JPS6281376A - Benzotriazole compound - Google Patents

Abstract

NEW MATERIAL:A benzotriazole compound expressed by the formula (R is H or CH3). EXAMPLE:2-(2'-Hydroxy-3'-methacryloylamino-5-tert-octyl)benzotriazole. USE:A light stabilizer for organic substances, e.g. synthetic polymers, having improved light stabilizing effect, heat and extraction resistance and solibility in organic solvents, intermediate for high-molecular weight light stabilizers or reactive light stabilizer bondable to high polymer materials. PREPARATION:2-(2'-Hydroxy-3'-amino-5'-tert-octylphenyl)benzotriazole is react-ed with (meth)acryloyl chloride to readily afford the compound expressed by the formula. A (co)polymer obtained from the above-mentioned compound has good solubility in high polymer materials and is capable of improving the light resistance of the high polymers for a long period.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides light stabilizers useful as light stabilizers for organic substances such as synthetic polymers, intermediates for high molecular weight light stabilizers, or reactive light stabilizers that can be bonded to polymeric materials. The present invention provides a benzotriazole compound having a (meth)acrylamide group in the molecule.

2-Hydroxyphenylhensitriazole compounds are known to be light stabilizers for various organic materials such as synthetic resins, but because these compounds generally have low molecular weights, they may be emitted once during processing of resins, or It was extracted from the resin by water, organic solvents, etc., and as a result, it was not possible to stabilize the organic substance for a long period of time.

For this reason, it has been proposed to introduce large substituents or to dimorphize the compound with aldehydes.

However, even with these compounds, the above drawbacks could not be improved satisfactorily.

In order to eliminate these drawbacks, high molecular weight light stabilizers have been proposed in which light stabilizers containing polymerizable double bonds are (co)polymerized.

For example, US Pat. No. 3,159,646, US Pat. No. 3,761
272 and JP-A-58-185677 describe 2-hydroxyphenylbenzotriazole compounds or (co)polymers thereof having a (meth)acryloyloxy or (meth)acryloylamino group.

However, the compounds described in the above publication do not have an alkyl substituent, or even if they do, they only have a lower alkyl group with up to 4 carbon atoms, and their solubility in organic solvents is poor. ) In order to obtain a polymer, it is necessary to polymerize it without a solvent or by dispersing it in an aqueous medium, which has disadvantages such as difficulty in controlling the reaction.

In addition, when these compounds are blended into polymeric materials such as synthetic resins, bloom or bleed may occur.
Its stabilizing effect was only short-lived.

The present inventors aimed to obtain a benzotriazole compound having a reactive double bond that itself has an excellent photostabilizing effect and can be derived into a (co)polymerizable photostabilizer having good heat resistance and extraction resistance. As a result of extensive research, we found that a benzotriazole compound with the following 2 has excellent solubility in organic solvents.
The inventors have found a way to solve all of the above problems and have arrived at the present invention.

t-CaH+t (In the formula, R represents a hydrogen atom or a methyl group.) Also,
The (co)polymer made from the above compound also has good compatibility with polymeric materials, and can improve the light resistance of polymeric materials over a long period of time.

The above compound can be easily produced, for example, by reacting 2-(2''-hydroxy-3'-amino-5'-tertiary octylphenyl)benzotriazole with (meth)acrylic chloride.

The compound represented by the above formula or its (co)polymer of the present invention is not only useful as a light stabilizer for organic materials such as various synthetic resins, rubbers, waxes, and oils, but also provides various polymers. It is useful as a reactive monomer to be (co)polymerized with monomers.

Examples of the organic material stabilized by the compound of the present invention or its (co)polymer include α-olefin polymers such as polyethylene, polypropylene, polybutene-11 poly-3-methylpentene, or ethylene-vinyl acetate copolymer. α-olefin copolymers such as ethylene-propylene copolymers, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, chlorinated rubber , vinyl chloride-vinyl acetate copolymer, vinyl chloride-
Halogen-containing resins such as ethylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-urethane copolymer, petroleum resin, coumaron resin, polystyrene, polyvinyl acetate, acrylic resin, methacrylic resin, polyacrylonitrile, styrene and Copolymers with other monomers (e.g. maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene terpolymers,
Methacrylic acid ester-butadiene-styrene terpolymer, polyvinyl alcohol, polyvinyl butyral,
Linear polyester or polyether ester such as polyethylene terephthalate, polybutylene terephthalate, polytetramethylene ether glycol terephthalate, polyphenylene oxide, polyamide, polycarbonate, polyacetal, polyurethane, cellulose resin, phenol resin, urea resin, melamine resin, epoxy resin , unsaturated polyester resin, silicone resin, isoprene rubber, butadiene rubber, acrylonitrile-butadiene rubber, styrene-butadiene rubber, and blends thereof, natural oils and fats, synthetic ester oils, mineral oils, and the like.

The present invention will be explained in more detail with reference to the following examples, but the present invention is not limited by these examples.

Example 1 2-(2″-hydroxy-3′-amino-5-tert-octyl)benzotriazole 16.9 g, methacryloyl chloride 6.7 g, sodium bicarbonate 1.1
g and m-dinitrobenzene 0.01 g xylene 5
The solution was dissolved in 0ml and stirred at 50°C for 5 hours under a nitrogen stream.

After washing with water and drying, the solvent was distilled off, and the residue was recrystallized from ethyl acetate to obtain a slightly yellow powder with a melting point of 167-170°C.

Infrared spectroscopy 1610 and 750 cm-' () lyazole ring) 34
50 and 1680 cm-' (anilide) 1630c
m-' (C=C double bond) Example 2 Same as Example 1 except that acryloyl chloride was used instead of methacryloyl chloride, melting point 173-1
A slightly yellow powder at 76°C was obtained.

Infrared spectroscopy 1610 and 750 cm-' () lyazole ring) 34
50 and 1680 cm-' (anilide) 1635c
m-' (C=C double bond) Example 3 4.1 g of 2-(2''-hydroxy-3'-methacryloylamino-5-tert-octyl)benzotriazole obtained in Example 1 and abbisiso Butyronitrile 0.2
Dissolve g in 50 ml of xylene and heat at 80°C under nitrogen stream.
The mixture was stirred for 30 hours. After cooling, this solution was dropped into 200 ml of methanol, and the resulting precipitate was filtered and dried at 80° C. under reduced pressure.

Average molecular weight: 2500 Melting point (softening point): 195-198°C Infrared spectroscopy: Disappearance of double bond at 1630 cm-' Example 4 A press sheet with a thickness of 0.3 mm was prepared using the following formulation, and this sheet was heated with high-pressure mercury. A light resistance test was conducted using a lamp. In addition, a light resistance test was also conducted on the sheet after being immersed in hot water at 80° C. for 48 hours. The results are shown in Table-1.

[Composition]

Polypropylene 100 parts by weight Calcium stearate 0.2 Stabilizer (see Table 1) 0.2 Table 1 Example 3 The compound of the present invention has excellent heat resistance, and its effect can be maintained even under severe processing conditions. It never decreases. In this example, the effect of repeating extrusion processing at high temperatures was examined.

After mixing the resin and additives in a mixer for 5 minutes according to the following formulation, I want to create a compound in an extruder.The cylinder temperature is 230°C and 240°C, and the head die temperature is 2.
50°C, rotation speed 2Orpm).

After repeating extrusion five times, test pieces were made using this compound in an injection molding machine (cylinder temperature 24
g/c+d at 0℃, nozzle temperature 250℃, injection pressure 475
).

A light resistance test was conducted using the obtained test piece using a high-pressure mercury lamp. In addition, a light resistance test was also conducted on a test piece using a compound that had been extruded once.

The results are shown in Table-2.

[Formulation] Ethylene-propylene copolymer resin 100 parts by weight Calcium stearate 0.2 Dilaurylthiodibropyrite tertiary 0.2 Stabilizer (see Table-2) 0.2 Table-2 Table-1 and Table-2 From the results, it is clear that the compounds of the present invention and their polymers have a significantly greater photostabilizing effect than similar lower alkyl-substituted compounds and their polymers, and are also superior in extraction resistance and heat resistance.

Claims (1)

[Claims] A benzotriazole compound represented by the following formula. ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R represents a hydrogen atom or a methyl group.)