JP2774232B2 - UV absorber and polymer material composition containing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art Polyester, polyamide, polyolefin, polyether, polystyrene resin, and other high-molecular materials are deteriorated or decomposed by the action of ultraviolet rays, and are resistant to long-term use, such as discoloration and reduced mechanical strength. Not known to be. Therefore, in order to prevent the deterioration of the polymer material, various ultraviolet absorbers have been conventionally used. As these ultraviolet absorbers, for example, benzophenone type, benzotriazole type, salicylic acid type, hydroquinone type and the like are known. However, these conventional ultraviolet absorbers are inferior in their heat resistance and decompose during processing of a polymer material, or are deteriorated or volatilized when used at a high temperature, and none are practically satisfactory.

[0003] Benzoxazinone-based ultraviolet absorbers have been proposed to satisfy these problems (JP-A-62-11744, JP-A-4-11685). Benzoxazinone-based UV absorbers certainly have high heat resistance and large UV-absorbing ability themselves, but there is a strong demand for higher light resistance improvement for polymer materials.
The improvement was required.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to control the compatibility of a benzoxazinone-based UV absorber with a polymer material, thereby further improving the polymer material compared to a conventional benzoxazinone-based UV absorber. To provide a novel ultraviolet absorber capable of improving the light fastness of the ink.

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

[0006]

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

[0007]

Embedded image

[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. Hereinafter, the present invention will be described in detail.

The novel ultraviolet absorber of the present invention is a compound represented by the above formula (I). In the 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 and trimethyloctyl. 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 Examples thereof include an aliphatic hydrocarbon residue having a hydrocarbon residue and / or an aromatic hydrocarbon residue as a substituent.

The hydrocarbon residue represented by R ₁ or R ₂ is preferably an aliphatic hydrocarbon residue, particularly an alkyl group.

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

Ar is preferably a p-phenylene group.

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

The compound represented by the above formula (I) includes
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-phenylenebis (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-phenylenebis (6-octadecanoyloxy-3,1-benzoxazin-4-one), 2,2'-p-phenylenebis (7
-Propionyloxy-3,1-benzoxazine-4
-One), 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-phenylenebis (7-tridecanoyloxy-3,1-benzoxazin-4-one), 2,
2'-p-phenylenebis (7-tetradecanoyloxy-3,1-benzoxazin-4-one), 2,2 '
-P-phenylenebis (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
-One), 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-phenylenebis (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-heptanolyl Oxy-3,1-benzoxazin-4-one), 2,2'-2,6-naphthylenebis (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-naphthylenebis (6-hexadecanoyloxy-3,1-benzoxazin-4-one), 2,2'-4,4 '-Biphenylenebis (6-butyryloxy-3,1-benzoxazin-4-one), 2,2'-4,4'-biphenylenebis (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, a bisamide carboxylic acid is produced by reacting hydroxyanthranilic acid with a dicarboxylic acid chloride represented by the following formula (II):

[0016]

Embedded image

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

[0018]

Embedded image

[In the formula (III), R represents the R in the formula (I).
Synonymous with ₁ . Next, a method of reacting with a carboxylic acid represented by the following formula (IV) to effect an acyl exchange reaction can be preferably exemplified.

[0020]

Embedded image

[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, whereby the compatibility with various polymer materials can be controlled.

The ultraviolet 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 for example, polyesters such as polyethylene terephthalate, polytetramethylene terephthalate, polyethylene naphthalate, polyester / polyether having polyester as a hard segment and polyether and / or polyester as a soft segment. Or polyester / polyester segmented thrusters, polycarbonate, polyethylene, polypropylene, poly-4
-Polyolefins such as methylpentene, polyolefin copolymers such as ethylene / propylene copolymer and ethylene / vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, vinyl chloride / ethylene copolymer, and vinyl chloride / Vinyl acetate copolymer, vinyl chloride copolymer such as vinyl chloride / acrylate copolymer, polyamide such as nylon 6, nylon 11, nylon 12, nylon 66, polystyrene, AS resin, AB
Various styrene resins such as S resin and MBS resin, 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. And the like.

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 added amount of the ultraviolet absorber is less than 0.01 part 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 undesirably impaired. The amount of the ultraviolet absorber added is preferably 0.05 to 8 parts by weight, particularly preferably 0.1 to 6 parts by weight, per 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, if necessary, a lubricant, a matting agent, a nucleating agent, a release agent, an antistatic agent, a plasticizer, an oxidation stabilizer, a fluorescent bleaching agent, a processing aid and other various substances Additives may be added.

[0026]

The ultraviolet absorber of the present invention is obtained by introducing a specific substituent into a benzoxazinone-based ultraviolet absorber. The compatibility with various polymer materials can be controlled by the type of the substituent. For example, when a polyester such as polyethylene terephthalate is used as the polymer material, a high concentration of the ultraviolet absorber can be distributed near the surface layer of the polymer. For this reason, ultraviolet light can be absorbed very efficiently, and the light stability of the polymer material can be significantly improved. 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 fastness of the polymer is improved.

[0027]

The present invention will be described in detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. In the examples, "part"
Means "parts by weight".

The melting point was measured at a heating rate of 10 ° C./min using DSC. 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 dropped into the above aqueous solution at room temperature, reacted for 2 hours with stirring, and further reacted for 1 hour under reflux with acetone. The resulting slurry reaction solution was cooled to room temperature, the reaction solution was acidified by adding hydrochloric acid, and then filtered and washed with water to obtain 103 parts of a bisamide carboxylic acid. 400 parts of acetic anhydride was added to the above bisamide carboxylic acid, and the mixture was heated under reflux with stirring for 2 hours. After the reaction solution was cooled to room temperature, the crystals were filtered, washed with water and methanol, and 2,2'-p-phenylenebis (6
-Acetoxy-3,1-benzoxazinone-4-one) in an amount of 102 parts.

Next, 2,2'-p-phenylenebis (6-
Acetoxy-3,1-benzoxazinone-4-one)
85 parts, 1500 parts of stearic acid and 0.06 parts of tetrabutyl titanate were reacted at 210 ° C. for 4 hours while stirring. During this reaction, generation of acetic acid generated by the carboxylic acid exchange reaction was observed. The reaction solution was slurried with heated ethanol, cooled, and filtered three times to remove stearic acid, thereby obtaining 86 parts of pale gray crystals. This was recrystallized from dimethylformamide to give 2,2'-p-phenylenebis (6-stearoyloxy-3,1-benzoxazin-4-one).
Was obtained as white crystals. The melting point is 227 ° C., and the results of elemental analysis (theoretical values in parentheses) are shown below. C 74.52% (74.64%), H 8.68%
(8.64%), N 3.15% (3.00%), O
13.65% (13.72%) The infrared absorption spectrum is shown in FIG. 1, and the 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-benzoxazinone-4-one), 500 parts of pelargonic acid and 0.06 part of tetrabutyl titanate are stirred at 200 ° C.
For 2 hours. During this reaction, generation of acetic acid generated by the carboxylic acid exchange reaction was observed. The reaction solution was thoroughly washed with methanol to obtain 93 parts of pale yellow crystals.
This was recrystallized from dimethylformamide,
2'-p-phenylenebis (6-nonanoyloxy-
3,1-benzoxazinone-4-one) was obtained as white crystals. The melting point is 256 ° C., and the results of elemental analysis (the values in parentheses are theoretical values) are shown below. C 70.75 (70.57%), H 6.56 (6.
51%) N 4.00% (4.11%), O 18.69% (1
FIG. 3 shows an infrared absorption spectrum and FIG. 4 shows an ultraviolet absorption spectrum.

[0032]

Example 3 25 parts of n-lacnic acid, 116 parts of acetic anhydride and 0.05 part of tetrabutyl titanate were charged into a reaction vessel having a distilling system equipped with a stirrer and a rectification column, and then charged with 130 to 130 parts.
The reaction was carried out by heating to 140 ° C., and acetic acid generated by the carboxylic acid exchange reaction was gradually distilled out of the system. After the distilling amount reached about 20 parts, the temperature was raised to about 160 ° C., acetic acid and unreacted acetic anhydride were distilled off, and lactic acid anhydride was synthesized.

5 parts of the bisamidocarboxylic acid (terephthaloylbis (2-carboxyl-4-hydroxybenzamide)) prepared in Example 1 was added to the lacnic anhydride synthesized by the above method, and the mixture was refluxed for 2.5 hours. Allowed to react 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-phenylenebis (6-butyryloxy-3,1-benzoxazinone-4-one). The melting point is 266 ° C., and the results of elemental analysis (theoretical values in parentheses) are as follows. C 66.85% (66.66%), H 4.45%
(4.48%), N 4.99% (5.18%), O
23.71% (23.68%) The infrared absorption spectrum is shown in FIG. 5, and the ultraviolet absorption spectrum is shown in FIG.

[0035]

Examples 4 and 5 and Comparative Example 1 Intrinsic viscosity (phenol /
Example 1 was prepared by melting 50 parts of polyethylene terephthalate (0.63 in 1,1,2,2-tetrachloroethane mixed solvent (weight ratio: 60/40) at 35 ° C.) at 280 ° C.
1.5 parts of the ultraviolet absorbent prepared in and 2 were added respectively,
Melt blend for 5 minutes while stirring, and add 2 mm thick
Into a plate. ESC of this plate sample
A, surface analysis was performed, and the surface detection element (C.N.
The detection ratio was determined from the peak intensity ratio of O). In addition, this analysis was performed on the surface of the plate-shaped sample and the surface after the surface of the sample was cut off by about 50 μm, and the element distribution in the surface layer and the inner layer was evaluated. Table 1 shows the results.

[0036]

[Table 1]

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

When the ultraviolet absorbent of the present invention is used,
The detection ratio of C and N is higher in the surface layer than in the inner layer, indicating that the ultraviolet absorber is distributed at 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 added to an intrinsic viscosity (phenol / phenol).
Dry blended with 0.63 polyethylene terephthalate in a 1,1,2,2-tetrachloroethane mixed solvent (weight ratio 60/40, measured at 35 ° C.), using a 24-hole nozzle at a polymer temperature of 285 ° C. And melt spun. Next, the undrawn yarn is drawn 4 times at 80 ° C.
And heat-fixed under fixed length. The fineness of the drawn yarn was 75 denier. Using a 100 W mercury lamp, the obtained drawn yarn was
Irradiation with ultraviolet light was carried out for a period of time, and the intensity retention at that time was measured. Table 2 shows the results.

[0040]

[Table 2]

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

[Brief description of the drawings]

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

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

Claims (2)

(57) [Claims] 1. An ultraviolet absorber represented by the following formula (I). Embedded image [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 absorbent according to claim 1 based on 100 parts by weight of the polymer material.