JPH02227454A - Resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a resin composition of polyamide and polyamide, which has excellent dispersibility, mechanical properties, and moldability.

[Conventional technology]

Resin compositions composed of polyarylate and polyamide are known; for example, Japanese Patent Publication No. 56-14699 discloses a resin composition having a composition ratio of 100 parts by weight or less of polyamide to 100 parts by weight of polyarylate.

It is said that such a resin composition improves the moldability of polyarylate and also improves the chemical resistance and oil resistance of polyarylate.

On the other hand, it is expected that by dispersing polyarylate in polyamide, taking advantage of polyamide's moldability and chemical resistance, and imparting the heat deformation resistance of polyamide, a resin composition with an excellent balance of properties can be obtained. Ru. However,
Generally, it is difficult to uniformly and finely disperse polyarylate in polyamide. If the polyarylate is unrestricted and coarsely dispersed, an excellent balance of properties cannot be obtained, leading to problems such as poor moldability, decreased chemical resistance, and decreased strength. Although uniform and fine dispersion of polyarylate is an essential requirement for exhibiting the excellent properties of the resin composition, the reality is that no effective method has yet been found.

[Problem that the invention seeks to solve]

In view of the above circumstances, an object of the present invention is to achieve uniform fine dispersion of polyarylate in a resin composition comprising polyarylate and polyamide, and to exhibit excellent physical properties in a well-balanced manner.

[Means for solving problems]

The present inventors have conducted extensive research for this purpose and have found that the amount of terminal carboxylic acid groups is 50×10−'! It has been found that the object of the present invention can be achieved by using a polyarylate having a molecular weight of at least /g. It is unexpected and surprising that homogeneous flfi dispersion of polyarylate can be achieved by increasing the amount of terminal carboxylic acid groups in polyarylate to a specific amount or more.

That is, the present invention includes a resin composition comprising 110 to 80 parts by weight of a polyamide having a terminal carboxylic acid group content of 50 x 101 equivalents/g or more and 90 to 20 parts by weight of a polyamide.

The polyarylate used in the present invention is generally not limited in its structure as long as it is an aromatic polyester synthesized from bisphenols or derivatives thereof and aromatic dibasic acids or derivatives thereof, but more preferably terephthalic acid and/or It is a polyarylate using isophthalic acid or its derivatives.

Derivatives of terephthalic acid or isophthalic acid are dichlorides or alkyl, aryl, etc. diesters of these acids.

Bisphenols have the following form (where -X- is selected from the group consisting of -o -, -s -, -so□-〇10-, an alkylene group or an alkylidene group, and Rl+ Rx+ R3+ Rt+ R't+
Preferably, those represented by R'x+3+R'4 are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group. Examples of such bisphenols include 2, 2-1: "S(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane,
4-hydroxy-3,5-dimethylphenyl)methane,
Bis(4-hydroxy-3,5-dichlorophenyl)methane, 1.1-bis(4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)cyclohexylmethane, bis(4-hydroxyphenyl)phenylmethane, 4
．． 4' dihydroxy-diphenyl ether, bis(4-
Hydroxy-3,5-dimethylphenyl)ether, bis(4-hydroxyphenyl)-sulfone, bis(4-
hydroxy-3,5-dimethylphenyl)-sulfone,
Examples include 4,4'-dihydroxybenzophenone. If necessary, other divalent compounds, such as 4.4'
-Biphenol, hydroquinone, resorcinol, 2,
A small amount of 6-hydroxynaphthalene or the like may be added to the above bisphenols.

The polyarylate used in the present invention can be produced by interfacial polycondensation method,
It can be synthesized by any method such as a solution polymerization method or a melt polymerization method, but in order to achieve the purpose of the present invention, it is essential that the amount of terminal carboxylic acid groups is 50XIO-6 equivalent/g or more. be. Although there is no upper limit to the amount of terminal carboxylic acid groups, the upper limit is determined by the molecular weight of the polyarylate.

The method for producing polyarylate having such a terminal carboxylic acid group amount is arbitrary, but for example, by adjusting the molar ratio of bisphenols and tere(iso)phthalic acid dichloride or the reaction temperature in an interfacial polycondensation method, the desired polyarylate can be produced. Arilate can be obtained.

As another method, a polyarylate having an amount of terminal carboxylic acid groups within the range of the present invention can be obtained by t-volume polycondensation using tere(iso)phthalic acid and diacetate of bisphenols. The weight average molecular weight of the polyarylate is preferably in the range of 10,000 to 100,000.

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, ll-aminoundecanoic acid, 1
Amino acids such as 2-aminododecanoic acid, lactams such as 8-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 and mixed polyamides 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), especially nylon-6 and nylon-66. is important.

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.

There is no particular restriction on the composition ratio of polyarylate and polyamide in the present invention, but the composition range is the composition range in which polyarylate is substantially dispersed in polyamide and the characteristics such as heat deformation resistance of polyarylate are exhibited. Preferably, the polyarylate is 10-80% by weight and the polyamide is 90-20% by weight. More preferably, the polyarylate is 20 to 70% by weight, and the polyamide is 80 to 70% by weight.
It is 30% by weight.

It is preferable to mix polyarylate and polyamide in a molten state. For example, a heated roll, extruder, Banbury mixer, Brabender, etc. can be used. The composition of the present invention may be mixed as needed to impart impact resistance. Conventional additives added to plastics such as rubber components, stabilizers, lubricants, inorganic fillers, and reinforcing fibers can be added.

〔Example〕

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

Example 1 664.3 g of bisphenol A, 27 g of pt-butylphenol, 5.28 g of sodium hydrosulfide
g and pencil tributylammonium chloride 1.
5N caustic soda aqueous solution 1536-g was added to 88 g, stirred and dissolved, and the liquid temperature was adjusted to 30'C. On the other hand, 487.2 g of isophthalic acid chloride and 121.8 g of terephthalic acid chloride were dissolved in 5000 ad of methylene chloride, and the liquid temperature was adjusted to 30°C.

The above two types of solutions were simultaneously added to a reaction vessel equipped with a stirrer and a jacket over a period of 15 minutes using a metering pump, and the reaction was carried out with vigorous stirring. The reaction temperature was adjusted to 30°C. After the addition was completed, the mixture was stirred for an additional 60 minutes, and then 4.2 g of benzoyl chloride was added and stirred for an additional 20 minutes.

Then, stirring was stopped and the mixture was allowed to stand still to separate into an aqueous layer and a methylene chloride layer. The aqueous layer was removed, 3000af of water was added, and the mixture was neutralized with hydrochloric acid while stirring. Furthermore, washing with water was performed three times, and acetone 500 (ld) was added to the methylene chloride layer to precipitate a polymer. The precipitated polymer was filtered and then dried at 120°C for 8 hours. The terminal carboxylic acid of the polyarylate thus obtained was The base amount was determined by titration with a benzyl alcohol solution of caustic soda using phenol red as an indicator.9
It was oxto-' equivalent/g.

Extrude the above polyalcohol and poly-caprolactam (Amilan Chi 1026' manufactured by Toshi Corporation) at 27 G'C using a two-axis directional extruder under the conditions shown in Table 1.
The obtained blend was injection molded, and the dispersion state and physical properties of the polyarylate were measured. The results are shown in Table 1.

Example 2 Polymerization was carried out in the same manner as in Example 1 except that the polymerization temperature was 10° C. to obtain a polyarylate. The amount of terminal carboxylic acid groups in the obtained polyarylate was 55 x 10-'' equivalents/g.

Using this polyarylate, polyC-
A blend with caprolactam was prepared, and the dispersion state and physical properties of polyarylate were measured.

The results are shown in Table 1.

Comparative Example Polymerization was carried out in the same manner as in Example 1 except that the polymerization temperature was 10° C. and the addition of the caustic soda aqueous solution of bisphenol A was started 30 seconds earlier to obtain a polyarylate.

The amount of terminal carboxylic acid in the obtained polyarylate was 13Xl
G-equivalent/g.

Using this polyarylate, a blend of poly and caprolactam was prepared in the same manner as in Example 1, and the dispersion state and physical properties of the polyarylate were measured.

The results are shown in Table 1.

[Action/Effect]

As mentioned above, according to the present invention, uniform fine dispersion of polyarylate is achieved, and the resulting resin composition has well-balanced mechanical properties and is excellent in moldability and oil resistance.

Patent applicant Kanebuchi Chemical Industry Co., Ltd.

Claims (1)

[Claims] 1. The amount of terminal carboxylic acid group is 50 x 10^-^6 equivalent/g
A resin composition comprising 10 to 80 parts by weight of the above polyarylate and 90 to 20 parts by weight of polyamide.