JPH04180966A - Polytetramethyleneadipamide composition - Google Patents

Abstract

PURPOSE:To prepare the title compsn. excellent in heat resistance, flame retardance, impact strength, and tensile strength and giving a molded article having low shrinkage due to water or moisture absorption by compounding polytetramethyleneadipamide, a polyester, a halogenated PS, and a specific graft copolymer. CONSTITUTION:100 pts.wt. the sum of 20-90 pts.wt. polytetramethyleneadipamide having a relative viscosity (25 deg.C, in 96wt.% sulfuric acid, 1g/dl) of 2.0-6.0 and 80-10 pts.wt. polyester having a relative viscosity [25 deg.C, in a mixed solvent of 60/40(wt. ratio) phenol/tetrachloroethane, 1g/dl] of 0.5-3.5 is compounded with 10-80 pts.wt. halogenated PS having a halogen content of 10-80wt.%, 0.1-30 pts.wt. Sb compd. (e.g. Sb2O3), and 1-20 pts.wt. graft copolymer comprising a main chain consisting of an olefinic polymer having epoxy groups and 20-60wt.% side chains consisting of vinyl polymers.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polytetramethylene adipamide composition, and more particularly, it has flame retardancy, excellent impact strength and tensile strength, and is resistant to water absorption and moisture absorption. The present invention relates to a polytetramethyladipamide composition that exhibits small dimensional changes in molded articles caused by.

[Conventional technology]

Polytetramethylene adipamide (hereinafter referred to as “nylon 4,6
'') is already a well-known polyamide, and is known to be a resin having excellent properties as an engineering plastic, especially excellent heat resistance.

Furthermore, polyesters, represented by polyethylene terephthalate, have excellent mechanical, chemical, and electrical properties, and are used in a wide range of applications such as fibers and films.

In general, polyamide has excellent mechanical properties such as strength, impact resistance, and abrasion resistance, as well as high heat resistance and chemical resistance, and has good moldability, so it is used in automobile parts, electrical parts, etc. It is used for various purposes such as general mechanical parts.

Among them, nylon 4,6 has excellent heat resistance, with a melting point of 224°C for nylon 6 and 224°C for nylon 6,6.
60°C, it is high at 295"C. Also, because the crystallization rate is fast, the molding cycle is short, and the melt viscosity is low, so the moldability is good. In this way,
In addition to the excellent chemical resistance of polyamide, nylon 4.6 also has excellent heat resistance, mechanical properties, and moldability, so it is a resin that is expected to be used as an engineering plastic from various quarters.

By the way, electrical circuits such as switches, connectors, and bobbins used in electrical and electronic components are often soldered onto printed circuit boards. When connecting the components on a printed circuit board, soldering is increasingly performed in a high-temperature glue flow furnace in order to arrange the components in a high-density manner. When soldering in a high-temperature glue flow furnace, the entire part is heated, and therefore the entire part, which previously did not require much heat resistance, is now heated to the temperature of the furnace, and flame-retardant resin that can withstand high temperatures is now required. It is now possible to do so. Therefore, as for the flame retardancy of the above parts,
Underwriters Laboratory
ters Laboratory (hereinafter abbreviated as rULJ)] in a combustion test using the UL-94 test method.
Many are required to pass -0 or V-1 standards.

As described above, materials used in the electrical and electronic fields are normally required to pass the ■-0 or V-1 standard according to the UL-94 test method, but nylon 6 and nylon 66 meet the requirements. It remains at rank ■-2 of the standard. In order to increase the flame retardancy level, JP-A-51-47044 (addition of brominated polystyrene) and JP-A-54-118054 (addition of brominated polyphenylene ether) include the addition of halogen flame retardants. , Japanese Patent Publication No. 58-8
No. 4854 (addition of brominated polystyrene and antimony oxide) has been proposed, but none of them has produced a material with heat resistance that can withstand soldering in a reflow oven.

On the other hand, regarding flame retardation of nylon 4.6, which has high heat resistance,
JP-A-61-1884.63 (addition of brominated polystyrene and brominated polyphenylene ether to nylon 4.6), JP-A-63-139942 (addition of brominated polystyrene and antimony oxide to nylon 4,6) However, these are insufficient in terms of reducing the dimensional stability and strength of molded products.

Polyamide resins, especially nylon 4.6, have the disadvantage that they cause dimensional changes and decreases in strength of molded products due to water absorption and moisture absorption. In order to improve the water absorption and hygroscopicity of nylon 4.6, blends of nylon 4.6 and other resins have been proposed (for example, in JP-A-57-49657).
No. 60-63256, JP-A No. 61-
213256, JP 61-213257, JP 63-202654, JP 64-31
No. 866, Japanese Unexamined Patent Publication No. 64-65168), but the effects are not sufficient. For example, in a blend of nylon 4.6 and polyester, simply mechanically melt-blending the two causes coarse phase separation, making it impossible to obtain a material with high practical value. When a fuel agent is added, it becomes even more difficult to control viscosity and miscibility, making it impossible to obtain a resin composition with the expected properties.

[Problem to be solved by the invention]

The present invention was made against the background of the problems of the prior art described above, and has heat resistance and flame retardancy that pass the ■-0 or V-1 standard according to the UL-94 test method, as well as impact strength and
The object of the present invention is to provide a nylon 4,6 composition that has excellent tensile strength and exhibits small dimensional changes in molded products due to water absorption and moisture absorption.

[Means to solve the problem]

The present invention provides (A) polytetramethylene adipamide 20-
(C) 10 to 80 parts by weight of halogenated polystyrene, (D
) 0.1 to 30 parts by weight of an antimony compound, and (E) an olefin copolymer containing an epoxy group as the main chain, a vinyl polymer as the side chain, and the ratio of the vinyl polymer as the side chain. The present invention provides a nylon 4.6 composition containing 1 to 20 parts by weight of a graft copolymer (hereinafter sometimes simply referred to as "graft copolymer") having 20 to 60% by weight.

Hereinafter, the present invention will be explained for each component.

A Ilon 46 Nylon 4.6 used in the present invention includes polytetramethylene adipamide obtained from tetramethylene diamine and adipic acid, and a copolyamide whose main constituents are polytetramethylene adipamide units. Furthermore, other polyamides may be included as copolymer components within a range that does not impair the properties of nylon 4,6.

The copolymerization component is not particularly limited, and known amide-forming components can be used. A typical example of a copolymer component is 6
-aminocaproic acid, 11-aminoundecanoic acid, 12
- Amino acids such as aminoundecanoic acid and para-aminomethylbenzoic acid; Lactams such as ε-caprolactam and ω-lauryllactam; Hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2,2
゜4-/2,4.4-)limethylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylenediamine, baraxylenediamine, 1゜3-bis(aminomethyl)cyclohexane, 1゜4-bis(amino methyl) cyclohexane, ■-amino-3-aminomethyl-3
．． Diamines such as 5.5-)limethylcyclohexane, bis(3-methyl-4-aminocyclohexyl)methane, 2.2-bis(aminopropyl)piperazine, and aminoethylpiperazine; adipic acid, speric acid, azelaic acid, Sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, diglycol Examples include dicarboxylic acids such as acids.

Further, the method for producing nylon 4, 6 used in the present invention is arbitrary. For example, JP-A-56-149430, JP-A-56-149431, JP-A-58-83
029 or Japanese Patent Application Laid-open No. 61-43631, etc., first, a prepolymer with few cyclic terminal groups is produced under specific conditions, and then this is solid-phase polymerized in a steam atmosphere to obtain a high-density polymer. A method for preparing nylon 4,6 viscosity, or by heating in a polar organic solvent such as 2-pyrrolidone or N-methylpyrrolidone.
For example, how to obtain

There are no particular restrictions on the degree of polymerization of nylon 4.6, but
Nylon 4°6 having a relative viscosity of 2.0 to 6.0 at 1 g/dfl in 296% by weight sulfuric acid at 25° C. is preferably used.

The blending ratio of (A) nylon 4.6 in the composition of the present invention is 20 to 90% by weight, preferably 25 to 80% by weight, more preferably 30 to 4% by weight among the components (A) to (B).
It is 5% by weight. The blending ratio of nylon 4.6 is (A)
If the content of the (B) polyester is less than 20% by weight (i.e., more than 80% by weight), the heat resistance of the resulting composition will be significantly poor, while if it exceeds 90% by weight (i.e., ( B) When the polyester content is less than 10% by weight], the dimensional change and strength reduction of the molded product due to water absorption and moisture absorption become large.

B Polyester The polyester used in the present invention is obtained from an aliphatic glycol and an aromatic dicarboxylic acid through a normal polymerization reaction, and each may contain one or more other copolymer components.

Particularly preferably used polyesters include polyethylene terephthalate, polybutylene terephthalate, polyethylene isophthalate, polytriethylene terephthalate, polytriethylene isophthalate, polytetraethylene terephthalate, polytetraethylene isophthalate, poly-1, Examples include 4-cyclohexylene dimethylene terephthalate and poly-1,4-cyclohexylene dimethylene isophthalate. There are no particular restrictions on the degree of polymerization of polyester, but
25℃, phenol/tetrachloroethane = 60/40
(Weight ratio) The relative viscosity at 1 g/d in the mixed solvent is
Preferably 0.5 to 3.5, more preferably 1.8 to
Polyesters in the range of 3.0 are preferably used.

C Polystyrene Brominated polystyrene can be produced, for example, by post-brominating polystyrene.

The bromine content of the brominated polystyrene is preferably 10 to
80% by weight, preferably 40-75% by weight.

The skeleton of brominated polystyrene is not limited to polystyrene, and may be a copolymer with other copolymerizable monomers as necessary.

The amount of brominated polystyrene (C) in the composition of the present invention is 10 to 80 parts by weight, preferably 20 to 65 parts by weight, based on 100 parts by weight of the total amount of components (A) to (B). Preferably it is 25 to 60 parts by weight. If the amount of brominated polystyrene is less than 10 parts by weight, it is difficult to reach the target level of flammability, while if it exceeds 80 parts by weight, the impact strength will decrease.

D Antimony Antimony oxide includes antimony trioxide and antimony pentoxide.

The amount of antimony oxide (D) in the composition of the present invention is 0.1 to 30 parts by weight, preferably 1 to 25 parts by weight, based on 100 parts by weight of the total amount of components (A) to (B). More preferably, it is 5 to 20 parts by weight. If brominated polystyrene is used alone as a retardant without adding antimony oxide, the molten resin drips significantly during combustion. If the amount of antimony oxide is less than 0.1 parts by weight, the level of flammability will be low, while if it exceeds 30 parts by weight, impact strength will decrease.

An example of this graft copolymer is an ethylene-glycidyl methacrylate copolymer (hereinafter referred to as rE-GMAJ) whose main chain is reactive, and which has functional groups such as condensed engineering plastics. Examples include extremely unique graft copolymers that can also be reacted with other compartments.

This graft copolymer differs from copolymers obtained by polymerizing, for example, one or more types of unsaturated glycidyl monomers and one or more types of olefinic monomers, and has 20 to 60% by weight of side chains. It is a graft copolymer characterized by having a vinyl polymer.

An olefin copolymer containing an epoxy group alone, such as E-GMA alone, is insufficiently effective as a compatibilizer component, and an olefin copolymer containing an epoxy group, such as component (E), Add 20 side chains of vinyl polymer to
The graft copolymer having a content of ~60% by weight has a greater compatibilizing effect.

(E) In the graft copolymer, the main chain E-0MA is preferably 50 to 70% by weight, and the side chain vinyl polymer is preferably 50 to 30% by weight.

In addition, the preferable range of GMA content in E-C and MA of the main chain is 10 to 30% by weight, and if it is less than 10% by weight, a sufficient compatibilizing effect cannot be obtained, while if it exceeds 30% by weight, The gel content due to crosslinking reaction increases.

In this (E) graft copolymer, examples of the side chain vinyl polymer include polystyrene, polymethyl methacrylate, acrylonitrile-styrene copolymer, polyacrylic acid, and styrene-maleic anhydride copolymer. preferably polystyrene, acrylonitrile-styrene copolymer (acrylonitrile content = 20-5
0i amount%).

As a compatibilizer, it is insufficient to simply use an olefin copolymer containing an epoxy group, such as the above-mentioned E-C;MA alone;
Graft copolymers with vinyl polymer side chains on olefin copolymers with epoxy groups are better than nylon 4
．． It is possible to stabilize the compatibilization effect between 6 and polyester and improve the dispersibility of both.

1 The blending amount of component (E) in the composition of the present invention is (
1 to 2 parts per 100 parts by weight of the total amount of components A) to (B)
0 parts by weight, preferably 1 to 15 parts by weight, more preferably 1 to 7 parts by weight.

If the amount of component (E) is less than 1 part by weight, (A) to (
D) The compatibilizing effect of component is significantly reduced, the extrudability is deteriorated, and a composition having sufficient strength and heat resistance cannot be obtained. On the other hand, if it exceeds 20 parts by weight, a large amount of gel content will be generated due to crosslinking reaction, causing problems during processing.

The composition of the present invention may contain other ingredients, such as pigments, dyes, reinforcing materials, fillers, heat resistant agents, heat stabilizers, antioxidants, weathering agents, and light stabilizers, as long as they do not impair their moldability and physical properties. Agents, lubricants, crystal nucleating agents, mold release agents, stabilizers, antistatic agents, other polymers, other flame retardants, etc. can be added.

In particular, it is important to add reinforcing materials and fillers, such as glass fiber, asbestos fiber, carbon fiber, graphite fiber, metal fiber, wollastenite, talc, calcium carbonate, mica, clay, potassium titanate whiskers, and metal flakes. A fibrous or powdery reinforcing material (inorganic filler) such as , glass peas, and glass flakes can be added and blended, and among them, fibrous reinforcing materials such as glass fiber and carbon fiber are preferably used. In particular, by adding glass fiber to the composition of the present invention, not only the mechanical strength and heat resistance temperature are significantly improved, but also the water resistance is improved, and the object of the present invention is achieved. It is preferable to do so.

The blending amount of these inorganic fillers is as follows:
The amount is 100 parts by weight or less, preferably 10 to 30 parts by weight in order to impart rigidity to 0 parts by weight.

Furthermore, stabilizers such as copper compounds and hindered phenol compounds, lubricants, colorants, and the like may be added to the composition of the present invention.

Furthermore, metal oxides such as zinc oxide and iron oxide can be used in combination as flame retardant aids.

Furthermore, an ethylene polymer can be added to the composition of the present invention for the purpose of improving impact strength.

The method for producing the composition of the present invention is not particularly limited; for example, (
The most common method is to supply components A) to (E) simultaneously, or pre-blend two or three components, or without pre-blending, to a single-screw or multi-screw extruder and melt-knead them. .

There is also a method of post-adding (C) brominated polystyrene among the constituent components of the present invention. For example, the components (A), (B), (D), and (E) of the present invention are introduced through the main supply port of the extruder, and the components (A), (B), (D), and (E) of the present invention are introduced through the sub-supply port.
The method of adding C) is particularly effective. This charging method significantly improves extrudability and injection moldability.

The composition of the present invention can be molded into a molded article with excellent physical properties by subjecting it to molding methods commonly used for thermoplastic resins, such as injection molding, extrusion molding, blow molding, and compression molding.

The composition of the present invention can be used for various purposes. For example, various automobile parts such as automobile interior parts and electrical parts, electrical and electronic parts such as switches, connectors, printed circuit boards, coil bobbins, and housing cases, general mechanical parts such as bearings, gears, rivets, nuts, etc. It can be used for miscellaneous goods, paint, insulation, etc. In particular, the composition of the present invention has excellent heat resistance, processability, corrosion resistance, flame retardance, etc., so it can be used for electrical and electronic parts such as switches, connectors, and coil bobbins that are soldered in a reflow oven. Suitable as a material.

[Function] Conventionally, blends of flame retardants such as (A) nylon 4.6, (B) polyester, and (C) brominated polystyrene cannot be easily melt-blended mechanically without causing coarse phase separation. A composition with high practical value cannot be obtained.

The present invention provides extrusion processing temperatures (A) nylon 4.6, (B) polyester, and (C) brominated polystyrene (
As a result of studying the relationship between each viscosity and blendability at 300 to 320 ° C) and these compatibilizers, we found that (E) By blending the graft copolymer,
It was discovered that the compatibilization effect of the three components has a significant effect.

[Examples] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

Various physical properties in Examples were measured as follows.

UL-944L property Based on UL-94 test method.

■Fly Yado Measured according to ASTM D63B.

Strain temperature is expressed as Izot impact strength determined in accordance with ASTM D256 (notched).

A test piece formed into a disc with a diameter of approximately 50 mm and a thickness of approximately 311 mm was immersed in water at 100° C. for 2 hours, and the water absorption rate was measured according to ASTM D570.

Moisture absorption rate A test piece formed into a disk having a diameter of about 50 mm and a thickness of about 3 tmn was measured for saturated moisture absorption rate (ISO) at a temperature of 70° C. and a relative humidity of 62%.

Reference Example ± 5TANYLKS300 manufactured by DSM, Netherlands, was used.

Oni” Deaf (Kyuu Polyethylene Terephthalate (manufactured by Mitsui Bett Resin ■, P
ETJ155), and polybutylene terephthalate (
PBTXD47B) manufactured by Polyplastics was used.

Bo1 Styrene Nissan Ferro Organic Chemical Co., Ltd., PYRO-CHEK68PB
(bromine content=68.5% by weight) was used.

Mogami Eetoto 2 PATOX-C manufactured by Nippon Shinko ■ was used.

A graft copolymer with an olefin copolymer containing an epoxy group as a main chain and a vinyl polymer as a side chain, which is a human compatibilizer component, is manufactured by Nippon Oil & Fats ■, Modipa-A4.
100, Modiper A4101, and Modiper A4
400 was used.

Among these, Modiva-A4100 has a main chain of E-GMA.
Among them, ethylene is 85% by weight, GMA is 15% by weight, the main chain is 70% by weight, and the side chain polystyrene is 30% by weight.
% by weight of graft copolymer. Also, Modipa-A
4101 is a graft copolymer in which the main chain of E-GMA is 85% by weight of ethylene and 15% by weight of GMA, and the main chain is 50% by weight and the side chain of polystyrene is 50% by weight. Furthermore, MODIPA-A4400 has a main chain of E
-GMA is a graft copolymer in which ethylene is 85% by weight and GMA is 15% by weight, and the main chain is 70% by weight and the side chain acrylonitrile-styrene copolymer is 30% by weight.

In addition, in the comparative example, NOF ■ was used as the compatibilizer E-1.
E-GMA (in E-GMA, ethylene - 85% by weight, GMA = 15% by weight) and as compatibilizer E-2,
A graft copolymer (produced by NOF ■) whose main chain is ethylene-maleic anhydride copolymer and whose side chain is polystyrene (
In the main chain, ethylene - 85% by weight, maleic anhydride = 15
A graft copolymer containing 70% by weight of the main chain and 30% by weight of polystyrene in the side chain was used.

Asahi fiberglass is used as a glass fiber filler material.
C3O3JAFT-2A, manufactured by Co., Ltd., was used.

Examples 1 to 7 Pellets were prepared by blending and extruding the formulations shown in Table 1 using a co-rotating meshing two-wheel extruder (cylinder temperature -290 to 320"C).The resulting pellets were injection molded. machine (cylinder temperature = 290 ~
A predetermined test piece was prepared at 320°C) and subjected to evaluation of physical properties.

The formulation and evaluation results are shown in the lower column of Table 1.

All of the compositions exhibited excellent flame retardancy and passed the V-0 or V-1 standard in the combustion test according to the UL-94 test method.

Furthermore, among the constituent components of the present invention, when a method of post-adding (C) brominated polystyrene is adopted, not only extrudability and injection moldability are significantly improved, but also flame retardancy, tensile strength, and izot impact Compositions with better strength were obtained (Examples 4 to 7).

Furthermore, as shown in Example 7, when reinforced with glass fibers, a composition with better flame retardancy, tensile strength, and Izot impact strength was obtained.

Comparative Examples 1 to 11 Predetermined test pieces were prepared in the same manner as Examples 1 to 7 using the formulations shown in Table 1, and subjected to evaluation of physical properties. The formulation and evaluation results are shown in Table 1.

Comparative Examples 1 and 2 are cases in which a compatibilizer that does not fall within the scope of the claims of the present invention is used, and not only are the tensile strength and Izot impact strength inferior, but the compatibilizer E-2 of Comparative Example 2 is inferior.
However, the extrudability was poor and the strands could not be taken out.

In Comparative Examples 3 and 4, the method of post-adding (C) brominated polystyrene among the constituent components to the same compositions as in Comparative Examples 1 and 2 was adopted, but as in Comparative Examples 1 and 2, the tensile strength, In addition to poor impact strength, the compatibilizer E-2 of Comparative Example 4 had poor extrudability and could not be drawn into strands.

Comparative Examples 5 and 6 are cases in which the compositions of nylon 4, 6 and polyester do not fall within the scope of the claims of the present invention, but in Comparative Example 5, the extrudability was poor and the strand could not be taken out. In Comparative Example 6, the water absorption rate and moisture absorption rate were too high, and there was a problem in dimensional stability during moisture absorption.

Comparative Examples 7 to 9 are cases in which the amounts of brominated polystyrene and antimony oxide are outside the scope of the claims of the present invention, but if the amount of brominated polystyrene is too large as in Comparative Example 7, extrudability If antimony oxide is not added at all as in Comparative Example 8, the molten resin will drop significantly during combustion, and the strands will not be able to be taken out.
A composition that passes the ■-0 or V-1 standard in the combustion test according to the 94 test method cannot be obtained, and if the amount of brominated polystyrene is too small as in Comparative Example 9, the flammability will be significantly poor.

Comparative Example 10 was a case in which the graft copolymer (E) as a compatibilizer component was not added, but the extrudability was poor and the strand could not be taken off.

Comparative Example 11 is a case where the amount of the graft copolymer (E) as a compatibilizer exceeds 20 parts by weight based on 100 parts by weight of the total amount of components (A) to (B). ，
6 or the polyester and the component (E), a significant decrease in tensile strength and Izot impact strength becomes inevitable.

(The following is a blank space) [Effect of the invention] The nylon 4.6 composition of the present invention has a thin-walled molded product with UL-
It has stable flame retardancy according to the standards of the 94 test method, and can particularly prevent melting and dripping during combustion.

It also has excellent heat resistance and mechanical properties, making it an excellent resin material for parts that require soldering at high temperatures, such as electrical and electronic parts such as connectors, switches, and bobbins.

Furthermore, in addition to excellent flame retardancy and mechanical strength, the nylon 4.6 composition of the present invention has excellent dimensional stability due to water absorption and moisture absorption.
It has the characteristic that there are few analytical changes.

Patent applicant: Japan Synthetic Rubber Co., Ltd. Agent: Patent Attorney Takashi Shirai

Claims (1)

[Claims] (1) (A) Polytetramethylene adipamide 20-90
(C) 10 to 80 parts by weight of halogenated polystyrene, (D
) 0.1 to 30 parts by weight of an antimony compound, and (E) an olefin copolymer containing an epoxy group as the main chain, a vinyl polymer as the side chain, and the ratio of the vinyl polymer as the side chain. 1 to 20 parts by weight of a graft copolymer having 20 to 60% by weight of a polytetramethylene adipamide composition.