JPH03237160A - Polyamide composition - Google Patents

Abstract

PURPOSE:To obtain a composition, excellent in tensile strength, impact strength, toughness, water resistance, etc., and suitable as engine head covers, bearing liners, etc., by blending an aromatic group-containing polyamide with a specific amount of a phenoxy resin. CONSTITUTION:A composition obtained by blending (A) 100 pts.wt. aromatic group-containing polyamide having i0.5dl/g, preferably 0.7-3dl/g intrinsic viscosity with (B) 1-100 pts.wt., preferably 5-50 pts.wt. phenoxy resin expressed by the formula (n is 80-125).

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to polyamide compositions, and more particularly to polyamide compositions that have excellent mechanical properties such as tensile strength, impact strength, and toughness, and physicochemical properties such as water resistance. relating to things.

Technical background of the invention and its problems Polyamide has superior strength, rigidity, heat resistance, oil resistance, abrasion resistance, etc. compared to thermoplastic resins such as polyolefin, and is widely used as an engineering plastic for various molding applications. It's being used.

However, polyamides such as those mentioned above do not necessarily have sufficient toughness and elongation to be used in the field of engineering plastics, which require even higher performance. , it is often done to impart elongation and subject it to processing.

In addition, polyamide does not have sufficient physical and chemical properties such as water resistance, boiling water resistance, salt water resistance, saturated water absorption, and chemical resistance.
Its use was limited.

On the other hand, in order to improve the toughness, elongation, and water resistance of the polyamide, a polyamide composition in which a modified α-olefin elastomer is blended with this polyamide has been proposed (
Special Publication No. 42-12546, Special Publication No. 55-4410
No. 8, JP-A-55-44108, JP-A-Sho 55
-9661, JP-A-55-9682)
.

In the polyamide compositions described in these publications, toughness,
Improvement effects on elongation and water resistance were observed.

However, since these polyamide compositions all use olefin-based elastomers, they have poor heat resistance,
Both mechanical properties and physical and chemical properties do not sufficiently meet the requirements for engineering plastics that require high performance.

By the way, JP-A-63-202855 discloses that 100 parts by weight of nylon 46 resin and 1 to 100 parts by weight of phenoxy resin
A resin composition in which parts by weight are blended has been proposed.

It is stated that the composition maintains the excellent properties of nylon 46 resin, such as tensile strength, and has better moldability than nylon 46 resin.

Furthermore, the same publication states that by blending an epoxy resin into the composition, stability of melt viscosity, hydrolysis resistance, etc. can be improved.

That is, the invention described in JP-A No. 63-202655 was made mainly for the purpose of improving the moldability of aliphatic nylon 46 resin, and the publication describes the mechanical strength of polyamide. , regarding how to significantly improve the water absorption and toughness of polyamide while maintaining its excellent properties such as heat resistance.
Iil et al. are not described.

Also, PLASTIC3ENGINEERING/N
ov, 1985 P, 37 has nylon 6, nylon 1
It is stated that blending a phenoxy resin with each of nylon 1 and nylon 12 improves the physical properties after water absorption, especially the elastic modulus, but there is no mention of improving the water absorption and toughness of polyamide.

Purpose of the Invention The present invention attempts to solve the problems associated with the prior art as described above, and is aimed at improving heat resistance properties such as heat distortion temperature, mechanical properties such as tensile strength, bending strength, impact strength, and toughness. , physical and chemical properties such as water resistance, water resistance, salt water resistance, saturated water absorption, and chemical resistance, fluidity of melt compositions, stretchability, melt compression moldability, melt injection moldability, and melt extrusion moldability. The object of the present invention is to provide a polyamide composition having excellent molding properties, particularly water absorption and toughness.

Summary of the Invention The polyamide composition according to the present invention comprises an aromatic group-containing polyamide (A) and a phenoxy resin (B) in an amount of 1 to 100 parts by weight based on 100 parts by weight of the aromatic group-containing polyamide. .

The polyamide composition according to the present invention includes the aromatic group-containing polyamide (A) as well as the phenoxy resin (
B), this polyamide composition has excellent mechanical properties such as tensile strength, impact strength, and toughness, and physical and chemical properties such as water absorption, and is particularly excellent in water absorption and toughness.

DETAILED DESCRIPTION OF THE INVENTION The polyamide composition according to the present invention will be specifically described below.

The polyamide composition according to the present invention comprises an aromatic group-containing polyamide (A) and a phenoxy resin (B).

Aromatic group-containing polyamide (A) The aromatic group-containing polyamide (A) contained in such a polyamide composition is made of, for example, the following dicarboxylic acid component unit (a) and diamine component unit (b). It has become.

That is, the dicarboxylic acid component unit (a) is an aliphatic dicarboxylic acid or an aromatic dicarboxylic acid, and the number of carbon atoms in the aliphatic dicarboxylic acid component unit is not particularly limited, preferably 4 to 25, more preferably is 6~
It is derived from 12 aliphatic dicarboxylic acids. Examples of aliphatic dicarboxylic acids used to derive such aliphatic dicarboxylic acid component units include succinic acid, adipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, undecanedicarboxylic acid and dodecanedicarboxylic acid. be able to. Specifically, the aromatic dicarboxylic acid component units include terephthalic acid, isophthalic acid,
Examples include component units derived from phthalic acid, 2-methylterephthalic acid, naphthalene dicarboxylic acid, and the like.

This dicarboxylic acid component unit (a) may consist only of aliphatic dicarboxylic acid component units, may consist only of aromatic dicarboxylic acid component units, or may consist of aliphatic dicarboxylic acid component units and aromatic dicarboxylic acid component units. It may also consist of acid component units.

Typical examples of the polyamide resin include polylactams such as nylon 6, nylon 11, and nylon 12, nylon 6.6, nylon 6.10, and nylon 6.1.
Polyamides obtained by cocondensation polymerization of dicarboxylic acids and diamines such as 2 and nylon 4/6, nylon 6/66, nylon 6/610, nylon 6/612, nylon 6/12, nylon 6/66/ 6
10 copolymerized polyamides, nylon 6/6T (
T Terephthalic acid component) Semi-aromatic polyamides, polyesteramides, polyetheramides, and polyesteramides obtained from aromatic dicarboxylic acids such as isophthalic acid and metaxylene diamine or alicyclic cyamine.

In addition, in the present invention, these polyamide resins may be used alone, or two or more types may be used in combination.

The polyamide resin that can be used in the present invention is not limited by the type of terminal group, strength, molecular weight, etc. of these polyamide resins as long as it is selected from the polyamide resins mentioned above, and various resins can be used. be able to.

It is also possible to use a polyamide resin containing a mixture of low molecular weight substances such as monomers and oligomers that remain or are produced when polymerizing the polyamide resin.

There is no limit to the degree of polymerization of the polyamide used, but one having an intrinsic viscosity of concentrated sulfuric acid of 0.5 or more is usually used.

In the present invention, the diamine component unit (b) constituting the aromatic group-containing polyamide (A) may consist only of an aliphatic diamine component unit, or may consist of an aliphatic diamine component unit and an alicyclic diamine component unit. units, or may consist only of alicyclic diamine component units.

Such aliphatic diamine component units may be linear alkylene diamine component units or may be branched chain alkylene diamine component units. Among these aliphatic cyamine component units, the number of carbon atoms is 4 or 4.
A straight chain or branched chain alkylene diamine component unit having 25 to 25 carbon atoms is preferred, and a straight chain or branched chain alkylene diamine component unit having 6 to 18 carbon atoms is more preferable.

Specifically, such aliphatic diamine component units include, for example, 1.8-diaminohexane, 1.7-diaminohebutane, 1.8-diaminooctane, 1.9-diaminononane, 1.10 -diaminodecane,
Component units derived from linear alkylene diamines such as 1.11-diaminoundecane and 1.12-diaminododecane; and 1.4-diamino-1,1-dimethylbutane, 1.4-
Diamino-i-ethylbutane, 1,4-diamino-1,
2-dimethylbutane, 1.4-diamino-1,3-dimethylbutane, 1.4-diamino-1,4-dimethylbutane, 1.4-diamino-2,3-dimethylbutane, 1.
2-diamino-1-butylethane, (,6-diamy2,5-dimethylhexane, 1,6-diamy2,4
-dimethylhexane, 1,6-diami2, 3.3-dimethylhexane, 1,6-diami2, 2.2-dimethylhexane, 1,6-diami2, 2.2.4-trimethylbeef san, 1.6-diami2 .4.4-) Dimethylhexane, 1,7-diami2-2,3-dimethylhebutane, 1,7-diami2-2,4-dimethylhebutane,
1,7-Diami2-2,5-dimethylhebutane, 1.7
-Diami2-2,2-dimethylhebutane, 1,8-diamino-1,3-dimethyloctane, 1,8-diamino-
1,4-dimethyloctane, 1,8-diamino-2,4
-dimethyloctane, 1°8-diamino-3,4-dimethyloctane, 1,8-diamino-4,5-dimethyloctane, 1,8-diamino-2,2-dimethyloctane, 1,8-diamino-3 , 3-dimethyloctane, 1.
Component unit derived from a branched chain alkylene diamine such as 8-diamino-4,4-dimethyloctane, 1,8-diamino-2,4-diethylhexane, 1,9-diamino-5-methylnonane, etc. I can list the following.

Among such linear or branched chain alkylene diamine component units, linear alkylene diamine component units are preferable, and in particular, 1,6-diethylhexane, 1,8-diaminooctane, 1, Preferably, the component unit is derived from one or more compounds of linear alkylene diamines such as IO-diaminodecane and 1,12-diaminododecane.

The alicyclic diamine component unit usually has 6 to 2 carbon atoms.
5 and is a component unit derived from a diamine containing at least one alicyclic hydrocarbon ring.

Specifically, such alicyclic diamine component units include, for example, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, (1), 3-bis(aminomethyl)cyclohexane, and 1.4-diaminocyclohexane.
-bis(aminomethyl)cyclohexane, isophoronediamine, piperazine, 2,5-dimethylpiperazine, bis(4-aminocyclohexyl)methane, bis(4-
aminocyclohexyl)propane, 4,4-diamino-
3,3'-dimethyldicyclohexylpropane, 4.4-diamino-3,3'-dimethyldicyclohexylmethane, 4.4-diamino-3,3'-dimethyl-5,5'-dimethyldicyclohexylmethane, 4.4- Diamino-3,3°-dimethyl-5,5"-dimethyldicyclohexylpropane, α-α-bis(4-aminocyclohexyl)-p-diisopropylhensen, α-α-bis(4-aminocyclohexyl)1-diisopropyl Benzene, α-α”-bis(4-aminocyclohexyl)-1,4
Cyclohexane, α-α°-bis(4-aminocyclohexyl)-1,3
- Component units derived from alicyclic diamines such as cyclohexane can be mentioned.

Among these alicyclic diamine component units, bis(aminomethyl)cyclohexane, bis(4-aminocyclohexyl)methane, and 4.4°-diamino-3,3°-dimethyldicyclohexylmethane are preferred, and particularly bis(
Preferred are component units derived from alicyclic diamines such as 4-aminocyclohexyl)methane, 1.3-bis(aminocyclohexyl)methane, and 1.3-bis(aminomethyl)cyclohexane.

The polyamide (A
), the intrinsic viscosity [η] measured in concentrated sulfuric acid at a temperature of 30°C is usually 0.56 l/g or more, preferably 0.
6 dN/g or more, more preferably 0.7 to 3.0 dl
l/g, particularly preferably in the range of 0.8 to 1.5 di)/g.

Such a polyamide (A) can be manufactured using, for example, a conventionally known method such as a melt & process, an interfacial polymerization method, a melt method, or a solid phase polymerization method.

In addition, the diamine component units forming the polyamide (A) may include aromatic diamine component units in addition to the alkylene diamine component described above, and such aromatic diamine component units include: Specifically, for example, component units derived from aromatic diamines such as -xylylene diamine and p-xylylene diamine can be mentioned. These aromatic diamines can be used alone or in combination of two or more.

Phenoxy resin (B) The phenoxy resin (B) used in the present invention consists of a structural unit represented by the following formula (B); and has an average molecular weight of 1.
0,000-100,000, preferably 10,000
~30,000 high molecular weight thermoplastic resin. Unlike epoxy resins, phenoxy resins have molecular chains such as molecular ends (
Because it does not contain any highly reactive epoxy groups in the ring),
The resin itself has excellent heat stability, ductility, and toughness. Such phenoxy resins are produced, for example, from bisphenol A and epichlorohydrin and are commercially available, for example, from Union Carbon and Carbide under the names PKHH, PAHJ, PKHC, etc., depending on their properties.

The characteristics of these phenoquine resins are detailed in "Plastic Handbook" (published by Asakura Shoten, 1984 edition).

In the present invention, such a phenoxy resin (B) is used together with the aromatic group-containing polyamide (A), so that the aromatic group-containing polyamide (A) has excellent tensile strength, bending strength, and bending strength. While substantially maintaining properties such as elastic modulus and impact strength, aromatic group-containing polyamide (A
), properties such as toughness (high elongation before breaking and high tensile strength) and water absorption can be significantly improved.

As described above, the properties of the polyamide composition using the phenoxy resin (B) together with the aromatic group-containing polyamide (A) are improved because of the appropriate interaction between the secondary hydroxyl group of the phenoxy resin and the amide bond of the polyamide. It is inferred that this is because it occurs.

Such phenoxy resin (B) is polyamide (A)
It is used in an amount of 1 to 100 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts by weight.

When the phenoxy resin (B) is used in the above-mentioned amount, the resulting polyamide composition can increase elongation while maintaining strength.

Note that the amount of phenoxy resin (B) is higher than that of polyamide (A).
) If the amount is less than 1 part by weight per 100 parts by weight, the resulting polyamide composition will not have sufficient tensile elongation or low water absorption.
Moreover, if the amount exceeds 100 parts by weight, the strength tends to decrease.

The polyamide composition according to the present invention has the aromatic group-containing polyamide (A) and the phenoxy resin (B) as essential components as described above, but in addition to these essential components, organic or Inorganic fillers, antioxidants, ultraviolet absorbers, photoprotectants, heat stabilizers, phosphite stabilizers, peroxide decomposers, basic adjuvants, nucleating agents, plasticizers, lubricants, electrostatic charges It may also contain inhibitors, flame retardants, pigments, dyes, etc.

Among the above fillers, inorganic or organic fillers include powder, granule, plate, fiber, strand,
Various fillers having cross-like or matte-like shapes can be mentioned, and specific examples include silica, alumina, silica-alumina, talc, diatomaceous earth, clay, kaolin, quartz, glass, mica, graphite, and molybdenum disulfide. ,
Powdered and plate-like inorganic compounds such as Ceracola, Hengara, titanium dioxide, zinc oxide, aluminum, copper, and stainless steel; fibrous materials such as glass fiber, carbon fiber, boron fiber, ceramic fiber, asbestos fiber, and stainless steel fiber; inorganic compounds or secondary processed products such as cross-shaped products of these, polyvara phenylene terephthalamide, polymethaphenylene terephthalamide, polyvara phenylene isophthalamide, polymethaphenylene isophthalamide,
Condensates of diaminodiphenyl ether and terephthalic acid (isophthalic acid), wholly aromatic polyamides such as condensates of p(11>-aminobenzoic acid), condensates of diaminodiphenyl ether and trimellitic anhydride or pyromellitic anhydride, etc. Fully aromatic polyamide-imide, fully aromatic polyimide, polybenzimidazole, heterocycle-containing compounds such as polyimidazophenanthroline, powdered, plate-like, fibrous, or cross-like materials such as polytetrafluoroethylene, etc. These secondary processed products can be exemplified.These fillers can be used in combination of two or more types.Also, these fillers can be combined with a silane coupling agent or a titanium coupling agent. It can also be processed and used.

Among the fillers, specific examples of the powder filler include silica, silica alumina, alumina, titanium dioxide, graphite, molybdenum disulfide, and polytetrafluoroethylene.

Such a powder filler is made of aromatic group-containing polyamide F.
'(A) It is usually contained in an amount of 200 parts by weight or less, preferably 100 parts by weight or less, and particularly preferably 0.5 to 50 parts by weight, relative to 100 parts by weight of (A). is desirable.

Further, among the fillers, examples of organic fibrous fillers include polyparaphenylene terephthalamide fiber, polymethaphenylene terephthalamide fiber, polyparaphenylene isophthalamide fiber, and polymethaphenylene isophthalamide fiber. , wholly aromatic polyamide fibers such as fibers obtained from condensates of cyaminophenyl ether and terephthalic acid or isophthalic acid. The use of such fibrous fillers increases the tensile strength of molded bodies obtained from polyamide compositions,
This is preferable because mechanical properties such as Izot impact strength and heat resistance properties such as heat distortion temperature are improved.

Further, among the fillers, specific examples of the inorganic fibrous filler include glass fiber, carbon fiber, and boron fiber. The use of such fibers improves the mechanical properties such as tensile strength, flexural strength, and flexural modulus of molded objects obtained from polyamide compositions, the heat resistance properties such as heat distortion temperature, and the physicochemical properties such as water resistance. This is preferable because it improves.

The average length of the above organic or inorganic fibrous filler is usually 0.1 to 20 m+s, preferably 1 to 20 m+s.
It is desirable that it be in the range of 10 degrees. When the average length of the fibrous filler is within this range, the moldability of the polyamide composition, especially the stretchability, is improved, and the heat resistance properties such as the heat distortion temperature of the molded product obtained from this polyamide composition are improved. This is preferable because mechanical properties such as tensile properties and bending strength are improved.

The organic or inorganic fibrous filler is usually used in an amount of 20 parts by weight per 100 parts by weight of the aromatic group-containing polyamide (A).
It is desirable to include it in the polyamide composition of the present invention in an amount of 0 parts by weight or less, preferably in an amount of 5 to 180 parts by weight, more preferably in an amount of 5 to 150 parts by weight.

The polyamide composition according to the present invention can be prepared by a method such as blending a filler while maintaining each component of the polyamide composition in a molten state. On this occasion,
An extruder, kneader, etc. can be used.

The polyamide composition according to the present invention as described above can be molded by a conventional melt molding method, such as a compression molding method, an injection molding method, or an extrusion molding method.

The polyamide composition according to the present invention can be used in various applications such as engineering plastics by ordinary molding methods, and is particularly preferably used in applications such as engine head covers, bearing retainer connectors, etc.

Effects of the Invention The polyamide composition according to the present invention consists of (A) an aromatic group-containing polyamide and (B) a phenoxy resin in an amount of 1 to 100 parts by weight per 100 parts by weight of the polyamide (A). , especially in water absorption and toughness.

[Example] Next, the polyamide composition according to the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples at all.

Example 1 66.70 parts by weight of nylon and the following phenoxy resin 3
0 parts by weight were supplied to a twin-screw extruder set at 280°C to prepare a blend (vellet). Thereafter, each test piece listed in Table 1 was produced using an injection molding machine, and the items listed in Table 2 were tested by the method listed in Table 1.

The results are shown in Table 2.

The abbreviations in Group 2 are as follows.

PAMXD6: metaxylylene diamine adipate Reny-6002 manufactured by Mitsubishi Gas Chemical Co., Ltd. PA6T6 is a copolymerized polyamide consisting of three components: terephthalic acid, adipic acid, and hexamethylene diamine.

T/A is terephthalic acid/adipic acid moiety shows the ratio.

T/^-70/30 Melting point 343℃ [η Co 1.1
6T bar 501501/3o8℃ 〃-1.02T/
^-30/70 /281℃/l-1.13PA6T
A copolyamide consisting of three components: I-terephthalic acid, isophthalic acid, and hexamethylene diamine.

T/l is terephthalic acid/isophthalic acid Indicates molar ratio.

T/1-80/20 Melting point 347℃ [η, l −1
,32T/l-70/30 7321℃/1-o9
4PA66 knee J-iron 66, made by Toshi CM30
01 N PA46: + Iron 46, manufactured by DsM in the Netherlands [manufactured by Phenoxy Resin Counion Carbide Co., Ltd. PKHH glass transition point 100
℃, number average molecular weight 14,000. Hydroxyl group content 6.0wt
% Comparative Examples 1 to 8, Examples 2 to 10 The same procedure as in Example 1 was carried out except that the composition of the polyamide composition was changed as shown in Table 2.

The results are also shown in Table 2.

In Table 2, Comparative Example 3 and Example 3, Comparative Example 4 and Example 4, Comparative Example 5 and Example 5, Comparative Example 6 and Example 6,
In Comparative Example 2 and Example 2, Comparative Example 1 and Example 1, Comparative Example 7 and Examples 7, 8, and 9, and Comparative Example 8 and Example 10, the same polyamide was used.

TANYL

Claims (1)

[Claims] (1) A composition comprising (A) an aromatic group-containing polyamide and (B) a phenoxy resin in an amount of 1 to 100 parts by weight based on 100 parts by weight of the aromatic group-containing polyamide.