JPH0952916A - Ultraviolet light absorbing composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition comprising a polymer of a specific polymerizable triazine-based ultraviolet light absorber, excellent in ultraviolet light absorbing ability and extraction resistance, providing excellent light resistance for a long period of time, useful as an agricultural film, etc. SOLUTION: This ultraviolet light absorbing composition comprises a polymer obtained from a compound of formula I [A is a direct bond, (CH2 CH2 O)n or CH2 CH(OH)-CH2 O ((n) is 1-5); X is H or methyl ; R1 to R8 are each H, a 1-10C alkyl, alkenyl or alkoxy] (e.g. a compound of formula II, etc.) alone or by copolymerization with another polymerizable monomer (e.g. methyl methacrylate, etc.). The polymer, for example, is obtained by dissolving a compound of formula II, methyl methacrylate and azobisisobutyronitrile in dimethylacetamide, reacting them at 70 deg.C for 24 hours and reprecipitating the reaction product with hexane.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet absorbing composition comprising a polymer of a polymerizable ultraviolet absorber, and more specifically, an ultraviolet absorbing composition comprising a polymer of a specific polymerizable triazine ultraviolet absorber. It relates to a composition. In the present specification, the “composition” of the “ultraviolet absorbing composition” means
It is used to show that molecules having different molecular weights or copolymer compositions are contained.

[0002]

2. Description of the Related Art Polymer materials such as polyethylene, polypropylene, styrene resin, polyvinyl chloride and polyester are deteriorated by the action of light and cause discoloration or deterioration of mechanical strength to endure long-term use. Not known to be.

Agricultural films, intraocular lenses, photographic filters and the like are required to selectively block light rays of harmful wavelengths, but resin or gelatin as a base material for film lenses and filters. It was difficult to control the wavelength of transmitted light only by itself.

Further, dyes and pigments used in thermal papers, paints, photographic materials, dyed fiber materials and the like have a problem that they are easily faded or discolored by ultraviolet rays.

Therefore, in order to prevent the deterioration of these organic materials and control the wavelength of transmitted light, various ultraviolet absorbers have been conventionally used. As these ultraviolet absorbers, benzophenone-based, benzotriazole-based, 2,4,6-triaryltriazine-based and cyanoacrylate-based ultraviolet absorbers are known.

However, when these ultraviolet absorbers are kneaded during the processing of the resin, a part of the ultraviolet absorber is volatilized by being exposed to a high temperature during the processing, and the effect is reduced.
The remaining ultraviolet absorber also volatilizes during long-term use and loses its effectiveness. Also, when applied to fibers, satisfactory long-term lightfastness has not been obtained because it is extracted by washing and loses its efficacy. In addition, when used in an intraocular lens or the like, an ultraviolet absorber that is difficult to extract from the viewpoint of safety has been desired. Therefore, an ultraviolet absorber having a high molecular weight, a low volatility, an excellent affinity for a synthetic polymer material, and a high absorptivity in a wide wavelength range has been desired.

[0007]

Means for Solving the Problems The inventors of the present invention have made earnest studies in view of the above-mentioned circumstances, and as a result, polymerization of a specific polymerizable triazine-based ultraviolet absorber represented by the following general formula (I). The inventors have found that the product has excellent ultraviolet absorption ability and extraction resistance, and imparts excellent light resistance for a long period of time, and has reached the present invention.

That is, the present invention provides an ultraviolet absorbing composition comprising a compound represented by the following general formula (I) alone or a polymer obtained by copolymerization with another polymerizable monomer. is there.

[0009]

Embedded image

Hereinafter, the present invention having the above gist will be described in detail.

In the general formula (I), R ₁ , R ₂ , R ₃ ,
1 carbon atom represented by R ₄ , R ₅ , R ₆ , R ₇ and R ₈
Examples of the alkyl group of 10 include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl,
Examples thereof include pentyl, hexyl, heptyl, octyl, nonyl and decyl, and examples of the alkenyl group and the alkoxy group include groups corresponding to the above alkyl groups.

Examples of the ultraviolet absorber represented by the above general formula (I) used for polymerization in the present invention include the following compound No. 1 to No. 6 is mentioned.

[0013]

Embedded image

[0014]

Embedded image

[0015]

Embedded image

[0016]

[Chemical 6]

[0017]

[Chemical 7]

[0018]

Embedded image

The compound represented by the above general formula (I) of the present invention may be polymerized alone, but may be methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, methacrylic acid. Isobutyl, secondary butyl methacrylate, tertiary butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, Acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, styrene, vinyltoluene,
α-methylstyrene, dimethylstyrene, vinyl acetate,
Diethyl maleate, dibutyl maleate, diethyl fumarate, dibutyl fumarate, dibutyl itaconic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, ethylene glycol Di (meth) acrylate, glycidyl (meth) acrylate,
Methyl glycidyl (meth) acrylate, ethyl glycidyl (meth) acrylate, (meth) acrylic acid, (anhydrous)
Monomers 1 or 2 such as maleic acid, fumaric acid, itaconic acid, monobutyl maleate, monobutyl itaconic acid
It may be copolymerized with one or more species. Further, the copolymerization ratio with the compound represented by the general formula (I) is not particularly limited, but the ratio of the compound represented by the general formula (I) is particularly preferably 5
It is at least wt%, more preferably at least 10 wt%.

The polymer of the present invention preferably has an average molecular weight of 1,000 or more and 20,000 or less.
It is more preferably 1500 or more and 10,000 or less. Below this, the effect of improving volatility is small, and above this, dispersibility is small. The average molecular weight is the number average molecular weight,
The molecular weight is shown in terms of standard polystyrene by gel permeation chromatography.

The organic material such as resin stabilized by the specific ultraviolet absorbing composition of the present invention is not particularly limited, but it is a molded article such as automobile parts, a film or sheet such as agricultural material, In addition to fiber materials such as PET and nylon fibers represented by PET, synthetic polymer materials such as intraocular lenses and tapes, thermal recording materials, paints, adhesives, putties, binders for lacquers, base materials for photographic materials And so on. The addition amount of the specific ultraviolet absorbing composition of the present invention is usually 0.001 with respect to 100 parts by weight of the resin material, depending on the type (copolymerization ratio, etc.), the type and application of the resin to be stabilized. -30 parts by weight, preferably 0.
01 to 10 parts by weight.

Since the ultraviolet absorbing composition of the present invention has a low volatility and imparts excellent light resistance for a long period of time, it is used in fields requiring high light resistance such as agricultural materials and automobile paints, and fibers. It is particularly useful in the field requiring fastness to washing.

As the resin which is a typical example of the organic material to be improved in stability in the present invention, for example, high density,
Α- such as low-density or linear low-density polyethylene, polypropylene, polybutene-1, poly-4-methylpentene
Olefin polymer or ethylene-vinyl acetate copolymer, polyolefin such as ethylene-propylene copolymer and copolymers thereof, polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene,
Polyvinylidene fluoride, rubber chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride- Acrylic ester copolymers, vinyl chloride-maleic acid ester copolymers, vinyl chloride-cyclohexylmaleimide copolymers, vinyl chloride-cyclohexylmaleimide copolymers and other halogen-containing resins, petroleum resins, coumarone resins, polystyrene, polyacetic acid Copolymers (for example, AS resin, ABS) of vinyl, acrylic resin, styrene and / or α-methylstyrene with other monomers (for example, maleic anhydride, phenylmaleimide, methyl methacrylate, butadiene, acrylonitrile, etc.) Resin, MBS resin, heat resistance A
BS resin etc.), polymethylmethacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyethylene terephthalate and linear polyesters such as polytetramethylene terephthalate, polyphenylene oxide, polyamide such as polycaprolactam and polyhexamethylene adipamide, polycarbonate,
Thermoplastic synthetic resins such as branched polycarbonate, polyacetal, polyphenylene sulfide, polyurethane, fibrous resin and blends thereof or thermosetting resins such as phenol resin, urea resin, melamine resin, epoxy resin and unsaturated polycastel resin I can give you. Further, it may be an elastomer such as isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber or styrene-butadiene copolymer rubber.

When the ultraviolet absorbing composition of the present invention is added to an organic material such as a resin, other general-purpose antioxidants, stabilizers and other additives can be used in combination, if necessary.

Particularly preferable as these additives are phenol type, sulfur type and phosphite type antioxidants, hindered amine type light stabilizers, and UV absorbing agents other than the specific UV absorbing composition of the present invention. Examples thereof include hindered amine-based light stabilizers typified by 2,2,6,6-tetramethylpiperidine compound because they exhibit a synergistic effect with the ultraviolet absorbing composition according to the present invention.

Examples of the above-mentioned phenolic antioxidants are 2,6-di-tert-butyl-p-cresol and 2,6
-Diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycol Bis [(3,5-ditert-butyl-
4-hydroxyphenyl) propionate], 1,6-
Hexamethylene bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylene bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], 4,4′-thiobis (6-tert-butyl-m-cresol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butyl) Tributylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butylic acid]
Glycol ester, 4,4'-butylidenebis (6-
Tert-butyl-m-cresol), 2,2′-ethylidenebis (4,6-di-tert-butylphenol), 2,2′-
Ethylidene bis (4-tert-butyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-
Tert-butyl-4-methyl-6- (2-hydroxy-3-
Tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-
Hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-
Hydroxybenzyl) isocyanurate, 1,3,5-
Tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-
Tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate,
Tetrakis [methylene-3- (3,5-di-tert-butyl-
4-hydroxyphenyl) propionate] methane, 2
-Tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [1,1-dimethyl-2-{(3-tertiary Butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [(3-tert-butyl-4-hydroxy) -5
Methylphenyl) propionate].

Examples of the sulfur-based antioxidants include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl and distearyl, and polyols such as pentaerythritol tetra (β-dodecylmercaptopropionate). Examples include β-alkyl mercaptopropionic acid esters.

Examples of the above-mentioned phosphite antioxidants include trisnonylphenyl phosphite, tris (2,4-ditertiary butylphenyl) phosphite,
Tris [2-tert-butyl-4- (3-tert-butyl-4-
[Hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, distearyl pentaerythritol Diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-ditertbutylphenyl) pentaerythritol diphosphite, bis (2,6-ditertbutyl-4-methylphenyl) penta Erythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (tridecyl) -4,
4'-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl)
-1,1,3-tris (2-methyl-4-hydroxy-
5-tert-butylphenyl) butane triphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
Examples include tris (2-[(2,4,8,10-tetrakis-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphepin-6-yl) oxy] ethyl) amine. .

Examples of the hindered amine light stabilizer include, for example, 2,2,6,6-tetramethyl-4-
Piperidyl benzoate, N- (2,2,6,6-tetramethyl-4-piperidyl) dodecylsuccinimide,
1-[(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] -2,2,6,6-tetramethyl-4-piperidyl- (3,5-di-tert-butyl-4- (Hydroxyphenyl) propionate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-
4-piperidyl) sebacate, bis (1, 2, 2, 6,
6-pentamethyl-4-piperidyl) -2-butyl-2
-(3,5-di-tert-butyl-4-hydroxybenzyl)
Malonate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, tetra (2,2,6,6-tetramethyl-4-piperidyl) butanetetracarboxylate, Tetra (1, 2,
2,6,6-pentamethyl-4-piperidyl) butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) di (tridecyl) butanetetracarboxylate, bis (1,2,2 2,6,6-pentamethyl-4-piperidyl) di (tridecyl) butanetetracarboxylate, 3,9-bis [1,1-dimethyl-2- {tris (2,2,6,6-tetramethyl- 4-piperidyloxycarbonyloxy) butylcarbonyloxydiethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,
1-dimethyl-2- {tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyloxy)
Butylcarbonyloxydiethyl] -2,4,8,10
-Tetraoxaspiro [5.5] undecane, 1,5
8,12-tetrakis [4,6-bis {N- (2,2,
6,6-tetramethyl-4-piperidyl) butylamino {-1,3,5-triazin-2-yl] -1,5.
8,12-tetraazadodecane, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / dimethyl succinate condensate, 2-tert-octylamino-4,6-dichloro -S-triazine / N, N '
-Bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine / And dibromoethane condensates.

Examples of ultraviolet absorbers other than the ultraviolet absorbing composition of the present invention include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone,
2-Hydroxybenzophenone compounds such as 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2-hydroxy-5-methylphenyl)
Benzotriazole, 2- (2-hydroxy-3,5-
Di-tert-butylphenyl) benzotriazole, 2- (2
-Hydroxy-3,5-di-tert-butylphenyl) -5-
Chlorobenzotriazole, 2- (2-hydroxy-3)
-Tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-carboctoxyethylphenyl) benzotriazole, 2- (2-hydroxy-5- Tertiary octylphenyl) benzotriazole, 2- (2-hydroxy-)
3,5-dicumylphenyl) benzotriazole, 2,
2-Hydroxyphenylbenzotriazole compounds such as 2'-methylenebis (4-tertiaryoctyl-6-benzotriazolylphenol); 2,4-diphenyl-6-
(2-Hydroxy-4-methoxyphenyl) -s-triazine, 2,4-bis (2,4-dimethylphenyl)-
6- (2-hydroxy-4-octoxyphenyl) -s
-Triazine compounds such as triazine; phenyl salicylate, resorcin monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-
Benzoate compounds such as 4-hydroxybenzoate;
Substituted oxanilide compounds such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; ethyl-α-cyano-β, β-diphenylacrylate, methyl-α-cyano-β- Methyl-β- (p
Examples include cyanoacrylate compounds such as -methoxyphenyl) acrylate.

In addition, if necessary, organic materials to which the ultraviolet absorbing composition of the present invention has been added, particularly resins, nucleating agents such as metal salts of benzoic acid, sorbitols and metal salts of aromatic phosphates, heavy metals. Deactivator, metal soap,
Organotin compounds, plasticizers, epoxy compounds, foaming agents, antistatic agents, flame retardants, lubricants, processing aids, dyes, pigments and the like can be included.

The method of applying the ultraviolet absorbing composition of the present invention to an organic material is not particularly limited, and the form of addition may be a powder or a water dispersion such as an emulsion or suspension, or a solution with an organic solvent. May be

However, since the ultraviolet absorbing composition of the present invention is a high molecular weight substance, when the organic material is a resin, the addition method is preferably kneading into the resin. Since the ultraviolet absorbing composition of the present invention has excellent extraction resistance, it can be added at a high concentration, and in addition to stabilizing the added resin itself, it is also excellent when the resin added at a high concentration is used as an ultraviolet shielding layer. Show the effect. For example, it is particularly useful for a film having a protective layer formed by two-layer extrusion, for controlling the transmittance of ultraviolet rays for agricultural materials, and for application to a top coat paint as a protective layer for the coated surface.

[0034]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be specifically described with reference to Examples, but the present invention is not limited to the following Examples.

(Synthesis Example 1: Preparation of Polymer No. 1 by Copolymerization of Compound No. 1 and Methyl Methacrylate) Compound No. 2.78 g (5.5 mmol) of 1 was dissolved in 5.0 ml (50 mmol) of methyl methacrylate and 0.13 g (0.8 mmol) of azobisisobutyronitrile in 40 ml of dimethylacetamide, and the solution was stirred at 70 ° C. for 24 hours. Reacted for hours. Reprecipitation from 500 ml of hexane gives a pale yellow powder 6.6.
g (yield 85%) was obtained. The obtained polymerized product had a number average molecular weight of 5,100, and compound No. 1 1 Noto methyl methacrylate in a molar ratio of: ¹ that are polymerized in 9 H-NM
Confirmed from R.

(Synthesis Example 2: Preparation of Polymer No. 2 by Polymerization of Compound No. 2 Alone) Compound No. 2 to 5g
(10 mmol), azobisisobutyronitrile 33 m
g (0.2 mmol) 50 ml of dimethylacetamide
And was reacted at 70 ° C. for 24 hours. Methanol 50
Reprecipitation from 0 ml gives a pale yellow powder 3.8 g (yield 75%)
I got The resulting polymer had a number average molecular weight of 9,500.

(Example 1) The composition shown in Table 1 below was used to obtain 2
Extrusion processing was performed at 50 ° C. to prepare pellets. Then, injection molding was performed at 250 ° C. to prepare a test piece having a thickness of 2 mm. The test piece was subjected to a weather resistance test using a sunshine weatherometer with a rain cycle of 18 minutes in 120 minutes at a black panel temperature of 83 ° C. The durability of the weather resistance was evaluated by the yellowness (measured by Hunter colorimeter) 1000 hours after the start of the test and 2000 hours later. Further, the time until the occurrence of cracks was measured as the weather resistance time. The results are shown in Table 2 below.

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

Embedded image

[0041]

Embedded image

Example 2 The formulations shown in Table 3 below were dissolved in chloroform to give a 1% by weight solution, and then 76 mm × 2
A cast film was prepared on a 6 mm glass plate. The color difference of the obtained film after 48 hours was measured with a xenon weatherometer at 63 ° C. and a humidity of 50%. The results are shown in Table 4 below.

[0043]

[Table 3]

[0044]

[Table 4]

Example 3 Using the formulations shown in Table 5 below,
The film was kneaded with a kneading roll to produce a film having a thickness of 0.1 mm. A test piece was cut out from this film, and a weather resistance test was performed using a sunshine weatherometer (without rain). The results are shown in Table-6.

[0046]

[Table 5]

[0047]

[Table 6]

Example 4 A cloth was woven from the fibers obtained by adding 0.5 parts by weight of an ultraviolet absorber (described in Table 7) to 100 parts by weight of a polyester resin and spinning at 280 ° C.
30 g of liquid finely dispersed in 1 part by weight of nonionic surfactant (adduct of nonylphenol and ethylene oxide) and 64 parts by weight of water, and anthraquinone type red dye (Resoli
n RedFB: Bayer) 10 g and acetic acid 0.3 g
Was dispersed in 1 liter of water to prepare a dyeing solution, and 100 g of polyester cloth was placed in a closed container at a bath ratio of 1:10 and dyed for 30 minutes in a 130 ° C. constant temperature bath. After cooling, the test piece was washed with water and reduction-washed by a conventional method. 240 of the obtained dyed cloth at sunshine weatherometer 83 ° C (without watering)
A weather resistance test was performed based on the color difference after a lapse of time from before the test.

[0049]

[Table 7]

[0050]

From the results of each of the above examples, the stabilizing effect of the specific ultraviolet absorbing composition of the present invention is higher than that of the conventionally known triazine type ultraviolet absorbent. It is clear that the stability is long and the stability of the stabilizing effect is remarkably superior to that of Example 1 and Comparative Example 1.

Claims (2)

[Claims] 1. An ultraviolet-absorbing composition comprising a compound represented by the following general formula (I) alone or a polymer obtained by copolymerization with another polymerizable monomer. Embedded image 2. An organic material to which the ultraviolet absorbing composition according to claim 1 is added.