JPH0222265A - Tetraalkylpiperidine compound - Google Patents

Abstract

NEW MATERIAL: A tetraalkylpiperidine compd. represented by formula I [wherein R is H, O, 1-8C alkyl or -COR₅, R₅ is -C(R₃)=CH₂, 1-6C alkyl, phenyl or -CO-O-1-4C alkyl, R₁ is independently -CH₃ or -CH₂ (1-4C alkyl) or two groups R₁ are combined to form -(CH₂)₅-, R₂ is -CH₃ or -CH₂ (1-4C alkyl) or two groups R₂ are combined to form -(CH₂)₃-, X is 1-12, R₃ is H or 1-4C alkyl and R₄ is H, 1-4C alkyl or 1-4C alkoxyl].

EXAMPLE: A compd. represented by formula II.

USE: This new material is useful as a light stabilizer in a polymer system and effective for car paint, especially effective for topcoat of two-layered metallic paint.

PROCESS: A compd. represented by formula III and a compd. represented by formula IV are reacted at raised temp. to obtain the compd. represented by compd. Ia (wherein Ra is H or 1-4C alkyl) of formula I.

COPYRIGHT: (C)1990,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides compounds suitable as light stabilizers in polymeric systems,
This invention relates to novel tetraalkylpiperidine compounds.

According to the present invention, a compound represented by the following formula (1) is provided.

In the above formula, R each independently represents hydrogen, oxygen, C0-8 alkyl or -CORs, and R6 is -C(Rff)
"CHt, C+ ~6 alkyl, phenyl, -〇〇-〇-C, ~4 alkyl or -NR?R11, C0CJs
, CHzCbHs , -C00Cl~, 2 alkyl or -C0OH, R7 is hydrogen, C, -, , alkyl, Cs++bcycloalkyl, phenyl, phenyl01
~4 alkyl or Cl-1□ alkylphenyl, R6 represents C3-1□ alkyl or hydrogen, and Rt each independently represents -CHs or -CH! (C, ~4
(alkyl), or two R1s together form a group -(CHz)s-, and R2 each independently represents -CH, or -CHl (C1~, alkyl), or two R1s R1 together form a group -(CHa)
, -, X represents an integer from 1 to 12, and R1
each independently represents hydrogen or 01-4 alkyl,
R4 is each independently hydrogen, C1-4 alkyl or 0
Represents 1-4 alkoxy.

Preferably, the oxy group is in the ortho or para position (more preferably ortho position) to the amino group in the phenyl group with R4 of formula I.

Preferably R is R' i.e. hydrogen, 01-4 alkyl or -Co-R5' and R% is -CH=CHz,
C+ ~4 alkyl or -co-oc, ~4 alkyl.

Preferably, RI and R2 are each -CHs.

Preferably R1 is R3', hydrogen or methyl, more preferably hydrogen.

Preferably R4 is hydrogen.

In this specification, any CI-s alkyl or CI-b alkyl group is preferably a C1-4 alkyl group, any C1-4 alkyl group is preferably methyl or ethyl, and any alkoxy group is preferably methoxy. or ethoxy.

In this specification, any group that can be straight or branched is straight or branched. When symbols appear more than once in a formula, their meanings are independent of each other.

Furthermore, according to the present invention, there is provided a method for producing a compound of formula I, which method comprises: converting a compound represented by the following formula (1), (wherein the symbols represent the same meanings as defined above) into a compound represented by the following formula (1). , (wherein the symbols represent the same as in the above definition) at elevated temperature to oxidize the compound of the following formula 1a to produce a compound in which Ra is oxygen in formula 1a, If desired, a compound in which Ra is hydrogen in formula 1a can be prepared by the following formula (1) or (2), (Ri-CoSO(m Ri-CO→a1 (V) (wherein, Hal represents chlorine or bromine, and R3 is the above-mentioned Representing the same thing as defined above) is reacted with a compound represented by the following formula 1c, (in the formula, R
a represents hydrogen or C1-4 alkyl, other symbols represent the same as in the above definition), and optionally in formula 1a, Ra is hydrogen (in the formula,
(symbols represent the same things as in the above definition).

In the method of the invention, the temperature is preferably between 40 and 160
°C range.

Compounds of formulas n, m, rv and V are known or can be produced from known compounds by known methods.

Further, according to the present invention, there is provided a composition comprising a polymeric material and a compound of formula (2).

Furthermore, according to the invention, a method for stabilizing lacquer paints based on acrylic, alkyd or polyester resins (if desired these may be crosslinked by melamine/formaldehyde resins, epoxide resins or polyisocyanates) is provided, the method comprising incorporating one or more compounds of Formula I into a resin.

Furthermore, according to the invention, acrylic, alkyd and/or polyester resins containing one or more compounds of formula (1) (if desired, these may be crosslinked by melamine/formaldehyde resins, epoxide resins or polyisocyanates) A lacquer paint based on the following is provided.

The concentration of the compound of formula (1) used in the polymeric material is 0.
0.01 to 8% by weight, preferably 0.02 to 1% by weight, giving a distinct improvement in the sunlight and weathering stability of organic pigments in baking paints and reducing the occurrence of hairline cracks as a result of outdoor exposure. and reduce the tendency to lose luster. It is also useful in metallic paints, providing excellent long-term stability of the clear top coat of two-layer metallic paints. In such coatings, the compound of formula I can be added to the metallic undercoat, the transparent topcoat or both, preferably to the transparent topcoat. The metal surface to be painted may be primed with a brimer paint as is conventional in the art of painting metal surfaces.

The compound of formula I may be added before, during or after the polymerization step, in solid form, in solution, preferably in liquid concentrate containing from 20 to 80% by weight of compound of formula I and from 80 to 20% of solvent. or as a solid masterbatch composition comprising 20-80% by weight of a compound of formula I and 80-20% by weight of a solid polymeric material identical to or compatible with the polymeric material to be stabilized. May be added.

Suitable polymeric materials include plastic materials, such as polyethylene, polypropylene, ethylene/propylene copolymers, polyvinyl chloride, polyester, polyamide,
Includes polyurethane, polyacrylonitrile, ABS, acrylates, terpolymers of styrene and acrylonitrile, styrene/acrylonitrile and styrene/butadiene. Other plastic materials can also be used such as polybutylene, polystyrene, chlorinated polyethylene, polycarbonate, polymethyl methacrylate, polyphenylene oxide, polypropylene oxide, polyacetal, phenol/formaldehyde resins and epoxy resins.

Preferred plastic materials are polypropylene, polyethylene, ethylene/propylene copolymers and ABS. Natural polymers, such as natural rubber, can be stabilized and are also useful in lubricating oils containing polymeric materials.

The compound of formula (II) can be incorporated into the polymeric material to be stabilized by known methods. Of particular importance are the formation of molded articles, including foils, films, tubes, containers, bottles, fibers and foams, for example in melt blenders or by extrusion, injection molding, blow molding, spinning or wire coating. , a mixture of these compounds with a molten thermoplastic polymer.

It is not essential that the polymeric materials are completely polymerized before mixing with the compounds according to the invention; these compounds can be mixed with monomers, prepolymers or precondensates, and the polymerization or condensation reaction can be carried out afterwards. This, of course, would be the preferred method for incorporating these compounds into thermosetting polymers that cannot be melt blended.

The compounds of formula (1) can be used together with one or more antioxidants in the compositions according to the invention.

Examples of antioxidants are benzofuran-2-ones, indolin-2-ones and sterically hindered phenols, sulfur- or phosphorus-containing compounds or mixtures thereof.

Preferred sterically hindered phenols include β-(4-hydroxy-3,5-di-tert-butylphenyl)propionyl stearate, methanetetrakis-(methylene-3-
(3',5-di-tert-butyl-4-hydroxyphenyl)propionate), 1°3.3-)lis-(2-
Methyl-4-hydroxy-5-tert-butylphenyl)butane, 1.3゜5-tris(4-tert-butyl-3-hydroxy 2.6-di-methylbenzyl)-1,
3,5-triazinyl-2,4,6(1)1.3H,5
H)-trione, bis-(4-tert-butyl-3-
Hydroxy-2,6-di-methylbenzyl)dithiol terephthalate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, β
-(4-hydroxy-3,5-di-tert-butylphenyl)propionic acid and 1.3.4-)lis-(2-hydroxyethyl)-5-)riazine-2,4,6(IH
,3H,5H)-)trione, bis(3
, 3-bis-(4′-hydroxy-3-tert-butylphenyl)butyfil glycol ester, 1,3.5
-)limethyl-2.4.6-)lis=(3,5-dite
r t-butyl-4-hydroxybenzyl)benzene,
2.2'-methylene-bis-(4-methyl-6tert
-butylphenyl) terephthalate, 4,4-methylene-bis(2,6-di-tert-butylphenol), 4
．． 4'-butylidene-bis-(tert-butylmetacresol) and 2,2'-methylene-bis-(4-methyl-6-tert-butyl)phenol.

Preferred sulfur-containing antioxidant co-stabilizers that can be used are di-tridecyl-3,3-thiodipropionate, distearyl-3,3-thiodipropionate, dilauryl-3,3-thiodipropionate. , methanetetrakis (methylene-3-hexylthiopropionate)
, methanetetrakis (methylene-3-dodecylthiopropionate) and dioctadecyl disulfide.

Preferred useful phosphorus-containing co-stabilizers are trinonylphenyl phosphite, 4,9-distearyl-3,5,8,
10-Tetraoxadiphosphaspiroundecane, tris-(2,4-di-tert-butylphenyl) phosphite, trilauryl phosphite, bis(2,6-di-butyl-4-methylphenyl)pentaerythrityldi Phosphite, bis(2,4-dibutylphenyl)pentaerythrityl diphosphite, distearylpentaerythrityl diphosphite and tetrakis(2
,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite.

Other additives that can be added to the polymer composition according to the invention include aminoaryl compounds, UV stabilizers, flame retardants, antistatic agents, softeners, nucleating agents, metal deactivators, biocides, Contains impact modifiers, fillers, pigments and fungicides.

Preferred aminoaryl compounds are N, N'dinaphthyl-p-phenylenediamine and N.

N'-hexamethylene-bis-3-(3,5-diter
Contains t-butyl-4-hydroxyphenyl)propionamide.

Preferred UV stabilizers are UV absorbers, such as 2-
(2'-hydroxyphenyl)benzotriazole, 2
-Hydroxybenzopheno, 1゜3-bis-(2'
UV quenchers such as -hydroxybenzoyl) benzene salicylates, cinnamates and oxalic diamides, benzoates and substituted benzoates and sterically hindered light stabilizers other than the present invention (e.g. N-unsubstituted,
N-alkyl or N-acyl substituted 2,2,6.6-tetraalkylbiveridine compounds. Other known types of additives may also be added, such as flame retardants and antistatic agents.

Preferably, a compound of formula xx below is added to a compound of formula I.

In the above formula, R3° is C1~! □Alkyl or ca-zz
Represents alkoxy, R31 and R3t are each hydrogen, 01-. Alkyl, 01~l! Alkoxy, C1~,
2 selected from alkylthio, phenoxy, and phenylthio (provided that only one of R3 and R3□ is alkylthio, phenoxy, or phenylthio), and R33 represents hydrogen, CI, or alkyl.

The compounds of formula (1) are particularly suitable for use in organic polymer-containing paints, especially automotive paints.

Automotive paints are generally solutions or dispersions of organic polymers or polymer precursors in organic solvents. Most are baking paints, which, once applied to a primed metal surface, involve the application of heat - typically 80°C or higher - to cure the paint within an acceptable time. Requires.

The curing process can be accelerated by the use of acid catalysts.

The effect of this heating is to promote chemical reactions between polymer precursors in thermosetting systems or to cause melting of particles of thermoplastic polymer.

Many automotive paints are metallic paints, which contain flakes of metal, usually aluminum, to provide a reflective optical effect. Such paints are often
The compound of formula I may be in the topcoat paint or in the basecoat paint, and is preferably a layer paint and the transparent topcoat paint is applied onto a basecoat paint containing a single pigment and/or metal flake. is the former. Such 2N metallic paints are difficult to apply because the polymers in the paint are not protected by light-absorbing pigments and are subjected to almost twice the normal dose due to light reflection from the underlying metallic layer. , requiring UV stabilizers in the top coat.

The compounds of formula I can be used in a wide range of liquid coatings, for example combinations of melamine formaldehyde resins with oil-modified polyester resins, polyacrylate resins with added crosslinkers, or saturated polyesters, or self-crosslinkers,
or suitable for use as UV stabilizers in saturated polyesters, or those based on self-crosslinked polyacrylates or polyacrylate resins copolymerized with styrene.

Other examples are two-component paints based on aliphatic or aromatic diisocyanates and hydroxy group-containing polyacrylate, polyester or polyether resins. These two-component polyurethane paints preferably have a polyurethane content of 60 to 12
Cured at 0°C. Thermoplastic polyacrylate resins can also be used, which are particularly useful in metallic coatings, and polyacrylate resins with added crosslinkers can also be used in combination with butanol-etherified melamine formaldehyde resins, as well as aliphatic Hydroxy-containing polyacrylate resins cured with diisocyanates are also useful. Such polyacrylate resins are disclosed in US Pat. No. 3,062,753.

The compounds of formula I are useful in acid-catalyzed stoving paints, especially top coats of 2M metallic paints.

The compound of formula ■ may be added to the paint at any stage of its manufacture, in solid form or in solution, preferably in the form of a liquid concentrate in a suitable solvent or as a dispersion in water or an organic solvent. It may also be added in liquid form.

In practice, the compound of formula ■ is added to the paint as a solution in an organic solvent (as a liquid paint), in which case the binder material is between 35% by weight (low solids paint) and 70% by weight (
High solid content paint). The binder material of the paint may be in the form of an aqueous emulsion or dispersion (as an aqueous paint) in which the binder material accounts for 20 to 30% by weight.

However, the compounds of formula I can also be added to known powder coating materials.

The compound of formula 1 should be added to the liquid or powder coating before baking or curing. Preferably, the compound of formula (1) is used in liquid coatings since it is easy to add in appropriate amounts. Low total weight of concentrates (both 4
Particular preference is given to using concentrates (preferably in hydrocarbon solvents) containing 0% by weight, preferably 60 to 80% by weight, of compounds of formula (1) in paints for stoving.

The compounds of the invention can also be used in photopolymerizable polymeric substrates containing photoinitiators for photopolymerization.

The invention is further illustrated by the following examples. In the examples, all parts and percentages are expressed by weight. Moreover, the temperature is °C.

Example 1 40.5 g of a compound of formula 1b, is reacted with 23.4 g of a compound of formula 1c, and 0.2 g of toluenesulfonic acid in 50d of xylene, and the mixture is then Stirred at °C for 20 hours until a pale yellow solution was obtained. The clear solution was then cooled to room temperature and 100 d of toluene was added followed by 1001 d of water. Separate the organic phase and add 100 m of water for an additional 4
After washing twice, the solvent was distilled off and the residue was purified by high vacuum distillation. The resulting product was then placed in an oven and treated at 230'C under a pressure of 0,05 rmHg for 30 minutes to remove volatiles.

The product obtained has the following formula 1a and is heated at 73-75°C.
It had a melting point of

Bean Examples 2-7 Starting from suitable compounds and following the method of Example 1, the compounds shown in the table below could be prepared.

[IL beans 80 parts Viacryl SC344 (Vianova
50% solution of acrylic resin from ), 13.9 parts of M
aprenal MF80 (72% solution of melamine resin from Hoechst) and 4.1 parts Byket
ol OK (from Byk-Malinckrodt)
2 parts of a compound of formula 1a (as described in Example 1) are added to a clear paint consisting of: After 1 minute, the light stabilizer material thus obtained is dissolved in the paint. Apply paint as usual (
and applied by spraying (according to the known two-layer operation) to the metallic or single-pigment paint while still wet to form a layer having a thickness of 30 to 40 mm. The resulting coating is then cured for 30 minutes at 140''C. The coating shows very good resistance to UV light and outdoor exposure.

Tekuri ■dan 29.5 part 5etalux C-1502XX-60
(Synthese B, V.

60% solution of acrylic resin from ), 39.2 parts of 5
etalux=c-13828X-45(Synthe
se B, V, 45% solution of acrylic resin)
, 21.4 parts of Setamins US-1388B-
70 (Synthese B, V, 70% solution of acrylic resin), 2.5 parts Baysilonoil
(a 2% solution in one xylene from Bayer) and 7.4 parts of Depanol Y (a solvent from Hoechst) was mixed with 2.5 parts of a compound of formula 1a (as described in Example 1) and Two parts of a phosphoric acid derived acid catalyst (Type: Catalyst 269-9 from American Cyanamid) are stirred together to obtain a homogeneous mixture. This paint is applied by spraying in the usual manner (according to the known two-layer operation) to the metallic or single pigment paint while both are still wet, to form a layer having a thickness of 30 to 40 degrees. obtain. The resulting coating is then cured at 110° C. for 20 minutes. The coating shows very good resistance to UV light and outdoor exposure.

FIacrynaI SH51ON (Bay
Acrylic resin containing hydroxyl from er), 2 parts of By
silonoil^ (1 in xylene from Bayer)
% solution), 0.3 parts diptylzinc dilaurate, 0.
35 parts jetanolamine, 5.0 parts ethyl glycol acetate, 5.0 parts 5olvesso 100
．． A clearcoat consisting of 6.0 parts of xylene and 6.36 parts of butyl acetate was mixed with 2.5 parts of a compound of formula 1a (described in Example 1) and 30 parts of Desmodur N 75 (
from Bayer). The homogeneous mixture formed is applied by spraying as usual (according to the known two-layer operation) to the metallic or single pigment paint, while both are still wet, to form a layer having a thickness of 30 to 40 nm. to form. The resulting coating is heated to 80-90℃
Let cure for 20 minutes. The resulting 2-PUR coating shows good resistance to UV radiation and outdoor exposure.

14.30 parts of Setamine ll5-1328B
70 (70% of melamine resin from Synthese
solution), 57.15 parts of 5eta184 W-70 (5
70% solution of acrylic resin from syntheses), 7
．． 1.38 parts of the product of formula 1a (Example 1) in a single white pigment paint consisting of 70 parts n-butanol, 1.85 parts butyl glycol acetate, 9.50 parts titanium dioxide (rutile type). Added. This paint is applied by spraying in a conventional manner to the primed steel metal, which has been annealed with a layer of filler 20 to 30 #ll thick, and after standing at room temperature for 30 minutes, the steel metal surface is annealed for 30 minutes at 120° C. The resulting coating shows very good resistance to UV radiation and outdoor exposure.

In application examples AD, suitable amounts of any of the products of examples 2 to 7 can be used in place of the product of formula 1a.

Furthermore, in application examples A-D, 2.5 parts of the following formula XX
'QC,H.

\ IC-CHC-CH \ / IC-CH \ l IC-CH UV absorbers can be added to give a higher stabilizing effect to the paint.

Claims (1)

[Claims] 1. A compound represented by the following formula I. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) In the above formula, R each independently represents hydrogen, oxygen, C_1_～_
8 alkyl or -COR_5, R_5 is -C(
R_3)=CH_2, C_1_-_6 alkyl, phenyl, -CO-O-C_1_-_4 alkyl or -NR
_7R_6, -COC_6H_5, -CH_2C_6H
_5, -CO-OC_1_~_1_2 alkyl or -
Represents COOH, R_7 is hydrogen, C_1_-_1_2 alkyl, C_5_-_6 cycloalkyl, phenyl, phenylC_1_-_4 alkyl or C_1_-_1_
2 represents alkylphenyl, R_8 is C_1_~_1_
2 alkyl or hydrogen, and R_1 each independently represents -CH_3 or -CH_2 (C_1_~_4 alkyl), or two R_1s taken together represent a group -(C
H_2)_5-, and each R_2 independently represents -CH_3 or -CH_2 (C_1_~_4 alkyl), or two R_2s together form a group -(
CH_2)_5- is formed, X represents an integer from 1 to 12, and R_3 is each independently hydrogen or C_1_~
_4 represents alkyl, R_4 each independently represents hydrogen, C
Represents _1_-_4 alkyl or C_1_-_4 alkoxy. 2. In producing the compound of formula I as defined in claim 1, the following formula II, ▲Mathematical formula, chemical formula, table, etc.▼(II) (In the formula, the symbols are the same as defined in claim 1. A compound represented by the following formula III, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ The following formula I a, ▲ There are mathematical formulas, chemical formulas, tables, etc. ), optionally oxidizing a compound in formula Ia in which Ra is hydrogen, optionally oxidizing a compound in formula Ia in which Ra is hydrogen, optionally in formula Ia in which Ra is hydrogen; A compound with the following formula IV or V, ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) R_5-CO-Hal(V) (In the formula, Hal represents chlorine or bromine, and R_5 is the provision of claim 1. (represents the same thing as)) to form the following formula Ic, ▲mathematical formula,
There are chemical formulas, tables, etc. ▼ (Ic) (In the formula, the symbols represent the same ones as defined in claim 1) A method comprising: producing a compound represented by the following. 3. A composition comprising a polymeric material and a compound of formula I as defined in claim 1. 4. In stabilizing lacquer paints based on acrylic, alkyd or polyester resins (which may be crosslinked, if desired, with melamine/formaldehyde resins, epoxide resins or polyisocyanates),
A method comprising incorporating one or more compounds of formula I as defined in claim 1 into a resin. 5. One or two compounds of formula I as defined in claim 1
Lacquer paints based on acrylic, alkyd and/or polyester resins, which may be crosslinked if desired with melamine/formaldehyde resins, epoxide resins or polyisocyanates, containing more than one species.