JPS61268755A - Stabilized nylon composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition prevented from discoloration or strength degradation on heating, by blending a nylon with mono- or polyfunctional cyanic ester compound or its prepolymer. CONSTITUTION:The objective composition can be obtained by incorporating (A) a nylon or its blend with at least one material selected from thermoplastic resin, flame-retardant, reinforcer, etc. for the purpose of modification with (B) 0.1-10wt% of mono- or polyfunctional cyanic ester compound having at least one cyanate group or its prepolymer, pref. a compound of formula (m is 1-5; R2 is aromatic organic group, the cyanate group being connected to the aromatic ring of said organic group) (e.g., monocyanate benzene, p-t-butyl cyanate bengene). In case that ingredient(s) (compound(s) having OH, COOH, NH2, etc.) reactive with cyanate group is to be incorporated, it is preferable that premixing of cyanate with the compound(s) is avoided.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a stabilized nylon composition, which does not color nylon and prevents nylon coloring and strength deterioration due to heating. This invention relates to a stabilizer that is odorless and has excellent workability.

[Conventional technology and its problems]

Although nylon is widely used in industry, it has drawbacks such as being easily colored and significantly deteriorating in strength when heated. As a solution to this problem, 1.3.5-tris(3,5
-di-t-butyl-4-hydrobenzyl)benzene,
4.4-Butylidenebis(6-t-butyl-3-methylphenol), N,N'-hexamethylenebis(3
, 5-di-t-butyl-4-hydroxy-hydrocinnamide) and the like are known.

The present invention has discovered a completely new method for stabilizing nylon, which is different from these known methods.

[Means for solving problems]

As a result of various studies on the utilization of the unique properties of the cyanato group of compounds having a cyanato group (-0-CmiN), the present invention has revealed that by adding a compound having a cyanato group to nylons, thermal deterioration of nylon can be prevented. This was completed after discovering that the properties were significantly improved.

That is, the present invention provides nylon with (1) a monofunctional or polyfunctional cyanate ester compound containing one or more cyanato groups in the molecule, or (2) a prepolymer of the cyanate ester compound (hereinafter simply referred to as This is a stabilized nylon composition containing 0.1 to 10% by weight of cyanate.

The present invention will be explained below.

The nylon of the present invention includes ordinary 6-nylon, 6-row nylon, 6/10-nylon, 6/12-nylon, 1
2-Nylon, metaxylylenediamine-based nylon (
= MX polyamide), and these include other thermoplastic resins for modification, nucleating agents, flame retardants, ultraviolet absorbers, etc., as well as glass fibers, asbestos, rock wool, carbon fibers, and carbon fibers. Fibrous materials such as calcium, aluminum hydroxide, talc, mica, magnesium hydroxide, clay, antimony oxide, iron oxide, gypsum, copper, iron, cobalt, nickel, chromium, aluminum, titanium oxide, carbon blank, phthalocyanine blue, ultramarine blue, etc. , powder, or other reinforcing agents, fillers, pigments, etc. are added as appropriate.The amount added is the usual amount, which is about 5 to 70% in the case of inorganic fillers, and about 5% to 70% of pigments. In this case, 0.
It is used in an amount of about 0.01 to 5%.

Containing one or more cyanato groups in the molecule of the present invention (1)
Suitable monofunctional or polyfunctional cyanate esters include the following general formula (1): % formula % (1) (in the formula, m is an integer of 1 or more and usually 5 or less, and R2 is an aromatic is an organic group in which the cyanato group is bonded to an aromatic ring of the organic group. Specific examples include monocyanatobenzene, alkylcyanatobenzene such as P-tert-butylcyanatobenzene, monocyanatonaphthalene, 1.3-monocyanatobenzene, 1,4-dicyanatobenzene, 1.
3.5- Tricyanatobenzene, 1.3-. 1.4-
.

1.6-. 1.8-. 2.6- or 2,7-dicyanatonaphthalene, 1.3.6-) dicyanatonaphthalene,
4,4'-dicyanatobiphenyl, bis(4-dicyanatophenyl)methane, 2,2-bis(4-cyanatophenyl)propane, 2,2-bis(3,5-dichloro-4
-cyanatophenyl)propane, 2,2-bis(3,5
-dibromo-4-cyanatophenyl)propane, bis(
4-cyanatophenyl) ether, bis(4-cyanatophenyl) thioether, bis(4-cyanatophenyl) sulfone, tris(4-cyanatophenyl) phosphite, tris(4-cyanatophenyl) phosphate,
and cyanate esters obtained by the reaction of novolak with cyanogen halides. In addition to these, Tokuko Sho 41-1928, Sho 43-18468, Sho 44-
4791, 45-1) 712, 46-41) 12,
Cyanic acid esters described in JP-A No. 47-26853 and JP-A-51-63149 can also be used.

In addition, in the molecule obtained by polymerizing the above-mentioned polyfunctional cyanate ester in the presence of mineral acids, Lewis acids, salts such as sodium carbonate or lithium chloride, phosphate esters such as tributylphosphine, organic metal salts, etc. It can be used as a prepolymer having a cyanato group, and it can also be used as a prepolymer with an amine.

The blending amount of the cyanate of the present invention explained above with respect to nylon is not particularly limited, but from the viewpoint of effectiveness, it is 0.1 to 10
% by weight, and monomers are more effective because they have a larger number of functional groups (-0CN groups) per unit weight.

If the amount added is less than 0.1%, the stabilizing effect will be insufficient, and if it is used in excess of 10% by weight, it will show a remarkable effect in preventing deterioration, but other properties such as a decrease in the elongation of nylon will be affected. This is not preferable because it damages the Furthermore, as explained above, since the effect of the present invention is due to the cyanato group, additives that react with this functional group, such as -〇H1
-COOH1-N1) □, -COOM, -5H, etc. (It
, metal atoms), it is preferable to avoid mixing cyanate and these compounds in advance before adding them.

The method of mixing cyanate with nylon is not particularly limited as long as the cyanate is uniformly dispersed, and can be the usual method, mixing by blending or other means and making pellets with an extruder, or mixing with nylon as a solution. There are two methods: drying, mixing with a Nigu, Henschel mixer, etc. and using as is or extruding into pellets, and when containing inorganic fillers or pigments, mix the inorganic fillers etc. with cyanate in advance and mix this with nylon. Methods such as the extrusion method and the masterbatch method in which a highly concentrated masterbatch is manufactured and mixed are also suitable.
As for the mixing conditions, in the case of an extruder, the extrusion conditions for nylon can be used as they are. In other cases, it is sufficient to mix at room temperature or under heating, and the mixing time depends on the relationship with the temperature, but at a temperature of about 200 to 260°C, the effect of the present invention is sufficient even by mixing for about 2 to 3 hours. However, a method that causes less cyanate reaction is more preferred.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples. Note that parts in Examples and the like are based on weight unless otherwise specified.

Example-1 6,6-nylon (manufactured by Asahi Kasei ■, product name: Leona 120
0S) was added with 2,2-bis(4-cyanatophenyl)propane (hereinafter referred to as BPA-CN) in the amount shown in Table 1, and pelletized using an extruder at a temperature of 260°C.

This pellet was molded by injection molding to produce a transparent, milky-white flat plate measuring 50×50 fl and 1.5 mm thick.

This flat plate was placed in a gear oven at 150°C for a deterioration test.

The results are shown in Table 1.

Comparative Example-1 The same procedure as in Example-1 was carried out except that 2,2-bis(4-cyanatophenyl)propane was not used.

The test results are shown in Table 1.

Example-2 6-nylon (manufactured by Toshi ■, product name: Alamine CM101
7) was added with BPA-CN in the amount shown in Table 1, and pelletized using an extruder at a temperature of 245°C.

This pellet is molded by injection molding to a thickness of 3.
A flat plate of xm was created.

This flat plate was subjected to a weather resistance test (referred to as "after weathering") using a sunshine weather meter for 150 hours.

The results are shown in Table 2.

Comparative Example 2 The same procedure as Example 2 was carried out except that 2,2-bis(4-cyanatophenyl)propane was not used.

The test results are shown in Table 2.

Example-3 6/10-nylon (manufactured by Toshi ■, product name: Alamine CM
2O01) was added with BPA-CN in the amount shown in Table 2, and pelletized using an extruder at a temperature of 230°C.

This pellet is molded by injection molding to a thickness of 2.
A flat plate of fi was created.

Using this flat plate, a deterioration test was conducted for 150 hours in a gear oven at 150°C and a sunshine weather meter. The results are shown in Table 2.

Comparative Example 3 The same procedure as Example 3 was carried out except that 2,2-bis(4-cyanatophenyl)propane was not used.

The test results are shown in Table 2.

[Operation and effects of the invention]

As is clear from the above detailed description and examples, the composition of the present invention has excellent appearance of molded products under normal conditions,
Moreover, thermal deterioration and weather resistance deterioration are significantly improved, and it is found that the composition is extremely excellent in practical use.

Patent applicant Mitsubishi Gas Chemical Co., Ltd. Agent Patent attorney (9070) Sadafumi Kobori Procedural amendment band (voluntary) February 17, 1986

Claims (1)

[Claims] Nylon contains one or more cyanato groups in its molecule (
A stabilized nylon composition comprising 0.1 to 10% by weight of 1) a monofunctional or polyfunctional cyanate ester compound or (2) a prepolymer of the cyanate ester compound.