JPS58217554A - Stabilized synthetic resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having excellent resistance to light and heat, by blending a specified triazine compd. with a synthetic resin. CONSTITUTION:Cyanuric chloride is reacted with a piperazine. The reaction product is reacted with 2,2,6,6-tetramethyl piperidine-4-spiro-ketalalcohol to obtain a triazine compd. of formula I wherein R1 is H, hydroxyl, alkyl; R2 is lower alkyl; R3-R6 are each H, lower alkyl; A is a group of formula II, III or IV; R9- O-; R7, R8 are each H, alkyl, a group of formula V; R9 is alkyl,aryl, a group of formula VI; B is H, a group of formula VII; n is 1-20. 0.001-10pts.wt. said triazine compd. is blended with 100pts.wt. synthetic resin such as PE.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a synthetic resin composition stabilized against the effects of light, more particularly a triazine composition containing a 2,2,6,6-tetramethylpiperidine-4-spiroketal group. The present invention relates to a synthetic resin composition whose light resistance is improved by containing a type compound.

Synthetic resins such as polyethylene, polypropylene, and polyvinyl chloride are generally sensitive to the effects of light, and may deteriorate due to the effects of light, causing discoloration or a decrease in mechanical strength, and may not be able to withstand long-term use. Are known.

Therefore, in order to prevent the synthetic resin from deteriorating due to this light,
Various stabilizers have been used in the past, but the stabilizing effect of the conventionally used light stabilizers is still insufficient, and the stabilizers themselves are unstable against heat or oxidation. Many of them are easily extracted from the resin by solvents such as water, and many of them also color the resin, making it impossible to stabilize the synthetic resin over a long period of time.

Among these conventionally used light stabilizers, piperidine-based compounds are themselves non-coloring, and they act as UV quenchers rather than UV absorbers.
It has attracted particular attention in recent years.

However, conventionally known piperidine-based compounds have insufficient photostabilizing ability and also have the disadvantage that they are easily extracted from the resin by water.

In addition, these piperidine-based compounds themselves have insufficient heat resistance, and when processing synthetic resins at high temperatures, they often decompose or volatilize, resulting in the loss of young fruits.

Among these piperidine-based compounds, compounds containing a triazine ring have advantages such as the compound itself has relatively good heat resistance, the inexpensive anuric acid chloride can be used as a raw material, and the reaction is easy. have.

Examples of piperidine compounds containing a triazine ring include JP-A-49-21389, JP-A-52-71,486,
IPf Publication No. 52-73,886, Japanese Patent Publication No. 53-9, 7
No. 82, JP-A-53-67.749, JP-A-54-1
06,483, JP-A-54-126,249, JP-A-5'5-98,180, JP-A-55-102,6!
No. 57, JP-A-55-104,279, JP-A-56-
No. 4,659 and Japanese Unexamined Patent Publication No. 1,974/1987 propose rice compounds.

However, all of the compounds described in these publications are derived from 4-hydroxy or 4-amino-piperidines, and their photostabilizing ability and heat resistance of the compounds themselves are not satisfactory. , further improvements were requested.

In view of the current situation, the present inventors have conducted intensive studies and found that the compound represented by the following general formula (1) has excellent photostabilizing ability, and the heat resistance of the compound itself is also extremely good. I found out.

That is, in the present invention, 100 parts by weight of a synthetic resin is mixed with 0.00 parts by weight of a compound represented by the following general formula (1). The present invention provides a stabilized synthetic resin composition containing 1 to 10 parts by weight of OO.

(In the formula, R1 represents a hydrogen atom, oxyl or an alkyl group, % R2 represents a lower alkyl group, R5, R11%
R5 and R6 are hydrogen atoms or concave aluminum R7 and R, respectively.
, Vi, respectively, a hydrogen atom, an alkyl group, and why the compound represented by the above general formula (1) used in the present invention has the above-mentioned 4
Although it is not yet clear whether the compounds used in the present invention have superior photostabilizing ability compared to compounds derived from -hydroxy or 4-aminopiveridines, the compounds used in the present invention are derived from polyhydric alcohols having a neopentyl structure. It is assumed that one of the reasons for this is that the heat resistance of the compound itself is significantly improved because it is a spiroketal compound.

Hereinafter, the compounds used in the present invention will be explained in more detail.

The alkyl group represented by R1 is methyl, ethyl,
Propyl, butyl, isobutyl, sec-butyl, tert-butyl, hexyl, heptyl, octyl, dodecyl, benzyl, hydroquinemethyl, 2-hydroquinethyl, 2-hydroxypropyl, 2,3-dihydroquinepropyl, 2
-Hydroxybutyl, 2-hydroxyoctyl, acetoxyethyl, propionylethyl, ofthyroylethyl, 2,3-evoquinprovil, and the like.

Examples of the lower alkyl group represented by R12, R5, R5, R5, and R6 include methyl, ethyl, propyl, butyl, and the like.

The alkyl groups represented by R7 and R8 include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tertiary-butyl, hexyl, octyl, 2-ethylhexyl, 5-octyl, amyl, doamyl, tetraamyl, hexaamyl, octaamyl. , hydroquine methyl, hydroxyethyl, metquinemethyl, methoxyethyl, butquinethyl, dimethylaminopropyl, and the like.

The alkyl group represented by R9 includes methyl, ethyl,
Butyl, amyl, hexyl, octyl, 2-ethylhexyl, amyl, isodecyl, dooramyl, trizocyl,
Examples include tetraamyl, octaamyl, methquinethyl, ethoxyethyl, butquinethyl, and examples of the aryl group include phenyl, tolyl, quinryl, tert-butylphenyl, octylphenyl, nonylphenyl, and the like.

Table-1 Abuse 2 /P64 5 A6 Black 7 8 &9 10 The compound represented by the general formula (1) used in the present invention is, for example, reacted with cyanuric chloride and piperazine, and then reacted with 2.2, 6.6-tetramethylpiperidi/
-4-Suviroke can be easily produced by reacting a cool alcohol compound. Alternatively, it can be easily produced by reacting cyanuric chloride with 2,2,6,6-tetramethylbiperidine-4-spiroketal alcohol compound and then reacting this with hyheridines.

The present invention will be explained in more detail below using specific synthesis examples, but the present invention is not limited by the following synthesis examples.

Synthesis Example I A) Preparation of N,N-bis(4,6-dichloro-1,5,5-triazid/Z-2-yl)piperazine Dissolve 12.9 r of anhydrous piperazine in 80 ml of acetone and 0 to 5°C. It was cooled to To this, cyanuric chloride 55.5
A solution of V dissolved in 500° C. of acetone was added dropwise over 1 hour, and the mixture was stirred at 10 to 5° C. for 1 hour. A solution of IJium 121 (hydroxide) dissolved in 80 d of water was added dropwise to this at the same temperature over 1 hour, and the mixture was further stirred for 4 hours. water 1
50- was added thereto, separated by r, washed with water, and dried to obtain a white powder product with a melting point of 300°C or higher.

B) N,N-bis[4,6-bis(9-aza-3-ethyl-8,8,10,10-tetramethyl-1,5-dioxaspiro[:s,s]-3-undecylmeth) Kin)−
1,3,5-triazin-2-yl]pibe2dine (ju-
1, A2 compound), bond 9-aza-3-nibble-8,8,10,10-tetramethyl-1,5-dioxaspiro[5,5]-]s-undenelmethanol 27.1f It was dissolved in 100ml of toluene, NaH3,5F was added, and the mixture was stirred at 80 to 100°C for 1 hour. To this, N,A-bis(4,6-dichloro-1,5,5-)riazin-2-yl)piperazine 8.
5v was gradually added, and the mixture was heated under refluxing toluene for 12 hours. The reaction solution was passed through hot cedite, washed with water, dried, and the solvent was removed to give 444ml of product 202 as a white powder. The desired product was obtained as a white powder with crystals 1 to 1 and a melting point of 229°C.

Synthesis Example 2 N,N-bis[4,6-bis(9-aza-3-ethyl-
8,8,9,,1n°, 1-leaf pentamethyl-1,5-dioxaspiro[S,S]-+-undi/rumethoxy)
-1,3,5-) Production of riazin-2-ylcopiperazine (Table 1, Mu3 compound) 9-aza-3-ethyl-8,11,9,10,10-pentamethyl-1,5- Dioxaspiro[:s,s)-3
-Undenelmethanol 6.5ft, N, with screws (4
゜6-dichloro-1,5,5-)riazin-2-yl)
Piperazine 1.9? , powdered sodium hydroxide 1.2f!
Then, 40 ml of toluene was taken and refluxed under a nitrogen stream for 20 hours. After washing with water and drying, it was treated with Gyoward 700 (adsorbent manufactured by Kyowa Chemical) to remove the solvent. 50% n-hexane to the residue
- was added to obtain the product 1.51 as a white powder. The product was recrystallized from benzene/hexane to obtain the desired product as a white powder with a melting point of 220°C.

The present invention improves the light resistance of a synthetic resin by adding the compound represented by the general formula (1) to the synthetic resin.
．． 0.001 to 10 parts by weight, preferably 0.01 to 3 parts by weight.

Examples of synthetic resins to be improved in light resistance in the present invention include α-olefin polymers such as polyethylene, polypropylene, polybutene, and poly-3-methylbutene, ethylene-vinyl acetate copolymers, and ethylene-propylene copolymers. Polyolefins such as polymers and their copolymers, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, brominated polyethylene, chlorinated rubber, vinyl chloride Vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-prohylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride -Styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride -Vinylidene chloride-
Vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, internal plasticization Copolymerization of halogen-containing synthetic resins such as polyvinyl chloride, petroleum resins, coumaron bark, polyvinyl acetate, acrylic resins, styrene and other monomers (e.g. maleic anhydride, butadiene, acrylonitrile, etc.) methacrylate III resins such as acrylonitrile-butadiene-styrene copolymers, acrylic ester-butadiene-styrene copolymers, methacrylic ester-butadiene-styrene copolymers, and polymethyl methacrylate;
Polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, linear polyester, polyphenylene oxide, polyamide, polycarbonate, polyacetal, polyurethane, cellulose resin, phenol resin, urea resin, melamine resin, epoxy l+4 resin,
Examples include unsaturated polyester resins and silicone resins. Further, rubbers such as imprene 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.

Oxidative stability can be improved by further adding a phenolic antioxidant to the composition of the invention.

Examples of these phenolic antioxidants include 2,
6-di-5-butyl-p-cresol, 2,6-diphenyl-4-octadenroquinephenol, stearyl-
(5,5-di-methyl-4-hydroquinbenzyl)thioglycolate, stearyl-β-(4-hydroΦ-5
, 5-di-tert-butylphenyl)propionate, distearyl-3,5-di-tert-butyl-4-hydroquine benzylphosphonate, 2,4.6-)lis(3',5'
-di-5-butyl-4'-hydroquinebenzylthio)-
1,5,5-triazine, distearyl (4-hydroquine-3-methyl-5-$5butyl)benzylmalonate, 2. E-methylenobis (4-methyl-6-tert-butylphenol), 4,4'-methylenebis (2,6-di-6-butylphenol), 2゜2'-methylenebis [
6-(1-methylcyclohexyl)p-cresol],
Bis[3,5-bis(4-hydroxy;/-5-5-butylphenyl)butyric and fuglycol ester, 4.4'-butylizo/bis(6-5-5-butyl-m-cresol), 2, 2'-ethylidene bis(4,6-di-tert-butylphenol), 2,2'-ethylidene bis(
4-sec-butyl-6-tert-butylphenol), i,
j, 3-) Lis (2-methyl-4-hydroxy-5-
tert-butyl phenyl) fluoride, bis[2-tert-butyl-
4-Methyl-6-(2-hydroxyN/-5-6th-butyl-5-methylbenzyl)phenyl]terephthalate, i
, 3.5-tris(2,6-dimethyl-3-hydroquine-4-tert-butyl)penzylisonanurate, 1.5
．． 5-tris(3,5-di-5-butyl-4-hydroquinbenzyl)-2,4,6-trinotylbenzene, tetrakis[methylene-5-(5,5-di-5-butyl-4
-hydroquinphenyl)globionet]methane, 1,
3.5-tris(5,5-di-5-butyl-4-hydroxybenzyl)isocyanurate, 1,3.5-)lis[(3,s-di-5-butyl-4-hydroxyphenyl)propionyl Quinethyl] isone anurate, 2-
Octylthio-4,6-di(4-hydroquine-5,5-
Phenols such as di-tert-butyl)phenoquine-1,5,5-)riazine, 4,-4-thiobis(6-5-butyl-m-cresol) and 4,4'-butylidenebis(2-57') methyl-5-methylphenol) carbonate oligoester (for example, polymerization degree 2,5,4°5.6,7
, 8, 9, 10, etc.).

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 alkylthioglopionic acids such as butyl, octyl, lauryl, and stearyl. Examples include esters of glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, trishydroquine ethyl isocyanurate (eg, pentaerythritol tetone lauryl thiopropionate).

Light resistance and heat resistance can be improved by further adding a phosphorus-containing compound such as phosphite to the composition of the present invention. Examples of the phosphorus-containing compound include trioctyl phosphite, trichouryl phosphite,
Tridenyl phosphite, octyl-diphenyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, triphenyl phosphite, tris(butquinethyl) phosphite, tris(nonylphenyl)
Phosphite, distearyl pentaerythritol diphosphite, tetonia (tridecyl)
-1,1,5-) squirrel (2-mether-5
-5th-butyl-4-hydroxyphenylene/I/)butafdiphospha-1to,teto2 (CI2-15 mixed alkyl)
-4,4'-inpropylidene diphenyl diphosphite, tetra(tridecyl) -4,4'-butylidene bis(5-methyl-6-5-phthylphenol) diphosphite, tris(3,5-di-5-butyl -4-hydroquinphenyl) phosphite, tris(7)-dimixed nonylphenyl) phosphite, hydrogenated -4,4'-improbiritene diphenol polyphosphite, bis(
octylphenyl)-bis(4,4'-butylidenebis(3-methyl-6-6-butylphenol)]・]1,
6-hexanediol diphosphite phenyl 4.4
-isopropylidene diphenol pentaerythritol diphosphite, bis(2,4-di-5-butylphenyl) pentaerythritol diphosphite, bis(2
, 6-di-5-butyl-4-methylphenyl) pentaerythritol diphosphite, TrisC4, 4'-impropylidene bis(2-5-phthylphenol)] phosphite, phenyl diindenle phosphite, (
nonylphenyl) pentaerythritol diphosphite, tris(1,!+-distearoyloxyinglovir) phosphite, 4,4'-isopropylidene bis(2-5th phthylphenol) cy(nonylphenyl)
Phosphite, 9.10-di-hydro-9-oxa-
10-phosphonoaphenanthrene-10-oxide,
Tetrakis(2,4-di-tert-butylphenyl) -4
, 4'-pyphenylene diphosphonite and the like.

The light resistance of the composition of the present invention can be further improved by adding other light stabilizers to the composition, such as 2-hydroquine-4-methquinenzophenol, 2-Hydroxy-4-n-octoquine benzphenone, 2,2'-dihydroquine-4-
Hydroacid benzophenones such as methquin benzophenone, 2,4-dihydroquimbe 7-cyphenone, 2-(2'
-Hydroquine-? -1-butyl-5'-methylphenyl)-S-chloroben/)ri7/-l, 2-(2'-hydroxy-3',c!-di-t-butylphenyl)-5-
Chlorobenztriazole, 2-(2'-hydroquine-
5'-methylphenyl)benzotriazole, 2-(
Benzotriazoles such as 2-hydroxy-s, s'-t-y mylphenyl) benzotriazole, phenylsaline), pt-butylphenylsaline), 2,4-di-t-butylphenyl- 3,5-
Benzoates such as di-t-butyl-4-hydroquine benzoate, hexatene-3,5-di-t-butyl-4-hydroquine benzoate, 2,2'-thiobis(4
-t-octylphenol)Nl salt, (: 2, 2'
-thiobis(4-t-octylphenolate))-n
-butylamine N1, (3,5-di-t-butyl-4-
Hydrogen dibenzyl)phosphonic acid monoethyl ester N
Nickel compounds such as i salts, α-cyano-β-methyl-
β-(p-NOTOKIL/), NINYL) ACRYLICS Methyl-substituted acrylonitrile fA and UN-2-:c, tylphenyl-g-2-nidoyasi-5-tert-butylphenyl-5-tert-butylphenyl sulfate diamide, N- 2-ethylphenyl-14-
Examples include oxalic acid dianilides such as 2-ethoxyphenyl oxalic acid diamide.

In addition, if necessary, the composition of the present invention may include a metal deactivator, a nucleating agent, a metal soap, an organic tin compound, a plasticizer, an evokinized compound, a pigment, a filler, a blowing agent, an antistatic agent, a It can include combustion side, extinguishing, force one-stroke auxiliary cutting, etc.

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

Example 1 Polypropylene 100 Heavy electric part stearyl β-3,5-di-5-butyl-4-0,
2-Hydroxyphenylglopionate stabilizer (Table 2) 0.3 A press sheet with a thickness of 0.3 m was prepared using the above formulation, and high-pressure mercury 2
A light resistance test was conducted using a lamp. A light resistance test was also conducted on the sheet after it had been immersed in hot water at 80° C. for 15 hours. The results are shown in Table-2.

Table 2 Example 2 It is known that ordinary stabilizers lose their effectiveness significantly due to volatilization, decomposition, etc. during high-temperature processing of resins.

In this example, the effect of high-temperature processing was confirmed by repeatedly performing extrusion processing.

After mixing the resin and additives in a mixer for 5 minutes according to the following formulation, a compound was prepared in an extruder. (Cylinder temperature 250℃, 240℃, head die temperature 250℃
After extrusion was repeated five times (at a rotation speed of 20° C. and a rotational speed of 2 rpm), a test piece was prepared using an injection molding machine using this compound.

(Cylinder temperature: 240°C, nozzle temperature: 250°C, injection pressure: 475 Kq/c!l) Using the obtained test piece, a light resistance test was conducted using a high-pressure mercury lamp. In addition, the same test was conducted for a sample that had been extruded once. The results are shown in Table-3.

<Blend> Ethylene-propylene copolymer resin 100 parts by weight Calcium stearate 0.2 parts by weight Stearyl-β-3,5-di-30.1-butyl-4-hydroxyphenylpropionate Dilaurylthiodiglobionate 0.2 Stable Agent (Table-s
) 0.2 Table -5 Example 3 Polyethylene 100 parts by weight Ca-stearate 1.0 Tetrakis [methylene-3-(5,5-0,1-di-tert-butyl-4-hydroxyphenyl)propionate cometanedi] Stearyl thiodiglobionate 0.3 Stabilizer (Table 4) 0.2 The above blend was mixed and then pressed to form a sheet with a thickness of 0.5 m. Using this sheet, the light resistance was measured in a weather oven, and the time until it became brittle was measured. The results are shown in Table 4.

Table 4 Example 4 Ethylene-vinyl acetate copolymer 1aa Part by weight 2.6-di-tert-butyl-p-cresol 0
．． 1Ca-stearate 0.
1 Zn-stearate 0.1 Diisodecyl phenyl phosphite 0.2 Stabilizer (Table 5) 0.2 The above blend was mixed on a roll at 130°C, then pressed at 140°C to form a 7-plate (thickness: 0.4 m). )It was created.

The residual tensile strength of this sheet was measured after 500 hours of irradiation in a weather camera. The results are shown in Table-5.

Table 5 Example 5 Polyvinyl chloride 1004-Dabe dioctyl phthalate 48 Eboki 7ated dog bean oil 2 Trisnonylnoenylphosnoai) 0.2Ca-stearate
1.0Zn-stearate
0.1 Stabilizer (Table 6) 0.3 The above blend was kneaded on a roll to form a sheet with a thickness of 1 layer.

Using this sheet, a light resistance test was conducted in a weather camera. The results are shown in Table-6.

Table-6 Example 6 ABS resin 100 @ placement part 4.4'-butylidene bis(2-5o, 1-butyl-
(m-cresol) Stabilizer (Table 7) 0.3 The above blend was kneaded with a roll and then pressed to make a 7-sheet with a thickness of 3 sheets. Using this sort, the residual tensile strength after 800 hours of irradiation was measured using a weatherometer. The results are shown in Table-7.

Table-7 Example 7 Polyurethane resin (Asahi Denka U-100) +00
Separate part Ba-stearate 0.7 Zn-stearate 0.3 2.6-di-tert-butyl-p-cresol 0.1
Stabilizer (Table 8 > 0.3 above formulation'
v1: Knead J on cole at 70℃ for 5 minutes, then knead at 120℃
Pressing was carried out for 5 minutes to create a sheet with a thickness of 0.5 mm.

This sort was irradiated for 30 hours and the residual elongation rate was measured using a fade meter.

The results are shown in Table-8.

Claims (1)

[Scope of Claims] A stabilized synthetic resin composition obtained by adding 0.001 to 10 parts by weight of a compound represented by the following general formula (1) to 100 parts by weight of a synthetic resin. (In the formula, R1 represents a hydrogen atom, oxyl or alkyl group, R2 represents a round alkyl group, R5, R11, R
, and R6 are hydrogen atoms or lower alkyl R7 and R8, respectively.
represent a hydrogen atom or an alkyl group, respectively. )