JPH0711232A - Ultraviolet absorber and polymer material composition containing the same - Google Patents

Abstract

(57) [Summary] [Object] To provide an ultraviolet absorber having an improved compatibility with a polymer material. The present invention provides an ultraviolet absorber represented by the following formula (I) [In the formula (I), R ₁ and R ₂ each independently have 2 to 2 carbon atoms.
20 represents a hydrocarbon residue, and Ar represents an aromatic hydrocarbon residue having 6 to 12 carbon atoms. n represents 0 or 1. ]
Is.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel ultraviolet absorber and a polymer material composition containing the same, and more particularly to a novel benzoxazinone ultraviolet absorber having a specific structure and a polymer material composition containing the same. Regarding things.

[0002]

2. Description of the Related Art Polymer materials such as polyester, polyamide, polyolefin, polyether, polystyrene resin and other polymeric materials are deteriorated or decomposed by the action of ultraviolet rays, and they endure long-term use such as discoloration or deterioration of mechanical strength. Not known to be. Therefore, in order to prevent deterioration of the polymer material, various ultraviolet absorbers have been conventionally used. As these ultraviolet absorbers, for example, benzophenone-based, benzotriazole-based, salicylic acid-based, hydroquinone-based, etc. are known. However, these conventional ultraviolet absorbers are inferior in heat resistance themselves, and are not practically satisfactory because they are decomposed during processing of a polymer material, deteriorated or volatilized during use at high temperature.

A benzoxazinone-based ultraviolet absorber has been proposed to satisfy these problems (Japanese Patent Laid-Open Nos. 62-11744 and 4-11685). The benzoxazinone-based UV absorbers have high heat resistance and large UV absorption ability by themselves, but there is a strong demand for higher light resistance improvement of polymer materials.
The improvement was demanded.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to control the compatibility of a benzoxazinone UV absorber with a polymer material, so that a higher polymer material than conventional benzoxazinone UV absorbers can be obtained. It is to provide a novel ultraviolet absorber capable of improving the light resistance of

Another object of the present invention is to provide a polymer material having improved light resistance as compared with the prior art.

[0006]

The object of the present invention can be achieved by a novel ultraviolet absorber represented by the following formula (I) and a polymeric material containing the same.

[0007]

[Chemical 2]

[In the formula (I), R ₁ and R ₂ each independently represent a hydrocarbon residue having 2 to 20 carbon atoms, and Ar represents an aromatic hydrocarbon residue having 6 to 12 carbon atoms. n represents 0 or 1. The present invention will be described in detail below.

The novel ultraviolet absorber of the present invention is a compound represented by the above formula (I). In formula (I), R
₁ and R ₂ each independently represent a hydrocarbon residue having 2 to 20 carbon atoms. Specific examples of R ₁ and R ₂ include ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, trimethylhexyl, trimethyloctyl and the like. Aliphatic hydrocarbon residue having a straight or branched chain, alicyclic hydrocarbon residue such as cyclopentyl, cyclohexyl, cyclooctyl, aromatic hydrocarbon residue such as phenyl, naphthyl, tolyl, or the above alicyclic group The aliphatic hydrocarbon residue which has a hydrocarbon residue and / or an aromatic hydrocarbon residue as a substituent can be mentioned.

Of these, the hydrocarbon residue represented by R ₁ and R ₂ is preferably an aliphatic hydrocarbon residue, particularly an alkyl group.

In the formula (I), Ar has 6 to 12 carbon atoms.
Is an aromatic hydrocarbon residue of. Specific examples of Ar include phenylene groups such as p-phenylene and m-phenylene,
2,6-naphthylene, 2,7-naphthylene, 1,4-naphthylene, 1,5-naphthylene and the like naphthylene groups, 4,4
-Biphenylene, 3,3'-biphenylene, p-tolylene and the like can be mentioned.

Of these, p-phenylene group is preferable as Ar.

N represents 0 or 1. When n is 0, it means that a direct bond is formed. It is preferable that n is 1.

As the compound represented by the above formula (I),
Specifically, 2,2'-bis (6-propionyloxy-3,1-benzoxazin-4-one), 2,2'-bis (6-butyryloxy-3,1-benzoxazin-4-one) , 2,2'-bis (6-hexanoyloxy-3,3
1-benzoxazin-4-one), 2,2'-bis (6-heptanoyloxy-3,1-benzoxazin-4-one), 2,2'-bis (6-octanoyloxy-3,3) 1-benzoxazin-4-one), 2,2 '
-Bis (6-nonyloxy-3,1-benzoxazin-4-one), 2,2'-bis (6-decanoyloxy-3,1-benzoxazin-4-one), 2,2 '
-Bis (6-dodecanoyloxy-3,1-benzoxazin-4-one), 2,2'-bis (6-tridecanoyloxy-3,1-benzoxazin-4-one),
2,2'-bis (6-tetradecanoyloxy-3,1
-Benzoxazin-4-one), 2,2'-bis (6
-Pentadecanoyloxy-3,1-benzoxazin-4-one), 2,2'-bis (6-hexadecanoyloxy-3,1-benzoxazin-4-one), 2,
2'-bis (6-octadecanoyloxy-3,1-benzoxazin-4-one), 2,2'-bis (7-propionyloxy-3,1-benzoxazin-4-one), 2, 2'-bis (7-butyryloxy-3,1-
Benzoxazin-4-one), 2,2'-bis (7-
Hexanoyloxy-3,1-benzoxazine-4-
ON), 2,2'-bis (7-heptanoyloxy-
3,1-benzoxazin-4-one), 2,2'-bis (7-octanoyloxy-3,1-benzoxazin-4-one), 2,2'-bis (7-nonanoyloxy-3,3 1-benzoxazin-4-one), 2,2 '
-Bis (7-decanoyloxy-3,1-benzoxazin-4-one), 2,2'-bis (7-dodecanoyloxy-3,1-benzoxazin-4-one), 2,
2'-bis (7-tridecanoyloxy-3,1-benzoxazin-4-one), 2,2'-bis (7-tetradecanoyloxy-3,1-benzoxazine-4-
On), 2,2'-bis (7-pentadecanoyloxy-3,1-benzoxazin-4-one), 2,2'-
Bis (7-hexadecanoyloxy-3,1-benzoxazin-4-one), 2,2'-bis (7-octadecanoyloxy-3,1-benzoxazin-4-one), 2,2 ′ -P-phenylenebis (6-propionyloxy-3,1-benzoxazin-4-one),
2,2'-p-phenylene bis (6-butyryloxy-
3,1-benzoxazin-4-one), 2,2'-p
-Phenylenebis (6-hexanoyloxy-3,1-
Benzoxazin-4-one), 2,2'-p-phenylenebis (6-heptanoyloxy-3,1-benzoxazin-4-one), 2,2'-p-phenylenebis (6-octanoyl) Oxy-3,1-benzoxazin-4-one), 2,2'-p-phenylenebis (6-nonanoyloxy-3,1-benzoxazin-4-one), 2,2'-p-phenylenebis ( 6-decanoyloxy-3,1-benzoxazin-4-one), 2,
2'-p-phenylenebis (6-dodecanoyloxy-
3,1-benzoxazin-4-one), 2,2'-p
-Phenylenebis (6-tridecanoyloxy-3,1
-Benzoxazin-4-one), 2,2'-p-phenylenebis (6-tetradecanoyloxy-3,1-benzoxazin-4-one), 2,2'-p-phenylenebis (6- Pentadecanoyloxy-3,1-benzoxazin-4-one), 2,2'-p-phenylenebis (6-hexadecanoyloxy-3,1-benzoxazin-4-one), 2,2 ' -P-phenylene bis (6-octadecanoyloxy-3,1-benzoxazin-4-one), 2,2'-p-phenylene bis (7
-Propionyloxy-3,1-benzoxazine-4
-On), 2,2'-p-phenylenebis (7-butyryloxy-3,1-benzoxazin-4-one),
2,2'-p-phenylenebis (7-hexanoyloxy-3,1-benzoxazin-4-one), 2,2 '
-P-phenylenebis (7-heptanoyloxy-3,3
1-benzoxazin-4-one), 2,2'-p-phenylenebis (7-octanoyloxy-3,1-benzoxazin-4-one), 2,2'-p-phenylenebis (7- Nonanoyloxy-3,1-benzoxazin-4-one), 2,2'-p-phenylenebis (7-
Decanoyloxy-3,1-benzoxazin-4-one), 2,2'-p-phenylenebis (7-dodecanoyloxy-3,1-benzoxazin-4-one),
2,2'-p-phenylene bis (7-tridecanoyloxy-3,1-benzoxazin-4-one), 2,
2'-p-phenylene bis (7-tetradecanoyloxy-3,1-benzoxazin-4-one), 2,2 '
-P-phenylene bis (7-pentadecanoyloxy-
3,1-benzoxazin-4-one), 2,2'-p
-Phenylenebis (7-hexadecanoyloxy-3,3
1-benzoxazin-4-one), 2,2'-p-phenylenebis (7-octadecanoyloxy-3,1-
Benzoxazin-4-one), 2,2'-m-phenylenebis (6-butyryloxy-3,1-benzoxazin-4-one), 2,2'-m-phenylenebis (6
-Heptanoyloxy-3,1-benzoxazine-4
-On), 2,2'-m-phenylenebis (6-octanoyloxy-3,1-benzoxazin-4-one), 2,2'-m-phenylenebis (6-decanoyloxy-3,3) 1-benzoxazin-4-one), 2,
2'-m-phenylene bis (6-dodecanoyloxy-
3,1-benzoxazin-4-one), 2,2'-m
-Phenylenebis (6-pentadecanoyloxy-3,3
1-benzoxazin-4-one), 2,2'-m-phenylenebis (6-hexadecanoyloxy-3,1-
Benzoxazin-4-one), 2,2'-2,6-naphthylenebis (6-butyryloxy-3,1-benzoxazin-4-one), 2,2'-2,6-naphthylenebis (6-heptanoyl) Oxy-3,1-benzoxazin-4-one), 2,2'-2,6-naphthylene bis (6-octanoyloxy-3,1-benzoxazin-4-one), 2,2'-2 6-naphthylene bis (6
-Decanoyloxy-3,1-benzoxazine-4-
On), 2,2'-2,6-naphthylenebis (6-dodecanoyloxy-3,1-benzoxazin-4-one), 2,2'-2,6-naphthylenebis (6-pentadecanoyloxy- 3,1-benzoxazin-4-one), 2,2'-2,6-naphthylene bis (6-hexadecanoyloxy-3,1-benzoxazin-4-one), 2,2'-4,4 ′ -Biphenylene bis (6-butyryloxy-3,1-benzoxazin-4-one), 2,2′-4,4′-biphenylene bis (6-heptanoyloxy-3,1-benzoxazin-4-one ), 2,2'-4,4'-biphenylenebis (6-octanoyloxy-3,1-benzoxazin-4-one), 2,2'-4,4'-biphenylenebis (6-decanoyl) Oxy-3,1 Benzoxazin-4-one), 2,2'-4,4'-biphenylenebis (6-dodecanoyloxy-3,1-benzoxazin-4-one), 2,2'-4,4'-biphenylene Bis (6-pentadecanoyloxy-3,1-benzoxazine-4
-On), 2,2'-4,4'-biphenylene bis (6
—Hexadecanoyloxy-3,1-benzoxazin-4-one) and the like.

The method for producing the above compound is not particularly limited. For example, hydroxyanthranilic acid is reacted with a dicarboxylic acid chloride represented by the following formula (II) to produce a bisamidocarboxylic acid,

[0016]

[Chemical 3]

[In the formula (II), Ar and n are the above formula (I).
Is synonymous with. Next, a method of reacting with a carboxylic acid anhydride represented by the following formula (III) to perform the acylation reaction of the hydroxyl group at the same time as the ring closure of the benzoxazinone ring, or the above bisamidocarboxylic acid with a lower aliphatic acid such as acetic anhydride Ring closure and acylation reaction with carboxylic acid anhydride,

[0018]

[Chemical 4]

[In the formula (III), R is R in the above formula (I).
Synonymous with ₁ . Next, a method of reacting with a carboxylic acid represented by the following formula (IV) to cause an acyl exchange reaction and the like can be preferably mentioned.

[0020]

[Chemical 5]

[In the formula (IV), R has the same meaning as in the above formula (III). The ultraviolet absorber of the present invention has a hydrocarbon residue via an ester group, and thereby it is possible to control the compatibility with various polymer materials.

The UV absorber of the present invention exhibits a function as a light stabilizer by blending it with a polymer material. The polymer material used here is not particularly limited, but examples thereof include polyesters such as polyethylene terephthalate, polytetramethylene terephthalate and polyethylene naphthalate, polyester / polyether having polyester as a hard segment and / or polyester as a soft segment. Or polyester / polyester segmented thrusters, polycarbonate, polyethylene, polypropylene, poly-4
-Polyolefin such as methylpentene, ethylene / propylene copolymer, polyolefin copolymer such as ethylene / vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, vinyl chloride / ethylene copolymer, vinyl chloride / Vinyl acetate copolymers, vinyl chloride copolymers such as vinyl chloride / acrylic acid ester copolymers, polyamides such as nylon 6, nylon 11, nylon 12, nylon 66, polystyrene, AS resins, AB
Various styrene resins such as S resins and MBS resins, thermoplastic resins such as polyvinyl acetate, polyacetal, polyurethane, polyphenylene oxide, polysulfone and polyarylate, phenol resins, melamine resins, urea resins, epoxy resins, unsaturated polyester resins, etc. The thermosetting resin and the like can be mentioned.

The amount of the ultraviolet absorber added to the polymer material is 0.01 to 10 parts by weight based on 100 parts by weight of the polymer material. If the amount of the ultraviolet absorber added is less than 0.01 parts by weight, the effect of improving the light resistance is insufficient, and if it is more than 10 parts by weight, the original properties of the polymer material are impaired, which is not preferable. The amount of the ultraviolet absorber added is preferably 0.05 to 8 parts by weight, and particularly preferably 0.1 to 6 parts by weight, based on 100 parts by weight of the polymer material.

The form of the polymer material is not particularly limited, and examples thereof include fibers, tapes, films, sheets and plastics.

In the polymer material of the present invention, various kinds of lubricants, matting agents, nucleating agents, releasing agents, antistatic agents, plasticizers, oxidation stabilizers, fluorescent bleaching agents, processing aids and the like may be added as required. Additives may be added.

[0026]

The ultraviolet absorber of the present invention is a benzoxazinone ultraviolet absorber having a specific substituent introduced therein. The compatibility with various polymer materials can be controlled by the kind of the substituent. For example, when polyester such as polyethylene terephthalate is used as the polymer material, a high concentration of the ultraviolet absorber can be distributed in the vicinity of the surface layer of the polymer. Therefore, ultraviolet rays can be absorbed very efficiently, and the photostability of the polymer material can be significantly improved. Further, when a polyolefin such as polyethylene or polypropylene is used as the polymer material, the compatibility between the ultraviolet absorber and the polymer is improved,
The light resistance of the polymer is improved.

[0027]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. "Part" in the examples
Means "parts by weight".

The melting point was measured by DSC at a temperature rising rate of 10 ° C./min. The IR spectrum was measured by the KBr method.
The UV spectrum was measured at a concentration of 5 × 10 ⁻³ g / l using 1,1,2,2-tetrachloroethane as a solvent.

[0029]

Example 1 77 parts of 5-hydroxyanthranilic acid and 58 parts of sodium carbonate were dissolved in 1200 parts of water. A solution prepared by dissolving 51 parts of terephthaloyl chloride in 300 parts of acetone was added dropwise to the above aqueous solution at room temperature, reacted for 2 hours while stirring, and further reacted for 1 hour under reflux of acetone. The obtained reaction liquid in the form of a slurry was cooled to room temperature, hydrochloric acid was added to acidify the reaction liquid, which was then filtered and washed with water to obtain 103 parts of bisamidocarboxylic acid. 400 parts of acetic anhydride was added to the above bisamidocarboxylic acid, and the mixture was heated under reflux for 2 hours with stirring. After cooling the reaction solution to room temperature, the crystals were filtered and washed with water and methanol to obtain 2,2'-p-phenylenebis (6
-Acetoxy-3,1-benzoxazinone-4-one) was obtained.

Next, 2,2'-p-phenylenebis (6-
Acetoxy-3,1-benzoxazinone-4-one)
85 parts, 1500 parts of stearic acid and 0.06 part of tetrabutyl titanate were reacted with stirring at 210 ° C. for 4 hours. During this reaction, generation of acetic acid generated by the exchange reaction of carboxylic acid was observed. The reaction solution was slurried with heated ethanol, cooled and filtered three times, and the stearic acid was washed off to obtain 86 parts of pale gray crystals. Further, this was recrystallized from dimethylformamide to obtain 2,2'-p-phenylenebis (6-stearoyloxy-3,1-benzoxazin-4-one)
White crystals were obtained. The melting point is 227 ° C., and the elemental analysis results (theoretical value in ()) are shown below. C 74.52% (74.64%), H 8.68%
(8.64%), N 3.15% (3.00%), O
13.65% (13.72%) An infrared absorption spectrum is shown in FIG. 1 and an ultraviolet absorption spectrum is shown in FIG.

[0031]

Example 2 2,2'-p- synthesized in the same manner as in Example 1
85 parts of phenylene bis (6-acetoxy-3,1-benzoxazinon-4-one), 500 parts of pelargonic acid and 0.06 part of tetrabutyl titanate are stirred at 200 ° C.
And reacted for 2 hours. During this reaction, generation of acetic acid generated by the exchange reaction of carboxylic acid was observed. The reaction solution was washed well with methanol to obtain 93 parts of pale yellow crystals.
Furthermore, this was recrystallized from dimethylformamide,
2'-p-phenylene bis (6-nonanoyloxy-
White crystals of 3,1-benzoxazinone-4-one) were obtained. The melting point is 256 ° C., and the elemental analysis results (theoretical values in parentheses) are shown below. C 70.75 (70.57%), H 6.56 (6.
51%) N 4.00% (4.11%), O 18.69% (1
Further, the infrared absorption spectrum is shown in FIG. 3 and the ultraviolet absorption spectrum is shown in FIG.

[0032]

Example 3 25 parts of n-lacic acid, 116 parts of acetic anhydride and 0.05 parts of tetrabutyl titanate were charged into a reaction vessel having a distillation system equipped with a stirrer and a rectification column, and the amount of 130-
The mixture was heated to 140 ° C. for reaction, and acetic acid produced by the carboxylic acid exchange reaction was gradually distilled out of the system. After the amount of distillate reached about 20 parts, the temperature was raised to about 160 ° C. to distill off acetic acid and unreacted acetic anhydride to synthesize lactic anhydride.

5 parts of the bisamidocarboxylic acid (terephthaloylbis (2-carboxyl-4-hydroxybenzamide)) prepared in Example 1 was added to the lactic acid anhydride synthesized by the above method, and the mixture was refluxed at 2.5%. Reacted for hours. After cooling the reaction solution, the crystals were separated by filtration, washed with water and washed with methanol to obtain 5.4 parts of gray crystals.

This was further recrystallized from dimethylformamide to obtain white crystals of 2,2'-p-phenylene bis (6-butyryloxy-3,1-benzoxazinon-4-one). The melting point is 266 ° C., and the elemental analysis results (theoretical value in ()) are as follows. C 66.85% (66.66%), H 4.45%
(4.48%), N 4.99% (5.18%), O
23.71% (23.68%) An infrared absorption spectrum is shown in FIG. 5 and an ultraviolet absorption spectrum is shown in FIG.

[0035]

Examples 4, 5 and Comparative Example 1 Intrinsic viscosity (phenol /
50 parts of polyethylene terephthalate of 0.63 in 1,1,2,2-tetrachloroethane mixed solvent (weight ratio 60/40) (measured at 35 ° C.) was melted at 280 ° C., and Example 1
And 1.5 parts of the UV absorber produced in 2 and 2, respectively,
Melt and blend for 5 minutes with stirring, and add this to a thickness of 2 mm.
Was molded into a plate shape. ESC of this plate sample
A surface analysis by A is performed to detect the surface detection element (C.N.
The detection ratio was determined from the peak intensity ratio of O). This analysis was carried out on the surface of the plate-shaped sample and the surface after the surface of this sample was scraped by about 50 μm to evaluate the element distribution in the surface layer and the inner layer. The results are shown in Table 1.

[0036]

[Table 1]

Table 1 also shows, as Comparative Example 1, the results when 2,2'-p-phenylenebis (3,1-benzoxazin-4-one) was used as the ultraviolet absorber.

When the ultraviolet absorber of the present invention is used,
It can be seen that the detection ratio of C and N is higher in the surface layer than in the inner layer, and the ultraviolet absorber is distributed in a higher concentration in the surface layer than in the inner layer.

[0039]

[Examples 6 and 7 and Comparative Example 2] 1% by weight of the ultraviolet absorbent prepared in Examples 1 and 2 was mixed with an intrinsic viscosity (phenol /
Dry blend with 0.63 polyethylene terephthalate in 1,1,2,2-tetrachloroethane mixed solvent (weight ratio 60/40), measured at 35 ° C., and use a 24-hole nozzle at a polymer temperature of 285 ° C. And melt-spun. Then, the unstretched yarn is stretched 4 times at 80 ° C. to 160 ° C.
It was heat fixed under a fixed length. The fineness of the drawn yarn was 75 denier. The drawn yarn obtained was 4 using a 100 W mercury lamp.
It was irradiated with ultraviolet rays for a period of time, and the strength retention rate at that time was measured. The results are shown in Table 2.

[0040]

[Table 2]

Table 2 shows, as Comparative Example 2, 2,2'-p-phenylenebis (3,1-benzoxazin-4-one).
Although the results of the case of using the are shown, it is understood that the ultraviolet absorbent of the present invention is effective for improving the light resistance of polyester.

[Brief description of drawings]

FIG. 1 shows an infrared absorption spectrum of the ultraviolet absorbent produced in Example 1.

FIG. 2 shows an ultraviolet absorption spectrum of the ultraviolet absorbent produced in Example 1.

FIG. 3 shows an infrared absorption spectrum of the ultraviolet absorbent produced in Example 2.

FIG. 4 shows an ultraviolet absorption spectrum of the ultraviolet absorbent produced in Example 2.

FIG. 5 shows an infrared absorption spectrum of the ultraviolet absorbent produced in Example 3.

FIG. 6 shows an ultraviolet absorption spectrum of the ultraviolet absorbent produced in Example 3.

Claims (2)

[Claims] 1. An ultraviolet absorber represented by the following formula (I). [Chemical 1] [In the formula (I), R ₁ and R ₂ each independently have 2 to 2 carbon atoms.
20 represents a hydrocarbon residue, and Ar represents an aromatic hydrocarbon residue having 6 to 12 carbon atoms. n represents 0 or 1. ] 2. A polymer material composition comprising 0.01 to 10 parts by weight of the ultraviolet absorber according to claim 1 with respect to 100 parts by weight of the polymer material.