JPS5915938B2 - Stabilizing composition for synthetic resins - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a stabilizer for synthetic resins, and particularly to a novel stabilizer that suppresses high-temperature decomposition of vinyl chloride polymers, copolymer ABS resins, and the like.

'5 When vinyl chloride resin is heated and molded,
It tends to cause thermal decomposition mainly due to dehydrochlorination,
For this reason, the mechanical properties and color tone of processed products tend to deteriorate, resulting in significant disadvantages.

In order to eliminate such drawbacks, it is necessary to add j0-type or several types of heat stabilizers to the synthetic resin to suppress deterioration during processing steps. Many metal soaps have been used for this purpose. However, it is still not sufficient in terms of thermal stability, and satisfactory results that can withstand practical use have not been obtained. In order to solve the drawbacks associated with conventional stabilizers, the present inventor has conducted intensive research and found that if carboxylic acid or hydrazide derivatives are added to the desired synthetic resin as a stabilizer, excellent stability can be achieved. It was revealed for the first time that a synthetic resin having the following properties can be obtained.

Preferred carboxylic acid and hydrazide derivatives used in the present invention have the following general formulas (1) and ().

In the above formula, a represents a number from 1 to 4, b represents a number from O to 3,
R' is a hydrogen atom, an alkyl group or a substituted alkyl group, R1
and R2 are each a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or one (R5-0)n-R6
and at least one of R1 and R2 is one (R5-
0) n indicates one present.

R3 represents a mono- or polycarboxylic acid residue, R4 is -0
R7, N8-NHN<.

Alternatively, it represents -NHRlO, and R5 represents an alkylene group or an arylalkylene group, which may be linear or have a side chain. R6 represents a hydrogen atom, -C-Rll or a phosphite ester residue, and R7 represents a hydrogen atom, an alcohol residue, a metal atom of Groups 1 to 1 of the periodic table, or alkyltin. R8 and R9 each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or (R5-0)n-R6, and may be the same or different from R1 and/or R2. RlO represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, and these may have a substituent such as a hydroxyl group. Rll is a carboxylic acid residue, n is one (R5-0
) indicates the degree of polymerization of 1 to 5. Note that when the same symbols exist in one molecule, they may be the same or different, and each group may be substituted. The compound represented by the above general formula is used in an amount of 0.001 to 10 parts by weight, preferably 0.01 to 10 parts by weight, based on 100 parts by weight of the synthetic resin.
1.5 parts by weight can be used depending on the purpose.

These compounds can be synthesized by decomposing lower esters of mono- or polycarboxylic acids with a hydrazine compound, and depending on the case, methylolation with formaldehyde or alkalolation with alkylene oxide.

Such carboxylic acids include ordinary carboxylic acids as well as oxyacids, amino acids, keto acids, mercaptocarboxylic acids, etc. Examples of polycarboxylic acids include succinic acid, adipic acid, butanetricarboxylic acid, and phthalic acid. , terephthalic acid, pyromellitic acid, etc., as well as tartaric acid, citric acid,
Examples include malic acid, thiodipropionic acid, iminoniacetic acid, and glutamic acid.

One or several types of plasticizers can be used in the composition of the present invention depending on the purpose, and these include phthalate esters, other esters, polyester plasticizers, phosphoric acid ester plasticizers, chlorine Examples include plasticizers such as epoxy plasticizers, epoxy plasticizers, and other plasticizers.
This is typified by No. 21169.

Adding an antioxidant to the synthetic resin used in the present invention can increase the oxidative deterioration prevention property of the synthetic resin.
It can be used as appropriate depending on the purpose of use.

These antioxidants include phenolic antioxidants, phosphite antioxidants, amine antioxidants, sulfur-containing compounds, and the like. By adding an ultraviolet absorber to the synthetic resin used in the present invention, the photostability can be improved, so it is also possible to select and use this as appropriate depending on the purpose of use.

These include benzophenones, benzotriazoles, succinates, substituted acrylonitriles, various metal salts or chelates, especially nickel or chromium salts or chelates, triazines, and the like.
In addition, if necessary, for example, plasticizers, metal soap epoxy stabilizers, organic chelates, pigments, fillers, foaming agents, antistatic agents, antifogging agents, plate-out prevention agents, surface treatment agents, etc.
Lubricants, antioxidants, flame retardants, light stabilizers, ultraviolet absorbers,
Fluorescent agents, antifouling agents, bactericidal agents, metal deactivators, photodegradants,
Nonmetallic stabilizers, epoxy resins, borate esters, thiourea derivatives, nucleating agents, clarifying agents, processing aids, mold release agents, and the like may also be included. In general, metal soaps can be used as stabilizers for synthetic resins. Metal soaps such as strontium, sodium, and potassium are often used in combination of two or more of these, and many combinations are adopted depending on the purpose of use.

In the synthetic resin composition of the present invention, it is possible to use a combination of metal soaps selected from many commonly used metal soap groups depending on the purpose, or to use a single metal soap.

As the synthetic resin used in the present invention, resins such as those listed in Japanese Patent Application No. 46-21169 (Japanese Unexamined Patent Publication No. 47-34639) can be used as appropriate.

Representative examples of the compounds represented by the general formulas [1] and [] of the present invention are as follows. Next, methods for producing these compounds will be shown. The following manufacturing method is just an example,
Production is also possible by methods other than this. Therefore, the present invention is not limited in any way by these manufacturing methods. Synthesis Example 1. 17.29 (0.1 mol) of synthetic ethyl furyl ester of 46.1 and 17.79 (0.3 mol) of hydrazine hydrate (8501) were reacted in 200 ml of absolute ethanol for about 3 hours. 15.89 (0.1 mol) of trifurylic acid hydrazide obtained by
was dissolved in water, 3.09 (0.1 mol) of formalin was added at 70°C, and the mixture was reacted for about 1 hour. Water was then distilled off and washed several times with methanol to obtain a colorless and transparent viscous liquid.

Synthesis Example 2 Synthesis of Taki 9 Thiodipropionic acid dihydrazide obtained by hydrazine decomposition of thiodipropionic acid dibutyl ester 20.6
After dissolving 9 (0.1 mol) in water, formalin 6.
When 0 (0.2 mol) is added, the mixture becomes cloudy and gels within a few minutes.

When heat is gradually added, it becomes a clear liquid. After continuing the reaction at 75°C for about 4 hours, a white solid precipitates out.

After filtering, recrystallization was performed with methanol to obtain a white solid.
Synthesis Example 3 Synthesis of Taki 22 After adding a 15% NaOH aqueous solution to glutamic acid, acetic anhydride was added dropwise to convert the resulting glutamic acid acetylated product into butyl ester, and then 2.179 (2.179) obtained by decomposing it with hydrazine in an ethanol solvent. 0.01 mole) to 37
01) 1.629 (0.02 mol) of formalin was reacted in water and washed with methanol and ether to obtain a white powder.

Synthesis Example 4/F6.24 (j) Synthesis Cyanoethylated acetophenone is hydrolyzed, then esterified, converted to thioketone with H2S, and 49 (0.01 mol) obtained by hydrazine decomposition is mixed with 37% formaldehyde 2,59 (0.032 mol) was reacted in methanol and washed with ether to obtain a white powder.

Other compounds are similarly synthesized by decomposing lower esters of carboxylic acids with hydrazine, followed by methylolization with formaldehyde or alkalolization with alkylene oxide. Next, the physical properties of each compound will be described.

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 In order to examine the excellent stabilizing effect of the carboxylic acid hydrazine derivative of the present invention, samples were prepared by calendering and hot pressing according to the following formulation, and were tested in a heat aging tester at 175°C. Then, the thermal stability, transparency and initial coloring property by hot press processing, and plate-out property were measured, and the results are shown in Table 1 below.

Regarding the initial coloring, the yellowness was determined using a Hunter colorimeter as shown in the formula below and compared.

Yellowness 5.5 or less is very excellent, 5.5-7 Good to Fairly Good 7-15 Average 15-20 Slightly Poor >20 Poor Transparency is also divided into 6 grades from 1 to 6, with 1 being Almost transparent, and 6 indicates almost opaque.

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

<Formulation> Polyvinyl chloride resin 100 parts by weight Dioctyl phthalate 50 Ba-stearate 1.0 Example 2 11-vinyl chloride-ABS resin (acrylonitrile-tadiene-styrene terpolymer of carboxylic acid hydrazide derivative) according to the present invention ) In order to see the effect on the length of the blend, samples were prepared using the following formulation using the same procedure as in Example 1, and tests were conducted for thermal stability, initial coloration, and transparency, and the results are shown in Table 2. t' Example 3 Next, in order to examine the stabilizing effect of the resin composition according to the present invention on an acrylonitrile-butadiene-styrene copolymer (ABS resin), a material with a thickness of 2 mTfL was prepared using a kneading roll with the following formulation. , 210℃, 50k9/
d. The color of the material was measured after 10 minutes.

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. The test results are shown in Table 3 below. Example 4 In order to examine the effect of the resin composition according to the present invention on ethylene monovinyl acetate copolymer, samples were prepared according to the following formulation, and the thermal stability and initial coloration in a gear oven at 190°C were evaluated. The results are shown in Table 4.

Example 2.5 parts of a sample was added to 100 parts by weight of an acetal copolymer consisting of 598 parts by weight of trioxane and 2 parts by weight of ethylene oxide, and after thorough kneading, a thin plate with a thickness of 3 mm was created by injection molding. did.

After the plates were treated in air at 230° C. for 30 minutes, the weight loss and coloration of the plates were measured and the results are shown in Table 5 below. Example 6 0.1 part by weight of 2-
Add 0.5 parts by weight of 6-jetarsialbutyl-4-hydroxypataresol and the sample, and use an extruder to
It was extruded at 900C and formed into pellets.

The heat distortion temperature of this pellet was measured and shown in Table 6.
Heat distortion temperature was measured according to ASTM D64856.
Example 7 In order to examine the effect of the stabilizing composition of the present invention on polyvinyl butyral resin, a film with a thickness of 1 mm was prepared using an extruder using the following formulation, and the film was heat stabilized in a gear oven at 13"C. The properties and effects were measured and the results are shown in Table 7.

Rice butyralization degree is about 65m01%, acetylation degree is about 1m
01% and alcoholization degree of about 34m01%, polymerization degree of about 1700.

Example 8 In order to examine the stabilizing effect of the compound according to the present invention on synthetic rubber, a mixture of synthetic rubbers was prepared on a roll mill with the following formulation, each was vulcanized at 150°C, and a tensile strength test and an elongation test were conducted. They are shown in Table 8.

Example 9 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.

30m7 of this mixed mixture! L extruder (rotation speed 30r)
A compound was created by extrusion at 230° C. using For 100 parts of this compound, 0.3
Copper phthalocyanine blue was added and mixed, and kneaded in a roll mill at 180℃ for 5 minutes.The film was heated to 180℃.
, 200kg/CfiLl 5 minutes compression molding 0.45
Create a sheet of mm.

This sheet was used as a 10 x 20 m71 test piece at 160°C.
The heating test was carried out in an oven that can stir the air at a temperature of .

The results are shown in Table 9. Note that 10 test pieces were used for the same sample, and the time when 5 or more pieces became discolored and brittle was defined as the deterioration start time.

Example 10 In order to examine the combined effect of adding other additives to the hydrazide derivative of the present invention, the same test as in Example 1 was conducted using the following formulation, and the results are shown in Table 10.

<Composition>

Claims (1)

[Claims] 1. The following general formula [I] for 100 parts by weight of synthetic resin:
Or a synthetic resin stabilizing composition containing 0.001 to 10 parts by weight of the carboxylic acid hydrazide derivative represented by [II]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I]▲There are mathematical formulas, chemical formulas, tables, etc.▼[II] [In the above formula, a is 1
-4, b is a number from 0 to 3, R' is a hydrogen atom, an alkyl group or a substituted alkyl group, R_1 and R_2 are each a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or -(R_5 -O)n-R_6,
At least one of R_1 and R_2 is -(R_5-O
)n-R_6. R_3 indicates a mono- or polycarboxylic acid residue, and R_4 indicates -OR_7, ▲There are numerical formulas, chemical formulas, tables, etc.▼ or -NHR_1_0. R_5 represents an alkylene group or an arylalkylene group, R_6 is a hydrogen atom,
▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ Or indicates phosphite ester residues. R_7 represents a hydrogen atom, an alcohol residue, a metal atom of Groups I to IV of the periodic table, or alkyltin. R_8 and R_9 each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or -(R_5-O)n-R_6, and R_1_0 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. R_1_1 represents a carboxylic acid residue. n indicates the degree of polymerization of -(R_5-O)-,
1 to 5 are shown. Note that when the same symbols exist in one molecule, they may be the same, or each group may be substituted. ]