JPS6230135A - Stabilizer for synthetic resin - Google Patents

Abstract

PURPOSE:A stabilizer for synthetic resins, consisting of a specific piperazine derivative and capable of remarkably improving not only heat aging resistance but also weather resistance by incorporation thereof together with various phenolic antioxidants in synthetic resins. CONSTITUTION:A stabilizer for synthetic resins consisting of a piperazine derivative expressed by formula I[R and R' and H or 1-6C alkyl; X is formula II, formula III, etc. (R1 and R2 are 1-18C alkyl, cycloalkyl, aryl, etc.; B is oxygen, sulfur atom, etc.); A is oxygen, sulfur or nitrogen atom; Z is formula IV, formula V, etc.; n and m are 0-4; l is 1-4]. 0.05-1pts.wt., preferably 0.08-0.5pts.wt. above-mentioned stabilizer, together with a phenolic antioxidant, is incorporated in 100pts.wt. synthetic resin. Preferably, a phosphite based compound, light stabilizer, etc., can be incorporated to further improve the heat and weather resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel stabilizer that is incorporated into synthetic resins to suppress thermal oxidative deterioration and photo-induced deterioration of the resins. Processed products of this synthetic resin are useful as beer crates, agricultural films, automobile exterior parts, and hollow containers.

[Conventional technology]

In general, synthetic resins such as polyethylene, polypropylene, polyvinyl chloride, and ABS undergo color change due to heat deterioration or oxidation during molding, or due to weather resistance deterioration mainly caused by ultraviolet rays and oxygen even after they are made into N-grade products. It is known that it cannot withstand long-term use due to changes in mechanical strength and a decrease in mechanical strength.

In order to eliminate such drawbacks, it is necessary to add one or more types of heat stabilizers or light stabilizers to the synthetic resin to suppress various types of deterioration. Such thermal stabilizers generally include tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)-probionate]methane (trade name, RA-1010, manufactured by Tepa Geigy) and the like (
7) 7:r-/--based antioxidants are mainly used, and as light stabilizers, bis(2,2,6,6-tetramethyl-4
Hindered amine compounds such as -piperidinyl)sepacate (trade name, Sanol L8770, manufactured by Sankyo@) are generally known.

However, the drawback is that there is an antagonistic effect between certain heat and light stabilizers. That is, for the purpose of improving both the heat aging resistance and weather resistance of synthetic resins, for example, RA-1010 is used as a heat stabilizer, and Sanol L is used as a light stabilizer.
It is known that when S 770 is added to a synthetic resin in combination, the heat aging resistance is significantly lowered compared to when each is added alone.

[Specific measures to solve the problem]

In view of the current situation, the inventors of the present invention have made extensive studies and found that when blending various phenolic antioxidants with the aim of improving the heat aging resistance of synthetic resins, the following general formula (I) is used.
It has been found that by adding a piperidine derivative represented by the following in combination, a polymeric material having significantly improved weather resistance as well as heat aging resistance can be obtained.

(Structure of the Invention) The present invention provides a stabilizer comprising a piperidine derivative represented by the following general formula (1).

[In the formula, R and R' may be a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and may be different from each other. X represents a hydrogen atom, R, -C-B-, or I; Y represents -C-B-R, -, -B-C-R5, or an alkylene group having 1 to 6 carbon atoms; A represents an oxygen atom, a sulfur atom, or -N-. R, and R2 and R
6 is an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group,
Indicates an aryl group, an alkylaryl group, or an arylalkyl group. R3 is an alkyl group having 1 to 4 carbon atoms, R4 and R
5 represents an alkylene group having 1 to 18 carbon atoms ○ Z is a hydrogen atom or +CH2-containing C or 4CHJ,
C-CH2CH, or -CH2-(,'H-CH
, -, etc. or Ca or Ba. n and m are numbers from 0 to 4, and l represents a number from 1 to 4. ] The formula of a typical compound as a stabilizer represented by the formula (I) is shown below.

N,N'-bis(2-(tetradecyloxycarbonyl)ethyl)hyperazine (melting point 44°C) N,N'-bis(2-(tetradecyloxycarbonyl)-1-methylethyl) (melting point 52~ 53°C) N,N'-bis(2-(tetradecyloxycarbonyl)ethyl)-2,5-cymetylhydrazine (melting point: 43°C) O N,lJ'-bis(2-(octadecyloxycarbonyl) ) Ethylcopiperazine (melting point 57-59°C) N,N'-bis[2-(tetradecyloxycarbonyl)methyl]hyperazine (melting point 87-88°C) N,N'-bis(2-(tIJ f-zylcarbonyloxy)ethylcopiperazine (melting point 48-50°C) N,N'-bis(2-(2,2,6,6-tetramethyl-4-piperidyloxycarbonyl)ethylcopiperazine (melting point 122 ~123℃) Tetrakis(3-(1-piperidyl)propionyloxymethylcomethane (liquid at 20℃) Tetrakis(3-(1-morpholyl)propionyloxymethylcomethane (liquid at 20℃) Tetrakis(3- (4-(2-(tetradecyloxycarbonyl)ethyl)-piperazyl]propionyloxymethyl]methane The amount of the piperazine derivative represented by the general formula (IJ) of the present invention is p 0 with respect to 100 parts by weight of the synthetic resin. .05 to 1 part by weight, preferably 0.08 to 0
．． Usually used in a proportion of 5 parts by weight.

(Other additives used in combination) When the stabilizer of the present invention is used in combination with a phenolic antioxidant, a sulfur antioxidant, or a light stabilizer, processed resin products with excellent thermal stability and weather resistance can be produced. can do.

Such phenolic antioxidants include, for example, 2,
6-di-t-butyl-p-cresol, stearyl-(
3,6-di-t-methyl-4-hydroxybenzyl)thioglycolate, stearyl-β-(4-hydroxy-
3,5-di-t-butylphenyl), propionate,
Distearyl (4-hytroquine-3-methyl-5-t-
butyl)benzylmalonate, 2.2'-methylenebis(4-methyl-6-t-butylphenol), 4.4'
-methylenebis(2,6-di-t-butylphenol)
, 2,2'-methylenebis(6-(1-methylcyclohexyl) p-cresol), bis[3,3-bis(4-
Hydroxy-3-t-butylphenyl)butyric acidora glycol ester, 4,4'-butylidene bis(
6-t-butyl-m-cresol), 1,1.3-)
Lis(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1. :(,5-)lis(3,5-c t-7'thyl-4-hydroxybenzyl) -2,4
, 6-trimethylbenzene, tetrakis[methylene-3
-(3,5-di-t-butyl-4-hydroxyphenyl)propionate comethane, 1.3.5-)lis(3
, 5-di-t-butyl-4-hydroxybenzyl)isocyanurate-1', 1.3.5-tris((3,5-di-
t-Butyl-4-hydroxyphenyl)propionyloxyethyl coin cyanurate, 2-octylthio-4
,6-di(4-hydroxy-3,5-di-t-butyl)
Examples include phenoxy-1,3,5-)riazine and 4,4'-thiobis(6-t-butyl-m-cresol).

In addition, examples of sulfur-based antioxidants include dilauryl thiodipropionate, dilauryl thiodipropionate, pentaerythritol tetra(β-laurylthiopropionate), 1.3.5-)lys-β-latearylthio Examples include propionyloxyethyl in cyanurate. These stabilizers are added in an amount of 0.0% per 100 parts by weight of the synthetic resin.
It is used in a proportion of 0.05 to 1 part by weight.

By further adding a phosphite-based compound to the resin composition containing the stabilizer of the present invention, heat resistance and weather resistance can be greatly improved. Examples of such compounds include phosphite-based compounds such as trioctyl phosphite, trilauryl phosphite, triphenyl phosphite, tris(nonylphenyl) phosphite, and distearyl pentaerythritol diphosphite.

In addition, depending on the use, weather resistance can be improved by further adding a light stabilizer (ultraviolet absorber). These include compounds such as benzophenone, benzotriazole, succinate, substituted acrylonitrile, and nickel complex salts. This is used in a proportion of 0.05 to 5 parts by weight, preferably 0.1 to 2 parts by weight, per 100 parts by weight of the synthetic resin.

In addition, if necessary, for example, pigments, fillers, foaming agents, antistatic agents, antifogging agents, surface treatment agents, lubricants, flame retardants, metal deactivators, nucleating agents, metal soaps, clarifying agents, Processing aids, antifungal agents, fungicides, mold release agents, and the like can also be included.

(Synthetic resin) Examples of synthetic resins in which the stabilizer of the present invention is blended are:
polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride,
Polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene chloride, brominated polyethylene, chlorinated rubber, vinyl chloride-vinyl acetate 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 terpolymer, vinyl chloride-styrene-acryloni) IJ
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-maleate ester copolymer, vinyl chloride-methacrylate ester copolymer, vinyl chloride-
Acrylonitrile copolymers, halogen-containing synthetic resins such as internally plasticized polyvinyl chloride, α-olefin polymers such as polyethylene, polypropylene, polybutene, poly-3-methylbutene, crosslinked polyethylene, or ethylene-
Polyolefins such as vinyl acetate copolymers, ethylene-propylene copolymers and their copolymers, polystyrene, polyvinyl acetate, acrylic resins, styrene and other monomers (e.g. maleic anhydride, butadiene, acrylonitrile, etc.) copolymers, acrylonitrile-butadiene-styrene copolymers, acrylic ester-butadiene-styrene copolymers, methacrylic ester-butadiene-styrene copolymers, methacrylate resins such as polymethyl methacrylate, polyvinyl alcohol,
Polyvinyl formal, polyvinyl butyral, linear polyester, polyamide, polycarbonate, polyacetal, polyurethane, cellulose resin, phenolic resin, area resin, melamine resin, evogishi resin,
Examples include unsaturated polyester resins and silicone resins. Furthermore, rubbers such as inbrene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, and blends of these resins may also be used.

Example 1 (Exemplary Compound No. 1) In a Yotsuro flask, myristyl acrylate 1o, oy
, 1.61 y of piperazine and 60 d of ethanol were added, stirred in a nitrogen stream, and heating started.

After continuing heating at a temperature of 60° C. for 5 hours, white crystals were precipitated when the mixture was cooled to room temperature.

These crystals are distributed from house to house and recrystallized using ethanol.
10.67 of the target product was obtained (yield: 91 cm).

(Analytical value) H”-NMR absorption spectrum (CDCl2.δ (ppm
)) o, 7o ~ 1.76 (s4H, m), 2.2
6-2.87 (16H, m), 4.05 (
4H,t) IR absorption spectrum (KBr wave number (C
m'))2910.1730.1325.1310゜1
185.1155.720゜MS (m/e * accurate mass spectrometry) 622.6
(M”) Example 2 (Exemplary Compound No. 2) In a four-piece flask, 10.0 y of myristyl crotonate was added.
, 1.537 liters of piperazine and 60 t/ml of ethanol were added, stirred in a nitrogen stream, and started heating. After continuing heating at a temperature of 60° C. for 10 hours, white crystals were precipitated when the mixture was cooled to room temperature.

The crystals were separated from each other and recrystallized with ethanol to obtain the desired product 2.71 (yield 23.4%).

(Analytical value) Hl-NMR absorption spectrum CCDCl3. δ(ppm
) ) 0.66-1.83 (60H, m), 2.0
7-2.75 (12H, m), 2.90-3.33
(2Lm), 4.03 (4H,t).

IR absorption spectrum/'(KBr wave number (Call")
) 2940, 1735, 1330, 1195.1155
゜MS (m/e (relative strength)) 650 (43, M”), 394 (62), 326
(43), 113 (100), 87 (41)
Example 3 (Exemplary Compound No. 7) 2,2,6.6-tetramethyl-
4-Acryloyloxy-piperidine 15.0y.

3.0y of piperazine and 60WI of ethanol were added, stirred in a nitrogen stream, and heating started. After continuing heating at a temperature of 60° C. for 5 hours, the mixture was cooled to room temperature, and ethanol was distilled off under reduced pressure to obtain white crystals.

This crystal was recrystallized with acetone, and the target object 164
y was obtained (yield: 93 cm).

(Analytical value) H'-NMR absorption spectrum (CDC63, δ (ppm
) ) 0.65-1.40 (30H, m), 1.9
3 (4H, dd), 2.26-2.90 (16H, m
), 4.92-5.55 (2H, m) IR absorption spectrum (KBr wave number (Cm-'')) 33
10.2975, 1720, 1345.1300, 1
235, 1175, 750MS (m/e (relative intensity)) 508 (1, M”), 140 (33) 124 (10o)
, 58 (27) Next, the stabilizing effect of the compounds of the present invention will be illustrated by application examples.

Polypropylene powder 1 with a limiting viscosity of 1.9 measured in tetralin at 135°C and 98% isotactic.
Each additive shown in Table 1 was added to 00 parts by weight and thoroughly mixed with a mixer.

Then, this mixture was melt-kneaded and granulated using an extruder with a cylinder temperature of 260° C., L/D=20°, and a diameter of 20 mm. The pellets thus obtained were heated to a thickness of 0.5 at 230°C.
A test piece was prepared by compression molding into a sheet of 50 m.

Heat aging resistance was determined by heating a test piece in a circulating air oven at 150°C and measuring the time required for the test piece to brown and become brittle due to oxidative deterioration.

Weather resistance was measured using an Atlas 65/XW-WR xenon weather meter, and when the test piece was irradiated with light at a black panel temperature of 80°C, and the test piece was bent at 180°C, the test piece became brittle and cracked. The time required to do so was measured.

The results were as shown in Table 1.

The abbreviations in the table are as follows.

*1 Tetrakis (3-(3,5-di-t-butyl-4-
(diphenyl in liquid) propionyloxymethyl comethane *2 Product name Sankyo ■Nol LS770 (product name) *3 Product name Tinuvin 326 manufactured by Adeka Argus (product name) *4 Product name Marri PEP-8 (Adeka Argus Sharif) (Left below)

Claims (1)

[Claims] 1) General formula, ▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R and R' represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and may be different from each other. X is a hydrogen atom, or ▲There is a mathematical formula, chemical formula, table, etc.▼, or ▲There is a mathematical formula, chemical formula, table, etc.▼, or ▲There is a mathematical formula, chemical formula, table, etc.▼. Y indicates ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or it indicates an alkylene group with 1 to 6 carbon atoms. A represents an oxygen atom, a sulfur atom, or a nitrogen atom. B indicates an oxygen atom, a sulfur atom, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. R_1, R_2 and R_6 represent an alkyl group, cycloalkyl group, aryl group, alkylaryl group or arylalkyl group having 1 to 18 carbon atoms. R_3 is carbon number 1
~4 alkyl group is shown. R_4 and R_5 represent an alkyl group having 1 to 18 carbon atoms. Z is -(CH_2)-_4C or -(CH_2)-
_3CCH_2CH_3 or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Alkylene group, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼or ▲There are mathematical formulas, chemical formulas, tables, etc.▼Or it indicates Ca or Ba. n and m are numbers from 0 to 4, and l represents a number from 1 to 4. ] A stabilizer for synthetic resins comprising a piperidine derivative represented by: