JPH10212469A - Ultraviolet absorber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject absorber, having excellent ultraviolet absorptivity and excellent in extraction resistance and capable of sustaining effects thereof for a long period due to chemical binding to various polymers by using a specific compound containing 1-propenyl group introduced thereinto. SOLUTION: This ultraviolet absorber comprises a compound having a structural part derived from compounds selected from (A) a benzophenone-based compound, (B) a benzotriazole-based compound and (C) a salicylate-based compound, respectively having phenolic OH group and vacant in the o-position with respect to the OH and further 1-propenyl at the o-position with respect to the OH on the aromatic ring. For example, 2-hydroxy-3-(1-propenyl)-4- methoxybenzophenone represented by formula III is obtained as the objective ultraviolet absorber by allyl etherifying a compound represented by formula I as the component A, then carrying out the Claisen rearrangement and transferring hydrogen of the resultant compound represented by formula II in the presence of an alkaline catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a synthetic polymer and the like.
The present invention relates to an ultraviolet absorber comprising a compound having a 1-propenyl group introduced into a molecule, which is useful as an intermediate for a high molecular weight ultraviolet absorber or as a reactive ultraviolet absorber capable of binding to a polymer material.

[0002]

2. Description of the Related Art Conventionally, various benzophenone compounds, benzotriazole compounds or salicylate compounds have been used as ultraviolet absorbers for synthetic polymers. However, since these compounds generally have a low molecular weight, when added to a synthetic resin, they volatilize during processing of the resin, or are extracted from the added synthetic resin by water, an organic solvent, or the like, and as a result, The effect could not be maintained for a long time, and the synthetic resin could not be stabilized.

[0003]

SUMMARY OF THE INVENTION
Although it has been proposed to introduce a large substituent into the compound or to increase the molecular weight of the compound itself, it has not yet been solved to solve the above problem.

[0004] The present invention has been made in view of such circumstances, and has an excellent ultraviolet absorbing function itself, and furthermore, is chemically bonded to various high molecular compounds, has excellent extraction resistance, and has a long life. It is an object of the present invention to provide an ultraviolet absorber capable of providing the effect.

[0005]

Means for Solving the Problems In order to achieve the above object, the ultraviolet absorbent of the present invention has a structural part derived from the following compound (A) in the molecular structure, It has a configuration of a compound in which a 1-propenyl group is introduced ortho to the OH group.

(A) Any one compound selected from the following (a) to (c): (A) A benzophenone-based compound having a phenolic OH group and an ortho position relative to the OH group being empty. (B) A benzotriazole-based compound having a phenolic OH group and an ortho position relative to the OH group being empty. (C) A salicylate compound having a phenolic OH group and having an empty ortho position relative to the OH group.

The present inventors have conducted a series of studies to improve the drawbacks of the conventional ultraviolet absorber and obtain a reactive monomer having an excellent function as an ultraviolet absorber. In other words, the polymer itself is useful as an ultraviolet absorber, and the polymer obtained by copolymerizing with a monomer that forms various polymer has no volatilization, has excellent extraction resistance, and has a permanent ultraviolet absorption function. A series of studies were conducted for the purpose of obtaining a monomer capable of imparting the following. As a result, various benzophenone-based compounds, benzotriazole-based compounds, and salicylate-based compounds conventionally used as ultraviolet absorbers have many phenolic OH groups. The phenolic OH group is subjected to allyl etherification, followed by Claisen rearrangement, and an allyl group (2-propenyl group) is ortho-positioned to the phenolic OH group. Introduced and further subjected to hydrogen transfer to convert to a 1-propenyl group, it was found that the monomer obtained as the ultraviolet absorber had the above-mentioned excellent properties, and the present invention was reached.

That is, 1) which is the ultraviolet absorbent of the present invention
-Propenyl phenols have a 1-propenyl group introduced into the molecular structure, so that not only homopolymerization but also copolymerization with other monomers exhibit excellent extraction resistance, and the polymer is It was confirmed that it had a sufficient ultraviolet absorbing function. Furthermore, since a 1-propenyl group is introduced, when these are blended with a synthetic resin and molded, they may be volatilized or extracted as compared with those obtained by simply blending a conventional ultraviolet absorber. Almost no, they found that they were reacting with the synthetic resin due to heat during molding.

[0009]

Next, an embodiment of the present invention will be described.

[0010] The ultraviolet absorbent of the present invention comprises,
It comprises a compound having a structural portion derived from the following compound (A) and having a 1-propenyl group introduced ortho to the OH group on the aromatic ring.

(A) Any one compound selected from the following (a) to (c): (A) A benzophenone-based compound having a phenolic OH group and an ortho position relative to the OH group being empty. (B) A benzotriazole-based compound having a phenolic OH group and an ortho position relative to the OH group being empty. (C) A salicylate compound having a phenolic OH group and having an empty ortho position relative to the OH group.

In the above compound (A), examples of the benzophenone-based compound (a) having a phenolic OH group and the ortho position to the OH group being vacant include, for example, 2-hydroxy-4-methoxybenzophenone,
-Hydroxy-4-n-octoxybenzophenone,
2,4-dihydroxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone,
2,2 ', 4,4'-tetrahydroxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane and the like.

In the above compound (A), examples of the benzotriazole-based compound (b) having a phenolic OH group and the ortho position to the OH group being vacant include, for example, 2- (2'-hydroxy-5) '-Methylphenyl) benzotriazole, 2- (2'-hydroxy-
5'-t-butylphenyl) benzotriazole, 2-
(2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole and the like can be mentioned.

In the above compound (A), the salicylate compound (c) having a phenolic OH group and the ortho position to the OH group is vacant includes 4-t-
Butylphenyl salicylate, 4-octyl salicylate, phenyl salicylate and the like.

Next, a method for synthesizing the ultraviolet absorbent of the present invention will be described.

(1) 2-hydroxy-4 as a benzophenone compound (a) having a phenolic OH group as a starting material and having an ortho position vacant with respect to the OH group;
The case where methoxybenzophenone is used will be described as an example.

First, as shown in the following reaction formula (A),
Using 2-hydroxy-4-methoxybenzophenone as a raw material and dissolving or dispersing the same in various solvents, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, or amines are added to the above 2-hydroxy-4-hydroxybenzophenone. After adding the phenolic OH group of 4-methoxybenzophenone in an equivalent amount or more and stirring, 20 to 1
Allyl etherification is performed by adding allyl chloride or allyl bromide at 00 ° C. Examples of the various solvents include alcohol solvents such as isopropyl alcohol, aromatic hydrocarbon solvents such as toluene, aliphatic hydrocarbon solvents such as hexane, ketone solvents such as acetone, and ester solvents such as ethyl acetate. And chlorinated solvents such as methylene chloride.

[0018]

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After removing salts, solvents and the like by-produced by the above reaction, the resulting allyl ether compound is isolated by recrystallization, and heated at about 200 ° C. for 1 to 15 hours to obtain the following reaction formula ( As shown in B), Claisen transition is performed. If necessary, purified allylphenol (2-propenylphenol) is obtained by distillation under reduced pressure or recrystallization.

[0020]

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Then, the conversion of the 2-propenyl group to the 1-propenyl group by hydrogen transfer of the allylphenol is carried out by adding an alkali catalyst to the allylphenol as shown in the following reaction formula (C). About 80-150 ° C
This is easily done by heating to. Then, after the transfer, the mixture is neutralized and distilled or recrystallized (only when purified allylphenols are used, only by filtration) to give 2-hydroxy-3- (1- Propenyl) -4-methoxybenzophenone is obtained. Examples of the alkali catalyst include, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium methoxide, potassium methoxide, and the like. About mol% is preferable.

[0022]

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(2) Next, a benzotriazole-based compound (b) having a phenolic OH group and having an ortho position vacant with respect to the OH group is used as a starting material.
The method of synthesizing (2'-hydroxy-5'-methylphenyl) benzotriazole will be described by way of example. Note that the synthesis method goes through almost the same reaction steps as the synthesis method of the above-mentioned benzophenone-based ultraviolet absorber.

First, as shown in the following reaction formula (D),
2- (2'-Hydroxy-5'-methylphenyl) benzotriazole is used as a raw material, and dissolved or dispersed in various solvents in the same manner as described above, and sodium hydroxide, potassium hydroxide, sodium methoxide, potassium After adding methoxide or amines in an amount equal to or more than the equivalent of the phenolic OH group of 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, and stirring,
Allyl etherification is carried out by adding allyl chloride or allyl bromide at 20 to 100 ° C.

[0025]

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After removing salts, solvents and the like by-produced by the above reaction, the resulting allyl ether compound is isolated by recrystallization and heated at about 200 ° C. for 1 to 15 hours to obtain the following reaction formula ( A Claisen transition is performed as shown in E). If necessary, purified allylphenol (2-propenylphenol) is obtained by distillation under reduced pressure or recrystallization.

[0027]

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Next, the conversion of the 2-propenyl group to the 1-propenyl group by hydrogen transfer of the allylphenol is carried out by adding an alkali catalyst to the allylphenol as shown in the following reaction formula (F). About 80-150 ° C
This is easily done by heating to. After the transfer, the mixture is neutralized and distilled or recrystallized (when using purified allylphenols, only filtration) to give 2, [2'-hydroxy-, which is the target benzotriazole-based ultraviolet absorber. 3 '-(1-propenyl)-
5'-Methylphenyl] benzotriazole is obtained.

[0029]

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(3) Next, an example in which phenyl salicylate is used as the salicylate compound (c) having a phenolic OH group as a starting material and having an ortho position vacant with respect to the OH group. The synthesis method will be described. In addition, about the synthesis method, it goes through substantially the same reaction process as the synthesis method of the said benzophenone type and benzotriazole type ultraviolet absorber.

First, as shown in the following reaction formula (G),
Using phenyl salicylate as a raw material, and as described above,
Dissolve or disperse in various solvents, add sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, or amines to the above-mentioned phenyl salicylate in an amount equal to or more than the phenolic OH group and stir. Thereafter, allyl etherification is carried out at 20 to 100 ° C. by adding allyl chloride or allyl bromide.

[0032]

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After removing salts, solvents and the like by-produced by the above reaction, the resulting allyl ether compound is isolated by recrystallization and heated at about 200 ° C. for 1 to 15 hours to obtain the following reaction formula ( As shown in H), a Claisen transition is performed. If necessary, purified allylphenol (2-propenylphenol) is obtained by distillation under reduced pressure or recrystallization.

[0034]

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Next, conversion of the 2-propenyl group to a 1-propenyl group by hydrogen transfer of the allylphenol is performed by adding an alkali catalyst to the allylphenol as shown in the following reaction formula (I). About 80-150 ° C
This is easily done by heating to. After the transfer, the mixture is neutralized and distilled or recrystallized (filtered only when purified allylphenols are used) to give a target salicylate-based ultraviolet absorber represented by the following formula (I): Phenyl 2-hydroxy-3- (1-propenyl) benzoate is obtained.

[0036]

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Through the above reactions (allyl etherification reaction, Claisen transfer reaction, hydrogen transfer reaction), a 1-propenyl group is located ortho to the OH group on the aromatic ring, which is the ultraviolet absorber of the present invention. Into which a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, and a salicylate-based ultraviolet absorber are obtained.

As the monomer thus obtained, which can be copolymerized with the 1-propenylphenol as the ultraviolet absorber of the present invention, a monoolefinic monomer such as ethylene and propylene, butadiene, isoprene and the like are preferable. Distyrene monomers, styrene monomers such as styrene and α-methylstyrene, vinyl carboxylate monomers such as vinyl acetate, chlorine monomers such as vinyl chloride, acrylonitrile monomers, vinyl ether monomers, acrylic acid monomers, methacrylic Examples include acid monomers, acrylate monomers, methacrylic monomers, and maleic anhydride monomers.

Further, the ultraviolet absorber of the present invention, 1-
When propenylphenols are used as a reactive ultraviolet absorber during resin molding, applicable synthetic resins are not particularly limited, and include various synthetic resins. For example, polyethylene, polypropylene, polybutene- Olefin resins such as 1), polyvinyl chloride,
Polyvinyl fluoride, chlorinated polypropylene, polyvinyl acetate, polyvinyl alcohol, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, petroleum resin,
Acrylic resin, methacrylic resin, styrene resin, copolymer resin of styrene and other monomers, acrylonitrile
Butadiene-styrene (ABS) copolymer, methyl methacrylate-butadiene-styrene (MBS) copolymer, styrene-butadiene (SB) rubber, acrylonitrile-butadiene (NB) rubber, polyphenylene oxide (PPO), polycarbonate (PC), Polyacetal, polysulfone, polybutylene terephthalate (PBT), polyethylene terephthalate (PET),
Examples thereof include polyamide, polyimide, epoxy resin, phenol resin, melamine resin, urethane resin, alkyd resin, unsaturated polyester resin, and silicone resin.

The amount of 1-propenylphenol added as a reactive ultraviolet absorber to the synthetic resin is not particularly limited, and may be appropriately adjusted in the same manner as the conventional ultraviolet absorber. Is set, but usually
It is about 0.001 to 70% by weight, preferably about 0.01 to 5% by weight, based on the synthetic resin. The 1-propenylphenol may be added to the above-mentioned synthetic resin in the form of a homopolymer or a copolymer with another copolymerizable monomer, or may be coated on the surface, or may be added in the form of a copolymer. In this case, the addition amount may be appropriately set depending on the content (copolymerization ratio) of the 1-propenyl phenols therein.

When 1-propenylphenol, which is an ultraviolet absorber of the present invention, is added to the above synthetic resin,
If necessary, various additives may be used in combination. For example, an ultraviolet stabilizer (light stabilizer), an antioxidant (antioxidant), a heavy metal deactivator, a lubricant, a plasticizer, a nucleating agent, a foaming agent, Examples include antistatic agents, flame retardants, processing aids, fillers, pigments, metal soaps, organotin compounds and the like. Among these, the combined use of a hindered amino-based ultraviolet stabilizer or the like and an antioxidant are particularly preferable because they have a large synergistic effect with the ultraviolet absorber in view of improving the weather resistance of the resin.

The synthetic resin treated with the ultraviolet absorbent according to the present invention includes, for example, paints for vehicles, textiles for clothing, lenses for glasses, contact lenses, intraocular lenses, agricultural materials, building materials, cosmetics, and skin tanning. It is applied to all kinds of applications such as stoppers, home appliances, thermal recording materials, etc., and protects molding materials, coating materials, structural materials, etc. from ultraviolet rays in the form of films, fibers, tapes, sheets, solutions, latex, emulsions, etc. Can be widely used for purposes.

Since the 1-propenylphenol, which is the ultraviolet absorbent of the present invention, is immobilized by a chemical bond with the synthetic resin, it can be compared with a conventional ultraviolet absorbent simply mixed with the synthetic resin. Thus, it has no volatilization, has almost no extraction into water or an organic solvent, and can impart a permanent ultraviolet absorbing function to the synthetic resin. Therefore, the synthetic resin treated with the ultraviolet absorbent of the present invention has remarkably excellent weather resistance and can contribute to a wide variety of industrial fields.

Next, the present invention will be described based on examples. In the following Examples and Comparative Examples, parts and% are based on weight.

[0045]

Example 1 Synthesis of 2-hydroxy-3- (1-propenyl) -4-methoxybenzophenone 228.2 parts of 2-hydroxy-4-methoxybenzophenone was added to 600 parts of toluene, and 28% CH ₃ was added thereto. 289.4 parts of a methanol solution of ONa (sodium methoxide) was added, and the mixture was stirred.
After heating to 0 to 90 ° C to distill off methanol, the mixture was cooled to 60 ° C and 242 parts of allyl bromide was added dropwise. After the dropping of the allyl bromide, the mixture is heated to 70 ° C.
Allyl etherification reaction was performed by stirring for hours. Next, after removing excess alkali and by-produced salts by washing with water, magnesium sulfate was added, followed by filtration after stirring. Further, unreacted allyl bromide, solvent and the like are distilled off under reduced pressure at 100 ° C. or lower, and then purified by recrystallization using toluene / methanol to obtain 220 parts of 2-allyloxy-4-methoxybenzophenone. Was. The yield of the obtained 2-allyloxy-4-methoxybenzophenone was 82%, and the purity was confirmed to be 99% by gas chromatography (GC) analysis.

Next, the 2-allyloxy-4-methoxybenzophenone was heated to 200 ° C. in a nitrogen atmosphere and maintained at this temperature for 2 hours to perform Claisen transition.
215 parts of -hydroxy-3-allyl-4-methoxybenzophenone were obtained. This reaction proceeded almost quantitatively, and the purity of the obtained 2-hydroxy-3-allyl-4-methoxybenzophenone was confirmed to be 99% by GC analysis.

Then, 5 parts of potassium hydroxide was added to 215 parts of the above 2-hydroxy-3-allyl-4-methoxybenzophenone, and the mixture was stirred and heated at 120 ° C. for 3 hours to perform a hydrogen transfer reaction. 210 parts of -3- (1-propenyl) -4-methoxybenzophenone were obtained.
By this reaction, the allyl group (2-propenyl group) of 2-hydroxy-3-allyl-4-methoxybenzophenone
Transferred to a 1-propenyl group. This reaction proceeded almost quantitatively, and the obtained 2-hydroxy-3-
The purity of (1-propenyl) -4-methoxybenzophenone was confirmed to be 98% from ¹ H-NMR analysis and the like.

The analysis results of the obtained 2-hydroxy-3- (1-propenyl) -4-methoxybenzophenone are shown below.

[Elemental analysis] C = 76.08%, H = 6.
00% (theoretical value as C ₁₇ H ₁₆ O ₃ : C = 76.10)
%, H = 6.01%)

[MS Analysis] The molecular ion peak of C ₁₇ H ₁₆ O ₃ , m / e 268, was confirmed.

[ ¹ H-NMR analysis] 2H (4.6 pp) at the 1-position of the allyl group (2-propenyl group) of the allyl ether
m) completely disappeared, and 2H (3.5) at the 1-position of the Claisen-transferred allyl group (2-propenyl group) was removed.
ppm) also disappeared, and a 3H (1.9 ppm) peak at the 3-position of the 1-propenyl group that had undergone hydrogen transfer was confirmed. All other peaks were assigned, and 2-hydroxy-3- (1-propenyl) was assigned. It was confirmed to be -4-methoxybenzophenone.

[0052]

Example 2 "2, [2'-Hydroxy-3 '-(1-propenyl)"
Synthesis of [-5'-methylphenyl] benzotriazole "

225.3 parts of 2, (2'-hydroxy-5'-methylphenyl) benzotriazole were added to toluene 8
After the addition to 00 parts, the allyl etherification reaction was carried out through exactly the same steps as in Example 1 to give 2, (2 ′
-(Allyloxy-5'-methylphenyl) benzotriazole was obtained in an amount of 206.9 parts. The yield was 78%, and the purity was confirmed to be 99% by GC analysis.

Next, the above-mentioned 2, (2'-allyloxy-
5'-Methylphenyl) benzotriazole was heated to 200 DEG C. under a nitrogen atmosphere, and this temperature was maintained for 2 hours to perform Claisen transition to give 2, (2'-hydroxy-3'-allyl-5'-methylphenyl). Benzotriazole 20
0 parts were obtained. The purity was confirmed to be 99% by GC analysis.

Next, the above 2, (2'-hydroxy-
To 200 parts of 3'-allyl-5'-methylphenyl) benzotriazole, 4 parts of sodium hydroxide was added, stirred, and heated at 130 ° C. for 4 hours to perform a hydrogen transfer reaction.
2, [2'-hydroxy-3 '-(1-propenyl)-
[5'-methylphenyl] benzotriazole (195 parts) was obtained. By this reaction, 2, (2'-hydroxy-3 '
The allyl group (2-propenyl group) of (-allyl-5'-methylphenyl) benzotriazole was transferred to a 1-propenyl group. The purity was confirmed to be 98% from ¹ H-NMR analysis and the like.

The obtained 2, [2'-hydroxy-3'-
The analysis results of (1-propenyl) -5'-methylphenyl] benzotriazole are shown below.

[Elemental analysis] C = 72.41%, H = 5.
69%, N = 15.86% (theoretical value as C ₁₆ H ₁₅ N ₃ O: C = 72.43%, H = 5.70%, N = 15.8)
4%)

[MS Analysis] The molecular ion peak of C ₁₆ H ₁₅ N ₃ O, m / e 265, was confirmed.

[ ¹ H-NMR analysis] 2H (4.6 pp) at the 1-position of the allyl group (2-propenyl group) of the allyl ether
m) completely disappeared, and 2H (3.5) at the 1-position of the Claisen-transferred allyl group (2-propenyl group) was removed.
ppm) disappeared, and a 3H (1.9 ppm) peak at the 3-position of the 1-propenyl group after hydrogen transfer was confirmed. All other peaks were assigned and 2, [2′-hydroxy-3′- (1-propenyl) -5'-methylphenyl] benzotriazole.

[0060]

Example 3 "Synthesis of phenyl 2-hydroxy-3- (1-propenyl) benzoate"

Phenyl 2-hydroxybenzoate (=
(Phenyl salicylate) 214.2 parts of toluene 400
After the addition, the allyl etherification reaction was carried out through exactly the same steps as in Example 1 to obtain 228.9 parts of phenyl 2-allyloxybenzoate. The yield is 9
It was 0%, and the purity was confirmed to be 99% by GC analysis.

Next, the phenyl 2-allyloxybenzoate was heated to 200 ° C. under a nitrogen atmosphere, and this temperature was maintained for 1 hour to carry out Claisen transition.
226 parts of hydroxy-3-allylbenzoate were obtained.
The purity was confirmed to be 99% by GC analysis.

Then, the above phenyl 2-hydroxy-3
After adding 3 parts of potassium hydroxide to 226 parts of allyl benzoate and stirring, the mixture was heated at 120 ° C. for 2 hours to perform a hydrogen transfer reaction to obtain 223 parts of phenyl 2-hydroxy-3- (1-propenyl) benzoate. . With this reaction,
The allyl group (2-propenyl group) of phenyl 2-hydroxy-3-allylbenzoate was transferred to a 1-propenyl group. The purity was confirmed to be 98% from ¹ H-NMR analysis and the like.

The obtained phenyl 2-hydroxy-3-
The analysis results of (1-propenyl) benzoate are shown below.

[Elemental analysis] C = 75.55%, H = 5.
54% (theoretical value as C ₁₆ H ₁₄ O ₃ : C = 75.58)
%, H = 5.55%)

[MS analysis] m / e 254, which is a molecular ion peak of C ₁₆ H ₁₄ O ₃ , was confirmed.

[ ¹ H-NMR analysis] 1H 2H (4.6 pp) of the allyl group (2-propenyl group) of the allyl ether
m) completely disappeared, and 2H (3.5) at the 1-position of the Claisen-transferred allyl group (2-propenyl group) was removed.
ppm) disappeared, and a 3H (1.9 ppm) peak at the 3-position of the 1-propenyl group to which hydrogen had been transferred was confirmed. All other peaks were assigned, and phenyl 2-hydroxy-3- (1-propenyl) was assigned. ) It was confirmed to be benzoate.

A performance evaluation test was performed on each of the ultraviolet absorbents of Examples 1 to 3 obtained as described above. As comparative examples, a conventional non-reactive (non-polymerizable) ultraviolet absorber and a compound before hydrogen transfer were also evaluated.

As a conventional non-reactive UV absorber, Comparative Example 1 was made of 2-hydroxy-4-methoxybenzophenone,
Comparative Example 2 was 2, (2'-hydroxy-5'-methylphenyl) benzotriazole, Comparative Example 3 was phenyl salicylate, and Comparative Example 4 was a compound before hydrogen transfer.
-Hydroxy-3-allyl-4-methoxybenzophenone, Comparative Example 5 was 2, (2'-hydroxy-3'-allyl-5'-methylphenyl) benzotriazole, and Comparative Example 6 was phenyl 2-allyloxybenzoate. .

[Ultraviolet absorption test] 90 parts of methyl methacrylate, 10 parts of butyl acrylate, 0.05 parts of azobisisobutyronitrile and 2-hydroxy-3- (1-propenyl) -4- obtained in Example 1 Put 2 parts of methoxybenzophenone into a pressure-resistant polymerization apparatus, and after replacing with nitrogen 80
C. for 4 hours to obtain a methyl methacrylate / butyl acrylate resin.

This methyl methacrylate / butyl acrylate resin was hot-pressed at 100 ° C. to produce a test piece having a thickness of 1 mm.
The ultraviolet transmittance of each wavelength of m, 350 nm, and 400 nm was measured. The lower the transmittance, the higher the ultraviolet absorption effect and the better the performance.

Similarly, the 2-hydroxy-3- (1-
Propenyl) -4-methoxybenzophenone was polymerized in place of each of the ultraviolet absorbers of Examples 2 and 3 and Comparative Examples 1 to 6, and a test piece was prepared and measured. The results are shown in Table 1 below.

[0073]

[Table 1]

[Extraction resistance test] Methyl methacrylate 9
8 parts, 2 parts of ethylene dimethacrylate, 0.1 part of azobisisobutyronitrile and 10 parts of 2-hydroxy-3- (1-propenyl) -4-methoxybenzophenone obtained in Example 1 were placed in a pressure-resistant polymerization apparatus. 5 after nitrogen replacement
The mixture was heated at 0 ° C. for 10 hours and further at 110 ° C. for 20 hours to obtain a methyl methacrylate resin.

10 parts of this methyl methacrylate resin was pulverized to an average particle size of 3.0 μm, put into a pressure-resistant tube together with 1000 parts of methanol,
After standing for a time, the mixture was cooled to room temperature.

Next, the content of the pressure tube was filtered with a 0.4 μm filter to completely remove the resin. The concentration of 2-hydroxy-3- (1-propenyl) -4-methoxybenzophenone in the filtrate was measured by GC. The lower the extraction rate, the better the extraction resistance.

Further, the above 2-hydroxy-3- (1-propenyl) -4-methoxybenzophenone was prepared in Example 2,
3. Polymerization was carried out in the same manner as in Comparative Examples 1 to 6 instead of the ultraviolet absorbents, and then the test and measurement were performed. The results are shown in Table 2 below.

[0078]

[Table 2]

In Tables 1 and 2 above, first, from the results in Table 1, the acrylic resin using the ultraviolet absorbent of each Example and each Comparative Example was obtained in the evaluation ultraviolet wavelength region (λ = 2
50 to 400 nm), all of which showed good ultraviolet absorbing ability. However, from the results in Table 2, it is clear that the acrylic resin using the ultraviolet absorbent of each comparative example has a very low extraction resistance (solvent type), and particularly the comparative examples 1 to 3 of the conventional type have resistance to extraction. It can be seen that the extractability is very poor.

[Ultraviolet resistance test] 1) Polypropylene resin 0.1 part of 2-hydroxy-3- (1-propenyl) -4-methoxybenzophenone was kneaded into 100 parts of a polypropylene resin (Mitsubishi Polypro MA3: manufactured by Mitsubishi Chemical Corporation). Injection molding was performed at 220 ° C. to prepare a test piece having a thickness of 3 mm. The test piece was tested using a xenon fade meter at a black panel temperature of 65 ° C. for 1500 hours, and the glossiness of the test piece was measured using a gloss meter. At an incident angle of 60 °. The higher the gloss, the better the UV resistance. In addition, the degree of coloring was visually evaluated on a five-point scale, and AA, A, B, C, and D were assigned in the order of good (less coloring).

The above-mentioned 2-hydroxy-3- (1-propenyl) -4-methoxybenzophenone was prepared in Example 2,
3. Tests and measurements were performed in the same manner as in Comparative Examples 1 to 6 in place of the ultraviolet absorbers. The results are shown in Table 3 below.

2) ABS resin ABS resin (JSR ABS45: manufactured by Nippon Synthetic Rubber Co., Ltd.)
100 parts of 2-hydroxy-3- (1-propenyl)-
0.6 part of 4-methoxybenzophenone was kneaded and 25
A test piece having a thickness of 3 mm was prepared by injection molding at 0 ° C., and the test piece was tested at a black panel temperature of 65 ° C. for 1000 hours using a xenon fade meter, and the glossiness of the test piece was measured using a gloss meter. It was measured at an incident angle of 60 °. The higher the gloss, the better the UV resistance. In addition, the degree of coloring was visually evaluated on a five-point scale, and AA, A, B, C, and D were assigned in the order of good (less coloring).

The above 2-hydroxy-3- (1-propenyl) -4-methoxybenzophenone was prepared in Example 2,
3. Tests and measurements were performed in the same manner as in Comparative Examples 1 to 6 in place of the ultraviolet absorbers. The results are shown in Table 3 below.

3) Vinyl chloride resin 0.3 part of 2-hydroxy-3- (1-propenyl) -4-methoxybenzophenone was kneaded into 100 parts of vinyl chloride resin (Sumicon VM-3783, manufactured by Sumitomo Bakelite Co., Ltd.), and A 3 mm thick test piece was prepared by injection molding at 100 ° C., and the test piece was tested with a xenon fade meter at a black panel temperature of 65 ° C. for 1000 hours.
The gloss of the test piece was measured at an incident angle of 60 ° using a gloss meter. The higher the gloss, the better the UV resistance.
In addition, the degree of coloring was visually evaluated on a five-point scale, and AA, A, B, C, and D were assigned in the order of good (less coloring).

Further, the above 2-hydroxy-3- (1-propenyl) -4-methoxybenzophenone was prepared in Example 2,
3. Tests and measurements were performed in the same manner as in Comparative Examples 1 to 6 in place of the ultraviolet absorbers. The results are shown in Table 3 below.

[0086]

[Table 3]

From the results shown in Table 3 above, it is clear that the resins using the ultraviolet absorbents of the respective examples have excellent ultraviolet resistance to all the resins. On the other hand, each comparative example was inferior in ultraviolet resistance.

[Weather resistance test] 1) Polypropylene resin 0.2 parts of 2-hydroxy-3- (1-propenyl) -4-methoxybenzophenone was kneaded into 100 parts of a polypropylene resin (Mitsubishi Polypro MA3: manufactured by Mitsubishi Chemical Corporation). Injection molding was performed at 220 ° C. to prepare a test piece having a thickness of 3 mm, and the test piece was tested using a xenon weatherometer at a black panel temperature of 65 ° C. for 18 hours in a spray cycle of 120 minutes for 1000 hours. The gloss of the piece was measured with a gloss meter at an incident angle of 60 °. The higher the gloss, the better the weather resistance. In addition, the degree of coloring was visually evaluated on a five-point scale.
A, A, B, C, and D were used.

Further, the above 2-hydroxy-3- (1-propenyl) -4-methoxybenzophenone was prepared in Example 2,
3. Tests and measurements were performed in the same manner as in Comparative Examples 1 to 6 in place of the ultraviolet absorbers. The results are shown in Table 4 below.

2) ABS resin ABS resin (JSR ABS45: manufactured by Nippon Synthetic Rubber Co., Ltd.)
100 parts of 2-hydroxy-3- (1-propenyl)-
Knead 0.7 parts of 4-methoxybenzophenone and add 25 parts.
A test piece having a thickness of 3 mm was prepared by injection molding at 0 ° C., and the test piece was tested with a xenon weatherometer at a black panel temperature of 65 ° C. for 18 hours in a spray cycle of 120 minutes for 500 hours. Was measured at an incident angle of 60 ° using a gloss meter. The higher the gloss, the better the weather resistance. In addition, the degree of coloring was visually evaluated on a five-point scale, and AA, A, B,
C and D.

The 2-hydroxy-3- (1-propenyl) -4-methoxybenzophenone described in Example 2,
3. Tests and measurements were performed in the same manner as in Comparative Examples 1 to 6 in place of the ultraviolet absorbers. The results are shown in Table 4 below.

3) Vinyl chloride resin 0.4 part of 2-hydroxy-3- (1-propenyl) -4-methoxybenzophenone was kneaded into 100 parts of vinyl chloride resin (Sumicon VM-3783, manufactured by Sumitomo Bakelite Co., Ltd.), and A 3 mm thick test piece was prepared by injection molding at 100 ° C., and the test piece was subjected to a black panel temperature of 65 ° C. and a spray cycle of 12 using a xenon weatherometer.
After a test of 500 minutes at 18 minutes in 0 minutes, the gloss of the test piece was measured at an incident angle of 60 ° using a gloss meter. The higher the gloss, the better the weather resistance. In addition, the degree of coloring is visually evaluated in five stages, and in order of good (less coloring),
AA, A, B, C, D

Further, the above 2-hydroxy-3- (1-propenyl) -4-methoxybenzophenone was prepared in Example 2,
3. Tests and measurements were performed in the same manner as in Comparative Examples 1 to 6 in place of the ultraviolet absorbers. The results are shown in Table 4 below.

[0094]

[Table 4]

From the results shown in Table 4 above, the resins using the ultraviolet absorbents of the respective examples impart excellent weather resistance, that is, extraction resistance (aqueous) and ultraviolet resistance effects to all the resins. It is clear that the comparative examples were inferior in these evaluations.

[0096]

As described above, the ultraviolet absorbent according to the present invention has a phenolic OH group, and the benzophenone-based compound (a) or the benzotriazole-based compound having an ortho position vacant with respect to the OH group. The compound (b) is a compound having a structural portion derived from the salicylate compound (c) and having a 1-propenyl group introduced ortho to the OH group on the aromatic ring. For this reason,
The 1-propenyl phenols, which are ultraviolet absorbers of the present invention, have a 1-propenyl group introduced into the molecular structure, and have an ultraviolet absorption function having excellent extraction resistance by copolymerizing with other monomers. Is added to the polymer, and furthermore, when these ultraviolet absorbers are blended with a synthetic resin and molded, compared to those obtained by simply blending conventional ultraviolet absorbers, they are mostly volatilized or extracted. Instead, it is possible to provide a permanent ultraviolet absorbing function to the synthetic resin. Therefore, the synthetic resin treated with the ultraviolet absorbent of the present invention has remarkably excellent weather resistance, and greatly contributes to various industrial fields.

Claims (4)

[Claims] 1. A compound having a structural portion derived from the following compound (A) in a molecular structure, and having a 1-propenyl group introduced ortho to an OH group on an aromatic ring. An ultraviolet absorber characterized by the above-mentioned. (A) any one compound selected from the following (a) to (c): (A) A benzophenone-based compound having a phenolic OH group and an ortho position relative to the OH group being empty. (B) A benzotriazole-based compound having a phenolic OH group and an ortho position relative to the OH group being empty. (C) A salicylate compound having a phenolic OH group and having an empty ortho position relative to the OH group. 2. It has a phenolic OH group and its O
Benzophenone-based compounds in which the ortho position to the H group is vacant are 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,4-dihydroxybenzophenone and 2-hydroxy-4-dodecyloxy The ultraviolet absorbent according to claim 1, wherein the ultraviolet absorbent is at least one benzophenone-based compound selected from the group consisting of benzophenone. 3. It has a phenolic OH group and its O
Benzotriazole compounds in which the ortho position to the H group is vacant are 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole , 2
-(2'-hydroxy-5'-t-octylphenyl)
Benzotriazole and 2- (2'-hydroxy-
The ultraviolet absorber according to claim 1, which is at least one benzotriazole-based compound selected from the group consisting of 4'-octoxyphenyl) benzotriazole. 4. It has a phenolic OH group and its O
The salicylate compound in which the ortho position to the H group is vacant is at least one salicylate compound selected from the group consisting of 4-t-butylphenyl salicylate, 4-octyl salicylate and phenyl salicylate. The ultraviolet absorbent according to claim 1.