JPS62141066A - Stabilized synthetic resin composition - Google Patents

Abstract

PURPOSE:To provide a synthetic resin compsn. having excellent resistance to heat and weather, processability, etc., by adding a specified phenol compd. and a phosphite compd. to a synthetic resin. CONSTITUTION:100pts.wt. synthetic resin such as PE is blended with 0.001-5pts. wt. phenol compd. of formula I (wherein R is a residue of a mono- to tetrahydric alcohol; n is 1-4), 0.001-10pts.wt. phosphite compd. of formula II (wherein R1 is H, methyl, ethyl) [e.g., bis(2,6-di-t-butylphenyl)pentaerythritol diphosphite] and optionally, an antioxidant (e.g., pentaerythritol tetralauryl thiopropionate), a light stabilizer, a heavy metal inactivating agent, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to stabilized synthetic resin compositions. Specifically, the present invention relates to a synthetic resin composition with improved heat resistance, weather resistance, processability, etc., which is obtained by adding a specific phenol compound and a specific phosphite compound.

[Conventional technology and problems]

It is known that synthetic resins such as polyethylene, polypropylene, ABS, and polyvinyl chloride deteriorate due to the action of heat and light, becoming discolored and having reduced mechanical strength, making them unusable. In order to prevent such deterioration of synthetic resins, many additives have been used singly or in various combinations. Among these additives, phenolic antioxidants and phosphite antioxidants have a relatively large stabilizing effect and have been widely used. For example, JP-A-51
-109050 discloses a combination of a phenolic antioxidant and tris(2,4-di-t-phenylphosphite), and JP-A-54-25951 discloses a combination of a phenolic anti-oxidant and bis(2,4-di-t-phenylphosphite); a combination of 4-di-t-butylphenyl) pentaerythritol diphosphite;
Further, JP-A-56-152863 proposes a combination of a phenolic antioxidant and bis(2,6-di-t-butyl-6-methylphenyl)pentaerythritol diphosphite. However, the combination effect of these compounds is still insufficient, and in particular, the effect is lost when processing synthetic resins at high temperatures, making it unsatisfactory in practice.

In view of the current situation, the inventors of the present invention have conducted extensive studies, and have found that
The inventors have completed the present invention by discovering that heat resistance, light resistance, and processability can be significantly improved by adding a specific phenol compound and a specific phosphite compound to a synthetic resin.

That is, the present invention provides a stabilized synthetic resin composition obtained by adding a phenol compound represented by the following general formula (I) and a phosphite compound represented by the following general formula (II) to a synthetic resin. It is something to do.

(In the formula, R represents a mono- to tetrahydric alcohol residue, and n is 1
~4 is shown. ) (In the formula, R1 represents a hydrogen atom, a methyl group, or an ethyl group.) The present invention will be explained in more detail below.

Specific examples of the phenol compound represented by general formula (I) include hexyl- and octyl-1 of 3-t-butyl-4-hydroxy-5-methylphenylpropionic acid.
2-ethylhexyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl,
Monoesters of monohydric alcohols such as octadecyl, eicosyl, tocosyl, tetracosyl, triacontyl alcohol; ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,6-hexanediol, thio 2 such as jetanol, 3,9-bis(l,■-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, hydrogenated bisphenol-A, etc.
Diesters of alcohols; Triesters of trihydric alcohols such as glycerin, trimethylolpropane, trimethylolethane, and tris(2-hydroxyethyl)isocyanurate; Triesters of tetrahydric alcohols such as pentaerythritol, ditrimethylolecune, and ditrimethylolpropane. Examples include tetraester; and the like.

The amount of these phenol compounds added is preferably 0.001 to 5 parts by weight per 100 parts by weight of the resin.

In addition, as the phosphite compound represented by the -a formula (II), bis(2,6-di-t-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-methylphenyl) Mention may be made of pentaerythritol diphosphite and bis(2,6-di-t-7'thyl-4-ethylphenyl)pentaerythritol diphosphite.

The amount of these phosphite compounds added is preferably 0.001 to 10 parts by weight per 100 parts by weight of the resin.

Examples of the synthetic resins stabilized by the present invention include polyethylene, polypropylene, polybutene, poly-3
- α-olefin polymers such as methyl butene, or polyolefins such as ethylene-vinyl acetate copolymers, ethylene-propylene copolymers, and copolymers thereof;
polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride,
Polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, brominated polyethylene, chlorinated rubber, vinyl chloride-acetate vinyl copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, Vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride ternary copolymer, vinyl chloride-styrene-acrylonitrile copolymer, chloride Vinyl-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, chloride Vinyl-maleate copolymer, vinyl chloride-methacrylate copolymer, vinyl chloride-acrylonitrile copolymer, halogen-containing synthetic resins such as internally plasticized polyvinyl chloride, polystyrene, polyvinyl acetate, acrylic resin, styrene and other monomers (e.g. maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene copolymers, acrylic ester-butadiene-styrene copolymers, methacrylic ester-butadiene-styrene copolymers Copolymers, polymethyl methacrylate and other methacrylate resins, heat-resistant BS resins, maleimide-modified ABS
resin, polyvinyl alcohol, polyvinyl formal,
polyvinyl butyral, polyethylene terephthalate,
Polybutylene terephthalate, etc., linear polyester, polyamide, polyimide, polycarbonate, polyacetal, polyurethane, polyphenylene oxide, polyphenylene sulfide, polyether sulfone, polyarylate, cellulose resin, or phenol resin,
Examples include urea resin, melamine resin, epoxy resin, unsaturated polyester resin, and silicone resin.

Furthermore, rubbers such as isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, and blends of these resins may also be used.

Also included are crosslinked polymers such as crosslinked polyethylene crosslinked with peroxide or radiation, and foamed polymers such as expanded polystyrene foamed with a foaming agent.

It is also possible to further add a sulfur-based antioxidant to the composition of the present invention to improve its oxidative stability. Examples of these sulfur-based antioxidants include dialkylthiodipropionates such as dilauryl, similystyl, and distearyl, and polyhydric alcohols of alkylthiopropionic acids such as butyl, octyl, lauryl, and stearyl. esters of glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate (e.g. pentaerythritol tetralauryl thiopropionate)
can be mentioned.

By adding light stabilizers to the compositions of the invention, their light resistance can be further improved. Examples of these light stabilizers include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-di-hydroxy-4-methoxyhensiphenone, 2,4 -Hydroxybenzophenones such as dihydroxybenzophenone, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)
-5-chlorobenzotriazole, 2--(2'-hydroxy-3',5''-di-t-butylphenyl)-5-
Chlorobenzotriazole, 2-(2”-hydroxy-
5'-methylphenyl)benzotriazole, 2-
Benzotriazoles such as (2'-hydroxy-3', 5'-di-t-amylphenyl)benzotriazole,
Phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5
Benzoates such as -di-t-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-L-butyl-4-hydroxybenzoate, 2□2゛-thiobis(4-t-octylphenol) Ni salt, (2 ,2'-
Thiobis(4-t-octylphenolate)) -n-
Butylamine N: (3,5-di-L-butyl-4
-Hydroxyhensyl)phosphonic acid monoethyl ester Ni salt and other Nisokefluor compounds, bis(2,2,6,6-
Tetramethyl-4-piperidyl) sebacate, bis(I
2,2,6゜6-bentamethyl-4-piperidyl)-n
-butyl-3,5-di-tert-butyl-4-hydroxyhensyl-malonate, bis(I-acryloyl-2,2
,6,6-tetramethyl-4-piperidyl)bis(3,
5-di-tert-butyl-4-hydroxybenzyl) malonate, tetrakis(2,2,6,6-tetramethyl-4
-piperidyl)butane-1゜2.3.4-tetracarboxylate, ■-Hydroxyethyl-2.2.6.6-
Tetramethyl-4-piperiditul/diethyl succinate condensate, cyanuric chloride/tertiary octylamine/1,6
-piperidine compounds such as bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane condensates, α-
Substituted acrylonitriles such as methyl cyano-β-methyl-β-(p-methoxyphenyl)acrylate and N-2
-Ethylphenyl-N'-2-ethoxy-5-tert-butylphenyl oxalic acid diamide, N-2-ethylphenyl-No-2-ethoxyphenyl oxalic acid diamide, and other oxalic acid dianilides.

If necessary, the composition of the present invention may also contain heavy metal deactivators, nucleating agents, metal soaps, organic tin compounds, plasticizers, epoxy compounds, pigments, fillers, blowing agents, antistatic agents, flame retardants, and lubricants. , processing aids, and the like.

〔Example〕

Next, the present invention will be specifically explained with reference to Examples. However, the present invention is not limited to these examples.

Example 1 The following composition was mixed in a mixer for 5 minutes, and then a compound was made in an extruder (cylinder temperature 230°C and 240°C, head die temperature 250°C, rotation speed 2Or
pm).

Using this compound, a 95×40×1 crane test piece was made using an injection molding machine (cylinder temperature 240°C, nozzle temperature 250°C, injection pressure 475 kg/cd).

Using the obtained test piece, the thermal stability was measured in a gear oven at 160°C, and the thermal stability was measured using a Hunter colorimeter*.
The yellowness (%) of the test piece was measured after being irradiated with a fluorescent lamp for 2 hours. The results are shown in Table 1.

<Formulation> Calcium stearate 0.2 Phenol compound (Table 1) 0.1 Table
1 Phenol Compound Comparison Phenol A 3.5-di-t-butylphenylpropionic acid octadecyl ester ± Comparison Phenol B 3.5-di-t-butylphenylpropionate pentaerythritol tetraesterphenol Na1 3-t-butyl- 4-Hydroxy-5-methylphenylpropionic acid octadecyl ester phenol fish 2 3-t-butyl-4-hydroxy-5-methylphenylpropionic acid triethylene glycol diester phenol! 1h3 3-t-Butyl-4-hydroxy-5-methylphenylpropionic acid 1,6-hexanediol diester phenol 4 3-t-butyl-4-hydroxy-5-methylphenylpropionic acid thiogetanol diester phenol 5 3-tert-butyl-4-hydroxy-5-methylphenylpropionic acid 3,9-bis(I,1-dimethyl-2-
hydroxyethyl)-2゜4.8.10-tetraoxaspiro(5,5)undecane diester phenol 6 3-tert-butyl-4-hydroxy-5-methylphenylpropionic acid trimethylolpropane triester phenol 11k17 3- t-Butyl-4-hydroxy-5-methylphenylpropionate tris(2-hydroxyethyl)isocyanurate triester phenol! 1h8 3-t-Butyl-4-hydroxy-5-methylphenylpropionic acid pentaerythritol tetraester Example 2 A test piece was prepared in the same manner as in Example 1 using the following formulation, and the same test as in Example 1 was carried out. I did it.

The results are shown in Table 2.

Calcium stearate 0.2 Phenol 2 (see Table 1) 0.1 Phosphite compound (Table 2) 0.2* Comparison of phosphite compounds Phosphite A Bis(2,4-di-t-butylphenyl ) Pentaerythritol diphosphite phosphite 1 Bis(2,6-di-t-butylphenyl)pentaerythritol Diphosphite phosphite 2 Bis(2,6-di-t-butylphenyl-4-methylphenyl)pentaerythritol Diphosphite phosphite 3 Bis(2,6-di-t-butylphenyl-4-ethylphenyl)pentaerythritol diphosphite Example 3 In order to examine the stabilizing effect of the composition of the present invention during high temperature processing, The following formulations were mixed and then extruded at 300°C. Compounds were extruded 1, 3, and 5 times and changes in melt index (g/10 m1n) were measured. The results are shown in Table 3.

Mixture> Calcium stearate 0.2 Phenol 5 (see Table 1) 0.2 Phosphite compound (Table 3) 0.1
3 *Similar to Table 2 Example 4 The following formulation was kneaded at 150°C for 5 minutes using a mixing roll, and then compression molded at 150°C and 180 kg/ad for 5 minutes to form a 1.0 mm thick product. I created a sheet. This sheet was used as a 10 x 20 crane test piece, and a thermal stability test was conducted on aluminum foil in a gear oven at a temperature of 150'C. The results are shown in Table 4.

<Formulation> Phosphite N12 (see Table 2) 0.2 phenol compound (Table 4 > 0.05 Table 4 * Same as Table 1 Example 5 Effect of the compound according to the present invention on ethylene vinyl acetate copolymer In order to see this, a sample was prepared with the following composition and
Thermal stability and initial coloration in a gear oven at °C were measured. Regarding initial coloration, yellowness was determined using a Hunter colorimeter. The results are shown in Table 5.

<Blend> Ethylene-vinyl acetate copolymer resin 100 parts by weight Montanic acid lubricant 0.3 phenol 2 (
See Table 1) 0.05 phosphite compound (Table 5) 0.1 Table 5 *Same as Table 2 Example 6 Polybutylene terephthalate Port O weight part phenol 11h5 (See Table 1) 0.2 phosphite compound (Table 6 ) 0.2 The above formulation was subjected to injection processing at 270°C to prepare test pieces. Using this test piece,
The residual tensile strength after heat aging at 50° C. for 300 hours was measured.

The results are shown in Table 6.

Table 6 *Same as Table 2 Example 7 Intrinsic viscosity 0.51/j/g (25°C in chloroform)
50 parts by weight of poly(2,6-dimethyl-1,4-phenylene oxide), 47.5 parts by weight of polystyrene, 2.5 parts by weight of polycarbonate, 3.0 parts by weight of titanium oxide, Hiroshi phosphite 2 (see Table 2) 0.1 parts by weight and 0.11 parts by weight of the phenol compound were added, thoroughly mixed using a Henschel mixer, pelletized using an extruder, and then injection molded to prepare test pieces. This test piece was heated in a gear oven at 125°C for 100 hours, and the elongation and Izot impact value retention were measured. The results are shown in Table 7.

Table 7 *Example 8 Same as Table 1 The following formulation was processed with a kneading roll to form a sheet with a thickness of 1 mm. Using this sheet, thermal stability and initial colorability tests at 190°C were conducted. A weather resistance test was also conducted using a weatherometer. The results are shown in Table 8.

<Blend> Polyvinyl chloride (vinyl strength 37H) 100 parts by weight Di-2-ethylhexyl phthalate 45 Trixylenyl phosphate 3.0 Bisphenol A diglycidyl 2.0 Ether zinc stearate 0.8 Barium stearate 0. 4 Barium nonyl phenate 0.5 Octyl diphenyl phosphite 0.
5 Sorbitan monopalmitate 3.0 Methylenebisstearylamide 0.3 Phosphite 2 (see Table 2) 0.05 Phenoyl compound (Table 8)
0.05 Table 8 *Same as Table 1 Example 9 0.2 g of phenol 11h2 (see Table 1) and phosphite per 100 g of cis-1,4-isoprene rubber (Ziglar catalyst, number average molecular weight 680,000) After adding 0.3 g of compound, dry isooctane 25
0 ml was added to prepare a homogeneous solution. Next, this solution was transferred to an evaporator and the solvent was removed on a hot bath. The obtained rubber composition was heat aged in a constant temperature bath at 100° C. for 4 hours.

A coloring test and intrinsic viscosity measurement (toluene solvent) were performed. The results are shown in Table 9.

Table 9 □□-□-Each bite * Same as Table 2 Example 10 100 parts by weight of polycarbonate resin, 5 parts by weight of phenolic compound dynamic magnet (see Table 1) Part by weight of O, OS and 0.1 part by weight of phosphite compound were mixed and pressed at 260°C to create a test piece with a thickness of 1.On+.The test piece was heated in a gear oven at 230°C for 45 minutes and the degree of discoloration of the test piece was observed.The results were Shown in Table 10.

Table 10 *Same as Table 2 Example 11 Calcium stearate 1.0 Phosphite 11h2 (see Table 2) 0.1 Phenol compound (Table 11) 0.2 The above blend was extruded at 200°C to form pellets. Created and using this pellet 2
A test piece was prepared by injection processing at 30°C.

The degree of coloration of this test piece after being heated for 30 hours at 135° C. in a gear open condition was expressed as the degree of whiteness measured with a Hunter colorimeter. Furthermore, the Izod impact value of the test piece at 20°C was also measured. The results are shown in Table 11.

Table 11

Claims (1)

[Scope of Claims] A stabilized synthetic resin composition obtained by adding a phenol compound represented by the following general formula (I) and a phosphite compound represented by the general formula (II) to a synthetic resin. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R represents a mono- to tetrahydric alcohol residue, and n is 1
~4 is shown. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R_1 represents a hydrogen atom, methyl group, or ethyl group.)