JPH0459866A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide a composition having excellent impact resistance, surface property, moisture absorbing dimensional stability, weld strength, etc., by adding an acid anhydride group-containing olefinic copolymer to a resin composition comprising an epoxy group-containing polyarylate and a polyamide. CONSTITUTION:(C) 1-40 pts.wt. of an acid anhydride group-containing olefinic copolymer (e.g. maleic anhydride-grafted ethylene-propylene copolymer) is added to 100 pts.wt. of a composition comprising (A) 20-80wt.% of an epoxy group- containing polyarylate, preferably an aromatic polyester prepared from bisphenol A and terephthalic acid and/or isophthalic acid and having an epoxy value (10<-6> equivalent of the epoxy groups contained in 1g of the resin) of 2-100 and an intrinsic viscosity (a chloroform solution 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 has excellent impact resistance, particularly high-speed punching impact resistance, surface properties, dimensional stability when absorbing moisture, and weld part strength, and has excellent resistance to retention in a molten state. The present invention relates to a thermoplastic resin composition that has excellent thermal stability and is particularly suitable for molding.

[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.

In addition, a resin composition composed of polyarylate and polyamide is expected to have an excellent balance of physical properties as a molding material that has the good moldability and chemical resistance of polyamide and 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 and Iu made only of polyarylate and polyamide
The composition has the disadvantage of low impact resistance. In order to improve these drawbacks, methods using various impact resistance imparting agents have been disclosed. For example, JP 62-944, JP 61-183353, JP 62-277462,
JP-A-62-283146 discloses a method using a specific modified polyolefin. 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. Especially -3
The high-speed punching impact resistance at a low temperature of about 0° C. remains extremely low, and this drawback becomes a major hindrance in applications that require impact resistance at low temperatures, such as automobile outer 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. Furthermore, molded articles made of polyamide undergo large dimensional changes due to moisture absorption, and resin compositions made of polyarylate and polyamide also have this problem. Furthermore, resin compositions made of polyarylate and polyamide generally have poor thermal stability when melted at high temperatures such as during injection molding. However, there is a problem in that the mechanical properties of the molded product deteriorate.

[Problem that the invention seeks to solve]

In view of these circumstances, the purpose of the present invention is to improve, firstly, high high-speed punching impact strength, surface properties and weld part strength of molded products, and dimensional stability during moisture absorption in a resin composition made of polyarylate and polyamide. The second objective is to improve the thermal stability during melting and retention at high temperatures.

[Means for Solving the Problems] As a result of intensive research for the above purpose, the present inventors used a polyarylate having an epoxy group as the polyarylate, and an olefin-based acid anhydride group-containing agent as the impact resistance imparting agent. It has been found that the objects of the present invention can be achieved to an extremely high level by using a copolymer.

That is, the present invention provides polyarylate 2 having an epoxy group.
Heat obtained by adding 1 to 40 parts by weight of an acid anhydride group-containing olefin 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. It contains a plastic resin composition.

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 represented by the following general formula [where -X- is -〇--S-CO-, an alkylene group or an alkylidene group (the hydrogen atom of these alkylene groups or alkylidene groups is one or more hydrocarbon groups). , a halogen group, or a halogenated hydrocarbon group), and R1-
R6 is selected from the group consisting of a hydrogen atom, a halogen atom, and a C0 to CZa hydrocarbon group. ] is preferable.

An example of such bisphenols is 2.2bis(
4-Hydroxyphenyl)propane (bisphenol A
), bis(4-hydroxyphenyl)methane, bis(4
-Hydroxy-3,5-dimethylphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, 1.1bis(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., and these may be used alone or in combination of two or more.

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, bisphenol A11゜1-bis(4-hydroxyphenyl)1-phenylethane or a mixture thereof is preferably used since it has an 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 content of epoxy groups is preferably in the range of 2 to 100 in terms of epoxy value (10-'' equivalent of epoxy groups contained in 1 g of resin), more preferably in the range of 10 to 100.
The range is 50. 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 RSO-3001 method (method for measuring the epoxy value of epoxy resin).

Epoxy value (10-' equivalent/g) 0, IXF ((Ts-Tb)xxlO'')/W1
oo.

However, in the above formula, Ts: Amount of 0, 1N HClO4 acetic acid solution required for titration of the sample (d) Tb: Amount of 0, 1N HClO4 required for titration of the blank test. Amount of acetic acid solution (d) F: 0.1 normal) Factor W of acetic acid solution of ICI04: 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 having acid chloride groups, for example, as disclosed in JP-A-1-22851, the dichloride of aromatic dicarboxylic acid is added to the 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 manner must contain the amount of acid chloride groups necessary to obtain the desired epoxy value in the present invention. That is, the acid chloride group content of the polyarylate having acid chloride groups is determined by the acid chloride value (
(10-6 equivalents of acid chloride groups contained in 1 g of resin)
and must be between 2 and 100.

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, 3. ,4-
Aliphatic and alicyclic compounds such as epoxy-cyclohexanol, ethylene glycol monoglycidyl ether, and tetramethylene glycol monoglycidyl ether, 4(1
Examples include aromatic compounds such as ',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 O12 to 1.5 a/g, more preferably in the range of 0.4 to 0.8 a/g in terms of intrinsic viscosity (chloroform solution, 30°C). Outside this range, high-speed punching impact resistance and moldability may deteriorate, which is not preferable.

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-aratsukaproic 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), polydodecanamide (nylon-12), among others nylon-6, nylon-66, Of particular interest is nylon-46. 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 acid anhydride-containing olefin copolymer in the present invention refers to a homopolymer of olefins such as polyethylene, polypropylene, polybutene-1, etc., ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-butene-1 copolymer, etc.
Copolymerization or grafting of alicyclic dicarboxylic acid anhydride or α,β-unsaturated dicarboxylic acid anhydride having a cis-type double bond in the ring to propylene-diene copolymer, ethylene-vinyl acetate copolymer, etc. These are polymerized and can be used alone or in combination of two or more.

Examples of alicyclic dicarboxylic acid anhydrides having a cis-type double bond in the ring include cis-4-cyclohexene-1,2-dicarboxylic acid, endo-bicyclo(2,2,1)-5-hebutene-2 , 3-dicarboxylic acid and the like are exemplified.

Examples of the α,β-unsaturated dicarboxylic acid anhydride include maleic anhydride, methylmaleic anhydride, chloromaleic anhydride,
Examples include citraconic anhydride. Copolymerization components of the acid anhydride-containing olefin copolymer used in the present invention include methacrylic acid esters such as methyl methacrylate and ethyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, etc. These acrylic esters may be used alone or in combination of two or more.

The content by copolymerization or graft polymerization of alicyclic dicarboxylic anhydride or α,β-unsaturated dicarboxylic acid anhydride containing a cis-type double bond in the ring is 0.01 to 10% in the olefin copolymer. % by weight, more preferably 0.1 to 5% by weight. Outside this range, the impact resistance and surface properties of the molded product deteriorate, which is not preferable.

The thermoplastic resin composition of the present invention comprises 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 an acid anhydride group-containing olefin copolymer (B), more preferably 100 parts by weight of a resin composition (A) consisting of 30 to 60% by weight of polyarylate having an epoxy group and 40 to 70% by weight of polyamide. 3 to 30 parts by weight of the acid anhydride group-containing polyolefin copolymer (B) is added. Outside this range, impact resistance, surface properties, dimensional stability upon moisture absorption, 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 melt-mixing method is particularly preferred, and for example, an extruder, hot roll, Brabender, Banbury mixer, etc. can be used.

The resin composition of the present invention may further include 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, a filler, Reinforcing 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 J 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 P-1 to P with epoxy groups
-9 synthesis) P-1: 2.2-bis(4-hydroxyphenyl)-propane (
Bisphenol A) 674.6 g (2,955 mol Lp-(t-butyl)phenol 13.52 (0,0
9 mol), sodium hydrosulfide 5.28g
, 4N sodium hydroxide 1,920 〆 and water 3.32
After mixing 0 ml in a 62 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 5,0O01d of methylene chloride and cooled to 5°C.

Then, yet another 151! , in a separable flask,
2,000 Id of water and 194 g (0.03 mol) of benzyltributylammonium chloride O 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 (10-' equivalent/g) of the dried polymer was measured,
It was 45. Also, the molecular weight is 0.627 expressed in intrinsic viscosity (chloroform solution, 30°C)! /g.

1,000 g of the polymer obtained in this way was
Pour into a separable flask and add 5 methylene chloride.
,000 m was added, and the polymer was dissolved under stirring and reflux. After the polymer solution became completely transparent, it was cooled to 5°C. Thereafter, under stirring, a solution of 44.45 g (0°6 mol) of 23-epoxy-1-propanol in methylene chloride (5
00+d) and triethylamine 6.68 g (0,
066 mol) in methylene chloride (50 m) was added. After 60 minutes, the same amount of acetone as methylene chloride was gradually added to precipitate the polymer powder. After filtration, the powder was washed with the same amount of acetone and filtered again in the same manner.

The epoxy value of the obtained polymer powder was measured by the following method.

Approximately 0.2 g of polymer powder was accurately weighed, and 20 #p of chloroform was added thereto and melted. After dissolution, a small amount of a 25% acetic acid solution of tetraethylammonium bromide (10I11) and a 0.1% acetic acid solution of crystal violet were added as indicators. Immediately add this purple sample solution to 0. I
Titration was carried out using an acetic acid solution of IcIO, N, with the end point being the point at which the color of the indicator changed to blue-green. Additionally, a blank test was conducted separately.

When the epoxy value was calculated by the previous generation, 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 2 dIl/g.

P-2 to 6 and P-8 = Various epoxy values were obtained by changing the ratio of 2,2-bis(4hydroxyphenyl)-propane (bisphenol A) and acid chloride components in the same manner as in P-1 above. 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 to 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: For comparison, polyarylates without 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 Reference Examples and Amilan CMI026 (polyε
- Caprolactam, relative viscosity 3゜2) and T manufactured by Nippon Synthetic Rubber as an acid anhydride group-containing polyolefin copolymer.
7711SP (maleic anhydride grafted ethylene-propylene copolymer, maleic anhydride content 0.8% by weight)
After blending and triblending in the proportions shown in Table 2,
Vacuum drying was performed at 80° C. for 15 hours, and then kneaded at 270° C. using a twin-screw extruder to obtain pellets. This pellet was vacuum dried at 120℃ for 15 hours, and the resin temperature was 29℃.
Test pieces were obtained by injection molding at 0°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]

5 m with a punch (5/8 inch diameter) using a high-speed punching impact tester model HRrT8000 manufactured by Rheometric.
A test piece (100×IO0×3 cabinets) was punched out at a speed of /s, and the energy required for punching was measured.

[Strength of weld part]

As a test piece, a flat plate (100 x 100 x 3
) was used. The molding conditions were an injection pressure 5 kg/d (gauge pressure) higher than the limit injection pressure for complete filling. The impact strength of high-speed punching was measured at 23° C. under the above conditions with the tip of the punch touching the weld portion.

[Surface properties of molded product]

A 100x100x3 plate 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 Δ: Slightly defective ×: Significantly defective [Dimension change during moisture absorption] A 100 x 100 x 3 flat plate immediately after molding was immersed in water at 23°C for 10 days. The dimensions in the vertical and horizontal directions were compared with the dimensions before dipping, and the elongation rate (%) was determined and evaluated as the average value in the vertical and horizontal directions.

[Retention thermal stability in molten state]

The above pellets were continuously injection molded at a resin temperature of 290°C to obtain test pieces. Tensile elongation at break of this test piece (
Measured at 23° C., ASTM D638). On the other hand, the pellets were kept in an injection molding machine at 290° C. for 20 minutes, and then injection molded, and the same measurements were made on the 1-th test piece and compared with the above tensile elongation at break.

Further, the viscosity of the pellet was measured using a capillary rheometer immediately after melting at 290°C and after staying at 290°C for 20 minutes (shear rate 1216 S-').

As is clear from the results in Table 2, the resin composition of the present invention has significantly improved melt viscosity and physical property deterioration after residence, and also has extremely excellent physical properties of molded articles.

[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 all of the above-mentioned problems of resin compositions made of polyarylate and polyamide can be solved by using an acid anhydride group-containing olefin copolymer as an impact resistance imparting agent.

According to the present invention, a resin composition having a well-balanced impact resistance, particularly high-speed punching impact resistance, surface properties, dimensional stability during moisture absorption, weld part strength, and retention stability in a molten state is obtained. is provided.

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 an acid anhydride group-containing olefin 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.