JPS5928349B2 - Stabilizer for resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a stabilizer containing phosphoric amide that has an excellent stabilizing effect on polyphenylene ether resins.

Polyphenylene ether is an engineering plastic that is attracting attention due to its excellent mechanical and electrical properties as well as heat resistance, chemical resistance, and dimensional stability. It has the disadvantages of poor workability due to its high temperature and relatively poor impact resistance.

A combination of polyphenylene ether and polystyrene has been proposed for the purpose of lowering the softening point and improving processability (see, for example, Japanese Patent Publication No. 17812/1983). When polystyrene is mixed with polyphenylene ether, a decrease in impact resistance is usually observed.

Compositions with rubbery polymers such as polybutadiene or styrene-butadiene copolymers have been provided for the purpose of improving impact resistance (Japanese Patent Publication No. 47-327).
30, etc.). Polyphenylene ether is originally
It is a resin that is resistant to main chain splitting and has relatively little deterioration in physical properties due to heating.

However, in the case of polystyrene or a mixture with a rubbery polymer, physical properties deteriorate due to main chain splitting of the polystyrene due to heat or thermal oxidation, cleavage of double bonds in the rubbery polymer, etc. For this reason, when the cylinder temperature increases during injection molding, the impact strength decreases, and even if exposed to a temperature below the softening point for a long time, the physical properties deteriorate. In extreme cases, low molecular weight substances generated during melt molding at high temperatures may remain as silver streaks on the surface of the molded product. In addition, deterioration of physical properties also occurs when exposed to light for a long time. The object of the present invention is to provide a stabilizer that can provide stabilizing effects such as excellent heat resistance, light resistance, and weather resistance when added to polyphenylene ether-based resins, particularly polyphenylene ether-containing resin compositions. It is about providing.

That is, the present invention provides a stabilizer for polyphenylene ether resins, which is characterized by containing at least one type of phosphoric amide compound represented by the following general formula (a) or (b): ( In the string, Rl, R2 and R each represent hydrogen, an alkyl group, an aryl group, an aralkyl group or an alkylaryl group, and R3, R4, R6, R7,
R8 and R each represent hydrogen or an alkyl group having 1 to 4 carbon atoms).

Typical examples of phosphoric amide compounds represented by the above general formula include dibutoxyphosphoric amide, diphenoxyphosphoric amide, bisnonylphenoxyphosphoric amide, di-n-propoxyphosphoric dibutyramide, Examples include diphenoxyphosphoric diethylamide, bismethylphenoxyphosphoric dipropylamide, bisphenylmethoxyphosphoricamide, phenoxyphosphoric diamide, and phenoxyphosphoric tetramethyldiamide.

Although it is essential that the stabilizer of the present invention contains the above-mentioned phosphoric amide compound, other compounds can also be used in combination.

Specific examples of these compounds include the following compound groups:1. Phosphite ester and phosphate ester L
Sterically hindered phenol]1. Hydroxybenzotrinoazole and hydroxybenzophenone Any one or more of the above compounds from group 1 can be used in combination with the phosphoric amide compound.

Specific examples of the phosphite referred to in the present invention include triphenylene phosphite, trisnonylphenyl phosphite, tridecyl phosphite, trioctyl phosphite, diphenyl monodecyl phosphite, monophenyl dioctyl phosphite, Tri-p-tertiary-amyl phosphite, tris-p-cumyl phenyl phosphite, tris-bisphenol A phosphite, dibisphenol A monopentaerythritol phosphite, monobisphenol A dipentaerythritol phosphite, bisphenol A penta Examples include erythritol phosphite polymer.

Specific examples of the phosphoric acid ester according to the present invention include triphenylene phosphate, trisnonylphenyl phosphate, trioctyl phosphate, tridecyl phosphate, diphenyl monooctyl phosphate, and the like.

When phosphoric amide is used alone, at high temperatures,
Resin may become colored.

This drawback is remedied by the use of phosphoric amides in combination with phosphorous esters and/or phosphoric esters. Furthermore, there is an advantage that deterioration of physical properties due to heat can be further suppressed. When hydroxybenzotriazole or hydroxybenzophenone and/or sterically hindered phenol is used to improve the weather resistance or light resistance of a composition containing polyphenylene ether, low temperature shock after outdoor exposure or irradiation with a weather meter may be used. Significant decrease in strength.

phosphoric amide and hydroxybenzotriazole,
By using a combination of hydroxybenzophenones and sterically hindered phenols, this drawback is significantly improved. Further, the combination of phosphoric amide and sterically hindered phenol or the combination of phosphoric amide, sterically hindered phenol and phosphite ester significantly suppresses the deterioration of physical properties due to heat or thermal oxidation. Specific examples of hydroxybenzotriazole according to the present invention include 2(2'
-hydroxy-5/-methylphenyl)benzotriazole, 2(2'-hydroxy-3',5/-di-t-methylphenyl)benzotriazole, 2(2'-hydroxy-5'-t-butylphenyl)benzotriazole, 2(2/-hydroxy-3/,5'-t-butylphenyl)benzotriazole, 2(2'-hydroxy-3
2-t-butyl-5/-methylphenyl)benzotriazole, 2(2/-hydroxy-4-octoxyphenyl)benzotriazole, 2(2'-hydroxy-3'
-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2(2/-hydroxy-3/,5/
-t-butylphenyl)-5-chlorobenzotriazole and the like.

Specific examples of hydroxybenzophenone include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5-chloro-2-hydroxybenzophenone, and 2,4-dihydroxybenzophenone. Examples include phenone, 2-hydroxy-4-benzoloxybenzophenone, 2-hydroxy-4(2-hydroxy-3-methacroxy)propioxybenzophenone, and the like. Specific examples of sterically hindered phenols according to the present invention include:
2,6-di-t-butyl-p-talesol, butylhydroxyanisole, 2,6-di-t-butyl-α-dimethylamino-p-cresol, n-octadecyl-3-
(4/-hydroxy-3',5'-di-t-butylphenol)propionate, methyl 3,4,5-trihydroxybenzoate, 2,2-methylene-bis(6-t
-butyl-4-methylphenol), bis[3,3-bis(4'-hydroxy-3'-tert-butylphenol)
Butirucamide] glycol ester, 4,4'-
Thio-bis(6-t-butyl-3-methylphenol)
, 4,4'-butyldenbis(3-methyl-6-t-butylphenol), 1,3,5-tris(3',5'-
di-t-butyl-4-hydroxybenzole) isocyanurate, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenol)butane, 1,3,
5-trimethyl-2,4,6-tris(3,5-di-t)
-butyl 4-hydroxybenzyl)benzene and the like.

When adding the stabilizer of the present invention to polyphenylene ether resin, the appropriate amount of phosphoric amide to be added is from 0.1 to
15% by weight (resin weight basis) More preferably 0.5~
It is 10% by weight.

If the amount added is less than 1% by weight, the stabilizing effect will be low, which is not preferable. If the amount added exceeds 15% by weight, the resin will be plasticized by phosphoric amide.
This is not preferable because heat resistance is extremely reduced. The amount added of any one or a mixture of two or more of the compound groups 11 and 11 that can be used in combination with the phosphoric amide compound is 0.0
5 to 6% by weight, more preferably 0.1 to 4% by weight.

If the amount added is less than 0.05% by weight, the stabilizing effect will be small, and if it is more than 6% by weight, the physical properties will deteriorate, which is not preferable. In the present invention, polyphenylene ether resin refers to polyphenylene ether and copolymers and resin compositions containing polyphenylene ether as a main component. Polyphenylene ether has the general formula (R, .
R2, R3, R4, current, R6 are the same or different Tert-
It is a monovalent residue such as an alkyl group having 1 to 4 carbon atoms excluding a butyl group, an aryl group, a halogen, or hydrogen, and R, and R6 are not hydrogen at the same time.

) is a repeating unit, and the constituent units are [1] or [1] and []. As specific examples, representative examples of homopolymers of polyphenylene ether include poly(2,6-dimethyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4
-phenylene)ether, poly(2,6-diethyl-1)
,4-phenylene)ether, poly(2-ethyl-6-
n-propyl-1,4-phenylene) ether, poly(2
, 6-di-1-n-propyl-1,4-phenylene) ether, poly(2-methyl-6-n-butyl-1,4-phenylene) ether, poly(2-ethyl-6-isopropyl-
1,4-phenylene)ether, poly(2-methyl-6)
-chloro-1,4-phenylene)ether, poly(2-
methyl-6-hydroxyethyl-1,4-phenylene)
ether, poly(2-methyl-6-chloroethyl-1,
Examples include homopolymers such as 4-phenylene) ether. The polyphenylene ether copolymer has the general formula (where R3, R, i, R5, R6 are alkyl groups having 1 to 4 carbon atoms excluding tert-butyl group, aryl group, halogen,
It is a monovalent residue such as hydrogen, and R5 and R6 are not hydrogen at the same time.

), or a polyphenylene ether copolymer mainly composed of a polyphenylene ether structure obtained by copolymerizing with an alkyl-substituted phenol such as 2,3,6-trimethylphenol or o-cresol. Moreover, these polyphenylene ethers may be blast polymerized with a styrene compound or a vinyl compound containing a styrene compound. The phosphoric amides of the present invention exhibit a particularly significant stabilizing effect on this type of glast polymer. The stabilizer of the present invention is particularly effectively used in copolymers or resin mixture compositions containing a styrene compound polymer and/or a rubbery polymer in addition to the above-mentioned polyphenylene ether. In the copolymer or resin mixture composition, the stabilizer of the present invention is particularly effective because:
This is a case where the contents of polyphenylene ether and rubbery polymer are 25% by weight or more and 30% by weight or less, respectively.

When the amount of polyphenylene ether is 25% by weight or less, there is no particular need to add the stabilizer of the present invention, and when the amount of rubbery polymer is 30% by weight or more, the stabilizing effect of the stabilizer of the present invention is achieved. This is because it is not fully demonstrated. The styrene compounds referred to in the present invention refer to styrene and alkylated, halogenated, etc. derivatives of styrene, and specific examples thereof include α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, and dichlorostyrene. ,
p-methylstyrene, p-t-butylstyrene,
Examples include ethylstyrene.

The copolymer containing a styrene compound as used in the present invention means a copolymer comprising a styrene compound and a vinyl compound copolymerizable with the styrene compound. Examples of copolymerizable vinyl monomers include methacrylic esters such as methyl methacrylate and ethyl methacrylate, acrylic esters such as butyl acrylate and 2-ethylhexyl acrylate, unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile, or anhydrous Examples include maleic acid, maleic acid or fumaric acid. The rubbery polymers referred to in the present invention include synthetic rubbers derived from conjugated dienes, ethylene-α-olefin-polyene copolymers, copolymers of ethylene and methacrylic acid esters, and other rubber-like polymers. Indicates a substance that exhibits

Specific examples include polybutadiene rubber, butadiene-styrene copolymer rubber or its hydrogenated product, butadiene-acrylonitrile copolymer rubber, polyisoprene rubber, ethylene-propylene copolymer rubber, and ethylene-methyl methacrylate copolymer. It is mentioned as. These rubbery polymers may be used alone or in combination of two or more. More preferably, the rubbery polymer is a glazed copolymer comprising a styrene compound or a copolymer containing a styrene compound. In the present invention, phosphoric amide, phosphite, phosphate ester,
Sterically hindered phenol, hydroxybenzotriazole,
Methods for mixing hydroxycobenzophenone with resin include melt kneading using an extruder or kneader, solution mixing, or adding and mixing when graft polymerizing polyphenylene ether and styrene compounds. Can be mentioned.

However, the method is not limited to these methods. Hereinafter, the present invention will be explained in more detail with reference to Examples.

However, the present invention is not limited to these examples. All parts and percentages in the examples are by weight. The color of the injection molded product was determined based on JIS-Z872l. The numbers in the column represent hue and brightness/saturation. Weather resistance was determined by the retention of Izot impact value at -30°C of the test piece irradiated in a sunshine weather meter using a carbon arc as a light source. Irradiation was carried out at 63° C. and 50% RH for 200 hours. Heat exposure resistance was determined by the retention of tensile elongation at break of a test piece heat-treated for 400 hours in a gear oven at 130°C. Heat resistance was determined based on what percentage of the Izod impact value was maintained when the cylinder temperature of the injection molding machine was 300°C compared to when it was 260°C. The presence or absence of silver streaks is determined by the cylinder temperature of 320
The molded product was evaluated at ℃. Heat distortion temperature is ASTM
- Measured based on D648. Example 1 50 parts of poly(2,6-dimethylphenylene-1,4-ether) and 14% of poly(2,6-dimethylphenylene-1,4-ether) having an intrinsic degree [η] of 0.45 d1/9 measured at 30°C using chloroform as a solvent
Table 1 shows the physical properties of a composition prepared by adding 2 parts of diphenoxyphosphoric amide to a resin/composition consisting of 50 parts of high-impact polystyrene containing , 4-trans-butadiene.

For comparison, Table 1 also shows the physical properties of a composition (Comparative Example 1) that does not contain diphenoxyphosphoric amide in Example 1.

Example 2 65 parts of a graft polymer consisting of poly(2,6-dimethyl-1,4-phenylene ether J mo V part and 23 parts of polystyrene) with [η] of 0.45 d1/9 and 20% of 1 ，
3 parts of diphenoxyphosphoric amide, 1 part of dibisphenol A monopentaerythritol phosphate, and 4 parts of triphenylene phosphate were added to a graft polymer composition consisting of high-impact polystyrene containing 4-trans-butadicone. Table 2 shows the physical properties of the composition.

For comparison, in Example 2, a composition in which diphenoxyphosphoric amide and dibisphenol A monopentaerythritol phosphite were all triphenylene phosphate, that is, 8 parts of only triphenylene phosphate was added. The physical properties of the composition (Comparative Example 2) are also shown in Table-2. Example 3 In Example 1, further 0.5
Table 3 shows the physical properties of the composition to which n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butyl-4-butylphenol)propionate was added.

For comparison, in Comparative Example 1, 0.5 parts of n
-octadecyl-3-(4'-hydroxy-
Table 3 also shows the physical properties of the composition (Comparative Example 3) to which 3',5'-di-t-butyl-4-butylphenol propionate was added. Example 4 65 parts of the same Goofft polymer used in Example 2, 20 parts of a graft copolymer consisting of 50 parts of ethylene-methyl methacrylate copolymer and 50 parts of polystyrene, and 2
A graft polymer resin composition consisting of 15 parts of high-impact polystyrene containing 0% 1,4-trans-butadiene, 2 parts of diphenoxyphosphoric amide, and 0.5 parts of tris-p-t-amyl fluoride. enylphosphite, 0.
5 parts of 2*(2'-hydroxy-5'-methylphenyl)benzotriazole and 0.5 parts of n-octadecyl-3-(4'-hydroxy-3
The physical properties of the composition obtained by adding ',5'-di-t-butyl-4-butylphenol) propionate are shown below.
4.

For comparison, Table 4 also shows the physical properties of a composition (Comparative Example 4) that does not contain diphenoxyphosphoric amide and tris-p-t-amyl phenyl phosphite in Example 4. Example 5''/, Table 5 shows the physical properties of compositions in which diphenoxyphosphoric dimethylamide was added to the same graft polymer composition used in Example 2 in different amounts.

Example 6 In Example 1, polyphenylene ether has [η] of 0.
．． Table 6 shows the physical properties of poly(2,6-diphenylphenylene-1,4-ether) with 38d1/y.
Shown below.

For comparison, when the polyphenylene ether in Comparative Example 1 is the same as that used in Example 6 (Comparative Example 5)
The physical properties of are also shown in Table-6.

Example 7 Graft polymer 65 consisting of 74 parts of the same polyphenylene ether used in Example 2 and 26 parts of a styrene-acrylonitrile copolymer containing 27% acrylonitrile.
1 part of phenoxyphosphoric diamide, 1 part of triphenylene phosphite, and 35 parts of acrylonitrile-butadiene-styrene terpolymer containing 40% butadiene. and 0
．． Table 7 shows the physical properties of the composition to which 5 parts of 2,2-methylene-bis(6-t-butyl-4-methylphenol) was added.

For comparison, Table 7 also shows the physical properties of a composition (Comparative Example 6) that does not contain one part of phenoxyphosphoric diamide in Example 7.

Example 8 To the same graft polymer composition used in Example 2 was added 1.5 parts of bismethylphenoxyphosphoric dipropylamide and 0.5 parts of 2-hydroxy-4-methoxybenzophenone. Table 8 shows the physical properties of the composition.

For comparison, Table 8 also shows the physical properties of a composition (Comparative Example 7) that does not contain bismethylphenoxyphosphoric propylamide in Example 8.

Claims (1)

[Scope of Claims] 1. A stabilizer for polyphenylene ether resins characterized by containing at least one phosphoric amide compound represented by the following general formula (a) or (b): (a)
) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (b) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (■ is R_1, R_2 and R_
5 each represents hydrogen, an alkyl group, an aryl group, an aralkyl group, or an alkylaryl group, R_3, R_4, R
_6, R_7, R_8 and R_9 each represent hydrogen or an alkyl group having 1 to 4 carbon atoms). 2. The stabilizer according to claim 1, which is substantially composed of one or more of the phosphoric amide compounds. 3. The stabilizer according to claim 1, which comprises one or more phosphoric amide compounds and one or more sterically hindered phenols. 4. The stabilizer according to claim 1, which comprises one or more of the phosphoric amide compounds and one or more selected from the group consisting of phosphorous esters and phosphoric esters. 5. A patent claim consisting of one or more phosphoric amide compounds, one or more sterically hindered phenols, and one or more selected from the group consisting of phosphorous esters and phosphoric esters. The stabilizer according to item 1. 6. The stabilizer according to claim 1, which comprises one or more of the phosphoric amide compounds and one or more selected from the group consisting of hydroxybenzotriazole and hydroxybenzophenone. 7 Claims consisting of one or more phosphoric amide compounds, one or more sterically hindered phenols, and one or more selected from the group consisting of hydroxybenzotriazole and hydroxybenzophenone. Stabilizer according to paragraph 1. 8 One or more of the phosphoric amide compounds, one or more selected from the group consisting of phosphorous esters and phosphoric esters, and one selected from the group consisting of hydroxybenzotriazole and hydroxybenzophenone. or the first claim consisting of two or more types.
Stabilizers listed in section. 9 One or more of the phosphoric amide compounds, one or more of the sterically hindered phenols, one or more of the phosphorous esters, and one or more of the phosphoric amide compounds, and one or more of the phosphoric amide compounds; The stabilizer according to claim 1, which comprises one or more selected from the group consisting of triazole and hydroxybenzophenone. 10. The stabilizer according to any one of claims 1 to 9, wherein the phosphoric amide compound is diphenoxyphosphoric amide. 11 The phosphite is triphenylene phosphite, tris-bisphenol A phosphite or tri-
The stabilizer according to claim 4, 5, 8 or 9, which is pt-amyl phenyl phosphite. 12. The stabilizer according to claim 4, 5, 8 or 9, wherein the phosphoric acid ester is triphenylene phosphate, tricresyl phosphate or diphenylnonyl phosphate. 13 Claim 11 or 1, wherein the phosphoric amide compound is diphenoxyphosphoric amide
Stabilizer according to item 2.