially -30°C
The high-speed punching impact resistance at moderately low temperatures remains extremely low, and such drawbacks are a major hindrance in applications requiring low-temperature impact resistance, such as automobile exterior panels.

Furthermore, when modified polyolefins are used, the surface properties of molded products are generally poor, resulting in problems such as silver marks, flow marks, etc., and low weld strength.

[Problem that the invention seeks to solve]

In view of these circumstances, an object of the present invention is to improve high-speed punching impact strength, surface properties of molded articles, and weld part strength in a resin composition comprising polyarylate and polyamide.

[Means for solving problems]

As a result of extensive research for this purpose, the present inventors have found that the purpose of the present invention has been extremely achieved by using a polyarylate having an epoxy group as the polyarylate and using a core-shell type graft copolymer as an impact resistance imparting agent. I discovered what I could achieve at a high level.

That is, the present invention provides polyarylate 2 having an epoxy group.
A thermoplastic resin composition obtained by adding 1 to 40 parts by weight of a core-shell type graft copolymer (B) to 100 parts by weight of a resin composition (A) consisting of 0 to 80% by weight and 80 to 20% by weight of polyamide. The content is as follows.

The polyarylate used in the present invention is generally not particularly limited in its main chain structure as long as it is an aromatic polyester obtained from bisphenols or derivatives thereof and aromatic dicarboxylic acids or derivatives thereof, but it is essential that it has an epoxy group. It is. Although the epoxy group may be present either in the main chain or at the end, it is preferable that the epoxy group be present at the end because the effects of the present invention are more clearly expressed.

Bisphenols are general 2 below. [However, in the formula, -X- is -o--s--s.

-CO-, an alkylene group or an alkylidene group (the hydrogen atom of these alkylene groups or alkylidene groups may be substituted with one or more hydrocarbon groups, halogen groups, or halogenated hydrocarbon groups) Selected, R1
-R8 is a hydrogen atom, a halogen atom, and CI""Ct.

selected from the group consisting of hydrocarbon groups. ] is preferable.

An example of such bisphenols is 2,2-bis(
4-Hydroxyphenyl)propane (bisphenol A
), bis(4-hydroxyphenyl)methane, bis(4
-hydroxy-3,5-dimethylphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, 1.1-bis(4-hydroxyphenyl)cyclohexylmethane, 1.1-bis(4-hydroxyphenyl) ) ethane, 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)propane, etc., which may be used alone or in combination with
Used in combination of more than one species.

If necessary, other divalent compounds, such as 4゜4'-
Biphenol, hydroquinone, resorcinol, 2.6
-Sihydroxynaphthalene or the like can be used by adding a small amount to the above-mentioned bisphenols.

The derivatives of bisphenols include their alkali metal salts, diacetates, and the like. Among these bisphenols, it is preferable to use bisphenol A, 1°1-bis(4-and-droxyphenyl)1-phenylethane, or a mixture thereof because of their excellent balance between molding fluidity and heat resistance.

As the aromatic dicarboxylic acid in the above polyarylate,
For example, terephthalic acid, isophthalic acid, diphenyl ether-4,4'-dicarboxylic acid, benzophenone-4,4
'-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, etc., which may be used alone or in combination of two or more.

In view of the balance between molding fluidity and heat resistance, preferred aromatic dicarboxylic acids are isophthalic acid and/or terephthalic acid, and more preferably the weight ratio of isophthalic acid and terephthalic acid in the polymer is 1010 to 7/3. Examples of the aromatic dicarboxylic acid derivatives include dichlorides of these acids, and diesters of alkyl, aryl, and the like.

In the present invention, the preferred content of epoxy groups is epoxy value (101 equivalents of epoxy groups contained in 1 g of resin).
is in the range of 2 to 100, more preferably 10 to 5
It is in the range of 0. Outside this range, high-speed punching impact strength and surface properties are reduced, and weld strength is reduced.

The above epoxy value is calculated by the following formula according to the 15O-3001 method (method for measuring the epoxy value of epoxy resin).

Epoxy value (10-' equivalent/g) However, in the above formula, TS: Amount of 0, 1 N HC104 acetic acid solution required for titration of the sample (d) Tb: 0, 1 N required for titration of blank test Amount of HC104 acetic acid solution 1d) F: 0.1N Factor W of HC104 acetic acid solution: Weight of sample (g).

The method for producing the polyarylate having an epoxy group of the present invention is not limited, but for example, as described below,
It can be obtained by reacting a polyarylate having a carboxylic acid chloride group with a compound having a hydroxyl group and an epoxy group in the same molecule.

For polyarylates containing acid chloride groups, for example, as disclosed in JP-A-1-22851, dichloride of an aromatic dicarboxylic acid is added to a functional group based on the total amount of bisphenols and phenolic compounds used as necessary. It can be obtained by carrying out polymerization using an amount in excess of the theoretical equivalent. The polyarylate having acid chloride groups obtained in this way must contain the amount of acid chloride groups necessary to obtain the desired epoxy value in the present invention. The chloride group content is determined by the acid chloride value (
It must be between 2 and 100 (in terms of 104 equivalents of acid chloride groups contained in 1 g of resin).

Specific examples of compounds having a hydroxyl group and an epoxy group in the same molecule to be reacted with the polyarylate having an acid chloride group include 2.3-epoxy-1-propatol, 3.4-epoxy-1-butanol, and 3.4-epoxy-1-propanol. 4-
Aliphatic and alicyclic compounds such as epoxy-cyclohexanol, ethylene glycol monoglycidyl ether, and tetramethylene glycol monoglycidyl ether, 4-(
Examples include aromatic compounds such as 1',2'-epoxyethyl)-phenol, glycidyl P-hydroxybenzoate, and 2,2-bis(4-hydroxyphenyl)-propane monoglycidyl ether.

The reaction between the acid chloride group of polyarylate and a compound having a hydroxyl group and an epoxy group in the same molecule can be carried out in the same manner as the reaction between the acid chloride group and hydroxyl group of a low-molecular compound.

That is, the reaction is carried out in the presence of an acid acceptor that traps the hydrogen chloride released by the reaction between the two. Specifically, a polyarylate having an acid chloride group is dissolved in an organic solvent that is substantially incompatible with water, and a compound having a hydroxyl group and an epoxy group in the same molecule is added in the presence of an acid acceptor. This is a method of causing a reaction. As the acid acceptor, an alkaline aqueous solution or tertiary amines are used.

The molecular weight of the polyarylate is preferably in the range of 0.2 to 1.5 d/g, more preferably in the range of 0.4 to 0.8 d1/g in terms of intrinsic viscosity (chloroform solution, 30°C). Outside this range, high-speed punching resistance and replaceability may decrease,
This is not preferable because moldability may deteriorate.

The polyamide used in the present invention includes aliphatic amino acids,
It is a polyamide whose main components are lactam or diamine and dicarboxylic acid. Typical examples of its main components are:
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, These include dicarboxylic acids such as dodecanoic acid and diglycolic acid, and it is also possible to use copolyamides into which small amounts of aromatic components and alicyclic components are introduced in addition to these aliphatic components.

Polyamides particularly useful in the present invention include polycaproamide (
Nylon-6), polyhexamethylene adipamide (Nylon-66), polytetramethylene adipamide (Nylon-46), and polydodecanamide (Nylon-12). Among them, nylon-6, nylon-66, and nylon-46 are particularly important. These may be used alone or in combination of two or more.

It is preferable that the relative viscosity of the polyamide resin is within the range of 2.0 to 5.0, as measured at 25° C. using a 1% concentrated sulfuric acid solution.

The core-shell type graft copolymer used in the present invention is obtained by graft-polymerizing a specific component onto a rubber-like elastic body. The rubber-like elastic body preferably has a glass transition temperature of 0°C or lower, more preferably -40°C or lower. Specifically, diene rubbers such as polybutadiene, butadiene-styrene copolymer, butadiene-butyl acrylate copolymer, acrylic rubbers such as butyl polyacrylate, polyacrylic acid, and 2-ethylhexyl polyacrylate, ethylene- Examples include olefin rubbers such as propylene copolymers and ethylene-propylene-diene copolymers. The gel content of the rubber-like elastic body is not particularly limited, but
The content is preferably 10% by weight or more.

The specific component used in the core-shell type graft copolymer is at least one type selected from vinyl monomers, carboxylic acid groups, carboxylic acid esters, acid anhydride groups, epoxy groups, imide groups, and acid amide groups. It is a monomer with a functional group. Examples of vinyl monomers include aromatic vinyl monomers such as styrene, methylstyrene, chlorostyrene, and α-methylstyrene, and vinyl cyanides such as acrylonitrile and methacrylonitrile. Examples of monomers with functional groups include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, maleic anhydride, and anhydride. Examples include itaconic acid, glycidyl acrylate, glycidyl methacrylate, acrylamide, methacrylamide, maleimide, phenylmaleimide, and the like.

The composition ratio of specific components used in the present invention is not particularly limited, but vinyl monomer 50 to 99.9% by weight
, the functional group-containing monomer is preferably 0.1 to 50% by weight. If it is outside this range, impact resistance may be lowered or moldability may be deteriorated, which is not preferable. Furthermore, the composition ratio of the vinyl monomer components is not particularly limited, but the aromatic vinyl monomer 4
0 to 90% by weight, preferably 10 to 60% by weight of vinyl cyanide monomer. Outside this range, impact resistance may decrease,
This is not preferable because thermal stability may decrease. The composition ratio of the rubbery elastic body and the specific monomer is preferably in the range of 30 to 95% by weight of the rubbery elastic body and 5 to 70% by weight of the specific monomer. Outside this range, impact resistance, rigidity, etc. may deteriorate, or defects may occur on the surface of the molded product, which is not preferable.

The method for producing the core-shell graft copolymer is not particularly limited, and any method such as solution polymerization, suspension polymerization, bulk polymerization, emulsion polymerization, etc. can be employed.

The thermoplastic resin composition of the present invention contains 20 to 80% by weight of polyarylate having epoxy groups and 80 to 20% by weight of polyamide.
With respect to 100 parts by weight of the resin composition (A) consisting of % by weight,
1 to 40 parts by weight of core-shell graft copolymer (B),
More preferably polyarylate 30 having an epoxy group
3 to 30 parts by weight of the core-shell type graft copolymer (B) is added to 100 parts by weight of the resin composition (A) consisting of ~60% by weight and 70 to 40% by weight of polyamide.

Outside this range, impact resistance, surface properties, weld strength, rigidity, moldability, chemical resistance, etc. deteriorate, making it undesirable.

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

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, and reinforcing agents. Fibers etc. can be added.

The resin composition of the present invention can be molded by injection molding, extrusion molding, blow molding, compression molding, etc. to produce molded products with excellent high-speed punching impact resistance, surface properties, dimensional stability upon moisture absorption, and weld strength. These molded products are used in various automotive exterior parts, automotive exterior panels, mechanical parts, electrical and
Useful for applications such as electronic components.

〔Example〕

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

Reference examples (polyarylates P1 to P- having epoxy groups
Synthesis of 9) P-1 = 2.2-bis(4-hydroxyphenyl)-propane (
Bisphenol A) 674.6g (2,955 mol)
, p-(t-butyl)phenol 13.52 (0,09
mole), sodium hydrosulfide 5.28 g
, 1,920 d of 4N sodium hydroxide and 3,32 d of water
After mixing 0 d in a 61 flask in a nitrogen atmosphere, the mixture was cooled to 5°C to prepare an alkaline aqueous solution of bisphenol.

Meanwhile, in another 61 flask, terephthalic acid chloride 1
24.25 g (0,612 mol) and 496.99 g (2,448 mol) of isophthalic acid chloride were dissolved in 5,000 d of methylene chloride and cooled to 5°C.

Then, in another 15f separable flask, add 2 ml of water.
．． 000m and 0.94 g (0.03 mol) of benzyltributylammonium chloride as a catalyst were charged under a nitrogen atmosphere, and the mixture was cooled to 5°C. While stirring the cooling liquid vigorously, the above two liquids prepared in advance were simultaneously added continuously using a pump over a period of 15 minutes.

When stirring was stopped 60 minutes after the addition was completed, the mixture was separated into two phases: a methylene chloride phase and an aqueous phase. After decanting the aqueous phase, the same amount of water was added and neutralized with a small amount of hydrochloric acid while stirring. Furthermore, after repeated desalination by water washing, the same amount of acetone was added to the methylene chloride phase to precipitate a polymer powder, and after filtration, the powder was washed with the same amount of acetone and water, and filtered again in the same manner. . When the acid chloride value (104 equivalents/g) of the dried polymer was measured, it was 4.
It was 5. Further, the molecular weight was 0.62 dl/g expressed in terms of intrinsic viscosity (chloroform solution, 30°C).

1,000 g of the polymer obtained in this way was
Pour into a separable flask and add 5 methylene chloride.
,0OOd was added and the polymer was dissolved under stirring and reflux. After the polymer solution became completely transparent, it was cooled to 5°C. Then, under stirring, a methylene chloride solution (500M) of 44.45 g (0.6 mol) of 2°3-epoxy-1-propanol and 6.68 g of triethylamine (
0.066 mol) of methylene chloride solution (50d) was added. After 60 minutes, the same amount of acetone as methylene chloride was gradually added to precipitate the polymer powder, and after filtration,
The powder was washed with the same amount of acetone and filtered again in the same manner, and the epoxy value of the resulting polymer powder was measured by the method described below.

Approximately 0.2 g of polymer powder was accurately weighed, and 2 (ld) of chloroform was added and dissolved. After dissolving, a 25% acetic acid solution of tetraethylammonium bromide and a 0.1% acetic acid solution of crystal violet were added as indicators. This purple sample solution was immediately diluted with 0.I.
Titration was carried out using an acetic acid solution of N ncton, with the point at which the color of the indicator changed to blue-green as the tip point. Additionally, a blank test was conducted separately.

When the epoxy value was calculated using the previous method, the epoxy value (
10-' equivalents/g) was 30. In addition, the molecular weight is expressed as an intrinsic viscosity (chloroform solution, 30°C) of 0.6
It was 2d1/g.

P-2 to 6 and P-8: Using the same method as P-1 above, various epoxy values were obtained by changing the ratio of 2,2-bis(4-hydroxyphenyl)-propane (bisphenol A) and acid chloride components. A polyarylate having the following was produced.

In addition, as a bisphenol component, the molar ratio of 2.2-bis(4-hydroxyphenyl)-propane (bisphenol A) and 1.1-bis(4-hydroxyphenyl)-1-phenylethane (bisphenol P) is 50: 5
A polyarylate was also produced using a mixture of 0 and 0 as the bisphenol component. Table 1 shows the epoxy value and intrinsic viscosity of the polyarylate measured in the same manner as P-1.

P-7 and P-9= In addition, for comparison, polyarylates having no epoxy groups were produced by a conventional interfacial polycondensation method. P-1
Table 1 shows the epoxy value and intrinsic viscosity of polyarylate measured in the same manner as above.

Examples 1 to 16 and Comparative Examples 1 to 7 Polyarylates P-1 to P-9 obtained in the reference examples and Amilan CM1026 (polyε
- caprolactam, relative viscosity 3°2), as a core-shell graft copolymer, 70% by weight of polybutadiene with an average particle size of 0.25μ and a gel content of 83%, 6% by weight of acrylonitrile, 21% by weight of styrene, methacrylic M3
A mixture of % by weight was subjected to a graft reaction using an emulsion polymerization method, and the mixture was blended in the proportions shown in Table 2 and triblended.
Vacuum drying was performed at 80° C. for 15 hours, and then kneaded at 270° C. using a two-wheel extruder to obtain pellets. This pellet was vacuum dried at 120°C for 15 hours, and the resin temperature was 2.
A test piece was obtained by injection molding at 90°C.

The properties of the test pieces were evaluated by the following method, and the results are shown in Table 2.

[High-speed punching impact strength]

Using a high-speed punching impact tester model HRI78000 made by Rheometric, a punch (5/8 inch diameter) was used to
A test piece (100 x 100 x 3 pieces) was punched out at a speed of 100 s, and the energy required for punching was measured. Measurements were performed at 23°C and -30°C.

[Strength of weld part]

A flat plate (100 x 100 x 3 m
) was used. The molding conditions were an injection pressure 5 kg/cd (gauge pressure) higher than the limit injection pressure for complete filling. Make sure the tip of the punch touches the weld part,
High-speed punching impact strength at 23° C. was measured under the above conditions.

[Surface properties of molded product]

A flat plate of 100×100×3− was molded, and the presence or absence of defects such as flow marks and silver marks near the gate was visually observed and evaluated.

O: Almost no defect △: Slightly defective ×: Significantly defective As is clear from the results in Table 2, the resin composition of the present invention shows no decrease in melt viscosity and physical properties after residence. This has been significantly improved, and the physical properties of the molded product are also excellent.

[Action/Effect]

Although it is not clear why the use of polyarylate having an epoxy group at the end produces a remarkable effect,
It was observed by scanning electron microscopy that the dispersed particle size of the polyarylate dispersed phase in the polyamide was much smaller and more uniform than when polyarylate without epoxy groups was used. Furthermore, it was found that even after this resin composition was allowed to remain in a molten state, the dispersed particle size remained almost unchanged. From these facts, it can be assumed that in the composition of the present invention, the interface between the polyarylate particles and the polyamide is particularly stabilized. Such an effect exerted by the epoxy group of polyarylate was completely unknown in the past, and was discovered for the first time by the present inventors.

Furthermore, it is surprising that by using a core-shell type graft copolymer as an impact resistance imparting agent, all of the above-mentioned problems of resin compositions made of polyarylate and polyamide can be solved.

As with soft soil, the present invention provides a resin composition having a well-balanced impact resistance, particularly high-speed punching impact resistance, surface properties, weld strength, and retention stability in a molten state.

Patent applicant Kanebuchi Chemical Industry Co., Ltd.

Claims (1)

[Scope of Claims] 1. A resin composition consisting of 20 to 80% by weight of polyarylate having an epoxy group and 80 to 20% by weight of polyamide (
A thermoplastic resin composition prepared by adding 1 to 40 parts by weight of a core-shell type graft copolymer (B) to 100 parts by weight of A). 2. The thermoplastic resin composition according to claim 1, wherein the epoxy group content of the polyarylate having epoxy groups is 2 to 100 in terms of epoxy value (10^-^6 equivalents of epoxy groups contained in 1 g of resin). . 3. The thermoplastic resin composition according to claim 1, wherein the polyarylate having epoxy groups has an epoxy group content of 10 to 50 in terms of epoxy value (10^-^6 equivalents of epoxy groups contained in 1 g of resin). . 4. The thermoplastic resin composition according to claims 1 to 3, wherein the polyarylate is an aromatic polyester consisting of 2,2-bis(4-hydroxyphenyl)-propane (bisphenol A) and terephthalic acid and/or isophthalic acid. . 5. Polyarylate is 2,2-bis(4-hydroxyphenyl)-propane (bisphenol A) and 1,1-
4. The thermoplastic resin composition according to claim 1, which is an aromatic polyester consisting of bis(4-hydroxyphenyl)1-phenylethane and terephthalic acid and/or isophthalic acid. 6. The thermoplastic resin composition according to claims 1 to 5, wherein the polyarylate has a molecular weight of 0.2 to 1.5 dl/g expressed in intrinsic viscosity (chloroform solution, 30°C). 7. The thermoplastic resin composition according to claims 1 to 5, wherein the polyarylate has a molecular weight of 0.4 to 0.8 dl/g expressed in intrinsic viscosity (chloroform solution, 30°C). 8. The thermoplastic resin composition according to claims 1 to 7, wherein the polyamide is nylon-6. 9. Claims 1 to 7 wherein the polyamide is nylon-6,6.
The thermoplastic resin composition described.