JPS605611B2 - Anti-deterioration agent for synthetic resins - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel anti-deterioration agent blended into synthetic resins.

Polyethylene: Many synthetic resins such as polyolefins such as polypropylene, polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymers, J-ethylene-vinyl acetate copolymers, polystyrene, polyesters, polyamides, acrylic resins, etc. are resistant to ultraviolet rays and heat. oxidation is promoted and
It has a practical drawback of deterioration and deterioration during use.

Conventionally, in order to remove light energy harmful to these synthetic resins, UV absorbers such as 2-hydroxybenzophenone derivatives, salicylic acid esters, benzotriazole derivatives, and antioxidants (hereinafter referred to as anti-deterioration agents, including UV absorbers) have been used. has been used. However, it cannot be said that the objective has been fully achieved yet, and an even better anti-deterioration agent has been desired. The present invention provides an excellent new anti-deterioration agent for this purpose.

That is, the present invention relates to the general formula: {wherein R and R2 are the same or different and are an alkyl group,
Alternatively, R, and R2 together form a 4- to 7-membered saturated alicyclic ring with the carbon atom to which they are bonded, X represents a hydrogen or oxygen atom, and Y,, Y2, Y3, and Y4
each represents an oxygen atom, a sulfur atom or an NH group.

} This is an anti-deterioration agent made of a piveridine derivative represented by the following formula.

All of these compounds are new substances and have been discovered to have superior properties as deterioration inhibitors compared to conventional compounds.

As mentioned above, the anti-deterioration agent of the present invention is a piverizine derivative (
These compounds do not absorb a lot of particularly harmful ultraviolet energy in light energy, but they act as radical stabilizers and prevent photo, thermal and oxidative deterioration of various synthetic resins. It has the effect of preventing

When used, it is desirable to select the most appropriate one from among these compounds depending on the properties of the final product, intended use, price, etc. The deterioration inhibitor of the present invention can be used in exactly the same way as conventional ones, and can be added to various synthetic resins in an amount of 0.01 to 2% by weight.
, preferably 0.1 to 1% by weight, can provide excellent anti-deterioration properties.

Depending on the type of synthetic resin, these deterioration inhibitors can be used alone or in combination in the form of powder or solution. It may also be used in combination with pigments and other additives, if necessary. The compound of the present invention is produced by the following procedure, for example.

2,2-dimethyl-616-disubstituted-4 made here
- Piverizinone can be derivatized into the following derivatives using conventional ketalization catalysts.

Paratoluenesulfonic acid is usually used as a ketalization catalyst. As an example, representative compounds of the present invention are illustrated below.

However, this is not necessarily the case. However, the compounds exemplified herein limit the present invention to 2,216D61-tetramethylpiveridine-4-spiro-3-(204'18,10'-
Tetraoxerspiro[5-5]undecane)-19-spiro-ee(2'', 2'', 2'', 6''-tetramethylpiveridine) (1}212,6,6-tetramethylpiveridine- 4-spiro 3'-(21418, 10'-tetrathioxerspiro[505]undecane)-9-spiro-ee (2'', 2'', 6'', 6'' tetramethylpiveridine) [212, 2, 6, 6-tetramethylpiveridine-4-spiro-3-(2,4,8,10'-tetraazherspiro[5-5]undecane)-9-spiro4''1 (2'', 2'', 6''・6″-tetramethylpiveridine)
[31 In addition, specific examples of the piveridine-N oxyl derivatives include the above-mentioned {11 to (1 and 1'' in the compound of 3')
Examples include things with a ○ atom in place of the number day.

Next, examples will be shown. Note that the numbers of the deterioration inhibitors below are the numbers of the compounds mentioned above. Example 1 Polyvinyl chloride (P=1300) 10 parts by weight Plasticizer (DOP) 50 Stabilizer (cadmium stearate) 0.5 (Barium stearate) 0.5 Anti-degradation agent
A test sheet having a thickness of 0.1 rib was prepared by uniformly mixing the various blends and rolling for 5 minutes using two rolls with a diameter of about 20 mm heated to about 160 to 170 oo.

This was exposed using a weather-o-meter, and the time until abnormalities such as spots were observed on the film surface was measured. The test results are shown in Table 1. Here, deterioration inhibitors for comparison are expressed by alphabetical symbols, and new deterioration inhibitors are expressed by the previously mentioned sample numbers. Table 1 As shown above, it is clear that the pibe IJ gin derivative of the present invention is effective in preventing the deterioration of softened polyvinyl chloride.

Example 2 Powdered polypropylene resin (without stabilizer) 1
0.3 parts by weight of each of the anti-deterioration agent of the present invention and the anti-deterioration agent for comparison were added and thoroughly mixed and homogenized.

Among these deterioration inhibitors, those that do not easily turn into powder or base
A predetermined amount of the straight or liquid material is dissolved in acetone in advance, and this acetone solution is mixed with the resin, and the acetone is evaporated in a fat store. Using a small injection molding machine, these were made into 5 x 7 x 1 side test pieces.

Further, this test piece was placed between two hard chrome plated head plates together with a thickness adjusting plate having a thickness of 0.5 ribs, and was heated to about 180°C while applying pressure for 20 minutes. The test piece is cooled while still being pressurized, and when the temperature reaches 60 to 5yo, the pressure is removed and the test piece is taken out. The obtained molded sheet is attached to the drum of an ultraviolet exposure tester having a 300 W ultraviolet light emitting lamp and a rotating drum for holding a sample.

The drum holding the samples rotates around the lamp so that the ultraviolet light hits each sample evenly. The sample was inspected at regular intervals, bent 1800 times, and the time at which the sample broke was determined.

Next, the test results are shown in Table 2.

Table 2 As described above, the anti-deterioration agent of the present invention exhibits superior effects in preventing deterioration compared to the comparative products.

Example 3 Polypropylene (Mitsui Toatsu Chemical Noprene JHH-G
, trade name, recrystallized twice from monochlorobenzene) 10
0.25 part of the anti-deterioration agent of the present invention is added to the anchor part, melt-mixed, and heated and pressed into a sheet having a thickness of 0.5 mm.

This was irradiated with ultraviolet rays at 45q0 in a fade meter and the time until it became vertical was measured.

The results are shown in Table 3.

Example 4 0.25 part of the deterioration inhibitor of the present invention was added to 100 parts of high-density polyethylene (Mitsui Toatsu Chemical's Hyzex, trade name, recrystallized twice from toluene) and melt-mixed to give a 0.5 side thickness. Heat and pressure mold it into a sheet.

This was irradiated with ultraviolet light at 4500 in a fade meter,
The time it took to form arms was measured. The results are shown in Table 3.

Table 3 Example 5 10 parts of polystyrene (manufactured by Asahi Dow, Styron, trade name, used after recrystallizing from benzene-methanol) was added with 0.25 part of the deterioration inhibitor of the present invention, and 180 parts of polystyrene was added.
Pressure mold it into a plate with a thickness of one skin.

After irradiating this plate with ultraviolet rays at 45:00 for 500 hours in a fade meter, the test piece was tested using the method of JISK7103. It was measured by the transmission method using a color difference meter, and the degree of yellowing was determined by the following formula. △YI Y1-YL where △YI: Yellowing degree YI: Yellowing degree after exposure Y1o: The initial yellowing degree results of the test piece are shown in Table 4.

Table 4 Example 6 6-Nylon resin (manufactured by Toray Industries, CMIOI1, trade name) 1
0.25 part of the deterioration inhibitor of the present invention is added to 0.00 parts, and after heating and melting, the mixture is molded into a film having a thickness of about 0.1 mm using a pressure molding machine.

After abusing this film under the following abuse conditions,
A tensile test was conducted to measure elongation and tensile strength retention.

Abuse conditions ■ Irradiation with ultraviolet rays for 20 feeding hours at 45 oo in a food meter ■ Heat abuse at 160° C. for 2 hours using Mr. Garr's heat aging tester The results are shown in Table 5.

Table 5 Example 7 Polyester resin (Ester G-13 trade name, manufactured by Mitsui Toatsu Chemical Co., Ltd.) 10 parts of polyester resin, 1 part of penzoyl peroxide and 0.2 part of the deterioration inhibitor of the present invention were dissolved and mixed, and the mixture was dissolved and mixed with 60 CO.
After heating the powder, heat it at 100qC for 1 hour to harden it and form it into a plate with a thickness of 3 ribs.

After this plate was irradiated for 6 hours using a Sungeine Weathermeter, the degree of yellowing was examined in the same manner as in Example 5. The results are shown in Table 6.

Table 6 Reference example 1 212,6,6-tetramethylpiveridine-4-spiro-3'-(2',4',8,10'-tetraoxerspiro[5,5]undecane)-9-spiro 4″1 (2
p-toluenesulfonate of triacetonamine 81.5, pentaerythritol 27.2, p-toluenesulfonic acid 1. Add 500 g of toluene and heat to reflux for 3 hours while removing generated water.

After wrapping, 30% aqueous sodium hydroxide solution was added to separate the layers, the toluene layer was taken, washed with water, dried and concentrated under reduced pressure, and the remaining crystals were recrystallized from petroleum benzene, melting point 136.5-137.
The desired product is obtained as a white crystal with q0. Analysis value as C23rd 42N204

Claims (1)

[Claims] 1 General formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ {In the formula, R_1 and R_2 are the same or different and are an alkyl group, or R_1 and R_2 are combined and they are bonded. Forms a 4- to 7-membered saturated alicyclic compound together with carbon atoms, X represents hydrogen or oxygen atom, Y_1, Y_2,
Y_3 and Y_4 are each an oxygen atom, a sulfur atom, or N
Represents any H group. } A deterioration inhibitor consisting of a piperidine derivative represented by.