JP2016033021A - Ultraviolet blocking container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ultraviolet blocking container that efficiently blocks ultraviolet rays in the long wavelength region of 380-400 nm and also excellently allows visible light to pass through.SOLUTION: A triazine compound of the formula (1) having a specific structure excellently absorbs ultraviolet rays and allows visible light to pass through, and the triazine compound is used as an ultraviolet absorber.SELECTED DRAWING: None

Description

  The present invention relates to an ultraviolet light shielding container, and more particularly, to an ultraviolet light shielding container having excellent transparency to visible light while efficiently shielding ultraviolet light in a long wavelength region of 380 to 400 nm.

  Containers are used for storing medicines, cosmetics, food and drinks, and the like. However, since medicines, cosmetics, foods and drinks and the like are easily changed by light, particularly ultraviolet rays, the container is required to shield ultraviolet rays. Regarding the light shielding property of ultraviolet rays, aluminum containers and colored containers are excellent, but aluminum containers and colored containers have a problem that it is difficult to visually check the amount and state of the contents in the container. Have.

  On the other hand, synthetic resins are widely used as containers because they are inexpensive and excellent in moldability and light weight. Although a synthetic resin container is excellent in transparency (visible light transmittance), it is inferior in ultraviolet light shielding properties compared to an aluminum container or a colored container. For this reason, conventionally, an ultraviolet absorber has been used in a synthetic resin container in order to shield ultraviolet rays (cited documents 1 and 2).

Special Table 2003-522242 JP-A-8-301363

  However, a conventional container using an ultraviolet absorber requires a large amount of an ultraviolet absorber, but the ultraviolet light shielding ability is not satisfactory. In particular, the shielding of ultraviolet rays in the long wavelength region of 380 nm to 400 nm is insufficient, and a solution has been desired. In addition, conventionally used ultraviolet absorbers absorb up to the visible light region (450 nm to 500 nm), so that the amount of visible light is attenuated and the amount and state of contents are difficult to understand. It was.

  Therefore, the object of the present invention is excellent for visible light while efficiently shielding ultraviolet rays, particularly ultraviolet rays in the long wavelength region of 380 to 400 nm, even when using a low additive amount of an ultraviolet absorber. It is to provide an ultraviolet light shielding container having transparency.

  As a result of intensive studies to solve the above problems, the present inventors have found that a triazine-based compound having a specific structure has excellent ultraviolet light absorbability and excellent visible light transmittance. It has been found that the above-mentioned problems can be solved by using a triazine compound as an ultraviolet absorber, and the present invention has been completed.

（式中、Ｒ^１〜Ｒ^３は、互いに同一でも異なっていてもよく、炭素原子数１〜１２の直鎖または分岐のアルキル基、炭素原子数３〜８のシクロアルキル基、炭素原子数２〜８のアルケニル基、炭素原子数６〜１８のアリール基、炭素原子数７〜１８のアルキルアリール基または炭素原子数７〜１８のアリールアルキル基を表し、アルキル基、シクロアルキル基、アルケニル基、アリール基、アルキルアリール基またはアリールアルキル基は、ヒドロキシ基、ハロゲン原子、炭素原子数１〜１２のアルキル基または炭素原子数１〜１２のアルコキシ基で置換されていてもよく、また、酸素原子、硫黄原子、カルボニル基、エステル基、アミド基またはイミノ基で中断されていてもよく、さらに、置換および中断は組み合わされてもよく、Ｒ^４〜Ｒ^６は、互いに同一でも異なっていてもよく、炭素原子数１〜８のアルキル基または炭素原子数２〜８のアルケニル基を表す。）で表されるトリアジン系化合物の一種以上であることを特徴とするものである。 That is, the ultraviolet light shielding container of the present invention is an ultraviolet light shielding container using an ultraviolet absorber,
The ultraviolet absorber is represented by the following general formula (1),

(Wherein R ^{1 to} R ³ may be the same as or different from each other, a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or 2 carbon atoms) Represents an alkenyl group having 8 to 8 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylaryl group having 7 to 18 carbon atoms, or an arylalkyl group having 7 to 18 carbon atoms, an alkyl group, a cycloalkyl group, an alkenyl group, The aryl group, alkylaryl group or arylalkyl group may be substituted with a hydroxy group, a halogen atom, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, It may be interrupted by a sulfur atom, a carbonyl group, an ester group, an amide group or an imino group, and further, substitution and interruption may be combined, and R ⁴ -R ⁶ may be the same or different from each other and represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms). It is characterized by.

（式中、Ｒ^７〜Ｒ^９は、互いに同一でも異なっていてもよく、炭素原子数１〜１２の直鎖または分岐のアルキル基を表し、アルキル基はヒドロキシ基、ハロゲン原子またはアルコキシ基で置換されていてもよく、また、酸素原子、硫黄原子、カルボニル基、エステル基、アミド基またはイミノ基で中断されていてもよい。）で表されるトリアジン系化合物であることが好ましい。特に、紫外線遮光容器としては、波長５００ｎｍの可視光線の透過率が８０％以上１００％以下であり、かつ、波長４００ｎｍの紫外線の透過率が０％以上５．０％以下のものが好適である。 In the ultraviolet light shielding container of the present invention, among the ultraviolet absorbers, the following general formula (2),

(Wherein R ^{7 to} R ⁹ may be the same as or different from each other, and represent a linear or branched alkyl group having 1 to 12 carbon atoms, and the alkyl group is substituted with a hydroxy group, a halogen atom or an alkoxy group) And may be interrupted by an oxygen atom, a sulfur atom, a carbonyl group, an ester group, an amide group, or an imino group). In particular, as the ultraviolet light shielding container, a visible light transmittance of a wavelength of 500 nm is 80% or more and 100% or less, and a transmittance of ultraviolet light of a wavelength of 400 nm is preferably 0% or more and 5.0% or less. .

  As the ultraviolet light shielding container of the present invention, those made of a synthetic resin into which the ultraviolet absorber is kneaded are preferable, and those having a bottle shape are particularly preferable. In addition, the ultraviolet light shielding container of the present invention may be coated with the ultraviolet absorber, and further may be a synthetic resin film kneaded with the ultraviolet absorber. In addition, a synthetic resin film coated with the ultraviolet absorber may be pasted.

  The ultraviolet light shielding container of the present invention can be suitably used for medicines, cosmetics, beverages and foods.

  ADVANTAGE OF THE INVENTION According to this invention, the ultraviolet light shielding container which has the outstanding transmittance | permeability with respect to visible light can be provided, shielding the ultraviolet-ray of a 380-400 nm long wavelength range efficiently.

で表されるトリアジン系化合物の一種以上を用いている。ここで、式中、Ｒ^１〜Ｒ^３は、互いに同一でも異なっていてもよく、炭素原子数１〜１２の直鎖または分岐のアルキル基、炭素原子数３〜８のシクロアルキル基、炭素原子数２〜８のアルケニル基、炭素原子数６〜１８のアリール基、炭素原子数７〜１８のアルキルアリール基または炭素原子数７〜１８のアリールアルキル基を表す。ただし、これらのアルキル基、シクロアルキル基、アルケニル基、アリール基、アルキルアリール基またはアリールアルキル基は、ヒドロキシ基、ハロゲン原子、炭素原子数１〜１２のアルキル基または炭素原子数１〜１２のアルコキシ基で置換されていてもよく、酸素原子、硫黄原子、カルボニル基、エステル基、アミド基またはイミノ基で中断されていてもよく、置換および中断は組み合わされていてもよい。また、式中、Ｒ^４〜Ｒ^６は、互いに同一でも異なっていてもよく、炭素原子数１〜８のアルキル基または炭素原子数２〜８のアルケニル基を表す。 Hereinafter, the present invention will be described in detail.
The ultraviolet light shielding container of the present invention is an ultraviolet light shielding container using an ultraviolet absorber. In the ultraviolet light shielding container of the present invention, the following general formula (1),

One or more triazine compounds represented by the formula: Here, in the formula, R ^{1 to} R ³ may be the same as or different from each other, a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a carbon atom. An alkenyl group having 2 to 8 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylaryl group having 7 to 18 carbon atoms, or an arylalkyl group having 7 to 18 carbon atoms is represented. However, these alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, alkylaryl groups or arylalkyl groups are hydroxy groups, halogen atoms, alkyl groups having 1 to 12 carbon atoms, or alkoxy having 1 to 12 carbon atoms. It may be substituted with a group, may be interrupted with an oxygen atom, a sulfur atom, a carbonyl group, an ester group, an amide group or an imino group, and the substitution and interruption may be combined. In the formula, R ^{4 to} R ⁶ may be the same as or different from each other, and each represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms.

Examples of the linear or branched alkyl group having 1 to 12 carbon atoms represented by R ^{1 to} R ³ in the general formula (1) include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, Examples include linear or branched alkyl groups such as tertiary butyl, pentyl, tertiary pentyl, hexyl, octyl, secondary octyl, tertiary octyl, 2-ethylhexyl, decyl, undecyl, dodecyl, etc. It is preferable because it is excellent in shielding ultraviolet rays in the wavelength region. Examples of the cycloalkyl group having 3 to 8 carbon atoms include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ^{4 to} R ⁶ include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl, tert-pentyl, and hexyl. , Octyl, tertiary octyl group, and the like. Among them, a methyl group is preferable because it is excellent in shielding ultraviolet rays in a long wavelength region.

Examples of the alkenyl group having 2 to 8 carbon atoms represented by R ^{1 to} R ³ and R ^{4 to} R ⁶ include linear and branched propenyl, butenyl, pentenyl, hexenyl, heptenyl and octenyl groups at the position of the unsaturated bond. Regardless.

Examples of the aryl group having 6 to 18 carbon atoms represented by R ^{1 to} R ³ include phenyl, naphthyl, and biphenyl groups. Examples of the alkylaryl group having 7 to 18 carbon atoms include methyl Examples thereof include phenyl, dimethylphenyl, ethylphenyl, octylphenyl groups, etc. Examples of the arylalkyl group having 7 to 18 carbon atoms include benzyl, 2-phenylethyl, 1-methyl-1-phenylethyl group and the like. It is done. Examples of the aryl group having a substituent or interruption include 4-methylphenyl, 3-chlorophenyl, 4-benzyloxyphenyl, 4-cyanophenyl, 4-phenoxyphenyl, 4-glycidyloxyphenyl, and 4-isocyanuratephenyl group. Etc.

  The alkyl group, cycloalkyl group, alkenyl group, aryl group, alkylaryl group or arylalkyl group of the general formula (1) is a hydroxy group, a halogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms. It may be substituted with an alkoxy group. Examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like. Examples of the alkyl group having 1 to 12 carbon atoms include the above alkyl groups. Examples of the alkoxy group having 1 to 12 carbon atoms include Examples include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexaoxy, octoxy, nonyloxy, decyloxy, undecyloxy, and dodecyloxy groups.

  In addition, the alkyl group, cycloalkyl group, alkenyl group, aryl group, alkylaryl group or arylalkyl group of the general formula (1) is interrupted by an oxygen atom, sulfur atom, carbonyl group, ester group, amide group or imino group. It may be. The ester group is a group formed by dehydration condensation of a carboxylic acid and an alcohol, the amide group is a group formed by dehydration condensation of a carboxylic acid and an amine, and the imino group is a group represented by ═NR. And R represents hydrogen or an alkyl group.

Examples of the alkyl group or cycloalkyl group of R ^{1 to} R ³ which may have a substituent or interruption include 2-hydroxypropyl, 2-methoxyethyl, 3-sulfonyl-2-hydroxypropyl, 4-methylcyclohexyl group Etc.

で表されるものを好適に用いることができる。ここで、式中、Ｒ^７〜Ｒ^９は、互いに同一でも異なっていてもよく、炭素原子数１〜１２の直鎖または分岐のアルキル基を表す。ただし、これらのアルキル基はヒドロキシ基、ハロゲン原子またはアルコキシ基で置換されていてもよく、酸素原子、硫黄原子、カルボニル基、エステル基、アミド基またはイミノ基で中断されていてもよい。） In the ultraviolet light shielding container of the present invention, among the triazine compounds represented by the general formula (1) according to the present invention, the following general formula (2),

What is represented by can be used suitably. Here, in formula, R < ⁷ > -R < ⁹ > may mutually be same or different and represents a C1-C12 linear or branched alkyl group. However, these alkyl groups may be substituted with a hydroxy group, a halogen atom or an alkoxy group, and may be interrupted with an oxygen atom, a sulfur atom, a carbonyl group, an ester group, an amide group or an imino group. )

The linear or branched alkyl group having 1 to 12 carbon atoms in R ^{7 to} R ⁹ represented by the general formula (2) is a linear or branched alkyl group represented by R ^{1 to} R ³ in the general formula (1). The same group as an alkyl group is mentioned. The halogen atom and the alkoxy group are the same as the halogen atom and the alkoxy group.

  Examples of the compound represented by the general formula (1) or (2) according to the present invention include the following compound Nos. 1-No. 5 compounds.

  The ultraviolet light shielding container of the present invention can be applied to a synthetic resin as it is or with a binder resin or an additive, for example, using a triazine compound represented by the general formula (1), particularly the general formula (2) as an ultraviolet absorber. It can be obtained by kneading and molding or filming. Moreover, you may apply | coat or coat the triazine type compound represented by General formula (1), especially General formula (2) as a ultraviolet absorber to the base material of the synthetic resin of a container surface.

The ultraviolet light shielding container of the present invention is preferably made of a synthetic resin from the viewpoint of light weight and moldability. The method for obtaining the ultraviolet light shielding container of the present invention is not particularly limited, but for example, the following six methods can be used.
(1) A method of preparing a container by blending and kneading an ultraviolet absorbent represented by the general formula (1) or (2) with a synthetic resin to obtain an ultraviolet absorbent resin composition, followed by thermoforming.
(2) A method in which a paint or coating liquid containing the ultraviolet absorber represented by the general formula (1) or (2) is prepared and coated on a container made of a synthetic resin.
(3) An ultraviolet absorber represented by the general formula (1) or (2) is blended in a synthetic resin and kneaded to form an ultraviolet-absorbing resin composition. How to process into a shape.
(4) The ultraviolet absorber represented by the general formula (1) or (2) is blended in a synthetic resin and kneaded to form an ultraviolet absorbing resin composition, which is then thermoformed to form a film or sheet. A method of attaching a sheet to a container.
(5) A paint or coating liquid containing the ultraviolet absorber represented by the general formula (1) or (2) is prepared and coated on a film or sheet based on a synthetic resin. How to stick to the container.
(6) A method in which an ultraviolet absorbent represented by the general formula (1) or (2) is contained in an adhesive to produce a laminated resin film or sheet, and the film or sheet is attached to a container.
In the ultraviolet light shielding container of the present invention, a plurality of these methods may be combined.

  The shape of the ultraviolet light shielding container of the present invention is not particularly limited, and may be any conventionally known shape. Examples thereof include a bottle shape, an ampule shape, a bag shape, and a box shape.

  The ultraviolet light shielding container of the present invention shields ultraviolet light and transmits visible light. Therefore, the transmittance of visible light having a wavelength of 500 nm is preferably 80% or more and 100% or less, and more preferably 90% or more and 100% or less. Further, the ultraviolet light shielding container of the present invention shields ultraviolet rays in a long wavelength region of 380 nm to 400 nm, and the transmittance of ultraviolet rays having a wavelength of 400 nm is preferably 0% or more and 5.0% or less, and more preferably. Is 0% or more and 1.0% or less. The ultraviolet absorption rate and visible light transmittance can be adjusted by the thickness of the container, the thickness of the coating layer, or the thickness of the attached film. The thickness of the container is not particularly limited as long as it sufficiently transmits visible light and sufficiently blocks ultraviolet rays in a long wavelength region of 380 nm to 400 nm, but is preferably 0.1 to 5.0 mm, more preferably 0.00. It is 2-4.0 mm, More preferably, it is 0.3-3.0 mm.

  As a synthetic resin used for the ultraviolet light shielding container of the present invention, a resin having a transparency as high as possible is preferable. Specific examples include polyethylene, polypropylene, polystyrene, copolymers of polyethylene and cycloolefins such as norbornene, polyacrylic acid, polyacrylic acid esters, polyvinyl acetate, polyacrylonitrile, polyvinyl chloride, polyvinyl compounds such as polyvinyl fluoride, and vinyl. Compound addition polymer, polymethacrylic acid, polymethacrylic ester, polyvinylidene chloride, polyvinylidene fluoride, polyvinylidene fluoride, vinylidene fluoride / trifluoroethylene copolymer, vinylidene fluoride / tetrafluoroethylene copolymer, cyanide Vinyl compounds such as vinylidene chloride / vinyl acetate copolymers or copolymers of fluorine compounds, and compounds containing fluorine such as polytrifluoroethylene, polytetrafluoroethylene, polyhexafluoropropylene, etc. Products, polyamides such as nylon 6 and nylon 66, polyimides, polyurethanes, polypeptides, polybutylene terephthalate, polyesters such as polyethylene terephthalate, polyethers such as polycarbonate, polyoxymethylene, polyethylene oxide, polypropylene oxide, epoxy resins, polyvinyl alcohol, Examples thereof include polyvinyl butyral, but are not limited to these resins. Among these, polyesters such as polyethylene terephthalate are preferable.

  As a method for producing the container, the processing temperature, processing conditions, and the like are slightly different depending on the base resin to be used. Usually, the ultraviolet absorber represented by the general formula (1), particularly, the general formula (2) is used for the base resin. A molded product can be obtained by adding to powder or pellets, heating and dissolving at 150 to 350 ° C., and then molding. The molding method is not particularly limited, and examples thereof include extrusion processing, calendar processing, injection molding, roll, compression molding, blow molding, and the like, and a molded body, a sheet, a film, and the like can be manufactured.

  0.001-20 mass% is preferable with respect to a synthetic resin, and, as for the addition amount of the ultraviolet absorber represented with General formula (1), especially General formula (2), 0.01-10 mass% is more Preferably, 0.1-5 mass% is especially preferable. If it is less than 0.001% by mass, the ultraviolet absorption effect is not sufficient, and if it is more than 20% by mass, the transparency may be lowered. In addition, in the case where a synthetic resin is kneaded with a UV absorber represented by the general formula (1), in particular, the general formula (2), and affixed to a container, the total amount of the resin of the container and the film is 100 parts by mass. On the other hand, an ultraviolet absorber may be kneaded into the film so as to be in the above range.

  When coating a container or a film, a method of dissolving the ultraviolet absorber represented by the general formula (1), particularly, the general formula (2) in a binder resin and an organic solvent to form a paint, and the general formula (1) In particular, there is a method in which an ultraviolet absorber represented by the general formula (2) is dissolved or dispersed in a binder resin and an aqueous solvent to form an aqueous paint.

  The former method is usually an aliphatic ester resin, acrylic resin, melamine resin, urethane resin, aromatic ester resin, polycarbonate resin, aliphatic polyolefin resin, aromatic polyolefin resin, polyvinyl resin, polyvinyl alcohol resin, A polyvinyl modified resin (PVB, EVA, etc.) or a copolymer resin thereof is used as a binder. As the solvent, a halogen-based, alcohol-based, ketone-based, ester-based, aliphatic hydrocarbon-based, aromatic hydrocarbon-based, ether-based solvent, or a mixture thereof is used.

  In the latter case, a method of dissolving or dispersing the ultraviolet absorber represented by the general formula (1), particularly the general formula (2), in the aqueous binder resin, the general formula (1), particularly the general formula (2). There is a method in which an ultraviolet absorber represented by the formula is atomized to several μm or less and dispersed in an aqueous solvent using an emulsifier if necessary.

  Examples of the aqueous binder resin include polyvinyl alcohol or a modified product thereof, polyacrylic acid or a copolymer thereof, cellulose or a modified product thereof. Examples of the aqueous solvent include water or an alcohol such as methyl alcohol, a ketone such as acetone, and an ether such as tetrahydrofuran added to water. As an example of an emulsion, an uncolored acrylic emulsion paint such as an acrylic emulsion water-based paint dispersed in an acrylic emulsion is added to an ultraviolet absorber represented by the general formula (1), particularly the general formula (2). The thing which disperse | distributed what was grind | pulverized (50-500 nm) is mentioned.

  In the coating, the amount of the ultraviolet absorber represented by the general formula (1), particularly the general formula (2) is 0.001 to 20% by mass with respect to the total of the binder resin and the synthetic resin of the container to be coated. Is preferable, 0.01-10 mass% is more preferable, 0.1-5 mass% is especially preferable. If it is less than 0.001% by mass, the ultraviolet absorption effect is not sufficient, and if it is more than 20% by mass, the transparency may be lowered. When a synthetic resin is kneaded with a UV absorber represented by the general formula (1), in particular, the general formula (2), and a film is pasted on the container, and this film is coated with the UV absorber, An ultraviolet absorber may be used so as to be within the above range with respect to a total of 100 parts by mass of the film and the binder resin.

  In addition to additives such as near-infrared absorbers, antioxidants, and light stabilizers used in ordinary paints, dyes, pigments, or other UV absorbers for color control are included in the paint or coating liquid. May be added. The paint or coating liquid prepared by the above method is applied to a bar coater, gravure coater, comma coater, lip coater, curtain coater, roll coater, blade coater, spin coater, reverse coater on a synthetic resin film or sheet as a substrate. Coating with a die coater or spray to produce a light-shielding film. In order to protect the coating surface, a protective layer may be provided, or it may be bonded to a coating surface such as a transparent resin plate or a transparent resin film. A cast film is also included in the method.

  In the production of a laminated resin film or sheet by incorporating an ultraviolet absorber represented by the general formula (1), particularly the general formula (2), into the adhesive, a general silicon-based or urethane is used as the adhesive. Known transparent adhesives such as adhesives for resins such as acrylic and acrylic, polyvinyl butyral adhesives (PVB), and ethylene-vinyl acetate adhesives can be used. The resin film is produced by bonding the resin films using an adhesive to which an ultraviolet absorber represented by the general formula (1), particularly, the general formula (2) is added. There is also a method of thermocompression bonding.

  In this case, the amount of the ultraviolet absorber represented by the general formula (1), particularly the general formula (2) is 0.001 to 20 with respect to the total of the solid content of the adhesive and the synthetic resin of the base material. % By mass is preferable, 0.01 to 10% by mass is more preferable, and 0.1 to 5% by mass is particularly preferable. If it is less than 0.001% by mass, the ultraviolet absorption effect is not sufficient, and if it is more than 20% by mass, the transparency may be lowered.

  Next, resin used as the base material of the film to be coated will be described. Although the resin used as the base material of the film is not particularly limited, a resin having transparency is preferable.

  Examples of resins include: cellulose esters such as diacetylcellulose, triacetylcellulose (TAC), propionylcellulose, butyrylcellulose, acetylpropionylcellulose, nitrocellulose; polyamides such as nylon 6 and nylon 66; polyimides; polyurethanes; Polycarbonate; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polyester such as polybutylene terephthalate Polystyrene, polyethylene, polypropylene, polymethylpentene, copolymers of polyethylene and cycloolefins such as norbornene, etc. Polyolefins; vinyl compounds such as polyacrylonitrile, polyvinyl acetate, polyvinyl chloride, polyvinyl fluoride; polyvinylidene chloride, polyvinylidene fluoride, polyvinylidene polycide, vinylidene fluoride / trifluoroethylene copolymer, vinylidene fluoride / tetrafluoro Vinyl compounds such as ethylene copolymers, vinylidene cyanide / vinyl acetate copolymers, or copolymers of fluorine compounds; acrylic resins such as polyacrylic acid, polymethyl methacrylate, and polyacrylate esters; polyhexafluoropropylene, etc. Compounds containing fluorine of: Polycarbonate; Polysulfone; Polyethersulfone; Polyetherketone; Polyetherimide; Polyether such as polyoxymethylene, polyethylene oxide, polypropylene oxide Polyvinyl alcohol; polyvinyl butyral; norbornene resins.

  The above resins may be used singly, or may be used as a mixture of two or more kinds and / or copolymers depending on the use, or laminated. The film may have a single layer structure or a laminated multilayer structure. In the case of a multilayer structure, the ultraviolet absorber of the general formula (1), in particular, the general formula (2) may be used more than one layer.

  Various additives may be used for the synthetic resin used in the ultraviolet light shielding container of the present invention as necessary, and surface treatment may be further performed.

  Examples of the additives include antioxidants (phenolic, phosphorus-based or thioether-based), UV absorbers other than the triazine compounds according to the present invention, hindered amine light stabilizers, near infrared absorbers, nucleating agents, charging Inhibitors, light-absorbing pigments, pigments, dyes, lubricants, processing aids, plasticizers, metal deactivators, inorganic fine particles, halogen compounds, phosphate ester compounds, phosphate amide compounds, melamine compounds And flame retardants such as fluororesin, silicon resin, metal oxide, (poly) melamine phosphate, and (poly) piperazine phosphate.

  Examples of the phenolic antioxidant include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-ditert-butyl-4). -Hydroxybenzyl) phosphonate, 1,6-hexamethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide], 4,4'-thiobis (6-tert-butyl-m-cresol ), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-butylidenebis (6-tert-butyl) -M-cresol), 2,2'-ethylidenebis (4,6-ditert-butylphenol), 2,2'-ethylidenebis (4-secondarybutyl-6-tert-butylphenol) Nol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tertiary) Butylbenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4- Hydroxybenzyl) -2,4,6-trimethylbenzene, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, stearyl (3,5- Di-tert-butyl-4-hydroxyphenyl) propionate, thiodiethylene glycol bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethy Bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, bis [2- Tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris [(3,5-ditert-butyl-4- Hydroxyphenyl) propionyloxyethyl] isocyanurate, 3,9-bis [1,1-dimethyl-2-{(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4 , 8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) Propionate], tocophenol and the like.

  Examples of the phosphorus antioxidant include trisnonylphenyl phosphite and tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl]. Phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di Tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritert-butylphenyl) pentaerythritol diphosphite Phosphite, bis (2,4-dicumylphenyl) penta Rithritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) -4,4'-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl)- 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane triphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, 9,10-dihydro- 9-oxa-10-phosphaphenanthrene-10-oxide, 2,2′-methylenebis (4,6-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2′-methylenebis (4,6- Tert-butylphenyl) -octadecyl phosphite, 2,2′-ethylidenebis (4 -Di-tert-butylphenyl) fluorophosphite, tris (2-[(2,4,8,10-tetrakis tert-butyldibenzo [d, f] [1,3,2] dioxaphosphine-6- Yl) oxy] ethyl) amine, 2- (1,1-dimethylethyl) -6-methyl-4- [3-[[2,4,8,10-trakis (1,1-dimethylethyl) dibenzo [d , F] [1,3,2] dioxaphosphin-6-yl] oxy] propyl] phenol, phosphite of 2-ethyl-2-butylpropylene glycol and 2,4,6-tritert-butylphenol, etc. Is mentioned.

  Examples of the thioether-based antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, and pentaerythritol tetra (β-dodecyl mercaptopropionate). Examples include β-alkyl mercaptopropionic esters of polyols.

  Examples of the ultraviolet absorber other than the triazine compound according to the present invention include benzotriazole-based, benzophenone-based, benzoate-based, and triazine-based ultraviolet absorbers other than the triazine-based ultraviolet absorber represented by the general formula (1) or (2). Agents.

  Although it does not specifically limit as said benzotriazole type ultraviolet absorber, For example, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-dairy). Tributylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-) Tert-octylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-dicumylphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-carboxyphenyl) 2- (2′-hydroxyphenol) such as benzotriazole, 2,2′-methylenebis (4-tert-octyl-6-benzotriazolyl) phenol Le) benzotriazoles, and the like.

  Although it does not specifically limit as said benzophenone series ultraviolet absorber, For example, 2, 4- dihydroxy benzophenone, 2-hydroxy-4- methoxy benzophenone, 2-hydroxy-4- octoxy benzophenone, 5,5'- methylenebis (2 2-hydroxybenzophenones such as -hydroxy-4-methoxybenzophenone).

  The benzoate ultraviolet absorber is not particularly limited, and examples thereof include phenyl salicylate, resorcinol monobenzoate, 2,4-ditertiarybutylphenyl-3,5-ditertiarybutyl-4-hydroxybenzoate, 2,4 -Ditertiary amylphenyl-3,5-ditertiarybutyl-4-hydroxybenzoate, hexadecyl-3,5-ditertiarybutyl-4-hydroxybenzoate and the like.

  Examples of the triazine-based UV absorber other than the triazine-based UV absorber represented by the general formula (1) or (2) include 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2 , 4-Dimethylphenyl) -s-triazine, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyl-s-triazine, 2- (2-hydroxy-4-propoxy-5-methylphenyl) ) -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-dibiphenyl-s-triazine, 2,4-bis (2-hydroxy-4-octoxyphenyl) -6- (2,4-dimethylphenyl) -s-triazine, 2,4,6-tris (2-hydroxy-4-octoxypheny ) -S-triazine, 2- (4-iso-octyloxycarbonylethoxy) -4,6 triaryl triazines such as diphenyl -s-triazine.

  Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2, 6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate , Tetrakis (2,2,6,6-tetramethyl-4-piperidylbutanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidylbutanetetracarboxylate, bis (2,2, 6,6-tetramethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2, , 6,6-pentamethyl-4-piperidyl) .di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2 -Butyl-2- (3,5-ditert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate Condensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1,6-bis (2,2,6,6-tetramethyl- 4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2 4- Chloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl- 4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,6,11-tris [2 , 4-Bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-ylaminoundecane, 1,6,11-tris [2, 4-Bis (N-butyl-N- (1,2,2,6,6-pentamethyl And hindered amine compounds such as -4-piperidyl) amino) -s-triazin-6-ylaminoundecane.

  Examples of the near infrared absorber include polymethine dyes (cyanine dyes), indolinocyanine dyes, phthalocyanine dyes, naphthalocyanine dyes, naphthol metal complex dyes, squarylium dyes, triazo dyes, dithiol metal complex dyes , Pyrium dyes, thiapyrylium dyes, indoaniline dyes, azoanthraquinone dyes, naphthoquinone dyes, anthroquinone dyes, bis (dithiolene) dyes, triphenylmethane dyes, aminium (aluminum) dyes, diimonium dyes, etc. Further, an inorganic near infrared absorber may be used, for example, tin oxide doped with carbon black, antimony oxide or indium oxide, an oxide, carbide or boron of a metal belonging to Group 4A, 5A or 6A of the periodic table. Monster It is below.

  Examples of the nucleating agent include metal salts of benzoic acids such as aluminum pt-butylbenzoate and sodium benzoate, sodium bis (2,4-di-t-butylphenyl) phosphate, methylene bis (2 , 4-di-t-butylphenyl) phosphate sodium salt, bis [methylenebis (2,4-di-t-butylphenyl) phosphate ester] hydroxyaluminum, etc., aromatic phosphate metal salts and aromatic phosphates Examples thereof include mixtures of ester metal salts and alkali metal compounds, dibenzylidene sorbitols such as dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, bis (dimethylbenzylidene sorbitol), amino acid metal salts, and rosin acid metal salts.

  Examples of the antistatic agent include cationic antistatic agents such as fatty acid quaternary ammonium ion salts and polyamine quaternary salts; higher alcohol phosphate esters, higher alcohol EO adducts, polyethylene glycol fatty acid esters, anionic type Anionic antistatic agents such as alkyl sulfonates, higher alcohol sulfates, higher alcohol ethylene oxide adduct sulfates, higher alcohol ethylene oxide adduct phosphates; polyhydric alcohol fatty acid esters, polyglycol phosphates, poly Nonionic antistatic agents such as oxyethylene alkyl allyl ether; amphoteric antistatic agents such as amphoteric alkylbetaines such as alkyldimethylaminoacetic acid betaine and imidazoline type amphoteric activators. Such an antistatic agent may be used alone, or two or more kinds of antistatic agents may be used in combination.

  Examples of the surface treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, and ozone oxidation treatment. Can be mentioned. A large number of irregularities, lines, etc. may be provided on the surface by the surface treatment.

  The use of the ultraviolet light shielding container of the present invention is not limited as long as it is for the purpose of shielding ultraviolet light, but it is a chemical container for pharmaceuticals, vitamins, drinks, eye drops, etc .; cosmetic container such as lotion, emulsion, sunscreen; food Can be used for containers, beverage containers such as liquor, wine, beer, fruit juice, soft drinks, tea, tea, coffee, etc .; daily necessities containers such as shampoo, rinse, gargle, toothpaste, disinfectant. In particular, it can be preferably used for a container having transparency capable of confirming the state of the contents.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by the following examples.

[Example 1]
With respect to 100 parts by mass of polyethylene terephthalate (intrinsic viscosity: 0.8 dL / g), compound no. 0.3 parts by mass of 1 UV absorber was added and mixed to obtain a polyethylene terephthalate resin composition. The obtained resin composition was dried in a gear oven at 160 ° C. for 4 hours, and then a preform (outer diameter 25 mm, weight 23 g) was molded with an injection molding machine at a molding temperature of 280 ° C. Next, the obtained preform was biaxially stretch blow molded at a mold temperature of 130 ° C. to produce a plastic bottle having a capacity of 500 mL and a thickness of 0.7 mm. About the obtained plastic bottle, the transmittance | permeability of visible light with a wavelength of 500 nm and the transmittance | permeability of the ultraviolet-ray with a wavelength of 400 nm were measured. The results are shown in Table 1.

  Further, a solution obtained by dissolving 80 mg of sodium azulenesulfonate, which is an anti-inflammatory drug, in 400 mL of purified water was sealed in the obtained plastic bottle and sealed with a cap. This plastic bottle was irradiated with a 27 W fluorescent lamp from a distance of 15 cm for 168 hours (one week), and the residual rate (%) of sodium azulenesulfonate was measured. The results are shown in Table 1.

[Comparative Example 1]
As an ultraviolet absorber, Compound No. 1 is a monohydroxyphenyl triazine compound having a structure similar to that of the present triazine compound, the following compound No. 1 A plastic bottle was prepared in the same manner as in Example 1 except that 6 was used. About the obtained plastic bottle, the transmittance | permeability of visible light with a wavelength of 500 nm and the transmittance | permeability of the ultraviolet-ray with a wavelength of 400 nm were measured. The results are shown in Table 1.

  Further, in the same manner as in Example 1, the obtained plastic bottle was sealed with a solution prepared by dissolving 80 mg of sodium azulenesulfonate, an anti-inflammatory drug, in 400 mL of purified water, sealed with a cap, and a 27 W fluorescent lamp was used. Irradiation was performed from a distance of 15 cm for 168 hours (one week), and the residual rate (%) of sodium azulenesulfonate was measured. The results are shown in Table 1.

[Comparative Example 2]
As an ultraviolet absorber, Compound No. In place of 1, a benzotriazole ultraviolet absorber, the following compound No. 1 A plastic bottle was prepared in the same manner as in Example 1 except that 7. About the obtained plastic bottle, the transmittance | permeability of visible light with a wavelength of 500 nm and the transmittance | permeability of the ultraviolet-ray with a wavelength of 400 nm were measured. The results are shown in Table 1.

  Further, in the same manner as in Example 1, the obtained plastic bottle was sealed with a solution prepared by dissolving 80 mg of sodium azulenesulfonate, an anti-inflammatory drug, in 400 mL of purified water, sealed with a cap, and a 27 W fluorescent lamp was used. Irradiation was performed from a distance of 15 cm for 168 hours (one week), and the residual rate (%) of sodium azulenesulfonate was measured. The results are shown in Table 1.

[Comparative Example 3]
As an ultraviolet absorber, Compound No. In place of 1, a benzotriazole ultraviolet absorber, the following compound No. 1 A plastic bottle was prepared in the same manner as in Example 1 except that 8 was used. About the obtained plastic bottle, the transmittance | permeability of visible light with a wavelength of 500 nm and the transmittance | permeability of the ultraviolet-ray with a wavelength of 400 nm were measured. The results are shown in Table 1.

  Further, in the same manner as in Example 1, the obtained plastic bottle was sealed with a solution prepared by dissolving 80 mg of sodium azulenesulfonate, an anti-inflammatory drug, in 400 mL of purified water, sealed with a cap, and a 27 W fluorescent lamp was used. Irradiation was performed from a distance of 15 cm for 168 hours (one week), and the residual rate (%) of sodium azulenesulfonate was measured. The results are shown in Table 1.

[Comparative Example 4]

  As an ultraviolet absorber, Compound No. In place of 1, a benzophenone ultraviolet absorber, the following compound No. A plastic bottle was prepared in the same manner as in Example 1 except that 9 was used. About the obtained plastic bottle, the transmittance | permeability of visible light with a wavelength of 500 nm and the transmittance | permeability of the ultraviolet-ray with a wavelength of 400 nm were measured. The results are shown in Table 1.

  Moreover, the solution which melt | dissolved 80 mg of sodium azulene sulfonate which is an anti-inflammatory drug in 400 mL of purified water was enclosed with the obtained plastic bottle like Example 1, and it sealed with the cap, and the 27W fluorescent lamp was 15 cm. Irradiation was performed for 168 hours (one week) from a distance, and the residual rate (%) of sodium azulenesulfonate was measured. The results are shown in Table 1.

[Comparative Example 5]
A plastic bottle was produced in the same manner as in Example 1 except that no ultraviolet absorber was used. About the obtained plastic bottle, the transmittance | permeability of visible light with a wavelength of 500 nm and the transmittance | permeability of the ultraviolet-ray with a wavelength of 400 nm were measured. The results are shown in Table 1.

  Further, a solution obtained by dissolving 80 mg of sodium azulenesulfonate, which is an anti-inflammatory drug, in 400 mL of purified water was sealed in the obtained plastic bottle and sealed with a cap. This plastic bottle was irradiated with a 27 W fluorescent lamp from a distance of 15 cm for 168 hours (one week), and the residual rate (%) of sodium azulenesulfonate was measured. The results are shown in Table 1.

From the above, it was confirmed that the ultraviolet light shielding container of the present invention efficiently absorbs ultraviolet rays and sufficiently secures visible light transmittance.

Claims (11)

In an ultraviolet light shielding container using an ultraviolet absorber,
The ultraviolet absorber is represented by the following general formula (1),

(Wherein R ^{1 to} R ³ may be the same as or different from each other, a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or 2 carbon atoms) Represents an alkenyl group having 8 to 8 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylaryl group having 7 to 18 carbon atoms, or an arylalkyl group having 7 to 18 carbon atoms, an alkyl group, a cycloalkyl group, an alkenyl group, The aryl group, alkylaryl group or arylalkyl group may be substituted with a hydroxy group, a halogen atom, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, It may be interrupted by a sulfur atom, a carbonyl group, an ester group, an amide group or an imino group, and further, substitution and interruption may be combined, and R ⁴ -R ⁶ may be the same or different from each other and represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms). Ultraviolet light shielding container characterized by The ultraviolet absorber is represented by the following general formula (2),

(Wherein R ^{7 to} R ⁹ may be the same as or different from each other, and represent a linear or branched alkyl group having 1 to 12 carbon atoms, and the alkyl group is substituted with a hydroxy group, a halogen atom or an alkoxy group) And may be interrupted by an oxygen atom, a sulfur atom, a carbonyl group, an ester group, an amide group, or an imino group). container.   The ultraviolet light shielding container according to claim 1 or 2, wherein the transmittance of visible light having a wavelength of 500 nm is from 80% to 100%, and the transmittance of ultraviolet light having a wavelength of 400 nm is from 0% to 5.0%.   The ultraviolet light shielding container according to any one of claims 1 to 3, comprising a synthetic resin into which the ultraviolet absorber is kneaded.   The ultraviolet light shielding container according to claim 4, which has a bottle shape.   The ultraviolet light shielding container according to claim 1, wherein the ultraviolet absorber is coated.   The ultraviolet light shielding container according to any one of claims 1 to 3, wherein a synthetic resin film in which the ultraviolet absorbent is kneaded is attached.   The ultraviolet light shielding container according to any one of claims 1 to 3, wherein a synthetic resin film coated with the ultraviolet absorber is attached.   The ultraviolet light shielding container according to any one of claims 1 to 8, which is used for medicine.   It is an object for cosmetics, The ultraviolet light shielding container of any one of Claims 1-8. The ultraviolet light shielding container according to any one of claims 1 to 8, which is used for beverages or foods.