JPS5813576B2 - Stabilized synthetic polymer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to stabilized synthetic polymeric compositions that are resistant to decomposition by heat, light, oxygen, and heavy metals.

Synthetic polymers such as synthetic resins and rubber decompose and deteriorate when supplied with heat, light, oxygen, and other external energy sources.

At this time, if heavy metals such as Mn, Co1CusFe, and Pb are present in the decomposition and deterioration reaction system in the form of ions or complex compounds, they participate in the reaction and have a catalytic action that significantly accelerates the reaction.

However, useful synthetic polymers such as synthetic resin rubber are often unintentionally mixed with heavy metals or used in contact with heavy metals.

In order to prevent these toxic effects, various improvements have been made by coexisting additives such as antioxidants and light stabilizers with synthetic polymers, but this is still insufficient and in extreme cases, the effects may not be effective at all. may be lost.

For example, among poly-α-olefins, polypropylene resin has been increasingly used in recent years due to its properties, and oxidative deterioration can be prevented to a large extent by combining various antioxidants. When used in materials, electrical insulators, printed wiring, etc., it deteriorates in a few months, reducing its mechanical strength and rendering it unusable.

In addition, plating on plastics has been increasing more and more in recent years, but for example, when copper plating is applied to polypropylene,
The first layer is chemically plated with nickel, and then copper is plated on top.

That is, the first layer is plated with chemical nickel to prevent deterioration due to contact between the polypropylene and the copper.

Furthermore, when coloring agents, especially pigments containing heavy metals such as phthalocyanine blue, are used to color polypropylene etc., there is a phenomenon in which the deterioration of the plastic is accelerated by the heavy metals, so there are restrictions on the use of colorants. There is.

Various efforts have been made to neutralize these toxic effects.

For example, Japanese Patent No. 405139, Japanese Patent No. 4613
No. 69, No. 461558, No. 482222, No. 482223, No. 421211, No. 4920
There are inventions of No. 05 and No. 505061.

However, these inventions are also insufficient to give satisfactory results.

It is also known that synthetic resins such as polyvinyl chloride and ethylene-vinyl acetate generally need to be stabilized by adding a stabilizer when they are used.

This tendency is particularly remarkable when used under harsh conditions such as exposure to heat, air, light, etc.

Similarly, when using acrylonitrile-butadiene-styrene resin, it is known that it is necessary to stabilize it by adding a stabilizer. This is a major obstacle in practical use because the impact strength, which is a characteristic of

In order to eliminate such drawbacks, it is necessary to add one or more types of thermal stability to the synthetic resin to suppress deterioration during processing steps.

Many metal soaps have been used for this purpose.

However, the thermal stability is still insufficient, and satisfactory results that can withstand practical use have not been obtained.

An object of the present invention is to provide a synthetic polymer composition that has an even better effect of preventing thermal oxidative deterioration than conventional inventions, and thereby to further develop and expand the uses of conventional synthetic polymers. be.

As a result of long-term research, the present inventors found that when a new compound not yet described in the literature was dissolved or uniformly dispersed in a large amount of synthetic polymers, thermal oxidative deterioration of the main component synthetic polymers and heavy metal It has been found that it is significantly resistant to the accelerated deterioration effects caused by the presence of.

That is, the present invention relates to a novel synthetic polymer composition containing at least one compound represented by the following general formula [I] in the synthetic polymer.

[In the formula, R1 represents a hydrogen atom, an alkyl group, or the formula:

R4 represents a polyvalent amine residue, R5 and R5' represent a hydrogen atom, an alkyl group, or a hydroxyalkyl group;
and RQ may be bonded to each other to form a ring.

R6 is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group, an alkylaryl group,
Represents a glycol, cellosolve or carbitol residue.

R7 and R8 represent a hydrogen atom, an alkyl group, an aryl group, a cycloalkyl group, an arylalkyl group, an alkylaryl group, a hydroxyalkyl group, or an alkoxyalkyl group, and R7 and R8 may be bonded to each other to form a ring. be.

Incidentally, each group may have a substituent, and when the same symbols are present in the molecule, they may be the same or may be different.

] Here, the formulas include, for example, ethylenediamine, 1,3-diaminopropane, 1,2-diaminopropane, monomethylaminopropylamine, 1,4-diaminobutane, iminobispropylamine, methyliminobispropylamine, Aminopropylethanolamine, aminoethylethanolamine, bisaminopropyl ether, hexamethylenediamine, diethylenetriamine, 1,3-diamino-
2-propanol, bisaminomethylcyclohexane,
Residues of aliphatic or alicyclic polyvalent amines such as triethylenetetramine, or phenylenediamine, xylenediamine, xylylenediamine, N-methylxylylenediamine, 2,6-diaminopyridine, 4,5-diaminouracil , piperazine, imidazolidine, N-aminoethyl-piperazine, and other aromatic or heterocyclic polyvalent amine residues.

Examples of the alkyl group represented by R6 in the present invention include methyl, ethyl, probyl, isopropyl, butyl,
Isobutyl, sec-butyl, tertiary-butyl, amyl, neopentyl, isoamyl, hexyl, isohexyl, hebutyl, isoheptyl, octyl, in-octyl, 2-ethylhexyl, decyl, isodecyl, lauryl, tridecyl, C12-15 mixed alkyl, stearyl, tetrahydride Examples include full mouth frills.

Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, 4-methylcyclohexyl, cyclodecyl, and the like.

Examples of arylalkyl groups include benzyl, methylbenzyl, β-phenylethyl, γ-phenylpropyl, β
-Phenylpropyl, etc.

Examples of alkylaryl groups include methylphenyl, nonylphenyl, dimethylphenyl, and tertiary butylphenyl.

Examples of glycol residues include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol, neopentyl glycol, diethylene glycol, triethylene. Examples include residues such as glycol and diglopylene glycol, and monoester residues of these glycols.

Examples of cellosolve residues include methyl, ethyl, inglovir, butyl, isobutyl, cyclohexyl, phenyl cellosolve, and the like.

Examples of carbitol residues include methyl, ethyl, isopropyl, butyl, isobutyl carbitol, and the like.

Examples of groups represented by R7 and R8 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, octyl, 2-ethylhexyl, phenyl,
Cyclohexyl, furfuryl, benzyl, methylphenyl, 2-hydroxyethyl, 2-hydroxyglopyl,
3-hydroxypropyl, 2-hydroxy-1-ethylethyl, 2-hydroxy-1,1-dimethylethyl, 2
-hydroxy-1,1-bishydroxymethylethyl,
Hydroxyethylaminoethyl, methylaminopropyl, dimethylaminopropyl, diethylaminepropyl,
Dibutylaminoglopyl, diethylaminoethyl, dimethylaminoethyl, 3-methoxyglopyl, 3-ethoxyglopyl, 3-propoxypropyl, 3-impropoxypropyl, 3-butoxypropyl, 3-isobutoxypropyl, etc.

Further, examples of cyclic amines include pyrrolidine, piperidine, morpholine, 2-pipecoline, and 3,5-lupetidine.

Each compound represented by the general formula CI) according to the present invention is used in an amount of 0.00 parts by weight per 100 parts by weight of the synthetic polymer. ooi~1
0 parts by weight, preferably 0.01 to 1.5 parts by weight can be used depending on the purpose.

The synthetic polymers stabilized against thermal oxidative degradation in the present invention include a variety of synthetic polymeric materials.

To be more specific, examples of synthetic polymer materials include polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, polyvinylidene fluoride, chlorinated polyethylene, chlorinated polypropylene, brominated Polyethylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl-styrene chloride copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer Polymer, vinyl styrene chloride-maleic anhydride terpolymer, vinyl styrene chloride-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer Polymers, vinyl chloride-vinylidene chloride-vinyl acetate terpolymers, vinyl chloride-acrylic ester copolymers, vinyl chloride-maleic ester copolymers, vinyl chloride-methacrylic ester copolymers, . Vinyl chloride-acrylonitrile copolymers, halogen-containing synthetic resins such as internally plasticized polyvinyl chloride, α-olefin polymers such as polyethylene, polypropylene, polybutene, and poly-3-methylbutene, or ethylene-vinyl acetate copolymers, ethylene-vinyl acetate copolymers, etc. Polyolefins such as propylene copolymers and their copolymers, polystyrene, polyvinyl acetate, acrylic resins, copolymers of styrene with other monomers (e.g. maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile she-butadiene -Styrene copolymer, acrylic acid ester-butadiene-styrene copolymer, methacrylic acid ester-butadiene-styrene copolymer, or blends of these resins, block copolymers, graft copolymers, polyoxyphenylene , polyoxymethylene polymer, polyethylene oxide, polypropylene oxide polymer, shrimp chlorohydrin polymer, shrimp chlorohydrin-ethylene oxide copolymer, epoxy resin, polyester resin,
and polyvinyl butyral resin.

Furthermore, organic materials intended for coatings such as lacquers may be mentioned.

In the present invention, phthalate plasticizers, other ester plasticizers, polyester plasticizers, phosphate ester plasticizers, epoxy plasticizers, chlorine plasticizers, and other plasticizers are used depending on the application. Various plasticizers such as those disclosed in JP-A-49-57052 can be used as specific examples.

Adding an antioxidant to the composition of the present invention increases the oxidative deterioration prevention properties of the present invention, so it can be used as appropriate depending on the purpose of use.

These antioxidants include phenolic antioxidants, phosphite antioxidants, amine antioxidants, sulfur-containing compounds, etc. Specific examples include JP-A No. 49-78
Various antioxidants such as those disclosed in Japanese Patent No. 692 can be used.

By adding an ultraviolet absorber to the composition of the present invention,
Since they can improve photostability, they can be appropriately selected and used depending on the purpose of use.

These include penzophenone series, penzotriazole series, oxilate series, substituted acrylonitrile series, various metal salts or metal chelates, especially nickel or chromium salts or chelates, triazine series, piperidine series, etc. It is disclosed in Japanese Patent Publication No. 49-78692.

In general, when metal soaps are used as stabilizers for halogen-containing synthetic resins, some are often used alone, such as organotin stabilizers and lead soaps, but cadmium barium, zinc, calcium, magnesium Metal soaps such as strontium, potassium, and sodium are often used in combination of two or more of these.

For example, Cd-Ba, Ca-Ba, Cd-Zn, Ba-
Zn, Ca-Zn, Ca-Mg, Ca-Mg-Z
n, Cd-Na-organotin, Cd-Ba-Pb, Ca-
Many combinations such as Sr, Zn-K, and Zn-Na are adopted depending on the purpose of use.

Other additives as necessary, such as epoxy stabilizers, organic chelators, pigments, fillers, foaming agents, antistatic agents, antifogging agents, plate-out inhibitors, surface treatment agents, other lubricants, antioxidants, and flame retardants. , light stabilizers, ultraviolet absorbers, fluorescent agents, antifungal agents, bactericidal agents, metal deactivators, photodegradants, nonmetallic stabilizers, epoxy resins, boric acid esters, thiourea derivatives,
Processing aids, mold release agents, etc. can be included.

Examples of average specific formulas of compounds represented by the general formula according to the present invention include the compounds shown in Table 1 below.

Next, a simple method for producing the compound shown in Table 1 is as shown in the synthesis example described below.

These manufacturing methods are merely examples, and manufacturing is also possible by methods other than those described below, but the present invention is not limited to these manufacturing methods in any way.

Synthesis Example 1 (Synthesis of No. 3) 2 moles of nitrilotriacetic acid tri-n-butyl ester and 1 mole of monomethylaminopropylamine, and 0.0% acetic acid as a catalyst.
1% by weight was added and reacted at 120°C for 4 hours.

Next, 4.2 mol of n-butylamine was added and the reaction was carried out for 5 hours at the amine boiling point.

After sufficient dealcoholization and deamination under reduced pressure, recrystallization was performed from a toluene-ether mixed solvent to give a melting point of 133-
A white powder at 135°C was obtained.

The progress of the reaction and confirmation of the product were performed using infrared absorption spectroscopy, etc.

Synthesis Example 2 (Synthesis of No. 6) 2 moles of tri-n-butyl nitrilotripropionic acid, 4 moles of octylamine, and 0.0% zinc acetate as a catalyst.
3% by weight was added and the reaction was carried out at 130°C for 3 hours.

After that, 1.3 mol of ethylenediamine was added and the temperature was heated to 130°C.
The reaction was carried out for 5 hours.

After the reaction was completed, unreacted raw materials and produced alcohol were removed under reduced pressure at 130° C., and white crystals were obtained by washing with cold ethanol.

Melting point 150-151°C Synthesis Example 3 (Synthesis of A11) Nitrilotripropionic acid trisethylene glycol ester 2 mol K n -7” thylamine 2.1 mol and 1,2-diaminopropane 2.1 mol, para-toluenesulfonic acid 0 .1% by weight was added and the reaction was carried out at 130°C for 6 hours.

After the reaction was completed, the unreacted raw material alcohol was removed under reduced pressure to obtain a yellow viscous liquid.

Synthesis Example 4 (Synthesis of Compound A25) Weigh out 1 mole of ethylenediamine and 2 moles of iminodipropionic acid diethyl ester, and add 0.1% by weight as a catalyst.
of acetic acid was added and the reaction was carried out at 90°C for 3 hours.

Next, 2.4 moles of glopanolamine? Then, the reaction was carried out at 100° C. for 5 hours, unreacted amine and produced alcohol were removed under reduced pressure, and the mixture was recrystallized in an ether-butyl acetate mixed solvent to obtain white powder crystals.

Melting point 138-139.5℃ Next, examples of the present invention will be shown.

All parts below are by weight.

Example 1 In order to examine the excellent stabilizing effect of the compound according to the present invention, samples were prepared by calender processing and heat press processing according to the following formulation, and the heat stability and heat press tests were performed using a heat aging tester at 175°C. Transparency and initial coloring properties due to processing, as well as plate-out properties were measured.

The results are shown in Table 2. Regarding the initial coloring, no.
The degree of yellowness was determined by the following formula using an internal colorimeter and compared.

The transparency is also divided into six levels from 1 to 6, with 1 indicating almost transparent and 6 indicating almost opaque.

Furthermore, the plate-out value (POV) was defined as the value expressed in ppm of the dye plated out in a test using the watching red method.

Example 2 Zn-C of the compound according to the present invention on vinyl chloride resin
In order to examine the effect with soap, samples were prepared using the following formulation and the same procedure as in Example 1, and tests were conducted on thermal stability, initial coloration, and transparency.

The results are shown in Table 3.

Example 3 In order to further examine the effect of the compound according to the present invention on vinyl chloride resin with an organotin compound, a sample was prepared using the same procedure as in Example 1 with the following formulation, and the thermal stability, initial coloration, and transparency were evaluated. A test was conducted.

The results are shown in Table 4.

Example 4 In order to examine the effect of the compound according to the present invention on a polyvinyl chloride-ABS resin (acrylonitrile-butadiene-styrene terpolymer) blend, samples were prepared using the same procedure as in Example 1 with the following formulation. A sample was prepared and tested for thermal stability, initial coloration, and transparency.

゛The results are shown in Table 5. Example 5 In order to examine the stabilizing effect of the compound according to the present invention on acrylonitrile-butadiene-styrene copolymer (ABS resin), a compound of 2 m thickness was prepared using a kneading roll using the following formulation.
A sample of m was prepared and heated at 210°C, 50k9/crA, 10
The color of the material was measured after minutes.

The results are shown in Table 6.

Note that the deterioration of ABS resin due to heat is accompanied by a change in color tone from white to light yellow, yellow, deep yellow, and brown in this order, regardless of the presence or absence of a stabilizer.

In this example, this was divided into 10 levels and compared.

That is, 1 represents white and 10 represents brown.

Example 6 In order to examine the effect of the compound according to the present invention on ethylene-vinyl acetate copolymer, samples were prepared with the following formulation,
Thermal stability and initial coloration in a 190° C. gar oven were determined.

The results are shown in Table 7.

Example 7 The same test as in Example 1 was conducted with the following formulation, in which other additives were further added to the compound according to the present invention, and the effects of their combined use were examined.

The results are shown in Table 8.

Example 8 0.1 part by weight of 2.
6-tertiarybutyl-4-hydroxypara-cresol and 0.5 parts by weight of the sample (Table 9) were added and extruded at 100°C using an extruder to form pellets.

The heat distortion temperature of this pellet was measured.

The results are shown in Table 9. In addition, the heat distortion temperature is ASTMD
648 56.

Example 9 In order to see the effect of the filler of the present invention on preventing deterioration, a 0.6-thick polypropylene film containing talc with the following formulation was processed with a mixing roll at 175°C for 5 minutes, and then processed at 180°C. , 250 kg/crA for 5 minutes.

This sheet film is heated in a hot back oven at 160℃ in an air atmosphere to cause discoloration or brittleness.
The time at which this occurred was defined as the deterioration start time.

The results are shown in Table 10.

Example 10 In order to examine the stabilizing effect of the compound according to the present invention on synthetic rubber, mixtures of synthetic rubber were prepared on a roll mill according to the following formulations, heated at 150°C, and tested for tensile strength and elongation. I conducted a test.

The results are shown in Table 11.

Example 11 In order to examine the stabilizing effect of the composition of the present invention when using a polypropylene resin containing a colorant, a composition having the following formulation was mixed for 10 minutes using a strainer.

This blended mixture was extruded using a 30 mm extruder (rotation speed: 30
rpm) at 230°C to create a compound.

To 100 parts of this compound, 0.3 parts of copper phthalocyanine blue was added and mixed, and the mixture was kneaded in a roll mill at 180°C for 5 minutes.
kg/crA, compression molded for 5 minutes to create a sheet of 0.45 kg/crA.

This sheet was used as a 10 x 20 mm test piece and was subjected to a heating test in an oven capable of stirring air at a temperature of 160°C.

The results are shown in Table 12. In addition, 10
Using 5 test pieces, the time when 5 or more pieces faded and became brittle was defined as the deterioration start time.

<Formulation> Example 12 In order to examine the effect of preventing the organic material composition of the present invention from deteriorating due to contact with heavy metals, the following formulation was used to prepare a 0.5mm thick organic material composition containing fine copper powder. A 5 mm polypropylene film was processed with a mixing roll at 180°C for 8 minutes, and then processed at 180°C.
It was obtained by compression molding for 5 minutes at a temperature of 200 kg/crA.

This sheet film was heat-degraded in air at 150° C. in a hot pack oven, and the time when it changed color or became brittle was defined as the deterioration start time.

The results are shown in Table 13. Example 13 The effect of polyethylene, which is often used for coating copper wires, etc., was tested by kneading copper powder into an organic material composition as follows.

<Formulation> Masticated with a stabilized medium-low pressure polyethylene mixing roll made by Mitsui Petrochemicals, then 150°C, 200kg/c
Compression molding was performed under the conditions of A for 5 minutes to create a sheet with a thickness of 0.5 mm.

This sheet film was subjected to a heating deterioration test in a hot back oven at 149° C. in an air atmosphere.

The results are shown in Table 14.

Note that the deterioration start time indicates the time when it becomes discolored and grease-like.

Example 14 The following composition was kneaded at 170°C for 5 minutes using a mixing roll to form a sheet with a thickness of 1.0 mm.

A test piece of 10 x 20 mm was prepared from this and subjected to an accelerated heating test in an oven at 190°C in an air atmosphere.

The results are shown in Table 15.

Note that the deterioration start time is the time when discoloration and blackening occur.

combination>

Claims (1)

[Scope of Claims] 1. A synthetic polymer composition stabilized by containing at least one compound represented by the following general formula [I] as a stabilizer. In the formula, R1 represents a hydrogen atom, an alkyl group, or the formula: R4 represents a polyvalent amine residue, R and R/, represent a hydrogen atom, an alkyl group, or a hydroxyalkyl group, R5 and R5', may be combined with each other to form a ring. R6 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group, an alkylaryl group, a glycol ζ cellosolve or carbitol residue,
R7 and R8 represent a hydrogen atom, an alkyl group, an aryl group, a cycloalkyl group, an arylalkyl group, an alkylaryl group, a hydroxyalkyl group, or an alkoxyalkyl group, and R7 and R8 may be bonded to each other to form a ring. be. Note that each group may have a substituent (and if the molecules have the same symbols, they may be the same or different). ].