JPS6015456A - Polyether ester amide composition - Google Patents

Abstract

PURPOSE:To improve resistance to heat and weather, by blending a specified arom. amine compd. and a hindered amine light stabilizer with a polyether ester amide. CONSTITUTION:0.05-5pts.wt. arom. amine compd. (A) of formula I , II, III or IV(wherein R1, R1' are each H, a 1-18C hydrocarbon group, etc.; R2 is a 1- 12C alkyl) such as phenyl-alpha-naphthylamine and 0.05-5pts.wt. hindered amine light stabilizer (B) of formula V (wherein R3 is H, a 1-12C alkyl; R4, R4' are each a 1-6C alkyl; X is -O-, -NH-; R5 is a 1-23C hydrocarbon group, etc.; lis 1-4) such as 4-benzoyloxy-2,2,6,6-tetramethylpiperidine are blended with 100pts.wt. polyether ester amide (C) to obtain the desired polyether ester amide compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyether ester amide resin composition having ambiguous properties in heat resistance and weather resistance.

Polyetheresteramide, which has polyamide repeating units, polyneedle repeating units, and ether linkages in the polymer main chain, is well-known in the field of elastomers because it has excellent impact resistance and rubber elasticity, similar to polyetherester or polyesteramide. In recent years, it has attracted attention as a new material.

In particular, polyether ester amide is excellent in lightness, transparency, and low-temperature impact resistance, and is less likely to produce flakes or whiskers during molding, so it is promising for various molding applications. However, polyetheresteramides are extremely susceptible to oxidative deterioration (a decrease in the degree of polymerization), resulting in undesirable phenomena such as a decrease in mechanical properties, surface cracking, and discoloration.

In particular, this oxidative deterioration is accelerated by heat, light, etc., and its use is restricted when exposed outdoors or in a high-temperature atmosphere. Therefore, is the purpose of tefolyether ester amide to prevent these deterioration phenomena? The addition of various stabilizers is being considered. However, there is little knowledge regarding the stabilization of polyether ester amide, and there has been no satisfactory method of stabilizing the polyether ester amide. In view of these points, the inventors of the present invention have conducted extensive studies and found that a specific group of compounds can be added as stabilizers to polyether ester amide, thereby achieving heat resistance that could not be obtained conventionally. It has been discovered that a polyether ester amide resin composition having extremely excellent properties and weather resistance can be obtained, and the present invention has been achieved.

That is, the present invention provides polyether ester amide (A)
, 100 parts by weight, the following general formulas (B), (C),
(D) Or (0.05 to 5 N parts of an aromatic amine compound represented by Q and 0.05 to 5 parts of a hindered amine light stabilizer represented by the following general formula (g)) This relates to a polyether ester amide composition.

(Tatashi, R+, R+' ha hydrogen atom, carbon a1-
18 U) Either a hydrocarbon group or a C1-C18 hydrocarbon group having a 10-bond, and each may be the same or different. R2 has 1 to 1 carbon atoms
2 shows an alkyl group. ) (However, R3 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R4 is a straight chain or branched alkyl group having 1 to 6 carbon atoms, and R4+ is the same alkyl group as R4, respectively. May be the same or different.X
is -O- or -N-, and R5 represents a hydrocarbon group having 1 to 26 carbon atoms or a -8-1 1 hydrocarbon group, which may be substituted with a hydroxyl group. β is an integer from 1 to 4. ) Three specific compositions of the present invention will be described below.

Kinoi IJI tkoreru polyether ester amide (
A) is a polymer composed of polyamide units and polyether ester amide, and has an amide bond, an ether bond, and an ether bond in the molecular chain.

The polyamide units are derived from aminocarboxylic acids, lactams, salts of dicarboxylic acids and diamines, or combinations of dicarboxylic acids and diisocyanates.

The polyether ester unit has a number average molecular weight of 600 to 60
00 poly(alkylene oxide) glycol and a dicarboxylic acid having 4 to 20 carbon atoms. The copolymerization ratio of polyamide units and polyetherester units is approximately 5:90 to 95:10 in terms of M ratio.

The method for polymerizing polyether ester amide (A) is not particularly limited, and known methods can be used.

For example, a polyamide prepolymer having carboxylic acid groups at both ends is prepared by reacting aminocarboxylic acid, lactam or dicarboxylic acid-diamine salt (a) with dicarboxylic acid (C) in an approximately equimolar ratio, and then poly(alkylene) Oxide) Glyco-1v (b) A method of reacting under full vacuum, or a method in which the compounds of (a), (b), and (C) above are charged into the reaction phase and then reacted at high temperature in the presence or absence of water. A method is known in which a carboxylic acid-terminated polyamide prepolymer is produced by a pressurized reaction, and then polymerization is proceeded under normal pressure or reduced pressure. In addition, the above (a), (
There is also a method in which the compounds 1)) and (c) are simultaneously charged into a reaction tank, melt-mixed, and then polymerized all at once under high vacuum; this method is preferable because it causes less coloring of the polymer.

Mata, poly(alkylene oxide) glycol 2
A solution polymerization method may also be used in which twice the molar amount of dicarboxylic acid is reacted to form a prepolymer having carboxylic acid groups at both ends, and this is reacted with dicarboxylic acid and diisocyanate in an inert solvent.

The aromatic amine compound, which is another component constituting the composition of the present invention, is represented by the general formula (B), (C), (b) or (E).

Examples of compounds represented by general formula (B) include phenyl-
Examples include α-naphthylamine and phenyl-β-naphthylamine.

Examples of compounds represented by general formula (C) include N, N'
-diphenyl-p-phenydiamine, N,N'-
β-naptyl p-phenylene diamine, N+N'
-bis(1-methyl/l/)-p-phenylenediamine, N,N'-bis(1-ethyl-6-methylheptyl)-p-phenylenediamine, N,N'-hy.

(1-ethyl)v-5-methylpentyl)-p-phenylenediamine, N,N'-bis(114-dimethylpentyl)v)-p-phenylenediamine, N-cyclohexyl-N'-phenylenetLy -p-phenylenediamine, N-offf)V -N'-phenyl-p-phenylenediamine, p-isopropoquine diphenylamine, N
, N'-diisoprohy)Lt-p-phenylenediamine, dioctylIV-p-phenylenediamine, and the like. Among these, N,N'-di-β-naphthyl-p-phenylenediamine is particularly preferred. General formula (I))
Examples of compounds represented by 414'-bis(4-
α, α-dimethylbenzyldiphenylamine), p,
Examples include p'-dioctyldiphenylamine, p,p'-dimethquine diphenylleamine, and the like. Among these, 414'-bis(4-α-dimethylbenzyldiphenyleamine) is particularly preferred. Examples of compounds represented by the general formula (support) include N,N'-diphenylethylenediamine, N,N'-diphenylhexamethylenediamine, di-p-tolylethylenediamine, di-p-)/
Examples include railhexamethylene diamine. Among them, N,N'-diphenylethylenediamine is preferred. Among these aromatic amine compounds, especially 4,4
Preference is given to using '-bis(4-α,α-dimethylbenzyldiphenylamine).

Further, the hindered amine light stabilizer, which is another component constituting the composition of the present invention, is represented by the general formula (FJ). Examples of compounds represented by the general formula [F] include 4-benzene. Zoyloxy-2.2.6.6-titramethylpiperidine, bis-(2,216,/>-tetramethyl-4
- Piperish 2. ) adipate, bu (2I2shiro, 6
-titramethy/l/ -4-piperidinyl) suberate, bis(2T2.6,6-titramethyl-4-piperidinyl) sebacate, bis(212I6?6-tetramethyl-4-piperidinyl)V) phthalate 1bi2('21
21616-thitramethyl-4-piperidini/L/) isotucrate, bis(2,2,6,6-titramethyl-
4-piperidinyl) terephthalate, bis(1+2+
2+6+6-pen1llfiv-4-piperidini)v
) sebacate, N, N'-bis(2,2゜616-tetramethyl--piperidinyl)adipamide, bis(1
r 2 + 2 + 6 + 6-hen l'/f
)L' 4-Piperidinyl)-n-butyl(3,5-di6th-butyl)v-4-hydroxybenzyl)malonate, bis(1,2,2,6,6-pentamethifle 4-piperi Cynyl dibenyl) malonate, bis(1,2,2
, 6゜6-pencumethyl/I/-4hyperidini)V) diethylmalonate, bis(2,2,6+6-titramethyl-4-piperidini)dibenzylmalonate, his(2+2++S+6-teI・lamethyl)/ l/-4-piperidi=)v) Benzylethylmalonate, bis(2ν2
,6.6-titramethyl-4-piperidini)v) −
n-butyl (3,5-cy-6-butyl-4-hydroxypencyl) Maloney 1-, butanetetracarboxylic acid tetra(2゜2.6.6-tetramethy)v-4-piperidini/l/) Nisdel, etc. Among them, special examples include tetra(2,2,6,6-tetramethyl-)sebacate and butanetetracarboxylic acid. 4-piperidini/di) esters may be mentioned as preferred compounds.

Each of these stabilizers consists of polyether ester amide (A)
They are used in a proportion of 0.05 to 5 parts by weight, preferably 2 parts by weight per 100 parts by weight. If the amount of each stabilizer added is less than this, the effect will not be sufficiently expressed, and if the amount added is more than this, the physical properties of the composition will be adversely affected, and undesirable phenomena such as pluming may occur. eKonaru.

Nao, the polyether ester amide (A) of the present invention is subjected to both oxidative deterioration and photo-staining deterioration.
), the general formula (B), (C), ■) or (
It is necessary to add both the aromatic group amine compound represented by E) and the hindered amine light stabilizer represented by the general formula (F), and if either of these is missing, However, compared to the composition of the present invention, only a composition can be obtained that has greater (inferior) heat resistance and/or weather resistance.

Furthermore, the method of adding each of these stabilizers to the polyether ester amide is not particularly limited, and the stabilizer can be added at any time after the polymerization during the polymerization of the polyether ester amide. A particularly preferred embodiment is a method of melt-mixing after polymerization (before molding).

In addition, when preparing the composition of the present invention, as long as it does not impede the desired heat resistance and weather resistance stability. In this case, other common additives such as hydrolysis resistance improvers, colorants (pigments, dyes), antistatic agents, conductive agents, crystal nucleating agents, lubricants, fillers, reinforcing agents, adhesion aids, Additives such as plasticizers, mold release agents, and flame retardants can be optionally added.

The present invention will be explained below with reference to Examples.

In addition, what is indicated by "part" or "chi" in the examples,
All are expressed as a ratio of 1 to 1.

In addition, the relative viscosities shown in the text and in Examples 9 are values measured in orthochlorophenol at 25°C and 0.5% Iff conditions, and the melting points are also specific. D unless you say otherwise
SC (Perkin Elmer DsC-IB)
7) tit M peak temperature.

Reference Example Polymerization of Polymer (A-1) 65.5 parts of aminododecanoic acid, 66.6 parts of polytetramethylene oxide glycol having a number average molecular weight of 680, and 8.2 parts of terephthalene were added to 1 Irganox' 109
8 (0.20 part of anti-cellulose) and 0.05 part of tetragutyl thichnate catalyst were charged into a reaction vessel equipped with a helical ribbon stirring blade, and purged with N2 to 240
Heat at 40°C for 40 minutes, stir to obtain a nearly transparent homogeneous liquid, and then heat to 270°C according to the depressurization program.
C, 0.5 parts m Hg or less. The polymerization reaction was carried out under these conditions for 6 hours and 50 minutes.

The melting point of the obtained polyether ester amide (A-1) was 166°C, and the relative viscosity was 1.65.

Polymer (A-2) 1145.6 parts of 11-part aminododecane, number average molecular weight 10
00 polytetramethylene oxide glycol s'5.
Using 1 part and 8.8 parts of terefucuric acid as starting materials, a polymerization reaction was carried out in the same manner as in Example 1 for 4 hours and 60 minutes to give 144 parts of polymer (A-2).

The obtained polyetheresteramide (A-2) had a melting point of 142'C and a relative viscosity of 1.79.

The structures and abbreviations of the stabilizers used in the stabilizer examples are as follows.

Polyether ester amide (A-1) and (A'-
2) After blending each stabilizer shown in Table 1, (A-1
200℃ for ')σ), 180℃ for (A-2)
The mixture was melted and blended in a 33 mmφ extruder heated to 33 mm, and then pelletized. After vacuum drying this pellet, if the polyether ester amide is (A-1), dry at 200°C.
, 1 when the polyether ester amide is (A-2)
Pressure was applied at 80°C to form a pressure plate with a thickness of 0.9 to 1.11, and a No. 6 dumbbell-shaped test piece according to JISK-6501 was prepared.
I punched this out.

Heat resistance was determined by aging the test piece in a hot air oven at 160°C, and the time required for the elongation at break to retain 50% was determined by 1l.
ij thermal life. Weather resistance was examined by irradiating the test piece with light in Sunshine Weather Makeup. 1 rack panel of Sunshine Weather-O-Meter (1.4 degrees is 66 degrees Celsius)
After 2 hours of hard work, I soaked it in water for 18 minutes. Weather resistance was evaluated by measuring the time at which the elongation retention rate reached 50 inches and the time at which cracks appeared on the irradiated surface. The elongation at break was measured in accordance with JIS K, 6301e. These results are shown in Table 1.

Table 1 Comparative Example Polyetheresteramide (A-1) or 1 is (A
-2) After blending either an aromatic amine compound (u-1) or a hindered amine light stabilizer (L), the mixture was pelletized in the same manner as in Example 1 above. Ko:c
P) Composition, Polymer (A-1) and Eye ε Limer
(A-2) was strained and punched into test pieces in the same manner as in the above example, and the heat resistance and four-weather properties of each test piece were evaluated. Table 2 shows the results.

(Blank below this page)

Claims (1)

[Claims] Polyether ester amide (A) 100 parts by weight t
On the other hand, the following general formulas (B), (C), (D) or (
A polyether obtained by adding 0.05 to 5 parts by weight of an aromatic amine compound represented by E) and 0.05 to 5 parts by weight of a hindered amine light stabilizer represented by the following general formula Esteramide composition. (However, R1 and R1' are hydrogen atoms and have 1 to 18 carbon atoms.)
1 to 1 carbon atoms having a hydrocarbon group or 10-bond
8 hydrocarbon groups, and each may be the same or different. R2 represents an alkyl group having 1 to 12 carbon atoms. ) (However, R3 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R4 is a straight chain or branched alkyl group having 1 to 6 carbon atoms, which may be the same or different. . It is an integer.)