JPH06145164A - Ultraviolet absorber, benzopyran derivative suitable for the same, thermoplastic resin composition containing the ultraviolet absorber and molded article - Google Patents

Abstract

PURPOSE:To obtain a new 2H-1-benzopyran-2-one derivative useful as an ultraviolet absorber. CONSTITUTION:A compound of formula I (Y1 is O or S; X1 to X4 are H, halogen, nitro, OH or acetoxy; Q1 to Q5 are H, halogen, nitro or cyano excluding the case wherein Q1 to Q5 are all H atoms) and a compound of formula II (Q6 to Q15 are H, halogen, nitro or cyano). The compound of formula I is obtained by reacting a compound of formula III with thionyl chloride and reacting the reaction product with a compound of formula IV in a solvent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet absorber, a 2H-1-benzopyran-2-one derivative suitable for the ultraviolet absorber, and a thermoplastic resin composition containing the ultraviolet absorber.

[0002]

2. Description of the Related Art Thermoplastic resins such as polyester, polymethylmethacrylate, and polyvinyl chloride have excellent mechanical strength and are widely used for processed products such as films because of their chemical properties. For example, in recent years, polyester has come to be used in large quantities as a container for foods such as beverages, seasonings, and sake because of its excellent transparency, gas barrier property, safety and hygiene. In addition, for building applications and vehicles, when a window glass is impacted, it is crushed and scattered and prevented, or with the aim of blocking heat rays from the outside with the purpose of energy saving, a window pasting film is It has been developed, and especially polyester films are used. Furthermore, recently, from the viewpoint of decorative use, a polyester film is colored to improve its design, and it has been put on the market, and a window that requires originality and high functionality in design. Demand is rapidly increasing as a film for window attachment to glass. On the other hand, as an example used for agriculture and horticulture, for the purpose of promoting growth and large-scale harvesting of useful plants such as root vegetables, especially light resistance, light transmittance, and polymethylmethacrylate from strength,
There is a mulching coating material using polyvinyl chloride as a base material (Japanese Patent Laid-Open No. 53-98242).

However, these thermoplastic resin containers and films are made of, for example, 320n polyester.
It is extremely excellent in blocking ultraviolet rays on the short wavelength side up to about m, but ultraviolet rays and visible rays on the longer wavelength side beyond that are
Almost passes. Therefore, for example, a polyester container is filled with juice or edible oil, or liquid seasoning such as mirin, dressing, or liquor, and after a storage period of several months, although there are differences depending on the storage conditions and the type of filled food, Often, the contents gradually deteriorate, for example, subtle changes in color, taste, and scent. Degradation of the contents occurs due to oxygen, heat, ultraviolet rays, invasion of microorganisms, etc., but in the case of a polyester container, since the oxygen barrier property is relatively excellent, if the ultraviolet barrier property is further improved, it can be stored even under long-term storage. It is possible to greatly improve the deterioration of the contents. Further, it has been pointed out that ultraviolet rays have an adverse effect on the human body, especially on the skin. Therefore, by using a film having an ultraviolet ray shielding effect in addition to the glass scattering prevention effect and the heat ray shielding effect as a window sticking film for construction, it is possible to protect the human body indoors. In addition, at least 3 for mulching cultivation in agriculture and horticulture.
It is known that by mulching with a transparent coating material that substantially blocks UV transmission of 70 nm or less, the growth of many useful plants can be promoted and high-quality crops can be harvested in large amounts at an early stage. Sho 53-124556).

[0004] At present, ultraviolet absorbers and the like are generally added and used in the industry for the purpose of blocking ultraviolet rays. However, currently known hydroquinone series,
UV absorbers such as salicylic acid-based, benzophenone-based, and benzotriazole-based UV absorbers are generally expensive compounds, and the process of applying them is complicated. Furthermore, many of them have poor thermal stability, and undesired coloring occurs in the resin due to thermal decomposition during molding processing, and the problems such as accelerating the cleavage of polymer chains in the resin and causing the resin to become brittle. is there. Also,
Since these compounds generally have a high sublimation property, adhesion of the sublimate to a machine or the like may occur during the applying step or the molding process, and when used in food containers or packaging, there is a risk of migration to the contents. Yes, it is not preferable. As a method for solving these problems, for example, in order to improve the sublimation property, as a UV absorber, naphthalenetetracarboxylic acid or an acid anhydride thereof, imide or ester, and further, naphthalene dicarboxylic acid or a derivative thereof is used. (JP-A-63-225650), and naphthalenetetracarboxylic acid or an acid anhydride thereof,
There is a method in which an imide or ester, and further, naphthalene dicarboxylic acid or a derivative thereof are directly added to a polybutylene terephthalate resin production tank to produce a uniform composition, and then blended with a polyethylene terephthalate resin (JP-A-3-20353). Issue).

However, JP-A-63-225650
A container or film made of the composition described in Japanese Patent Publication,
It has a strong tendency to be colored in yellow and is not sufficiently satisfactory as a packaging material for colorless and transparent beverages, alcoholic beverages and the like. In addition, in the method for producing a resin molded body described in JP-A-3-20353, in order to improve the yellow coloring property, a poly (naphthalene tetracarboxylic acid) and / or a derivative of naphthalene tetracarboxylic acid having an ultraviolet absorbing ability is added. Since the butylene terephthalate resin composition is manufactured once and further has a step of blending with a polyethylene terephthalate resin, the manufacturing process is complicated, and the naphthalene tetracarboxylic acid and / or the naphthalene tetracarboxylic acid derivative is polybutylene terephthalate. Unless it is added directly to the resin production tank and bonded to the polymer chain, the effect of blocking ultraviolet rays cannot be expected, so it is not always preferable as a method for producing a resin molded product used in a large amount.

Further, as a resin composition suitable for use as a food container or a packaging film, a hydroxy group, an alkoxy group, an acyloxy group, an amino group, an acyloxyalkylamino group or the like which is a reactive group at the 7-position is used. Have 2
Polyester resin composition having ultraviolet absorption ability without elution into the content of the compound by directly adding the H-1-benzopyran-2-one derivative to a polyethylene terephthalate resin production tank and binding to the polymer chain Have been proposed (US Pat. No. 4,882,412, US Pat. No. 4,892,922). Furthermore, the known 2
Regarding the production of a polyester resin composition containing an H-1-benzopyran-2-one derivative, a production method in which the production process of the derivative and the production process of the polyester resin are integrated, that is, o-halocinnamon which is a raw material of the derivative A new method for producing a polyester resin composition has been proposed, in which an acid or its ester is directly added to a polyester production tank to produce the polyester resin and the derivative at the same time (US Patent No. 5). , 091,501).

However, US Pat. No. 4,882,4
The resin compositions described in JP-A No. 12 and US Pat. No. 4,892,922 do not substantially block ultraviolet rays having a short wavelength of up to 370 nm, and for example, 250 n
m to 351nm wavelength light, or 250n
10% for incident light of wavelength from m to 371 nm
The following light transmissions are observed (eg US Pat. No. 4,
No. 882,412 Publication Example 98 and Example 9
9). Therefore, when a polyester container using the resin composition is filled with juice, edible oil, liquor, etc., deterioration of these contents due to the ultraviolet rays transmitted through the container cannot be avoided. Furthermore, the resin composition described in US Pat. No. 4,892,922, and US Pat. No. 5,091,5
The resin composition obtained by the production method described in Japanese Patent Publication No. 01 is colored yellow (for example, US Pat. No. 4,892,9).
No. 22, gazette, Example 92, and US Pat.
Example 3 described in Japanese Patent Publication No. 1,501). Therefore, even if a colorant is added, a desired color tone cannot be obtained, so that the resin composition is unsuitable as a decorative window sticking film material having an ultraviolet blocking effect.

[0008]

SUMMARY OF THE INVENTION In order to solve the above problems, an object of the present invention is to provide an ultraviolet absorber having excellent thermal stability and extremely low sublimation property. It is intended to provide a thermoplastic resin composition and a molded article having an excellent ability to block ultraviolet rays by adding them to a plastic resin.

[0009]

[Means for Solving the Problems] In order to achieve the above object, as a result of extensive studies, a 2H-1-benzopyran-2-one derivative which is suitable as an ultraviolet absorber and has excellent thermal stability and extremely low sublimation property was obtained. Heading The present invention has been reached. That is, the present invention provides the following general formula (I)

[0010]

[Chemical 4] (In the formula, Y ₁ is an oxygen atom or a sulfur atom, and X ₁ ,
X ₂ , X ₃ and X ₄ are each independently a hydrogen atom, a halogen atom, a nitro group, a hydroxy group or an acetoxy group, and Q ₁ , Q ₂ , Q ₃ , Q ₄ and Q ₅ are each independently
A hydrogen atom, a halogen atom, a nitro group, and a cyano group.
Where Q ₁ , Q ₂ , Q ₃ , Q ₄ and Q ₅ are all hydrogen atoms) or the following general formula (II)

[0011]

[Chemical 5] (In the formula, Y ₁ , X ₁ , X ₂ , X ₃ and X ₄ have the same meanings as defined in the general formula (I), and Q ₆ , Q ₇ ,
_{Q 8, Q 9, Q 10} , Q 11, Q 12, Q 13, Q 14 and Q ₁₅
Are each independently a hydrogen atom, a halogen atom, a nitro group, or a cyano group.) 2H-1-benzopyran-2
TECHNICAL FIELD The present invention relates to an -one derivative, an ultraviolet absorber comprising the same, and a thermoplastic resin composition and a molded product containing the ultraviolet absorber.

In the thermoplastic resin composition of the present invention, at least one kind of the UV absorber comprising the 2H-1-benzopyran-2-one derivative of the present invention is added to the thermoplastic resin in an amount effective for blocking UV rays. By doing so, ultraviolet rays on the long wavelength side can be substantially blocked.
Here, the term "UV blocking" means that when the resin composition is used as a molded article, it completely (almost 100%) blocks UV rays having a short wavelength of at least 370 nm or less.

2H-1 represented by the general formula (I) of the present invention
In the benzopyran-2-one derivative, the substituents X ₁ , X ₂ , X ₃ and X ₄ are hydrogen atom, halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom, nitro group, hydroxy group, acetoxy. Groups. Examples of the substituents Q ₁ , Q ₂ , Q ₃ , Q ₄ and Q ₅ include a hydrogen atom, a halogen atom, a nitro group and a cyano group. Where Q ₁ , Q ₂ , Q ₃ , Q ₄ and Q
_A combination in which ₅ is all hydrogen atoms is excluded. Some of the specific examples of the 2H-1-benzopyran-2-one derivative represented by the general formula (I) of the present invention are shown in Table 1 (Tables 1 to 5). It is not limited.

[0014]

[Table 1]

[0015]

[Table 2]

[0016]

[Table 3]

[0017]

[Table 4]

[0018]

[Table 5] As the method for producing the 2H-1-benzopyran-2-one derivative represented by the general formula (I) of the present invention, the general formula (IV) is used.
(Chemical formula 6)

[0019]

[Chemical 6] (Wherein Y ₁ , X ₁ , X ₂ , X ₃ and X ₄ have the same meanings as defined in formula (I)) are obtained by reacting the compound with thionyl chloride in a solvent. The following general formula (V) (Chemical formula 7)

[0020]

[Chemical 7] (Wherein Y ₁ , X ₁ , X ₂ , X ₃ and X ₄ have the same meanings as defined in the general formula (I)) and a compound represented by the following general formula (VI)

[0021]

[Chemical 8] (In the formula, Q ₁ , Q ₂ , Q ₃ , Q ₄ and Q ₅ have the same meanings as defined in the general formula (I)) and are obtained by reacting in a solvent. Here, the compound of general formula (IV) can be easily produced by a known method. For example, salicylaldehyde and malonic acid are reacted with acetic acid as a condensing agent to give coumarin-
Method for Obtaining 3-Carboxylic Acids (CM Stuart,
J. C. S. , 49 , 367 (1886). ), Various salicylaldehyde derivatives and diethyl malonate are reacted by using piperidine as a solvent, followed by acid treatment and hydrolysis (E. Knoevenagel, Ber., 31 , 31) .
2619 (1898), E.I. Knoevenagel,
ibid. , 37 , 4461 (1904)), various salicylaldehyde derivatives and malononitrile are reacted by using piperidine as a solvent, and then hydrolyzed after acid treatment (L. Woods, and J. Sapp, J.O.
C. , 30 , 312 (1965)).

Examples of the compound represented by the general formula (IV) include coumarin-3-carboxylic acid, 6-fluorocoumarin-3-carboxylic acid and 6-chlorocoumarin-3-.
Carboxylic acid, 6-bromocoumarin-3-carboxylic acid, 6
-Iodocoumarin-3-carboxylic acid, 6-nitrocoumarin-3-carboxylic acid, 7-nitrocoumarin-3-carboxylic acid, 7-hydroxycoumarin-3-carboxylic acid, 7-
Acetoxycoumarin-3-carboxylic acid, 6,8-difluorocoumarin-3-carboxylic acid, 6,8-dichlorocoumarin-3-carboxylic acid, 6,8-dibromocoumarin-3
-Carboxylic acid, 6,8-diiodocoumarin-3-carboxylic acid and the like.

Examples of the compound represented by the general formula (VI) include o-nitroaniline, m-nitroaniline, p-nitroaniline, o-cyanoaniline and m-nitroaniline.
Cyanoaniline, p-cyanoaniline, 2,4-dinitroaniline, 3,5-dinitroaniline, 2,6-dinitroaniline o-nitroaniline, m-nitroaniline, p-nitroaniline, o-cyanoaniline, m- Cyanoaniline, p-cyanoaniline, 2,4-dinitroaniline, 3,5-dinitroaniline, 2,6-dinitroaniline, o-fluoroaniline, m-fluoroaniline, p-fluoroaniline, o-chloroaniline, m
-Chloroaniline, p-chloroaniline, o-bromoaniline, m-bromoaniline, p-bromoaniline, o
-Iodoaniline, m-iodoaniline, p-iodoaniline, 2,3-difluoroaniline, 2,4-difluoroaniline, 2,5-difluoroaniline, 2,6-
Difluoroaniline, 3,4-difluoroaniline,
3,5-difluoroaniline, 2,3-dichloroaniline, 3,5-dichloroaniline, 2,6-dichloroaniline, 2,4-dichloroaniline, 3,5-dichloroaniline, 2,3-dibromoaniline, 2 , 4-dibromoaniline, 2,5-dibromoaniline, 2,6-dibromoaniline, 2,3-diiodoaniline, 2,4-diiodoaniline, 2,5-diiodoaniline, 2,6-diiodo Aniline, 3,4-diiodoaniline, 3,5-
Diiodoaniline, 2,3,4-trifluoroaniline, 2,3,6-trifluoroaniline, 2,4,5-
Trifluoroaniline, 2,4,6-trifluoroaniline, 2,3,4-trichloroaniline, 2,3,6-
Trichloroaniline, 2,4,5-trichloroaniline, 2,4,6-trichloroaniline, 2,4,6-tribromoaniline, 2-fluoro-4-nitroaniline, 4-fluoro-2-nitroaniline, 4 -Fluoro-3-nitroaniline, 2-chloro-4-nitroaniline, 2-chloro-5-nitroaniline, 4-chloro-2
-Nitroaniline, 4-chloro-3-nitroaniline,
5-chloro-2-nitroaniline and the like can be mentioned. Preferred is aniline having a substituent at the 4-position.

The molar ratio of thionyl chloride to the compound represented by the general formula (IV) is preferably 1 to 1.1 when the total number of moles of the general formula (IV) is 1.
5, and the molar ratio of the aniline derivative represented by the general formula (VI) is preferably 1 to 1.5 when the total molar number of the general formula (IV) is 1. Is.

The solvent used is preferably N,
Examples thereof include aprotic polar solvents such as N-dimethylimidazolidinone, sulfolane and N-methyl-2-pyrrolidone, and aromatic solvents such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, chloronaphthalene and nitrobenzene. The amount of the solvent used is represented by the general formula (I
1 to 100 parts by weight of the compound of V) may be used. The reaction temperature for reacting the compound of general formula (IV) with thionyl chloride in a solvent to form the compound of general formula (V) is
It is preferably 0 to 120 ° C. and the reaction time is 1 minute to 10 minutes.
It's about time. The temperature for reacting the compound of general formula (VI) with general formula (V) in a solvent is 10 ° C to 200 ° C.
The degree is good, preferably 40 to 150 ° C. The reaction time is about 30 minutes to 10 hours.

2H- represented by the general formula (II) of the present invention
Among the specific examples of the 1-benzopyran-2-one derivative,
Some of the cases where Q ₁₁ , Q ₁₂ , Q ₁₃ , Q ₁₄ and Q ₁₅ are hydrogen atoms are shown in Table 2 (Table 6), but of course the present invention is not limited to these compounds.

[0027]

[Table 6] The 2H-1-benzopyran-2-one derivative represented by the general formula (II) of the present invention includes a compound represented by the general formula (V) obtained as described above and the following general formula (VII) )

[0028]

[Chemical 9] (In the formula, Y ₁ , Q ₆ , Q ₇ , Q ₈ , Q ₉ , Q ₁₀ , Q ₁₁ ,
Q ₁₂ , Q ₁₃ , Q ₁₄ and Q ₁₅ have the same meanings as defined in formula (II)) and are obtained by reacting the compound represented by the formula (II) in a solvent.

Examples of the compound represented by the general formula (VII) include diphenylamine, 2-nitrodiphenylamine, 4-nitrodiphenylamine, 2,4-dinitrodiphenylamine, 3-chlorodiphenylamine, 2
-Nitro-5-chlorodiphenylamine and the like. The molar ratio of the aniline derivative represented by the general formula (VII) is preferably 1 to 1.5 when the total molar number of the general formula (IV) is 1. The solvent used is preferably an aprotic polar solvent such as N, N-dimethylimidazolidinone, sulfolane or N-methyl-2-pyrrolidone, benzene, toluene,
Aromatic solvents such as xylene, chlorobenzene, dichlorobenzene, chloronaphthalene and nitrobenzene can be mentioned. The amount of the solvent used is 1 to 1 of the compound of the general formula (IV).
100 parts by weight are used. The temperature for reacting the compound of general formula (VII) with general formula (V) in a solvent is from 10 ° C to 20 ° C.
The temperature is preferably about 0 ° C, preferably 40 to 150 ° C. The reaction time is about 30 minutes to 10 hours.

The thermoplastic resin composition of the present invention is
It contains at least one -1-benzopyran-2-one derivative, and these may be used alone or in combination. Further, the 2H-1-benzopyran-2-one derivative used can be used as it is, but it is preferable that the 2H-1-benzopyran-2-one derivative is purified by recrystallization or other purification means, and is ground to several microns or less. It is preferable to use. 2H- used in the thermoplastic resin composition of the present invention
As the 1-benzopyran-2-one derivative, especially the following formula (III)

[0031]

[Chemical 10] The 2H-1-benzopyran-2-one derivative represented by is particularly excellent in that it does not color the resin when added to a transparent thermoplastic resin, and is a particularly preferable compound as an ultraviolet absorber.

The thermoplastic resin composition of the present invention is prepared by adding at least one kind of the ultraviolet absorber of the present invention to the thermoplastic resin in an amount effective for blocking ultraviolet rays. The -1-benzopyran-2-one derivative is added at any stage of the thermoplastic resin production, for example, before the polycondensation reaction is started, during the polycondensation reaction, after the polycondensation reaction is finished, in a powder state, a molding stage, or the like. Also, the ultraviolet blocking effect can be similarly exhibited even if the compound is added at any stage before molding. In particular, it is convenient and most preferable to use a commercially available thermoplastic resin and to add it at any stage before molding and processing in terms of production of the thermoplastic resin composition of the present invention. At that time, the temperature at which the ultraviolet absorber of the present invention is added to the thermoplastic resin is 4
The temperature is preferably 00 ° C. or lower, particularly preferably 290 ° C. or lower.
Alternatively, a so-called masterbatch is prepared by adding such an ultraviolet absorber to a concentration of several times to 100 times, or practically 5 to 50 times the predetermined concentration, and the so-called masterbatch is added to the so-called masterbatch. It is also possible to finally obtain a resin composition having a desired ultraviolet blocking ability by diluting with a thermoplastic resin that is not present.

The amount of the 2H-1-benzopyran-2-one derivative, which is the ultraviolet absorber of the present invention, to be added varies widely depending on the kind of the thermoplastic resin used, the thickness of the molded article such as a film or sheet, and the like. However, 0.001 parts by weight or more is added to 100 parts by weight of the thermoplastic resin so that the transmittance of ultraviolet rays having a short wavelength of 370 nm or less, which is the object of the method of the present invention, is almost 0%. do it. When it is less than 0.001 part by weight, it does not show a sufficient UV blocking property. In addition, the amount of the resin 100 is sufficient to block ultraviolet rays having a short wavelength of 370 nm or less.
20 parts by weight per part may be sufficient, and a suitable range of addition amount is 0.01 to 10 parts by weight. Further, between the compounding amount of the ultraviolet absorber and the thickness of the obtained molded product, the following formula (VIII) 10 ≦ AB (VIII), preferably the following formula (IX) 15 ≦ AB (IX) [wherein A is It is known that it is preferable that the relationship represented by the expression (A) represents the amount of the ultraviolet absorber added per 100 parts by weight of the thermoplastic resin (parts by weight), and B represents the thickness (μm) of the molded product]. Therefore, these should be taken into consideration.

Examples of the thermoplastic resin that can be used in the thermoplastic resin composition of the present invention include polystyrene, polyester, polymethylmethacrylate, polycarbonate,
Polyether sulfone, polyamide, polyvinyl chloride,
Alternatively, a copolymer containing these polymers as a main component, a mixture, or the like is included. From the viewpoint of light resistance, light transmittance, mechanical strength, etc., polyester, polymethylmethacrylate,
Polycarbonate is preferable, and polyester is particularly preferable because it has excellent mechanical strength and moldability.

The polyester used in the present invention is not particularly limited due to its molecular structure, but it is preferable that it has thermoplasticity. Specifically, terephthalic acid, isotaric acid, phthalic acid, naphthalenedicarboxylic acid,
Aromatic dicarboxylic acids such as bis-α, β- (2-chlorophenoxy) butanoic acid and diphenyl ether dicarboxylic acid and ester derivatives thereof, cyclohexane-1,4-
Alicyclic dicarboxylic acids such as dicarboxylic acids and ester derivatives thereof, aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid and ester derivatives thereof, unsaturated dicarboxylic acids such as fumaric acid and 4-carboxycinnamic acid One or more dicarboxylic acid components represented by acids and ester derivatives thereof, aliphatic dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol and butanediol, alicyclic glycols such as cyclohexanedimethanol, bis- ( 4'-β
A bisphenol derivative such as -hydroxyethoxyphenyl) propane, and further a compound represented by the general formula (X)

[0036]

[Chemical 11] A polyester obtained from one or more dihydric alcohol components represented by a polyether diol as shown in
And polyglycolic acid and polylactic acid obtained by polycondensing oxyacids such as glycolic acid, lactic acid, hydroxypropionic acid, and hydroxybutyric acid, or polyesters obtained by copolymerizing various oxyacids. Among them, polyethylene terephthalate, polyethylene naphthalate, polyethylene bis-α, β-, which have excellent heat resistance and moisture resistance
(2-Chlorophenoxy) ethane-4,4'-dicarboxylate is preferred. Particularly, polyethylene terephthalate and polyethylene naphthalate, which are excellent in transparency, are most useful and preferred. The polyester resin composition of the present invention is a resin composition containing at least 50% by weight, preferably 80% by weight or more of such a polyester component.
Further, the polyester resin composition of the present invention may contain other thermoplastic resins such as polymethylmethacrylate and polycarbonate.

Since the ultraviolet absorbent of the present invention does not color the thermoplastic resin, a thermoplastic resin composition having a desired color tone can be obtained by using the colorant. As the colorant used in the thermoplastic resin composition of the present invention, for example, a heat-resistant hydrophobic dye centered on a polycyclic system, specifically, perinone system, anthrapyridone system, quinophthalone system, anthraquinone system, etc. A hydrophobic dye having a skeleton of
These colorants have good compatibility with thermoplastic resins, exhibit sufficient heat resistance stability and color stability at the thermoplastic resin production and processing temperatures, and when used as a packaging container for foods, etc. Is to be used after selecting dyes and pigments that have no problems in safety and hygiene. Alternatively, these colorants may be used at several times to 100 times the predetermined concentration.
Double, practically, it is added to a concentration of about 5 to 50 times, so-called masterbatch is prepared and diluted with uncolored or colored thermoplastic resin to finally obtain a desired color tone. It is also possible to obtain a resin composition.
The thermoplastic resin composition of the present invention, if necessary, other usual resin additives, for example, a light stabilizer, a heat stabilizer, a release agent,
Antistatic agents, antioxidants, dispersants and the like can also be added.

The thermoplastic resin composition obtained in the present invention having an excellent ultraviolet blocking property can be used to produce a useful molded product by using a general melt molding method. For example, for a polyester resin composition, a sheet is produced by an extrusion molding method, and then a film obtained by uniaxially stretching and biaxially stretching is used as a packaging material for foods, etc., and also as a mulching material for agriculture and horticulture. Use is particularly preferred. Further, by using the blow molding method, it is possible to manufacture a hollow molded article having an ultraviolet blocking property, a gas blocking property, a toughness, and a non-colored transparency. This hollow molded article is preferably used as a container for food such as juice, edible oil, seasoning and liquor. Alternatively, a non-colored molded product having a desired shape can be manufactured by an injection molding method.

Alternatively, the thermoplastic resin composition containing the colorant of the present invention can also be used to produce a useful molded product by using a general melt molding method. For example,
Using a polyester resin composition having a desired color tone,
A sheet is prepared by an extrusion molding method, and then a uniaxially stretched film, a functional film provided with an adhesive layer, an aluminum vapor deposition layer, etc. on the film obtained by biaxially stretching is a glass shatterproof film in architectural use or vehicle use, And its use as a heat-shielding film. Furthermore, it is possible to manufacture a molded product having a desired color tone and shape by the injection molding method.

[0040]

EXAMPLES The present invention will be described in detail below based on examples. In the examples, "parts" means "parts by weight". In addition, the thermogravimetric measurement shown in the examples was carried out using a "TGA-50" thermogravimetric measuring device manufactured by Shimadzu Corporation, with a sample weight of 3 mg and a temperature rising rate of 10 ° C / min. Further, the ultraviolet and visible light transmittance spectra were measured in a wavelength range of 300 to 700 nm using a "UV-240" spectrophotometer manufactured by Shimadzu Corporation for the film of about 100 µm obtained in each example. . Example 1 340 parts of coumarin-3-carboxylic acid was dissolved in 3600 parts of N, N-dimethylimidazolidinone at 25 ° C and cooled to 5 ° C. 215 parts of thionyl chloride was added at 15 ° C. or lower to give a solution of coumarin-3-carboxylic acid chloride. To this solution, while adding 296 parts of p-nitroaniline,
The content liquid was heated to 0 ° C. After keeping the temperature at the same temperature for 3 hours, the content liquid was cooled to 25 ° C. The inner solution was filtered, the filter cake was washed with dimethylformamide and methanol, and dried to obtain 510 parts of a 2H-1-benzopyran-2-one derivative. When the compound was thermogravimetrically measured, no mass change was observed up to 259 ° C. The mass change at 295 ° C was 0.67% by weight of the initial weight. The structural formula and maximum absorption wavelength of this compound are shown in Table 3 (Table 7).

[0041]

[Table 7]

Example 2 177 parts of 6-nitrocoumarin-3-carboxylic acid was added to N, N
-Dissolved in 1400 parts of dimethylimidazolidinone at 20 ° C and cooled to 5 ° C. Thionyl chloride 10 at 15 ° C or below
7 parts was added to give a solution of 6-nitrocoumarin-3-carboxylic acid chloride. The content liquid was heated to 150 ° C. while adding 107 parts of 4-cyanoaniline to the solution. After keeping the temperature at the same temperature for 1 hour, the content liquid was cooled to 25 ° C. The inner solution was filtered, the filter cake was washed with dimethylformamide and methanol, and dried to obtain 201 parts of a 2H-1-benzopyran-2-one derivative. When the compound was thermogravimetrically measured, no mass change was observed up to 276 ° C. The mass change at 295 ° C was 0.23% by weight of the initial weight. The structural formula and maximum absorption wavelength of this compound are shown in Table 3 (Table 7).

Example 3 225 parts of 6-chlorocoumarin-3-carboxylic acid was dissolved in 700 parts of sulfolane and 1000 parts of p-xylene at 30 ° C. 135 parts of thionyl chloride was added at 40 ° C. or lower to obtain a solution of 6-chlorocoumarin-3-carboxylic acid chloride. The content liquid was heated to 150 ° C. while adding 204 parts of 3-chlorodiphenylamine to the solution.
After keeping the temperature at the same temperature for 5 hours, the content liquid was cooled to 20 ° C. The inner solution was filtered, the filter cake was washed with dimethylformamide and methanol, and dried to give 2H-1-benzopyran-
387 parts of a 2-one derivative was obtained. When the compound was thermogravimetrically measured, no mass change was observed up to 289 ° C. The change in mass at 295 ° C. is 0.
It was 05% by weight. The structural formula and maximum absorption wavelength of this compound are shown in Table 3 (Table 7).

Comparative Example 1 2 was prepared under the same conditions except that 200 parts of aniline was used instead of 296 parts of p-nitroaniline of Example 1.
212 parts of H-1-benzopyran-2-one derivative were obtained. This compound was colored yellow. When the compound was thermogravimetrically measured, no mass change was observed up to 203 ° C. The mass change at 295 ° C was 17.8% by weight of the initial weight. The structural formula and maximum absorption wavelength of this compound are shown in Table 3 (Table 7).

Comparative Example 2 Instead of 296 parts of p-nitroaniline of Example 1, m
-Preparation was performed under the same conditions except that 229 parts of toluidine were used to obtain 483 parts of a 2H-1-benzopyran-2-one derivative. This compound was colored yellow. When the compound was thermogravimetrically measured, no mass change was observed up to 212 ° C. The mass change at 295 ° C was 9.40% by weight of the initial weight. The structural formula and maximum absorption wavelength of this compound are shown in Table 3 (Table 7).

Example 4 Polyethylene terephthalate (manufactured by Unitika Ltd.) 10
2,000 parts of Example 1 was melted at 280 ° C.
100 parts of H-1-benzopyran-2-one derivative was added and dissolved at 280 ° C. Melted product is 30 mmφ
Using an extruder, a thin sheet having a thickness of about 200 μm was obtained. Then, using a batch type stretching machine, preheat 75
The thin sheet was uniaxially stretched in a fixed width at a stretching temperature of 75 ° C. to obtain a transparent film of Example 4 having a film thickness of 108 μm. 370 nm and 380 n of the film
The ultraviolet transmittances at m were both 0.0%. Further, no coloring was observed on the film. The ultraviolet and visible light absorption spectra are shown in FIG. Also,
When obtaining a thin sheet using the ultraviolet absorber, no deposit was observed on the nozzle of the extruder.

Example 5 Polyethylene terephthalate (manufactured by Unitika Ltd.) 10
2,000 parts of Example 2 was melted at 280 ° C.
120 parts of H-1-benzopyran-2-one derivative was added and dissolved at 280 ° C. Melted product is 30 mmφ
Using an extruder, a thin sheet having a thickness of about 200 μm was obtained. Then, using a batch type stretching machine, preheat 80
The thin sheet was uniaxially stretched with a fixed width at a stretching temperature of 80 ° C. to obtain a transparent film of Example 5 having a film thickness of 111 μm. 370 nm and 380 n of the film
The ultraviolet transmittance at m was 0.0% and 0.2%, respectively. Further, no coloring was observed on the film. The ultraviolet and visible light absorption spectra are shown in FIG. Further, when a thin sheet was obtained using the ultraviolet absorbent, no deposit was observed on the nozzle of the extruder.

Example 6 Polyethylene terephthalate (manufactured by Unitika Ltd.) 10
2,000 parts of Example 2 was melted at 280 ° C.
250 parts of H-1-benzopyran-2-one derivative was added and dissolved at 280 ° C. Melted product is 30 mmφ
Using an extruder, a thin sheet having a thickness of about 200 μm was obtained. Then, using a batch type stretching machine, preheat 80
The thin sheet was uniaxially stretched in a fixed width at a stretching temperature of 80 ° C. to obtain a transparent film of Example 6 having a film thickness of 103 μm. 370 nm and 380 n of the film
The ultraviolet transmittances at m were 0.0% and 7.0%, respectively. Further, no coloring was observed on the film. The ultraviolet and visible light absorption spectra are shown in FIG. Further, when a thin sheet was obtained using the ultraviolet absorbent, no deposit was observed on the nozzle of the extruder.

Comparative Example 3 In Example 4, 2H-1-benzopyran of Example 1 was used.
Instead of using 100 parts of the 2-one derivative, the commercially available benzotriazole-based UV absorber TINUVIN (TINUV
IN) 326R (2- (3-t-butyl-5-methyl-
2-Hydroxyphenyl) -5-chlorobenzotriazole; manufactured by Ciba Geigy) was used under the same conditions except that 100 parts was used to obtain a transparent film. The ultraviolet transmittances at 370 nm and 380 nm of the film were 0.7% and 3.7%, respectively.
Further, no coloring was observed on the film. The ultraviolet and visible light absorption spectra are shown in FIG. Further, when a thin sheet is obtained using the ultraviolet absorbent, a pale yellow powder adheres to the nozzle of the extruder, and a yellow adhered substance gradually appears in the extruded sheet from the time when about 1 kg of the molded sheet is obtained. It became noticeable.

Comparative Example 4 In Example 4, 2H-1-benzopyran of Example 1 was used.
Instead of using 100 parts of the 2-one derivative, the commercially available benzotriazole-based UV absorber TINUVIN (TINUV
IN) 326R (2- (3-t-butyl-5-methyl-
2-Hydroxyphenyl) -5-chlorobenzotriazol; manufactured by Ciba Geigy) except that 150 parts was used to obtain a transparent film under the same conditions. The ultraviolet transmittances of the film at 370 nm and 380 nm were 0.0% and 0.5%, respectively.
In addition, a pale yellow coloration was observed in the film. In addition,
The ultraviolet and visible light absorption spectra are shown in FIG. Further, when a thin sheet is obtained using the ultraviolet absorbent, as in Comparative Example 2, light yellow powder adheres to the nozzle of the extruder,
Further, from the time when about 1 kg of the molded sheet was obtained, yellow deposits became gradually noticeable in the extruded sheet.

Comparative Example 5 In Example 4, 2H-1-benzopyran of Example 1 was used.
Instead of using 100 parts of the 2-one derivative, Comparative Example 1
A 2H-1-benzopyran-2-one derivative was prepared under the same conditions, except that 100 parts of the 2H-1-benzopyran-2-one derivative was used to obtain a transparent film. The ultraviolet transmittances of the film at 370 nm and 380 nm were 0.0% and 0.5, respectively.
%showed that. In addition, a pale yellow coloration was observed in the film. The UV and visible light absorption spectra are shown in Fig. 2.
Shown in. In addition, when a thin sheet is obtained using the ultraviolet absorbent, a pale yellow powder adheres to the nozzle of the extruder, and a yellow adhered substance gradually appears in the extruded sheet from the time when about 2 kg of the molded sheet is obtained. It became noticeable.

Comparative Example 6 In Example 4, 2H-1-benzopyran of Example 1 was used.
Instead of using 100 parts of the 2-one derivative, Comparative Example 2
A 2H-1-benzopyran-2-one derivative was prepared under the same conditions, except that 100 parts of the 2H-1-benzopyran-2-one derivative was used to obtain a transparent film. The ultraviolet transmittances of the film at 370 nm and 380 nm were 0.0% and 0.1, respectively.
%showed that. In addition, the film was observed to be colored deep yellow. The UV and visible light absorption spectra are shown in Fig. 2.
Shown in. In addition, when a thin sheet is obtained using the ultraviolet absorbent, a pale yellow powder adheres to the nozzle of the extruder, and a yellow adhered substance gradually appears in the extruded sheet from the time when about 2 kg of the molded sheet is obtained. It became noticeable.

Example 7 Polyethylene terephthalate (manufactured by Unitika Ltd.) 10
2,000 parts of Example 1 was melted at 280 ° C.
100 parts of the H-1-benzopyran-2-one derivative and 10 parts of the following red dye, Indanthrene Red FBB, which is a commercially available anthraquinone vat dye, were added and dissolved at 280 ° C. The melted material is used with a 30 mmφ extruder, and the original thickness is about 200μ
A thin sheet of m was obtained. Subsequently, using a batch-type stretching machine, the thin sheet was uniaxially stretched with a fixed width at a preheating temperature of 75 ° C. and a stretching temperature of 75 ° C. to obtain a transparent film having a film thickness of 108 μm. 370 nm and 38 of the film
The ultraviolet transmittances at 0 nm were both 0.0%. In addition, the film was observed to be colored red. The ultraviolet and visible light absorption spectra are shown in FIG.

[0054]

The ultraviolet absorber of the present invention has excellent thermal stability and extremely low sublimation property. Furthermore, by adding the ultraviolet absorber to a thermoplastic resin, it is possible to obtain excellent heat-shielding ability against ultraviolet rays. Since a plastic resin composition can be produced, it greatly contributes to the production of functional molded articles such as containers and films that require an ultraviolet blocking effect.

[Brief description of drawings]

FIG. 1 shows ultraviolet and visible light transmittance spectra of the thermoplastic resin compositions obtained in Example 4 and Comparative Examples 3 and 4. The vertical axis of the figure represents the transmittance, and the horizontal axis represents the wavelength. ---- shows Example 4, --- shows Comparative Example 3, and --- shows Comparative Example 4.

FIG. 2 shows ultraviolet and visible light transmittance spectra of the thermoplastic resin compositions obtained in Examples 5 and 6 and Comparative Examples 5 and 6. The vertical axis of the figure represents the transmittance, and the horizontal axis represents the wavelength. ---- shows Example 5, ---- shows Example 6, --- shows Comparative Example 5, and --- shows Comparative Example 6.

FIG. 3 shows ultraviolet and visible light transmittance spectra of the thermoplastic resin composition obtained in Example 7. The vertical axis of the figure represents the transmittance, and the horizontal axis represents the wavelength.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical display location C08L 67/00 KJW 8933-4J C09K 3/00 104 8517-4H (72) Inventor Naoto Ito Kanagawa Mitsui Toatsu Chemicals, Inc. 1190 Kasama-cho, Sakae-ku, Yokohama

Claims (7)

[Claims] 1. The following general formula (I) (Chemical formula 1) (In the formula, Y ₁ is an oxygen atom or a sulfur atom, and X ₁ ,
X ₂ , X ₃ and X ₄ are each independently a hydrogen atom, a halogen atom, a nitro group, a hydroxy group or an acetoxy group, and Q ₁ , Q ₂ , Q ₃ , Q ₄ and Q ₅ are each independently
A hydrogen atom, a halogen atom, a nitro group, and a cyano group.
Where Q ₁ , Q ₂ , Q ₃ , Q ₄ and Q ₅ are all hydrogen atoms) or the following general formula (II) (Chemical formula 2) (In the formula, Y ₁ , X ₁ , X ₂ , X ₃ and X ₄ have the same meanings as defined in the general formula (I), and Q ₆ , Q ₇ ,
_{Q 8, Q 9, Q 10} , Q 11, Q 12, Q 13, Q 14 and Q ₁₅
Are each independently a hydrogen atom, a halogen atom, a nitro group, or a cyano group.) 2H-1-benzopyran-2
-One derivatives. 2. The general formula (I) is represented by the following formula (III)
The 2H-1-benzopyran-2-one derivative according to claim 1, which is [Chemical 3] 3. The 2H-1 according to claim 1 or 2.
-A UV absorber comprising a benzopyran-2-one derivative. 4. A thermoplastic resin composition comprising a thermoplastic resin and at least one kind of the ultraviolet absorber according to claim 3 added in an amount effective for blocking ultraviolet rays. 5. The thermoplastic resin composition according to claim 4, wherein an ultraviolet absorber is added to the thermoplastic resin in an amount of 0.001 part by weight or more per 100 parts by weight of the resin. 6. The thermoplastic resin composition according to claim 4 or 5, wherein the thermoplastic resin is a polyester resin. 7. A thermoplastic resin molded article obtained by molding the thermoplastic resin composition according to claim 4.